Electrolysis cell stimulation

NASA Technical Reports Server (NTRS)

Gordon, L. H.; Phillips, B. R.; Evangelista, J.

1978-01-01

Computer program represents attempt to understand and model characteristics of electrolysis cells. It allows user to determine how cell efficiency is affected by temperature, pressure, current density, electrolyte concentration, characteristic dimensions, membrane resistance, and electrolyte circulation rate. It also calculates ratio of bubble velocity to electrolyte velocity for anode and cathode chambers.

Influence of γ-phase on corrosion resistance of Zn–Ni alloy electrodeposition from acetate electrolytic bath

NASA Astrophysics Data System (ADS)

Selvaraju, V.; Thangaraj, V.

2018-05-01

The electrodeposition of Zn–Ni alloy containing 10% to 15% nickel was deposited from acetate electrolytic bath. The effect of current density, pH, temperature, cathodic current efficiency on the deposition of Zn–Ni alloy and the throwing power ability of the solution was investigated. The composition of the deposits and the morphology were strongly influenced by the temperature and applied current density. Corrosion resistance of a Zn–Ni alloy deposit was increases with the increase of current density. Zn–Ni alloy deposits shows higher corrosion resistance at optimum current density of 3.0 A dm‑2. X-Ray diffraction measurement confirms the presence of γ –phase Zn–Ni alloy deposition. The XRD reflection of Zn–Ni (831) was found to be increased with increase in current density. SEM studies reveal that the nanovial structure of Zn–Ni alloy deposited at 3.0 A dm‑2 gives high protection against corrosion.

Battery using a metal particle bed electrode

DOEpatents

Evans, J.V.; Savaskan, G.

1991-04-09

A zinc-air battery in a case is described including a zinc particle bed supported adjacent the current feeder and diaphragm on a porous support plate which holds the particles but passes electrolyte solution. Electrolyte is recycled through a conduit between the support plate and top of the bed by convective forces created by a density of differential caused by a higher concentration of high density discharge products in the interstices of the bed than in the electrolyte recycle conduit. 7 figures.

All-solid-state Al-air batteries with polymer alkaline gel electrolyte

NASA Astrophysics Data System (ADS)

Zhang, Zhao; Zuo, Chuncheng; Liu, Zihui; Yu, Ying; Zuo, Yuxin; Song, Yu

2014-04-01

Aluminum-air (Al-air) battery is one of the most promising candidates for next-generation energy storage systems because of its high capacity and energy density, and abundance. The polyacrylic acid (PAA)-based alkaline gel electrolyte is used in all-solid-state Al-air batteries instead of aqueous electrolytes to prevent leakage. The optimal gel electrolyte exhibits an ionic conductivity of 460 mS cm-1, which is close to that of aqueous electrolytes. The Al-air battery peak capacity and energy density considering only Al can reach 1166 mAh g-1-Al and 1230 mWh g-1-Al, respectively, during constant current discharge. The battery prototype also exhibits a high power density of 91.13 mW cm-2. For the battery is a laminated structure, area densities of 29.2 mAh cm-2 and 30.8 mWh cm-2 are presented to appraise the performance of the whole cell. A novel design to inhibit anodic corrosion is proposed by separating the Al anode from the gel electrolyte when not in use, thereby effectively maintaining the available capacity of the battery.

Stabilizing electrodeposition in elastic solid electrolytes containing immobilized anions

PubMed Central

Tikekar, Mukul D.; Archer, Lynden A.; Koch, Donald L.

2016-01-01

Ion transport–driven instabilities in electrodeposition of metals that lead to morphological instabilities and dendrites are receiving renewed attention because mitigation strategies are needed for improving rechargeability and safety of lithium batteries. The growth rate of these morphological instabilities can be slowed by immobilizing a fraction of anions within the electrolyte to reduce the electric field at the metal electrode. We analyze the role of elastic deformation of the solid electrolyte with immobilized anions and present theory combining the roles of separator elasticity and modified transport to evaluate the factors affecting the stability of planar deposition over a wide range of current densities. We find that stable electrodeposition can be easily achieved even at relatively high current densities in electrolytes/separators with moderate polymer-like mechanical moduli, provided a small fraction of anions are immobilized in the separator. PMID:27453943

The anodizing behavior of aluminum in malonic acid solution and morphology of the anodic films

NASA Astrophysics Data System (ADS)

Ren, Jianjun; Zuo, Yu

2012-11-01

The anodizing behavior of aluminum in malonic acid solution and morphology of the anodic films were studied. The voltage-time response for galvanostatic anodization of aluminum in malonic acid solution exhibits a conventional three-stage feature but the formation voltage is much higher. With the increase of electrolyte concentration, the electrolyte viscosity increases simultaneously and the high viscosity decreases the film growth rate. With the concentration increase of the malonic acid electrolyte, the critical current density that initiates local "burning" on the sample surface decreases. For malonic acid anodization, the field-assisted dissolution on the oxide surface is relatively weak and the nucleation of pores is more difficult, which results in greater barrier layer thickness and larger cell dimension. The embryo of the porous structure of anodic film has been created within the linear region of the first transient stage, and the definite porous structure has been established before the end of the first transient stage. The self-ordering behavior of the porous film is influenced by the electrolyte concentration, film thickness and the applied current density. Great current density not only improves the cell arrangement order but also brings about larger cell dimension.

Computational Fluid Dynamics-Population Balance Model Simulation of Effects of Cell Design and Operating Parameters on Gas-Liquid Two-Phase Flows and Bubble Distribution Characteristics in Aluminum Electrolysis Cells

NASA Astrophysics Data System (ADS)

Zhan, Shuiqing; Wang, Junfeng; Wang, Zhentao; Yang, Jianhong

2018-02-01

The effects of different cell design and operating parameters on the gas-liquid two-phase flows and bubble distribution characteristics under the anode bottom regions in aluminum electrolysis cells were analyzed using a three-dimensional computational fluid dynamics-population balance model. These parameters include inter-anode channel width, anode-cathode distance (ACD), anode width and length, current density, and electrolyte depth. The simulations results show that the inter-anode channel width has no significant effect on the gas volume fraction, electrolyte velocity, and bubble size. With increasing ACD, the above values decrease and more uniform bubbles can be obtained. Different effects of the anode width and length can be concluded in different cell regions. With increasing current density, the gas volume fraction and electrolyte velocity increase, but the bubble size keeps nearly the same. Increasing electrolyte depth decreased the gas volume fraction and bubble size in particular areas and the electrolyte velocity increased.

Novel Non-Carbonate Based Electrolytes for Silicon Anodes

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zhu, Ye; Yang, Johnny; Cheng, Gang

2016-09-09

Substantial improvement in the energy density of rechargeable lithium batteries is required to meet the future needs for electric and plug-in electric vehicles (EV and PHEV). Present day lithium ion battery technology is based on shuttling lithium between graphitic carbon and inorganic oxides. Non-graphitic anodes, such as silicon can provide significant improvements in energy density but are currently limited in cycle life due to reactivity with the electrolyte. Wildcat/3M proposes the development of non-carbonate electrolyte formulations tailored for silicon alloy anodes. Combining these electrolytes with 3M’s anode and an NMC cathode will enable up to a 20% increase in themore » volumetric cell energy density, while still meeting the PHEV/EV cell level cycle/calendar life goals.« less

A review of electrolyte materials and compositions for electrochemical supercapacitors.

PubMed

Zhong, Cheng; Deng, Yida; Hu, Wenbin; Qiao, Jinli; Zhang, Lei; Zhang, Jiujun

2015-11-07

Electrolytes have been identified as some of the most influential components in the performance of electrochemical supercapacitors (ESs), which include: electrical double-layer capacitors, pseudocapacitors and hybrid supercapacitors. This paper reviews recent progress in the research and development of ES electrolytes. The electrolytes are classified into several categories, including: aqueous, organic, ionic liquids, solid-state or quasi-solid-state, as well as redox-active electrolytes. Effects of electrolyte properties on ES performance are discussed in detail. The principles and methods of designing and optimizing electrolytes for ES performance and application are highlighted through a comprehensive analysis of the literature. Interaction among the electrolytes, electro-active materials and inactive components (current collectors, binders, and separators) is discussed. The challenges in producing high-performing electrolytes are analyzed. Several possible research directions to overcome these challenges are proposed for future efforts, with the main aim of improving ESs' energy density without sacrificing existing advantages (e.g., a high power density and a long cycle-life) (507 references).

An empirical model for parameters affecting energy consumption in boron removal from boron-containing wastewaters by electrocoagulation.

PubMed

Yilmaz, A Erdem; Boncukcuoğlu, Recep; Kocakerim, M Muhtar

2007-06-01

In this study, it was investigated parameters affecting energy consumption in boron removal from boron containing wastewaters prepared synthetically, via electrocoagulation method. The solution pH, initial boron concentration, dose of supporting electrolyte, current density and temperature of solution were selected as experimental parameters affecting energy consumption. The obtained experimental results showed that boron removal efficiency reached up to 99% under optimum conditions, in which solution pH was 8.0, current density 6.0 mA/cm(2), initial boron concentration 100mg/L and solution temperature 293 K. The current density was an important parameter affecting energy consumption too. High current density applied to electrocoagulation cell increased energy consumption. Increasing solution temperature caused to decrease energy consumption that high temperature decreased potential applied under constant current density. That increasing initial boron concentration and dose of supporting electrolyte caused to increase specific conductivity of solution decreased energy consumption. As a result, it was seen that energy consumption for boron removal via electrocoagulation method could be minimized at optimum conditions. An empirical model was predicted by statistically. Experimentally obtained values were fitted with values predicted from empirical model being as following; [formula in text]. Unfortunately, the conditions obtained for optimum boron removal were not the conditions obtained for minimum energy consumption. It was determined that support electrolyte must be used for increase boron removal and decrease electrical energy consumption.

Spiro-(1,1‧)-bipyrrolidinium tetrafluoroborate salt as high voltage electrolyte for electric double layer capacitors

NASA Astrophysics Data System (ADS)

Yu, Xuewen; Ruan, Dianbo; Wu, Changcheng; Wang, Jing; Shi, Zhiqiang

2014-11-01

A novel quaternary ammonium salt based on spiro-(1,1‧)-bipyrolidinium tetrafluoroborate (SBP-BF4) has been synthesized and dissolved in propylene carbonate (PC) with 1.5 mol L-1 (M) concentration for electric double-layer capacitors (EDLCs). The physic-chemical properties and electrochemical performance of SBP-BF4/PC electrolyte are investigated. Compared with the standard electrolyte 1.5 M TEMA-BF4 in PC, the novel SBP-BF4/PC electrolyte exhibited much better electrochemical performance due to its smaller cation size, lower viscosity and higher conductivity. The specific discharge capacitance of activated carbon electrode based EDLCs using SBP-BF4/PC electrolyte is 120 F g-1, the energy density and power density can reach 31 kW kg-1 and 6938 W kg-1, respectively, when the working voltage is 2.7 V and current density is 50 mA g-1. The withstand voltage of activated carbon based EDLCs with SBP-BF4/PC electrolyte can reach to 3.2 V, where the stable discharge capacitance and energy density are 121 F g-1 and 43 Wh kg-1, respectively.

Status and applicability of solid polymer electrolyte technology to electrolytic hydrogen and oxygen production

NASA Technical Reports Server (NTRS)

Titterington, W. A.

1973-01-01

The solid polymer electrolyte (SPE) water electrolysis technology is presented as a potential energy conversion method for wind driven generator systems. Electrolysis life and performance data are presented from laboratory sized single cells (7.2 sq in active area) with high cell current density selected (1000 ASF) for normal operation.

Effects of temperature and gas-liquid mass transfer on the operation of small electrochemical cells for the quantitative evaluation of CO2 reduction electrocatalysts.

PubMed

Lobaccaro, Peter; Singh, Meenesh R; Clark, Ezra Lee; Kwon, Youngkook; Bell, Alexis T; Ager, Joel W

2016-09-29

In the last few years, there has been increased interest in electrochemical CO 2 reduction (CO2R). Many experimental studies employ a membrane separated, electrochemical cell with a mini H-cell geometry to characterize CO2R catalysts in aqueous solution. This type of electrochemical cell is a mini-chemical reactor and it is important to monitor the reaction conditions within the reactor to ensure that they are constant throughout the study. We show that operating cells with high catalyst surface area to electrolyte volume ratios (S/V) at high current densities can have subtle consequences due to the complexity of the physical phenomena taking place on electrode surfaces during CO2R, particularly as they relate to the cell temperature and bulk electrolyte CO 2 concentration. Both effects were evaluated quantitatively in high S/V cells using Cu electrodes and a bicarbonate buffer electrolyte. Electrolyte temperature is a function of the current/total voltage passed through the cell and the cell geometry. Even at a very high current density, 20 mA cm -2 , the temperature increase was less than 4 °C and a decrease of <10% in the dissolved CO 2 concentration is predicted. In contrast, limits on the CO 2 gas-liquid mass transfer into the cells produce much larger effects. By using the pH in the cell to measure the CO 2 concentration, significant undersaturation of CO 2 is observed in the bulk electrolyte, even at more modest current densities of 10 mA cm -2 . Undersaturation of CO 2 produces large changes in the faradaic efficiency observed on Cu electrodes, with H 2 production becoming increasingly favored. We show that the size of the CO 2 bubbles being introduced into the cell is critical for maintaining the equilibrium CO 2 concentration in the electrolyte, and we have designed a high S/V cell that is able to maintain the near-equilibrium CO 2 concentration at current densities up to 15 mA cm -2 .

Effects of temperature and gas–liquid mass transfer on the operation of small electrochemical cells for the quantitative evaluation of CO 2 reduction electrocatalysts

DOE PAGES

Lobaccaro, Peter; Singh, Meenesh R.; Clark, Ezra Lee; ...

2016-09-06

In the last few years, there has been increased interest in electrochemical CO 2 reduction (CO2R). Many experimental studies employ a membrane separated, electrochemical cell with a mini H-cell geometry to characterize CO2R catalysts in aqueous solution. This type of electrochemical cell is a mini-chemical reactor and it is important to monitor the reaction conditions within the reactor to ensure that they are constant throughout the study. Here we show that operating cells with high catalyst surface area to electrolyte volume ratios (S/V) at high current densities can have subtle consequences due to the complexity of the physical phenomena takingmore » place on electrode surfaces during CO2R, particularly as they relate to the cell temperature and bulk electrolyte CO 2 concentration. Both effects were evaluated quantitatively in high S/V cells using Cu electrodes and a bicarbonate buffer electrolyte. Electrolyte temperature is a function of the current/total voltage passed through the cell and the cell geometry. Even at a very high current density, 20 mA cm -2 , the temperature increase was less than 4 °C and a decrease of < 10% in the dissolved CO 2 concentration is predicted. In contrast, limits on the CO 2 gas-liquid mass transfer into the cells produce much larger effects. By using the pH in the cell to measure the CO 2 concentration, significant undersaturation of CO 2 is observed in the bulk electrolyte, even at more modest current densities of 10 mA cm -2 . Undersaturation of CO 2 produces large changes in the faradaic efficiency observed on Cu electrodes, with H 2 production becoming increasingly favored. Finally, we show that the size of the CO 2 bubbles being introduced into the cell is critical for maintaining the equilibrium CO 2 concentration in the electrolyte, and we have designed a high S/V cell that is able to maintain the near-equilibrium CO 2 concentration at current densities up to 15 mA cm -2.« less

Effects of temperature and gas–liquid mass transfer on the operation of small electrochemical cells for the quantitative evaluation of CO 2 reduction electrocatalysts

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lobaccaro, Peter; Singh, Meenesh R.; Clark, Ezra Lee

In the last few years, there has been increased interest in electrochemical CO 2 reduction (CO2R). Many experimental studies employ a membrane separated, electrochemical cell with a mini H-cell geometry to characterize CO2R catalysts in aqueous solution. This type of electrochemical cell is a mini-chemical reactor and it is important to monitor the reaction conditions within the reactor to ensure that they are constant throughout the study. Here we show that operating cells with high catalyst surface area to electrolyte volume ratios (S/V) at high current densities can have subtle consequences due to the complexity of the physical phenomena takingmore » place on electrode surfaces during CO2R, particularly as they relate to the cell temperature and bulk electrolyte CO 2 concentration. Both effects were evaluated quantitatively in high S/V cells using Cu electrodes and a bicarbonate buffer electrolyte. Electrolyte temperature is a function of the current/total voltage passed through the cell and the cell geometry. Even at a very high current density, 20 mA cm -2 , the temperature increase was less than 4 °C and a decrease of < 10% in the dissolved CO 2 concentration is predicted. In contrast, limits on the CO 2 gas-liquid mass transfer into the cells produce much larger effects. By using the pH in the cell to measure the CO 2 concentration, significant undersaturation of CO 2 is observed in the bulk electrolyte, even at more modest current densities of 10 mA cm -2 . Undersaturation of CO 2 produces large changes in the faradaic efficiency observed on Cu electrodes, with H 2 production becoming increasingly favored. Finally, we show that the size of the CO 2 bubbles being introduced into the cell is critical for maintaining the equilibrium CO 2 concentration in the electrolyte, and we have designed a high S/V cell that is able to maintain the near-equilibrium CO 2 concentration at current densities up to 15 mA cm -2.« less

Green synthesis of in situ electrodeposited rGO/MnO2 nanocomposite for high energy density supercapacitors.

PubMed

Rusi; Majid, S R

2015-11-05

This paper presents the preparation of in situ electrodeposited rGO/MnO2 nanocomposite as a binder-free electrode for supercapacitor application. The work describes and evaluates the performance of prepared electrode via green and facile electrodeposition technique of in situ rGO/MnO2-glucose carbon nanocomposites. The carbon content in the composite electrode increased after GO and D (+) glucose solution has been added in the deposition electrolyte. This study found that a suitable concentration of D (+) glucose in the deposition electrolyte can slow down the nucleation process of MnO2 particles and lead to uniform and ultrathin nanoflakes structure. The optimize electrode exhibited low transfer resistance and resulted on excellent electrochemical performance in three electrolyte systems viz. Na2SO4, KOH and KOH/K3Fe(CN)6 redox electrolytes. The optimum energy density and power density were 1851 Whkg(-1) and 68 kWkg(-1) at current density of 20 Ag(-1) in mixed KOH/K3Fe(CN)6 electrolyte.

Green synthesis of in situ electrodeposited rGO/MnO2 nanocomposite for high energy density supercapacitors

NASA Astrophysics Data System (ADS)

Rusi; Majid, S. R.

2015-11-01

This paper presents the preparation of in situ electrodeposited rGO/MnO2 nanocomposite as a binder-free electrode for supercapacitor application. The work describes and evaluates the performance of prepared electrode via green and facile electrodeposition technique of in situ rGO/MnO2-glucose carbon nanocomposites. The carbon content in the composite electrode increased after GO and D (+) glucose solution has been added in the deposition electrolyte. This study found that a suitable concentration of D (+) glucose in the deposition electrolyte can slow down the nucleation process of MnO2 particles and lead to uniform and ultrathin nanoflakes structure. The optimize electrode exhibited low transfer resistance and resulted on excellent electrochemical performance in three electrolyte systems viz. Na2SO4, KOH and KOH/K3Fe(CN)6 redox electrolytes. The optimum energy density and power density were 1851 Whkg-1 and 68 kWkg-1 at current density of 20 Ag-1 in mixed KOH/K3Fe(CN)6 electrolyte.

Green synthesis of in situ electrodeposited rGO/MnO2 nanocomposite for high energy density supercapacitors

PubMed Central

Rusi; Majid, S. R.

2015-01-01

This paper presents the preparation of in situ electrodeposited rGO/MnO2 nanocomposite as a binder-free electrode for supercapacitor application. The work describes and evaluates the performance of prepared electrode via green and facile electrodeposition technique of in situ rGO/MnO2-glucose carbon nanocomposites. The carbon content in the composite electrode increased after GO and D (+) glucose solution has been added in the deposition electrolyte. This study found that a suitable concentration of D (+) glucose in the deposition electrolyte can slow down the nucleation process of MnO2 particles and lead to uniform and ultrathin nanoflakes structure. The optimize electrode exhibited low transfer resistance and resulted on excellent electrochemical performance in three electrolyte systems viz. Na2SO4, KOH and KOH/K3Fe(CN)6 redox electrolytes. The optimum energy density and power density were 1851 Whkg−1 and 68 kWkg−1 at current density of 20 Ag−1 in mixed KOH/K3Fe(CN)6 electrolyte. PMID:26537363

Electrode kinetics of a water vapor electrolysis cell

NASA Technical Reports Server (NTRS)

Jacobs, G.

1974-01-01

The anodic electrochemical behavior of the water vapor electrolysis cell was investigated. A theoretical review of various aspects of cell overvoltage is presented with special emphasis on concentration overvoltage and activation overvoltage. Other sources of overvoltage are described. The experimental apparatus controlled and measured anode potential and cell current. Potentials between 1.10 and 2.60 V (vs NHE) and currents between 0.1 and 3000 mA were investigated. Different behavior was observed between the standard cell and the free electrolyte cell. The free electrolyte cell followed typical Tafel behavior (i.e. activation overvoltage) with Tafel slopes of about 0.15, and the exchange current densities of 10 to the minus 9th power A/sq cm, both in good agreement with literature values. The standard cell exhibitied this same Tafel behavior at lower current densities but deviated toward lower than expected current densities at higher potentials. This behavior and other results were examined to determine their origin.

Stable electrolyte for high voltage electrochemical double-layer capacitors

DOE PAGES

Ruther, Rose E.; Sun, Che -Nan; Holliday, Adam; ...

2016-12-28

A simple electrolyte consisting of NaPF 6 salt in 1,2-dimethoxyethane (DME) can extend the voltage window of electric double-layer capacitors (EDLCs) to >3.5 V. DME does not passivate carbon electrodes at very negative potentials (near Na/Na +), extending the practical voltage window by about 1.0 V compared to standard, non-aqueous electrolytes based on acetonitrile. The voltage window is demonstrated in two- and three-electrode cells using a combination of electrochemical impedance spectroscopy (EIS), charge-discharge cycling, and measurements of leakage current. DME-based electrolytes cannot match the high conductivity of acetonitrile solutions, but they can satisfy applications that demand high energy density atmore » moderate power. The conductivity of NaPF 6 in DME is comparable to commercial lithium-ion battery electrolytes and superior to most ionic liquids. Lastly, factors that limit the voltage window and EDLC energy density are discussed, and strategies to further boost energy density are proposed.« less

Comparison of chitosan and chitosan nanoparticles on the performance and charge recombination of water-based gel electrolyte in dye sensitized solar cells.

PubMed

Khalili, Malihe; Abedi, Mohammad; Amoli, Hossein Salar; Mozaffari, Seyed Ahmad

2017-11-01

In commercialization of liquid dye-sensitized solar cells (DSSCs), whose leakage, evaporation and toxicity of organic solvents are limiting factors, replacement of organic solvents with water-based gel electrolyte is recommended. This work reports on utilizing and comparison of chitosan and chitosan nanoparticle as different gelling agents in preparation of water-based gel electrolyte in fabrication of dye sensitized solar cells. All photovoltaic parameters such as open circuit voltage (V oc ), fill factor (FF), short circuit current density (J sc ) and conversion efficiency (η) were measured. For further characterization, electrochemical impedance spectroscopy (EIS) was used to study the charge transfer at Pt/electrolyte interface and charge recombination and electron transport at TiO 2 /dye/electrolyte interface. Significant improvements in conversion efficiency and short circuit current density of DSSCs fabricated by chitosan nanoparticle were observed that can be attributed to the higher mobility of I 3 - due to the lower viscosity and smaller size of chitosan nanoparticles. Copyright © 2017 Elsevier Ltd. All rights reserved.

Novel operation and control of an electric vehicle aluminum/air battery system

NASA Astrophysics Data System (ADS)

Zhang, Xin; Yang, Shao Hua; Knickle, Harold

The objective of this paper is to create a method to size battery subsystems for an electric vehicle to optimize battery performance. Optimization of performance includes minimizing corrosion by operating at a constant current density. These subsystems will allow for easy mechanical recharging. A proper choice of battery subsystem will allow for longer battery life, greater range and performance. For longer life, the current density and reaction rate should be nearly constant. The control method requires control of power by controlling electrolyte flow in battery sub modules. As power is increased more sub modules come on line and more electrolyte is needed. Solenoid valves open in a sequence to provide the required power. Corrosion is limited because there is no electrolyte in the modules not being used.

Electrolyte additive enabled fast charging and stable cycling lithium metal batteries

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zheng, Jianming; Engelhard, Mark H.; Mei, Donghai

2017-03-01

Batteries using lithium (Li) metal as anodes are considered promising energy storage systems because of their high energy densities. However, safety concerns associated with dendrite growth along with limited cycle life, especially at high charge current densities, hinder their practical uses. Here we report that an optimal amount (0.05 M) of LiPF6 as an additive in LiTFSI-LiBOB dual-salt/carbonate-solvent-based electrolytes significantly enhances the charging capability and cycling stability of Li metal batteries. In a Li metal battery using a 4-V Li-ion cathode at a moderately high loading of 1.75mAh cm(-2), a cyclability of 97.1% capacity retention after 500 cycles along withmore » very limited increase in electrode overpotential is accomplished at a charge/discharge current density up to 1.75 mA cm(-2). The fast charging and stable cycling performances are ascribed to the generation of a robust and conductive solid electrolyte interphase at the Li metal surface and stabilization of the Al cathode current collector.« less

Studies of metals electroprocessing in molten salts

NASA Technical Reports Server (NTRS)

Sadoway, D. R.

1982-01-01

Fluid flow patterns in molten salt electrolytes were observed in order to determine how mass transport affects the morphology of the metal deposit. Studies conducted on the same metal, both in aqueous electrolytes in which coherent solid electrodeposits are produced, as well as in transparent molten salt electrolytes are described. Process variables such as current density and composition of the electrolyte are adjusted to change the morphology of the electrodeposit and, thus, to permit the study of the nature of electrolyte flow in relation to the quality of the electrodeposit.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ruther, Rose E.; Sun, Che -Nan; Holliday, Adam

A simple electrolyte consisting of NaPF 6 salt in 1,2-dimethoxyethane (DME) can extend the voltage window of electric double-layer capacitors (EDLCs) to >3.5 V. DME does not passivate carbon electrodes at very negative potentials (near Na/Na +), extending the practical voltage window by about 1.0 V compared to standard, non-aqueous electrolytes based on acetonitrile. The voltage window is demonstrated in two- and three-electrode cells using a combination of electrochemical impedance spectroscopy (EIS), charge-discharge cycling, and measurements of leakage current. DME-based electrolytes cannot match the high conductivity of acetonitrile solutions, but they can satisfy applications that demand high energy density atmore » moderate power. The conductivity of NaPF 6 in DME is comparable to commercial lithium-ion battery electrolytes and superior to most ionic liquids. Lastly, factors that limit the voltage window and EDLC energy density are discussed, and strategies to further boost energy density are proposed.« less

Synthesis of Mesoporous Carbons from Rice Husk for Supercapacitors with High Energy Density in Ionic Liquid Electrolytes.

PubMed

He, Xiaojun; Zhang, Hebao; Xie, Kang; Xia, Youyi; Zhao, Zhigang; Wang, Xiaoting

2016-03-01

High-performance mesoporous carbons (MCs) for supercapacitors were made from rice husk by one-step microwave-assisted ZnCl2 activation. The microstructures of MCs as-made were characterized by field emission scanning electron microscopy and transmission electron microscopy. The pore structure parameters of MCs were obtained by N2 adsorption technique. The electrochemical properties of MC electrodes were studied by constant current charge-discharge, cyclic voltammetry and electrochemical impedance spectroscopy in different electrolytes. The results showed that the specific surface area of MC4 made at the ZnCl2/rice husk mass of 4:1 reached 1737 m2 g(-1). The specific capacitance and energy density of the electrodes fabricated from the mixture of MC4 and microporous carbon increased with the mass percentage of MC4, reaching 157 F g(-1) and 84 Wh kg(-1) at 0.05 A g(-1), and showed good cycle stability in 1-butyl-3-methylimidazolium hexafluorophosphate electrolyte. Compared to the often-used aqueous and organic electrolytes, MC4 capacitor exhibited extremely high energy density in ionic liquid electrolyte, remaining at 28 Wh kg(-1) at 1684 W kg(-1). This work paves a new way to produce cost-effective MCs from biomass for supercapacitors with extremely high energy density in ionic liquid electrolytes.

The development of a new type of rechargeable batteries based on hybrid electrolytes.

PubMed

Zhou, Haoshen; Wang, Yonggang; Li, Huiqiao; He, Ping

2010-09-24

Lithium ion batteries (LIBs), which have the highest energy density among all currently available rechargeable batteries, have recently been considered for use in hybrid electric vehicles (HEVs), plug-in hybrid electric vehicles (PHEVs), and pure electric vehicles (PEV). A major challenge in this effort is to increase the energy density of LIBs to satisfy the industrial needs of HEVs, PHEVs, and PEVs. Recently, new types of lithium-air and lithium-copper batteries that employ hybrid electrolytes have attracted significant attention; these batteries are expected to succeed lithium ion batteries as next-generation power sources. Herein, we review the concept of hybrid electrolytes, as well as their advantages and disadvantages. In addition, we examine new battery types that use hybrid electrolytes.

Development and validation of chemistry agnostic flow battery cost performance model and application to nonaqueous electrolyte systems: Chemistry agnostic flow battery cost performance model

DOE Office of Scientific and Technical Information (OSTI.GOV)

Crawford, Alasdair; Thomsen, Edwin; Reed, David

2016-04-20

A chemistry agnostic cost performance model is described for a nonaqueous flow battery. The model predicts flow battery performance by estimating the active reaction zone thickness at each electrode as a function of current density, state of charge, and flow rate using measured data for electrode kinetics, electrolyte conductivity, and electrode-specific surface area. Validation of the model is conducted using a 4kW stack data at various current densities and flow rates. This model is used to estimate the performance of a nonaqueous flow battery with electrode and electrolyte properties used from the literature. The optimized cost for this system ismore » estimated for various power and energy levels using component costs provided by vendors. The model allows optimization of design parameters such as electrode thickness, area, flow path design, and operating parameters such as power density, flow rate, and operating SOC range for various application duty cycles. A parametric analysis is done to identify components and electrode/electrolyte properties with the highest impact on system cost for various application durations. A pathway to 100$kWh -1 for the storage system is identified.« less

Composition and particle size of electrolytic copper powders prepared in water-containing dimethyl sulfoxide electrolytes

NASA Astrophysics Data System (ADS)

Mamyrbekova, Aigul'; Abzhalov, B. S.; Mamyrbekova, Aizhan

2017-07-01

The possibility of the electroprecipitation of copper powder via the cathodic reduction of an electrolyte solution containing copper(II) nitrate trihydrate and dimethyl sulfoxide (DMSO) is shown. The effect electrolysis conditions (current density, concentration and temperature of electrolyte) have on the dimensional characteristics of copper powder is studied. The size and shape of the particles of the powders were determined by means of electron microscopy; the qualitative composition of the powders, with X-ray diffraction.

The influence of electrolyte additives on the anodic dissolution of aluminum in alkaline solutions

NASA Astrophysics Data System (ADS)

Boehnstedt, W.

1980-09-01

The paper describes the effect of electrolyte additives on the anodic dissolution of aluminum in alkaline solutions. The dissolution is accelerated by the addition of small quantities of gallium or indium ions to the electrolyte indicated by the shift of the zero current potential by about 250 mV on the current-potential curve. Scanning electron microscope studies showed that gallium ions produce many small cracks in the aluminum electrode and collect at the grain boundary areas, increasing the electrode surface; this enlargement, in combination with increased electrolyte agitation due to greater hydrogen evolution, provides higher current densities at the same potential. It is concluded that this process will widen the possibilities of using aluminum and its alloys in high-rate batteries.

Effect of Applied Current Density on Cavitation-Erosion Characteristics for Anodized Al Alloy.

PubMed

Lee, Seung-Jun; Kim, Seong-Jong

2018-02-01

Surface finishing is as important as selection of material to achieve durability. Surface finishing is a process to provide surface with the desired performance and features by applying external forces such as thermal energy or stress. This study investigated the optimum supply current density for preventing from cavitation damages by applying to an anodizing technique that artificially forms on the surface an oxide coating that has excellent mechanical characteristics, such as hardness, wear resistance. Result of hardness test, the greater hardness was associated with greater brittleness, resulting in deleterious characteristics. Consequently, under conditions such as the electrolyte concentration of 10 vol.%, the processing time of 40 min, the electrolyte temperature of 10 °C, and the current density of 20 mA/cm2 were considered to be the optimum anodizing conditions for improvement of durability in seawater.

Rotating disk electrode study of borohydride oxidation in a molten eutectic electrolyte and advancements in the intermediate temperature borohydride battery

NASA Astrophysics Data System (ADS)

Wang, Andrew; Gyenge, Előd L.

2017-08-01

The electrode kinetics of the NaBH4 oxidation reaction (BOR) in a molten NaOH-KOH eutectic mixture is investigated by rotating disk electrode (RDE) voltammetry on electrochemically oxidized Ni at temperatures between 458 K and 503 K. The BH4- diffusion coefficient in the molten alkali eutectic together with the BOR activation energy, exchange current density, transfer coefficient and number of electrons exchanged, are determined. Electrochemically oxidized Ni shows excellent BOR electrocatalytic activity with a maximum of seven electrons exchanged and a transfer coefficient up to one. X-ray photoelectron spectroscopy (XPS) reveals the formation of NiO as the catalytically active species. The high faradaic efficiency and BOR rate on oxidized Ni anode in the molten electrolyte compared to aqueous alkaline electrolytes is advantageous for power sources. A novel molten electrolyte battery design is investigated using dissolved NaBH4 at the anode and immobilized KIO4 at the cathode. This battery produces a stable open-circuit cell potential of 1.04 V, and a peak power density of 130 mW cm-2 corresponding to a superficial current density of 160 mA cm-2 at 458 K. With further improvements and scale-up borohydride molten electrolyte batteries and fuel cells could be integrated with thermal energy storage systems.

Anode film formation and control

DOEpatents

Koski, Oscar; Marschman, Steven C.

1990-01-01

A protective film is created about the anode within a cryolite-based electrolyte during electrolytic production of aluminum from alumina. The film function to minimize corrosion of the anode by the cryolitic electrolyte and thereby extend the life of the anode. Various operating parameters of the electrolytic process are controlled to maintain the protective film about the anode in a protective state throughout the electrolytic reduction of alumina. Such parameters include electrolyte temperature, electrolyte ratio, current density, and Al.sub.2 O.sub.3 concentration. An apparatus is also disclosed to enable identification of the onset of anode corrosion due to disruption of the film to provide real time information regarding the state of the film.

Anode film formation and control

DOEpatents

Koski, O.; Marschman, S.C.

1990-05-01

A protective film is created about the anode within a cryolite-based electrolyte during electrolytic production of aluminum from alumina. The film functions to minimize corrosion of the anode by the cryolitic electrolyte and thereby extend the life of the anode. Various operating parameters of the electrolytic process are controlled to maintain the protective film about the anode in a protective state throughout the electrolytic reduction of alumina. Such parameters include electrolyte temperature, electrolyte ratio, current density, and Al[sub 2]O[sub 3] concentration. An apparatus is also disclosed to enable identification of the onset of anode corrosion due to disruption of the film to provide real time information regarding the state of the film. 3 figs.

High energy density electrochemical cell

NASA Technical Reports Server (NTRS)

Byrne, J. J.; Williams, D. L.

1970-01-01

Primary cell has an anode of lithium, a cathode containing dihaloisocyanuric acid, and a nonaqueous electrolyte comprised of a solution of lithium perchlorate in methyl formate. It produces an energy density of 213 watt hrs/lb and can achieve a high current density.

High Current Plasma Electrolytic Oxidation Coating Processes for Wear and Corrosion Prevention of Al 2024

NASA Astrophysics Data System (ADS)

Wang, Rui

Plasma electrolytic oxidation (PEO) treatments have been used in the aerospace and automotive industries because the coating formed on light metals or alloys has great hardness, high wear, corrosion, and oxidation resistance, and a low friction coefficient that improves lifetime length and provide a higher surface quality. However, the PEO treatments that are presently used for industrial applications require a long period of time to confirm the quality of the coating. For this reason, the present study seeks to increase the current density of PEO treatments to improve their efficiency and explore the performance of the obtained coatings. It was found that for high current density (0.18A/cm2) PEO treatments, smaller ratio, such as 50% and 70%, is beneficial to obtaining a better performance coating. When compared with the coating of a "normal" (current density: 0.09A/cm2) PEO treatment, it had better wear resistance; however, for corrosion resistance, it had a lower performance than the coatings obtained by the "normal" current density PEO treatment which was attributed to the negative influence of porosity increase.

Improved electrolyte for zinc-bromine flow batteries

NASA Astrophysics Data System (ADS)

Wu, M. C.; Zhao, T. S.; Wei, L.; Jiang, H. R.; Zhang, R. H.

2018-04-01

Conventional zinc bromide electrolytes offer low ionic conductivity and often trigger severe zinc dendrite growth in zinc-bromine flow batteries. Here we report an improved electrolyte modified with methanesulfonic acid, which not only improves the electrolyte conductivity but also ameliorates zinc dendrite. Experimental results also reveal that the kinetics and reversibility of Zn2+/Zn and Br2/Br- are improved in this modified electrolyte. Moreover, the battery's internal resistance is significantly reduced from 4.9 to 2.0 Ω cm2 after adding 1 M methanesulfonic acid, thus leading to an improved energy efficiency from 64% to 75% at a current density of 40 mA cm-2. More impressively, the battery is capable of delivering an energy efficiency of about 78% at a current density of as high as 80 mA cm-2 when the electrode is replaced by a thermally treated one. Additionally, zinc dendrite growth is found to be effectively suppressed in methanesulfonic acid supported media, which, as a result, enables the battery to be operated for 50 cycles without degradation, whereas the one without methanesulfonic acid suffers from significant decay after only 40 cycles, primarily due to severe zinc dendrite growth. These superior results indicate methanesulfonic acid is a promising supporting electrolyte for zinc-bromine flow batteries.

Enhanced electrochemical performance of monoclinic WO3 thin film with redox additive aqueous electrolyte.

PubMed

Shinde, Pragati A; Lokhande, Vaibhav C; Chodankar, Nilesh R; Ji, Taeksoo; Kim, Jin Hyeok; Lokhande, Chandrakant D

2016-12-01

To achieve the highest electrochemical performance for supercapacitor, it is very essential to find out a suitable pair of an active electrode material and an electrolyte. In the present work, a simple approach is employed to enhance the supercapacitor performance of WO3 thin film. The WO3 thin film is prepared by a simple and cost effective chemical bath deposition method and its electrochemical performance is tested in conventional (H2SO4) and redox additive [H2SO4+hydroquinone (HQ)] electrolytes. Two-fold increment in electrochemical performance for WO3 thin film is observed in redox additive aqueous electrolyte compared to conventional electrolyte. WO3 thin film showed maximum specific capacitance of 725Fg(-1), energy density of 25.18Whkg(-1) at current density of 7mAcm(-2) with better cycling stability in redox electrolyte. This strategy provides the versatile way for designing the high performance energy storage devices. Copyright © 2016 Elsevier Inc. All rights reserved.

Detonation nanodiamond introduced into samarium doped ceria electrolyte improving performance of solid oxide fuel cell

NASA Astrophysics Data System (ADS)

Pei, Kai; Li, Hongdong; Zou, Guangtian; Yu, Richeng; Zhao, Haofei; Shen, Xi; Wang, Liying; Song, Yanpeng; Qiu, Dongchao

2017-02-01

A novel electrolyte materials of introducing detonation nanodiamond (DNDs) into samarium doped ceria (SDC) is reported here. 1%wt. DNDs doping SDC (named SDC/ND) can enlarge the electrotyle grain size and change the valence of partial ceria. DNDs provide the widen channel to accelerate the mobility of oxygen ions in electrolyte. Larger grain size means that oxygen ions move easier in electrolyte, it can also reduce the alternating current (AC) impedance spectra of internal grains. The lower valence of partial Ce provides more oxygen vacancies to enhance mobility rate of oxygen ions. Hence all of them enhance the transportation of oxygen ions in SDC/ND electrolyte and the OCV. Ultimately the power density of SOFC can reach 762 mw cm-2 at 800 °C (twice higher than pure SDC, which is 319 mw cm-2 at 800 °C), and it remains high power density in the intermediate temperature (600-800 °C). It is relatively high for the electrolyte supported (300 μm) cells.

Supercapacitors based on self-assembled graphene organogel.

PubMed

Sun, Yiqing; Wu, Qiong; Shi, Gaoquan

2011-10-14

Self-assembled graphene organogel (SGO) with 3-dimensional (3D) macrostructure was prepared by solvothermal reduction of a graphene oxide (GO) dispersion in propylene carbonate (PC). This SGO was used as an electrode material for fabricating supercapacitors with a PC electrolyte. The supercapacitor can be operated in a wide voltage range of 0-3 V and exhibits a high specific capacitance of 140 F g(-1) at a discharge current density of 1 A g(-1). Furthermore, it can still keep a specific capacitance of 90 F g(-1) at a high current density of 30 A g(-1). The maximum energy density of the SGO based supercapacitor was tested to be 43.5 Wh kg(-1), and this value is higher than those of the graphene based supercapacitors with aqueous or PC electrolytes reported previously. Furthermore, at a high discharge current density of 30 A g(-1), the energy and power densities of the supercapacitor were measured to be 15.4 Wh kg(-1) and 16,300 W kg(-1), respectively. These results indicate that the supercapacitor has a high specific capacitance and power density, and excellent rate capability.

Electrochemical performance and interfacial properties of Li-metal in lithium bis(fluorosulfonyl)imide based electrolytes.

PubMed

Younesi, Reza; Bardé, Fanny

2017-11-21

Successful usage of lithium metal as the negative electrode or anode in rechargeable batteries can be an important step to increase the energy density of lithium batteries. Performance of lithium metal in a relatively promising electrolyte solution composed of lithium bis(fluorosulfonyl)imide (LiN(SO 2 F) 2 ; LiFSI) salt dissolved in 1,2-dimethoxyethane (DME) is here studied. The influence of the concentration of the electrolyte salt -1 M or 4 M LiFSI- is investigated by varying important electrochemical parameters such as applied current density and plating capacity. X-ray photoelectron spectroscopy analysis as a surface sensitive technique is here used to analyze that how the composition of the solid electrolyte interphase varies with the salt concentration and with the number of cycles.

Effect of aqueous electrolytes on the electrochemical behaviors of supercapacitors based on hierarchically porous carbons

NASA Astrophysics Data System (ADS)

Zhang, Xiaoyan; Wang, Xianyou; Jiang, Lanlan; Wu, Hao; Wu, Chun; Su, Jingcang

2012-10-01

Hierarchically porous carbons (HPCs) have been prepared by sol-gel self-assembly technology with nickel oxide and surfactant as the dual template. The porous carbons are further activated by nitric acid. The electrochemical behaviors of supercapacitors using HPCs as electrode material in different aqueous electrolytes, e.g., (NH4)2SO4, Na2SO4, H2SO4 and KOH are studied by cyclic voltametry, galvanostatic charge/discharge, cyclic life, leakage current, self-discharge and electrochemical impedance spectroscopy. The results demonstrate that the supercapacitors in various electrolytes perform definitely capacitive behaviors; especially in 6 M KOH electrolyte the supercapacitor represents the best electrochemical performance, the shortest relaxation time, and nearly ideal polarisability. The energy density of 8.42 Wh kg-1 and power density of 17.22 kW kg-1 are obtained at the operated voltage window of 1.0 V. Especially, the energy density of 11.54 Wh kg-1 and power density of 10.58 kW kg-1 can be achieved when the voltage is up to 1.2 V.

Influence of supporting electrolyte in electricity generation and degradation of organic pollutants in photocatalytic fuel cell.

PubMed

Khalik, Wan Fadhilah; Ong, Soon-An; Ho, Li-Ngee; Wong, Yee-Shian; Voon, Chun-Hong; Yusuf, Sara Yasina; Yusoff, Nik Athirah; Lee, Sin-Li

2016-08-01

This study investigated the effect of different supporting electrolyte (Na2SO4, MgSO4, NaCl) in degradation of Reactive Black 5 (RB5) and generation of electricity. Zinc oxide (ZnO) was immobilized onto carbon felt acted as photoanode, while Pt-coated carbon paper as photocathode was placed in a single chamber photocatalytic fuel cell, which then irradiated by UV lamp for 24 h. The degradation and mineralization of RB5 with 0.1 M NaCl rapidly decreased after 24-h irradiation time, followed by MgSO4, Na2SO4 and without electrolyte. The voltage outputs for Na2SO4, MgSO4 and NaCl were 908, 628 and 523 mV, respectively, after 24-h irradiation time; meanwhile, their short-circuit current density, J SC, was 1.3, 1.2 and 1.05 mA cm(-2), respectively. The power densities for Na2SO4, MgSO4 and NaCl were 0.335, 0.256 and 0.245 mW cm(-2), respectively. On the other hand, for without supporting electrolyte, the voltage output and short-circuit current density was 271.6 mV and 0.055 mA cm(-2), respectively. The supporting electrolyte NaCl showed greater performance in degradation of RB5 and generation of electricity due to the formation of superoxide radical anions which enhance the degradation of dye. The mineralization of RB5 with different supporting electrolyte was measured through spectrum analysis and reduction in COD concentration.

Electrochemical treatment of cork boiling wastewater with a boron-doped diamond anode.

PubMed

Fernandes, Annabel; Santos, Diana; Pacheco, Maria José; Ciríaco, Lurdes; Simões, Rogério; Gomes, Arlindo C; Lopes, Ana

2015-01-01

Anodic oxidation at a boron-doped diamond anode of cork boiling wastewater was successfully used for mineralization and biodegradability enhancement required for effluent discharge or subsequent biological treatment, respectively. The influence of the applied current density (30-70 mA/cm2) and the background electrolyte concentration (0-1.5 g/L Na2SO4) on the performance of the electrochemical oxidation was investigated. The supporting electrolyte was required to achieve conductivities that enabled anodic oxidation at the highest current intensities applied. The results indicated that pollutant removal increased with the applied current density, and after 8 h, reductions greater than 90% were achieved for COD, dissolved organic carbon, total phenols and colour. The biodegradability enhancement was from 0.13 to 0.59 and from 0.23 to 0.72 for the BOD/COD ratios with BOD of 5 and 20 days' incubation period, respectively. The tests without added electrolyte were performed at lower applied electrical charges (15 mA/cm2 or 30 V) with good organic load removal (up to 80%). For an applied current density of 30 mA/cm2, there was a minimum of electric conductivity of 1.9 mS/cm (corresponding to 0.75 g/L of Na2SO4), which minimized the specific energy consumption.

Solvent effects on polysulfide redox kinetics and ionic conductivity in lithium-sulfur batteries

DOE PAGES

Fan, Frank Y.; Pan, Menghsuan Sam; Lau, Kah Chun; ...

2016-11-25

Lithium-sulfur (Li-S) batteries have high theoretical energy density and low raw materials cost compared to present lithium-ion batteries and are thus promising for use in electric transportation and other applications. A major obstacle for Li-S batteries is low rate capability, especially at the low electrolyte/sulfur (E/S) ratios required for high energy density. Herein, we investigate several potentially rate-limiting factors for Li-S batteries. We study the ionic conductivity of lithium polysulfide solutions of varying concentration and in different ether-based solvents and their exchange current density on glassy carbon working electrodes. We believe this is the first such investigation of exchange currentmore » density for lithium polysulfide in solution. Exchange current densities are measured using both electrochemical impedance spectroscopy and steady-state galvanostatic polarization. In the range of interest (1-8 M [S]), the ionic conductivity monotonically decreases with increasing sulfur concentration while exchange current density shows a more complicated relationship to sulfur concentration. The electrolyte solvent dramatically affects ionic conductivity and exchange current density. Finally, the measured ionic conductivities and exchange current densities are also used to interpret the overpotential and rate capability of polysulfide-nanocarbon suspensions; this analysis demonstrates that ionic conductivity is the rate-limiting property in the solution regime (i.e. between Li 2S 8 and Li 2S 4).« less

Radical Compatibility with Nonaqueous Electrolytes and Its Impact on an All-Organic Redox Flow Battery.

PubMed

Wei, Xiaoliang; Xu, Wu; Huang, Jinhua; Zhang, Lu; Walter, Eric; Lawrence, Chad; Vijayakumar, M; Henderson, Wesley A; Liu, Tianbiao; Cosimbescu, Lelia; Li, Bin; Sprenkle, Vincent; Wang, Wei

2015-07-20

Nonaqueous redox flow batteries hold the promise of achieving higher energy density because of the broader voltage window than aqueous systems, but their current performance is limited by low redox material concentration, cell efficiency, cycling stability, and current density. We report a new nonaqueous all-organic flow battery based on high concentrations of redox materials, which shows significant, comprehensive improvement in flow battery performance. A mechanistic electron spin resonance study reveals that the choice of supporting electrolytes greatly affects the chemical stability of the charged radical species especially the negative side radical anion, which dominates the cycling stability of these flow cells. This finding not only increases our fundamental understanding of performance degradation in flow batteries using radical-based redox species, but also offers insights toward rational electrolyte optimization for improving the cycling stability of these flow batteries. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Maximizing ion current rectification in a bipolar conical nanopore fluidic diode using optimum junction location.

PubMed

Singh, Kunwar Pal

2016-10-12

The ion current rectification has been obtained as a function of the location of a heterojunction in a bipolar conical nanopore fluidic diode for different parameters to determine the junction location for maximum ion current rectification using numerical simulations. Forward current peaks for a specific location of the junction and reverse current decreases with the junction location due to a change in ion enrichment/depletion in the pore. The optimum location of the heterojunction shifts towards the tip with base/tip diameter and surface charge density, and towards the base with the electrolyte concentration. The optimum location of the heterojunction has been approximated by an equation as a function of pore length, base/tip diameter, surface charge density and electrolyte concentration. The study is useful to design a rectifier with maximum ion current rectification for practical purposes.

Further studies of the anodic dissolution in sodium chloride electrolyte of aluminium alloys containing tin and gallium

NASA Astrophysics Data System (ADS)

Nestoridi, Maria; Pletcher, Derek; Wharton, Julian A.; Wood, Robert J. K.

As part of a programme to develop a high power density, Al/air battery with a NaCl brine electrolyte, the high rate dissolution of an aluminium alloy containing tin and gallium was investigated in a small volume cell. The objective was to define the factors that limit aluminium dissolution in condition that mimic a high power density battery. In a cell with a large ratio of aluminium alloy to electrolyte, over a range of current densities the extent of dissolution was limited to ∼1000 C cm -2 of anode surface by a thick layer of loosely bound, crystalline deposit on the Al alloy anode formed by precipitation from solution. This leads to a large increase in impedance and acts as a barrier to transport of ions.

Fabrication of ultrathin solid electrolyte membranes of β-Li 3PS 4 nanoflakes by evaporation-induced self-assembly for all-solid-state batteries

DOE PAGES

Wang, Hui; Hood, Zachary D.; Xia, Younan; ...

2016-04-25

All-solid-state lithium batteries are attractive candidates for next-generation energy storage devices because of their anticipated high energy density and intrinsic safety. Owing to their excellent ionic conductivity and stability with metallic lithium anodes, nanostructured lithium thiophosphate solid electrolytes such as β-Li 3PS 4 have found use in the fabrication of all-solid lithium batteries for large-scale energy storage systems. However, current methods for preparing air-sensitive solid electrolyte membranes of lithium thiophosphates can only generate thick membranes that compromise the battery's gravimetric/volumetric energy density and thus its rate performance. To overcome this limitation, the solid electrolyte's thickness needs to be effectively decreasedmore » to achieve ideal energy density and enhanced rate performance. In this paper, we show that the evaporation-induced self-assembly (EISA) technique produces ultrathin membranes of a lithium thiophosphate solid electrolyte with controllable thicknesses between 8 and 50 μm while maintaining the high ionic conductivity of β-Li 3PS 4 and stability with metallic lithium anodes up to 5 V. Finally, it is clearly demonstrated that this facile EISA approach allows for the preparation of ultrathin lithium thiophosphate solid electrolyte membranes for all-solid-state batteries.« less

Characterization of a membrane-based, electrochemically driven pumping system using aqueous electrolyte solutions.

PubMed

Norman, Mya A; Evans, Christine E; Fuoco, Anthony R; Noble, Richard D; Koval, Carl A

2005-10-01

Electrokinetic flow provides a mechanism for a variety of fluid pumping schemes. The design and characterization of an electrochemically driven pump that utilizes porous carbon electrodes, iodide/triiodide redox electrolytes, and Nafion membranes is described. Fluid pumping by the cell is reversible and controlled by the cell current. Chronopotentiometry experiments indicate that the total available fluid that can be pumped in a single electrolysis without gas evolution is determined solely by the initial concentration of electrolyte and the applied current. The magnitude of the fluid flow at a given current is determined by the nature of the cation in the electrolyte and by the water absorption properties of the Nafion membrane. For 1 M aqueous electrolytes, pumping rates ranging from 1 to 14 microL/min were obtained for current densities of 10-30 mA/cm2 of membrane area. Molar volume changes for the I3-/I- redox couple and for the alkali cation migration contribute little to the observed volumetric flow rates; the magnitude of the flow is dominated by the migration-induced flow of water.

Effect of Concentration on the Electrochemistry and Speciation of the Magnesium Aluminum Chloride Complex Electrolyte Solution.

PubMed

See, Kimberly A; Liu, Yao-Min; Ha, Yeyoung; Barile, Christopher J; Gewirth, Andrew A

2017-10-18

Magnesium batteries offer an opportunity to use naturally abundant Mg and achieve large volumetric capacities reaching over four times that of conventional Li-based intercalation anodes. High volumetric capacity is enabled by the use of a Mg metal anode in which charge is stored via electrodeposition and stripping processes, however, electrolytes that support efficient Mg electrodeposition and stripping are few and are often prepared from highly reactive compounds. One interesting electrolyte solution that supports Mg deposition and stripping without the use of highly reactive reagents is the magnesium aluminum chloride complex (MACC) electrolyte. The MACC exhibits high Coulombic efficiencies and low deposition overpotentials following an electrolytic conditioning protocol that stabilizes species necessary for such behavior. Here, we discuss the effect of the MgCl 2 and AlCl 3 concentrations on the deposition overpotential, current density, and the conditioning process. Higher concentrations of MACC exhibit enhanced Mg electrodeposition current density and much faster conditioning. An increase in the salt concentrations causes a shift in the complex equilibria involving both cations. The conditioning process is strongly dependent on the concentration suggesting that the electrolyte is activated through a change in speciation of electrolyte complexes and is not simply due to the annihilation of electrolyte impurities. Additionally, the presence of the [Mg 2 (μ-Cl) 3 ·6THF] + in the electrolyte solution is again confirmed through careful analysis of experimental Raman spectra coupled with simulation and direct observation of the complex in sonic spray ionization mass spectrometry. Importantly, we suggest that the ∼210 cm -1 mode commonly observed in the Raman spectra of many Mg electrolytes is indicative of the C 3v symmetric [Mg 2 (μ-Cl) 3 ·6THF] + . The 210 cm -1 mode is present in many electrolytes containing MgCl 2 , so its assignment is of broad interest to the Mg electrolyte community.

Improving performance of MFC by design alteration and adding cathodic electrolytes.

PubMed

Jadhav, G S; Ghangrekar, M M

2008-12-01

Performance of two microbial fuel cells (MFCs) was investigated under batch and continuous mode of operation using different cathodic electrolyte. The wastewater was supplied from the bottom port provided to the anode chamber in both the MFCs and the effluent left the anode chamber from the top port in MFC-1, whereas in MFC-2, the effluent exit was provided close to membrane. Stainless steel (SS) mesh anode was used in both the MFCs with surface area of 167 and 100 cm(2) in MFC-1 and MFC-2, respectively. Under batch mode and continuous mode of operation, these MFCs gave chemical oxygen demand removal efficiency more than 85% and about 68%, respectively. Under batch mode of operation, maximum power density of 39.95 and 56.87 mW/m(2) and maximum current density of 180.83 and 295 mA/m(2) were obtained in MFC-1 and MFC-2, respectively. Under continuous mode of operation, a reduction in power and current density was observed. Even with less surface area of the anode, MFC-2 produced more current (1.77 mA) than MFC-1 (1.40 mA). Among the cathodic electrolyte tested, these can be listed in decreasing order of power density as aerated KMnO(4) solution > KMnO(4) solution without aeration > aerated tap water > aerated tap water with NaCl.

Electrolysis cell for the manufacture of persulfates

NASA Technical Reports Server (NTRS)

Cueto, J. M.

1986-01-01

A cell for the electrolytic generation of persulfates, characterized by the fact that a housing acts as cathode, is made of metal, and consists of a lower electrolytically active section and an upper electrolytically inactive section. It is designed so that there is produced the greatest possible current density suited to produce the desired electrolysis effect. This invention, compared to the devices used until now, exhibits considerable advantages whereby it is particularly suited for the production of potassium persulfate.

Preparation and characterization of anodic films on AZ31B Mg alloy formed in the silicate electrolytes with ethylene glycol oligomers as additives

NASA Astrophysics Data System (ADS)

Zhu, Feng; Wang, Jinwei; Li, Shanghua; Zhang, Jin

2012-09-01

Oxide coatings are prepared on AZ31B Mg alloy in an environment-friendly electrolyte with additives by plasma electrolytic anodization, and the effect of ethylene glycol oligmers on the performances of the anodized film is investigated. Under a constant current density of 10 mA cm-2, the reaction overpotential of the silicate electrolytes with additives are found higher than that of the original electrolyte as measured by potential-time test. The EIS and DC polarization results reveal that the addition of PEG increases the impedance of the film and reduces its corrosion current density (Icorr) at least by one order of magnitude. The surface morphologies are more and more compact and homogeneous with the increase in EG numbers, while a rougher surface appeared again if the PEG4000 is used as observed by SEM. As detected by XRD, the anodic films are found mainly consist of MgO, MgSiO3 and Mg2SiO4, and their relative amounts are related to the lengths of EGs, resulting in the differences in morphology and anticorrosion variations. Furthermore, the improvement in abrasive resistance of the anodic film formed in the electrolyte with PEG1000 may be attributed to its much more compact surface and the incorporation of ductile PEG chains among those oxides.

Study of Stable Cathodes and Electrolytes for High Specific Density Lithium-Air Battery

NASA Technical Reports Server (NTRS)

Hernandez-Lugo, Dionne M.; Wu, James; Bennett, William; Ming, Yu; Zhu, Yu

2015-01-01

Future NASA missions require high specific energy battery technologies, greater than 400 Wh/kg. Current NASA missions are using "state-of-the-art" (SOA) Li-ion batteries (LIB), which consist of a metal oxide cathode, a graphite anode and an organic electrolyte. NASA Glenn Research Center is currently studying the physical and electrochemical properties of the anode-electrolyte interface for ionic liquid based Li-air batteries. The voltage-time profiles for Pyr13FSI and Pyr14TFSI ionic liquids electrolytes studies on symmetric cells show low over-potentials and no dendritic lithium morphology. Cyclic voltammetry measurements indicate that these ionic liquids have a wide electrochemical window. As a continuation of this work, sp2 carbon cathode and these low flammability electrolytes were paired and the physical and electrochemical properties were studied in a Li-air battery system under an oxygen environment.

High resolution electrolyte for thinning InP by anodic dissolution and its applications to EC-V profiling, defect revealing and surface passivation

NASA Technical Reports Server (NTRS)

Faur, Maria; Faur, Mircea; Weinberg, Irving; Goradia, Manju; Vargas, Carlos

1991-01-01

An extensive experimental study was conducted using various electrolytes in an effort to find an appropriate electrolyte for anodic dissolution of InP. From the analysis of electrochemical characteristics in the dark and under different illumination levels, x ray photoelectron spectroscopy and SEM/Nomarski inspection of the surfaces, it was determined that the anodic dissolution of InP front surface layers by FAP electrolyte is a very good choice for rendering smooth surfaces, free of oxides and contaminants and with good electrical characteristics. The FAP electrolyte, based on HF, CH3COOH, and H2O2 appears to be inherently superior to previously reported electrolytes for performing accurate EC-V profiling of InP at current densities of up to 0.3 mA/sq cm. It can also be used for accurate electrochemical revealing of either precipitates or dislocation density with application to EPD mapping as a function of depth, and for defect revealing of multilayer InP structures at any depth and/or at the interfaces.

Metals Electroprocessing in Molten Salts

NASA Technical Reports Server (NTRS)

Sadoway, D. R.

1985-01-01

The present study seeks to explain the poor quality of solid electrodeposits in molten salts through a consideration of the effects of fluid flow of the electrolyte. Transparent cells allow observation of electrolyte circulation by a laser schlieren optical technique during the electrodeposition of solid zinc from the molten salt electrolyte, ZnCl2 - LiCl-KCl. Experimental variables are current, density, electrolyte composition, and cell geometry. Based on the results of earlier electrodeposition studies as well as reports in the literature, these parameters are identified as having the primary influence on cell performance and deposit quality. Experiments are conducted to measure the fluid flow patterns and the electrochemical cell characteristics, and to correlate this information with the morphology of the solid electrodeposit produced. Specifically, cell voltage, cell current, characteristic time for dendrite evolution, and dendrite growth directions are noted. Their relationship to electrolyte flow patterns and the morphology of the resulting electrodeposit are derived. Results to date indicate that laser schlieren imaging is capable of revealing fluid flow patterns in a molten salt electrolyte.

Ionic liquid hybrids: Progress toward non-corrosive electrolytes with high-voltage oxidation stability for magnesium-ion based batteries

DOE PAGES

Huie, Matthew M.; Cama, Christina A.; Smith, Paul F.; ...

2016-10-01

Magnesium – ion batteries have the potential for high energy density but require new types of electrolytes for practical application. Ionic liquid (IL) electrolytes offer the opportunity for increased safety and broader voltage windows relative to traditional electrolytes. We present here a systematic study of both the conductivity and oxidative stability of hybrid electrolytes consisting of eleven ILs mixed with dipropylene glycol dimethylether (DPGDME) or acetonitrile (ACN) cosolvents and magnesium bis(trifluoromethylsulfonyl)imide (Mg(TFSI) 2). Our study finds a correlation of higher conductivity of ILs with unsaturated rings and short carbon chain lengths, but by contrast, these ILs also exhibited lower oxidationmore » voltage limits. For the cosolvent additive, although glymes have a demonstrated capability of coordination with Mg 2+ ions, a decrease in conductivity compared to acetonitrile hybrid electrolytes was observed. Lastly, when cycled within the appropriate voltage range, the IL-hybrid electrolytes that show the highest conductivity provide the best cathode magnesiation current densities and lowest polarization as demonstrated with a Mg 0.15MnO 2 and Mg 0.07V 2O 5 cathodes.« less

Solid Polymer Electrolyte (SPE) fuel cell technology program

NASA Technical Reports Server (NTRS)

1979-01-01

The overall objectives of the Phase IV Solid Polymer Electrolyte Fuel Cell Technology Program were to: (1) establish fuel cell life and performance at temperatures, pressures and current densities significantly higher than those previously demonstrated; (2) provide the ground work for a space energy storage system based on the solid polymer electrolyte technology (i.e., regenerative H2/O2 fuel cell); (3) design, fabricate and test evaluate a full-scale single cell unit. During this phase, significant progress was made toward the accomplishment of these objectives.

Symmetric supercapacitors using urea-modified lignin derived N-doped porous carbon as electrode materials in liquid and solid electrolytes

NASA Astrophysics Data System (ADS)

Wang, Keliang; Xu, Ming; Gu, Yan; Gu, Zhengrong; Fan, Qi Hua

2016-11-01

N-doped porous carbon materials derived from urea-modified lignin were prepared via efficient KOH activation under carbonization. The synthesized N-doped carbon materials, which displayed a well-developed porous morphology with high specific surface area of 3130 m2 g-1, were used as electrode materials in symmetric supercapacitors with aqueous and solid electrolytes. In consistent with the observed physical structures and properties, the supercapacitors exhibited specific capacitances of 273 and 306 F g-1, small resistances of 2.6 and 7.7 Ω, stable charge/discharge at different current densities for over 5000 cycles and comparable energy and power density in 6 mol L-1 KOH liquid and KOH-PVA solid electrolytes, respectively.

Functionalized carbon nanotube based hybrid electrochemical capacitors using neutral bromide redox-active electrolyte for enhancing energy density

NASA Astrophysics Data System (ADS)

Tang, Xiaohui; Lui, Yu Hui; Chen, Bolin; Hu, Shan

2017-06-01

A hybrid electrochemical capacitor (EC) with enhanced energy density is realized by integrating functionalized carbon nanotube (FCNT) electrodes with redox-active electrolyte that has a neutral pH value (1 M Na2SO4 and 0.5 M KBr mixed aqueous solution). The negative electrode shows an electric double layer capacitor-type behavior. On the positive electrode, highly reversible Br-/Br3- redox reactions take place, presenting a battery-type behavior, which contributes to increase the capacitance of the hybrid cell. The voltage window of the whole cell is extended up to 1.5 V because of the high over-potentials of oxygen and hydrogen evolution reactions in the neutral electrolyte. Compared with raw CNT, the FCNT has better wettability in the aqueous electrolyte and contributes to increase the electric double layer capacitance of the cell. As a result, the maximum energy density of 28.3 Wh kg-1 is obtained from the hybrid EC at 0.5 A g-1 without sacrificing its power density, which is around 4 times larger than that of the electrical double layer capacitor constructed by FCNT electrodes and 1 M Na2SO4 electrolyte. Moreover, the discharge capacity retained 86.3% of its initial performance after 10000 cycles of galvanostatic charge and discharge test (10 A/g), suggesting its long life cycle even at high current loading.

Carbon Nanotube-CoF2 Multifunctional Cathode for Lithium Ion Batteries: Effect of Electrolyte on Cycle Stability.

PubMed

Wang, Xinran; Gu, Wentian; Lee, Jung Tae; Nitta, Naoki; Benson, Jim; Magasinski, Alexandre; Schauer, Mark W; Yushin, Gleb

2015-10-01

Transition metal fluorides (MFx ) offer remarkably high theoretical energy density. However, the low cycling stability, low electrical and ionic conductivity of metal fluorides have severely limited their applications as conversion-type cathode materials for lithium ion batteries. Here, a scalable and low-cost strategy is reported on the fabrication of multifunctional cobalt fluoride/carbon nanotube nonwoven fabric nanocomposite, which demonstrates a combination of high capacity (near-theoretical, 550mAhgCoF2-1) and excellent mechanical properties. Its strength and modulus of toughness exceed that of many aluminum alloys, cast iron, and other structural materials, fulfilling the use of MFx -based materials in batteries with load-bearing capabilities. In the course of this study, cathode dissolution in conventional electrolytes has been discovered as the main reason that leads to the rapid growth of the solid electrolyte interphase layer and attributes to rapid cell degradation. And such largely overlooked degradation mechanism is overcome by utilizing electrolyte comprising a fluorinated solvent, which forms a protective ionically conductive layer on the cathode and anode surfaces. With this approach, 93% capacity retention is achieved after 200 cycles at the current density of 100 mA g(-1) and over 50% after 10 000 cycles at the current density of 1000 mA g(-1) . © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Directing the Lithium-Sulfur Reaction Pathway via Sparingly Solvating Electrolytes for High Energy Density Batteries.

PubMed

Lee, Chang-Wook; Pang, Quan; Ha, Seungbum; Cheng, Lei; Han, Sang-Don; Zavadil, Kevin R; Gallagher, Kevin G; Nazar, Linda F; Balasubramanian, Mahalingam

2017-06-28

The lithium-sulfur battery has long been seen as a potential next generation battery chemistry for electric vehicles owing to the high theoretical specific energy and low cost of sulfur. However, even state-of-the-art lithium-sulfur batteries suffer from short lifetimes due to the migration of highly soluble polysulfide intermediates and exhibit less than desired energy density due to the required excess electrolyte. The use of sparingly solvating electrolytes in lithium-sulfur batteries is a promising approach to decouple electrolyte quantity from reaction mechanism, thus creating a pathway toward high energy density that deviates from the current catholyte approach. Herein, we demonstrate that sparingly solvating electrolytes based on compact, polar molecules with a 2:1 ratio of a functional group to lithium salt can fundamentally redirect the lithium-sulfur reaction pathway by inhibiting the traditional mechanism that is based on fully solvated intermediates. In contrast to the standard catholyte sulfur electrochemistry, sparingly solvating electrolytes promote intermediate- and short-chain polysulfide formation during the first third of discharge, before disproportionation results in crystalline lithium sulfide and a restricted fraction of soluble polysulfides which are further reduced during the remaining discharge. Moreover, operation at intermediate temperatures ca. 50 °C allows for minimal overpotentials and high utilization of sulfur at practical rates. This discovery opens the door to a new wave of scientific inquiry based on modifying the electrolyte local structure to tune and control the reaction pathway of many precipitation-dissolution chemistries, lithium-sulfur and beyond.

Spatial Distribution of Oxygen Chemical Potential under Potential Gradients and Theoretical Maximum Power Density with 8YSZ Electrolyte

NASA Astrophysics Data System (ADS)

Lim, Dae-Kwang; Im, Ha-Ni; Song, Sun-Ju

2016-01-01

The maximum power density of SOFC with 8YSZ electrolyte as the function of thickness was calculated by integrating partial conductivities of charge carriers under various DC bias conditions at a fixed oxygen chemical potential gradient at both sides of the electrolyte. The partial conductivities were successfully taken using the Hebb-Wagner polarization method as a function of temperature and oxygen partial pressure, and the spatial distribution of oxygen partial pressure across the electrolyte was calculated based on Choudhury and Patterson’s model by considering zero electrode polarization. At positive voltage conditions corresponding to SOFC and SOEC, the high conductivity region was expanded, but at negative cell voltage condition, the low conductivity region near n-type to p-type transition was expanded. In addition, the maximum power density calculated from the current-voltage characteristic showed approximately 5.76 W/cm2 at 700 oC with 10 μm thick-8YSZ, while the oxygen partial pressure of the cathode and anode sides maintained ≈0.21 and 10-22 atm.

Electrochemical reduction of UO2 in LiCl-Li2O molten salt using porous and nonporous anode shrouds

NASA Astrophysics Data System (ADS)

Choi, Eun-Young; Won, Chan Yeon; Cha, Ju-Sun; Park, Wooshin; Im, Hun Suk; Hong, Sun-Seok; Hur, Jin-Mok

2014-01-01

Electrochemical reductions of uranium oxide in a molten LiCl-Li2O electrolyte were carried out using porous and nonporous anode shrouds. The study focused on the effect of the type of anode shroud on the current density by running experiments with six anode shrouds. Dense ceramics, MgO, and MgO (3 wt%) stabilized ZrO2 (ZrO2-MgO) were used as nonporous shrouds. STS 20, 100, and 300 meshes and ZrO2-MgO coated STS 40 mesh were used as porous shrouds. The current densities (0.34-0.40 A cm-2) of the electrolysis runs using the nonporous anode shrouds were much lower than those (0.76-0.79 A cm-2) of the runs using the porous shrouds. The ZrO2-MgO shroud (600-700 MPa at 25 °C) showed better bending strength than that of MgO (170 MPa at 25 °C). The high current densities achieved in the electrolysis runs using the porous anode shrouds were attributed to the transport of O2- ions through the pores in meshes of the shroud wall. ZrO2-MgO coating on STS mesh was chemically unstable in a molten LiCl-Li2O electrolyte containing Li metal. The electrochemical reduction runs using STS 20, 100, and 300 meshes showed similar current densities in spite of their different opening sizes. The STS mesh shrouds which were immersed in a LiCl-Li2O electrolyte were stable without any damage or corrosion.

Non-Aqueous Primary Li-Air Flow Battery and Optimization of its Cathode through Experiment and Modeling.

PubMed

Kim, Byoungsu; Takechi, Kensuke; Ma, Sichao; Verma, Sumit; Fu, Shiqi; Desai, Amit; Pawate, Ashtamurthy S; Mizuno, Fuminori; Kenis, Paul J A

2017-09-22

A primary Li-air battery has been developed with a flowing Li-ion free ionic liquid as the recyclable electrolyte, boosting power capability by promoting superoxide diffusion and enhancing discharge capacity through separately stored discharge products. Experimental and computational tools are used to analyze the cathode properties, leading to a set of parameters that improve the discharge current density of the non-aqueous Li-air flow battery. The structure and configuration of the cathode gas diffusion layers (GDLs) are systematically modified by using different levels of hot pressing and the presence or absence of a microporous layer (MPL). These experiments reveal that the use of thinner but denser MPLs is key for performance optimization; indeed, this leads to an improvement in discharge current density. Also, computational results indicate that the extent of electrolyte immersion and porosity of the cathode can be optimized to achieve higher current density. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Self-Passivating Lithium/Solid Electrolyte/Iodine Cells

NASA Technical Reports Server (NTRS)

Bugga, Ratnakumar; Whitcare, Jay; Narayanan, Sekharipuram; West, William

2006-01-01

Robust lithium/solid electrolyte/iodine electrochemical cells that offer significant advantages over commercial lithium/ iodine cells have been developed. At room temperature, these cells can be discharged at current densities 10 to 30 times those of commercial lithium/iodine cells. Moreover, from room temperature up to 80 C, the maximum discharge-current densities of these cells exceed those of all other solid-electrolyte-based cells. A cell of this type includes a metallic lithium anode in contact with a commercial flexible solid electrolyte film that, in turn, is in contact with an iodine/ graphite cathode. The solid electrolyte (the chemical composition of which has not been reported) offers the high ionic conductivity needed for high cell performance. However, the solid electrolyte exhibits an undesirable chemical reactivity to lithium that, if not mitigated, would render the solid electrolyte unsuitable for use in a lithium cell. In this cell, such mitigation is affected by the formation of a thin passivating layer of lithium iodide at the anode/electrolyte interface. Test cells of this type were fabricated from iodine/graphite cathode pellets, free-standing solid-electrolyte films, and lithium-foil anodes. The cathode mixtures were made by grinding together blends of nominally 10 weight percent graphite and 90 weight percent iodine. The cathode mixtures were then pressed into pellets at 36 kpsi (248 MPa) and inserted into coin-shaped stainless-steel cell cases that were coated with graphite paste to minimize corrosion. The solid-electrolyte film material was stamped to form circular pieces to fit in the coin cell cases, inserted in the cases, and pressed against the cathode pellets with polyethylene gaskets. Lithium-foil anodes were placed directly onto the electrolyte films. The layers described thus far were pressed and held together by stainless- steel shims, wave springs, and coin cell caps. The assembled cells were then crimped to form hermetic seals. It was found that the solid electrolyte films became discolored within seconds after they were placed in contact with the cathodes - a result of facile diffusion of iodine through the solid electrolyte material (see figure).

Electrochemical performance of C4O6H4KNa aqueous electrolytes

NASA Astrophysics Data System (ADS)

Zhang, Jianqiang; Song, Senyang; Chen, Yanzheng; Huang, Siyun; Li, Ping; Luo, Heming

2018-06-01

The paper is devoted in the study of the simple method to study the performance of aqueous electrolytes, whereas the custom-made FBNC-700 (FB represents FAC-brown, N represents "nitrogen-self-doped," C represents mesoporous-carbon materials, and 700 represents carbonization temperature.) was utilized as the electrode material, where the C4O6H4KNa solution was utilized as an aqueous electrolyte. The polarization curves was be used in the three-electrode system to conduct the voltage window preliminary selection of the C4O6H4KNa solution, the voltage window was 1.3 V (-0.8 V to 0.5 V). The concentration had minimal effects on the voltage window. The method is faster and more efficient way to study the performance of aqueous electrolytes for supercapacitors. In the 2 M C4O6H4KNa solution, the FBNC-700 displayed a 97 F g-1 specific capacitance at the current density of 0.5 A g-1 in the two-electrodes tests. Also, following 5000 cycles at a current density of 1 A g-1, the FBNC-700 had good stability with 76.22% capacitance retention.

High-Performance Cells Containing Lithium Metal Anodes, LiNi0.6Co0.2Mn0.2O2 (NCM 622) Cathodes, and Fluoroethylene Carbonate-Based Electrolyte Solution with Practical Loading.

PubMed

Salitra, Gregory; Markevich, Elena; Afri, Michal; Talyosef, Yosef; Hartmann, Pascal; Kulisch, Joern; Sun, Yang-Kook; Aurbach, Doron

2018-06-13

We report on the highly stable lithium metal|LiNi 0.6 Co 0.2 Mn 0.2 O 2 (NCM 622) cells with practical electrodes' loading of 3.3 mA h g -1 , which can undergo many hundreds of stable cycles, demonstrating high rate capability. A key issue was the use of fluoroethylene carbonate (FEC)-based electrolyte solutions (1 M LiPF 6 in FEC/dimethyl carbonate). Li|NCM 622 cells can be cycled at 1.5 mA cm -2 for more than 600 cycles, whereas symmetric Li|Li cells demonstrate stable performance for more than 1000 cycles even at higher areal capacity and current density. We attribute the excellent performance of both Li|NCM and Li|Li cells to the formation of a stable and efficient solid electrolyte interphase (SEI) on the surface of the Li metal electrodes cycled in FEC-based electrolyte solutions. The composition of the SEI on the Li and the NCM electrodes is analyzed by X-ray photoelectron spectroscopy and Fourier transform infrared spectroscopy. A drastic capacity fading of Li|NCM cells is observed, followed by spontaneous capacity recovery during prolonged cycling. This phenomenon depends on the current density and the amount of the electrolyte solution and relates to kinetic limitations because of SEI formation on the Li anodes in the FEC-based electrolyte solution.

Flexible asymmetric supercapacitors based upon Co9S8 nanorod//Co3O4@RuO2 nanosheet arrays on carbon cloth.

PubMed

Xu, Jing; Wang, Qiufan; Wang, Xiaowei; Xiang, Qingyi; Liang, Bo; Chen, Di; Shen, Guozhen

2013-06-25

We have successfully fabricated flexible asymmetric supercapacitors (ASCs) based on acicular Co9S8 nanorod arrays as positive materials and Co3O4@RuO2 nanosheet arrays as negative materials on woven carbon fabrics. Co9S8 nanorod arrays were synthesized by a hydrothermal sulfuration treatment of acicular Co3O4 nanorod arrays, while the RuO2 was directly deposited on the Co3O4 nanorod arrays. Carbon cloth was selected as both the substrate and the current collector for its good conductivity, high flexibility, good physical strength, and lightweight architecture. Both aqueous KOH solutions and polyvinyl alcohol (PVA)/KOH were employed as electrolyte for electrochemical measurements. The as-fabricated ASCs can be cycled reversibly in the range of 0-1.6 V and exhibit superior electrochemical performance with an energy density of 1.21 mWh/cm(3) at a power density of 13.29 W/cm(3) in aqueous electrolyte and an energy density of 1.44 mWh/cm(3) at the power density of 0.89 W/cm(3) in solid-state electrolyte, which are almost 10-fold higher than those reported in early ASC work. Moreover, they present excellent cycling performance at multirate currents and large currents after thousands of cycles. The high-performance nanostructured ASCs have significant potential applications in portable electronics and electrical vehicles.

Electrodeposition of hierarchically structured three-dimensional nickel–iron electrodes for efficient oxygen evolution at high current densities

PubMed Central

Lu, Xunyu; Zhao, Chuan

2015-01-01

Large-scale industrial application of electrolytic splitting of water has called for the development of oxygen evolution electrodes that are inexpensive, robust and can deliver large current density (>500 mA cm−2) at low applied potentials. Here we show that an efficient oxygen electrode can be developed by electrodepositing amorphous mesoporous nickel–iron composite nanosheets directly onto macroporous nickel foam substrates. The as-prepared oxygen electrode exhibits high catalytic activity towards water oxidation in alkaline solutions, which only requires an overpotential of 200 mV to initiate the reaction, and is capable of delivering current densities of 500 and 1,000 mA cm−2 at overpotentials of 240 and 270 mV, respectively. The electrode also shows prolonged stability against bulk water electrolysis at large current. Collectively, the as-prepared three-dimensional structured electrode is the most efficient oxygen evolution electrode in alkaline electrolytes reported to the best of our knowledge, and can potentially be applied for industrial scale water electrolysis. PMID:25776015

Ambipolar zinc-polyiodide electrolyte for a high-energy density aqueous redox flow battery

DOE PAGES

Li, Bin; Nie, Zimin; Vijayakumar, M.; ...

2015-02-24

Large-scale energy storage systems are crucial for substantial deployment of renewable energy sources. Energy storage systems with high energy density, high safety, and low cost and environmental friendliness are desired. To overcome the major limitations of the current aqueous redox flow battery systems, namely lower energy density (~25 Wh L -1) and presence of strong acids and/or other hazardous, a high energy density aqueous zinc/polyiodide flow battery (ZIB) is designed with near neutral ZnI 2 solutions as catholytes. The energy density of ZIB could reach 322 Wh L -1 at the solubility limit of ZnI 2 in water (~7 M).more » We demonstrate charge and discharge energy densities of 245.9 Wh/L and 166.7 Wh L-1 with ZnI 2 electrolyte at 5.0 M, respectively. The addition of ethanol (EtOH) in ZnI 2 electrolyte can effectively mitigate the growth of zinc dendrite at the anode and improve the stability of catholytes with wider temperature window (-20 to 50°C), which enable ZIB system to be a promising alternative as a high-energy and high- safety stationary energy storage system.« less

Quaternary Polymer Electrolytes Containing an Ionic Liquid and a Ceramic Filler.

PubMed

Sharova, Varvara; Kim, Guk-Tae; Giffin, Guinevere A; Lex-Balducci, Alexandra; Passerini, Stefano

2016-07-01

In this work, the individual and combined effects of an ionic liquid 1-butyl-1-methylpyrrolidinium bis(trifluoromethanesulfonyl)imide and ceramic filler silicon dioxide on the thermal and electrochemical properties of poly(ethylene oxide) electrolytes have been investigated. The electrolyte containing both components has the lowest glass transition (-60 °C) and melting temperatures (27 °C), the highest conductivity at any investigated temperature, and the highest limiting current density (at 40 °C). This solid polymer electrolyte also exhibits the best long-term cycling performance in Li/LiFePO4 cells. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Optimization of return electrodes in neurostimulating arrays

NASA Astrophysics Data System (ADS)

Flores, Thomas; Goetz, Georges; Lei, Xin; Palanker, Daniel

2016-06-01

Objective. High resolution visual prostheses require dense stimulating arrays with localized inputs of individual electrodes. We study the electric field produced by multielectrode arrays in electrolyte to determine an optimal configuration of return electrodes and activation sequence. Approach. To determine the boundary conditions for computation of the electric field in electrolyte, we assessed current dynamics using an equivalent circuit of a multielectrode array with interleaved return electrodes. The electric field modeled with two different boundary conditions derived from the equivalent circuit was then compared to measurements of electric potential in electrolyte. To assess the effect of return electrode configuration on retinal stimulation, we transformed the computed electric fields into retinal response using a model of neural network-mediated stimulation. Main results. Electric currents at the capacitive electrode-electrolyte interface redistribute over time, so that boundary conditions transition from equipotential surfaces at the beginning of the pulse to uniform current density in steady state. Experimental measurements confirmed that, in steady state, the boundary condition corresponds to a uniform current density on electrode surfaces. Arrays with local return electrodes exhibit improved field confinement and can elicit stronger network-mediated retinal response compared to those with a common remote return. Connecting local return electrodes enhances the field penetration depth and allows reducing the return electrode area. Sequential activation of the pixels in large monopolar arrays reduces electrical cross-talk and improves the contrast in pattern stimulation. Significance. Accurate modeling of multielectrode arrays helps optimize the electrode configuration to maximize the spatial resolution, contrast and dynamic range of retinal prostheses.

Ionomer-Liquid Electrolyte Hybrid Ionic Conductor for High Cycling Stability of Lithium Metal Electrodes

PubMed Central

Song, Jongchan; Lee, Hongkyung; Choo, Min-Ju; Park, Jung-Ki; Kim, Hee-Tak

2015-01-01

The inhomogeneous Li electrodeposition of lithium metal electrode has been a major impediment to the realization of rechargeable lithium metal batteries. Although single ion conducting ionomers can induce more homogeneous Li electrodeposition by preventing Li+ depletion at Li surface, currently available materials do not allow room-temperature operation due to their low room temperature conductivities. In the paper, we report that a highly conductive ionomer/liquid electrolyte hybrid layer tightly laminated on Li metal electrode can realize stable Li electrodeposition at high current densities up to 10 mA cm−2 and permit room-temperature operation of corresponding Li metal batteries with low polarizations. The hybrid layer is fabricated by laminating few micron-thick Nafion layer on Li metal electrode followed by soaking 1 M LiPF6 EC/DEC (1/1) electrolyte. The Li/Li symmetric cell with the hybrid layer stably operates at a high current density of 10 mA cm−2 for more than 2000 h, which corresponds to more than five-fold enhancement compared with bare Li metal electrode. Also, the prototype Li/LiCoO2 battery with the hybrid layer offers cycling stability more than 350 cycles. These results demonstrate that the hybrid strategy successfully combines the advantages of bi-ionic liquid electrolyte (fast Li+ transport) and single ionic ionomer (prevention of Li+ depletion). PMID:26411701

Ionomer-Liquid Electrolyte Hybrid Ionic Conductor for High Cycling Stability of Lithium Metal Electrodes

NASA Astrophysics Data System (ADS)

Song, Jongchan; Lee, Hongkyung; Choo, Min-Ju; Park, Jung-Ki; Kim, Hee-Tak

2015-09-01

The inhomogeneous Li electrodeposition of lithium metal electrode has been a major impediment to the realization of rechargeable lithium metal batteries. Although single ion conducting ionomers can induce more homogeneous Li electrodeposition by preventing Li+ depletion at Li surface, currently available materials do not allow room-temperature operation due to their low room temperature conductivities. In the paper, we report that a highly conductive ionomer/liquid electrolyte hybrid layer tightly laminated on Li metal electrode can realize stable Li electrodeposition at high current densities up to 10 mA cm-2 and permit room-temperature operation of corresponding Li metal batteries with low polarizations. The hybrid layer is fabricated by laminating few micron-thick Nafion layer on Li metal electrode followed by soaking 1 M LiPF6 EC/DEC (1/1) electrolyte. The Li/Li symmetric cell with the hybrid layer stably operates at a high current density of 10 mA cm-2 for more than 2000 h, which corresponds to more than five-fold enhancement compared with bare Li metal electrode. Also, the prototype Li/LiCoO2 battery with the hybrid layer offers cycling stability more than 350 cycles. These results demonstrate that the hybrid strategy successfully combines the advantages of bi-ionic liquid electrolyte (fast Li+ transport) and single ionic ionomer (prevention of Li+ depletion).

All-solid-state flexible supercapacitors based on papers coated with carbon nanotubes and ionic-liquid-based gel electrolytes.

PubMed

Kang, Yu Jin; Chung, Haegeun; Han, Chi-Hwan; Kim, Woong

2012-02-17

All-solid-state flexible supercapacitors were fabricated using carbon nanotubes (CNTs), regular office papers, and ionic-liquid-based gel electrolytes. Flexible electrodes were made by coating CNTs on office papers by a drop-dry method. The gel electrolyte was prepared by mixing fumed silica nanopowders with ionic liquid, 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide ([EMIM][NTf(2)]). This supercapacitor showed high power and energy performance as a solid-state flexible supercapacitor. The specific capacitance of the CNT electrodes was 135 F g(-1) at a current density of 2 A g(-1), when considering the mass of active materials only. The maximum power and energy density of the supercapacitors were 164 kW kg(-1) and 41 Wh kg(-1), respectively. Interestingly, the solid-state supercapacitor with the gel electrolyte showed comparable performance to the supercapacitors with ionic-liquid electrolyte. Moreover, the supercapacitor showed excellent stability and flexibility. The CNT/paper- and gel-based supercapacitors may hold great potential for low-cost and high-performance flexible energy storage applications.

All-solid-state flexible supercapacitors based on papers coated with carbon nanotubes and ionic-liquid-based gel electrolytes

NASA Astrophysics Data System (ADS)

Kang, Yu Jin; Chung, Haegeun; Han, Chi-Hwan; Kim, Woong

2012-02-01

All-solid-state flexible supercapacitors were fabricated using carbon nanotubes (CNTs), regular office papers, and ionic-liquid-based gel electrolytes. Flexible electrodes were made by coating CNTs on office papers by a drop-dry method. The gel electrolyte was prepared by mixing fumed silica nanopowders with ionic liquid, 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide ([EMIM][NTf2]). This supercapacitor showed high power and energy performance as a solid-state flexible supercapacitor. The specific capacitance of the CNT electrodes was 135 F g-1 at a current density of 2 A g-1, when considering the mass of active materials only. The maximum power and energy density of the supercapacitors were 164 kW kg-1 and 41 Wh kg-1, respectively. Interestingly, the solid-state supercapacitor with the gel electrolyte showed comparable performance to the supercapacitors with ionic-liquid electrolyte. Moreover, the supercapacitor showed excellent stability and flexibility. The CNT/paper- and gel-based supercapacitors may hold great potential for low-cost and high-performance flexible energy storage applications.

ZnCl 2- and NH 4Cl-hydroponics gel electrolytes for zinc-carbon batteries

NASA Astrophysics Data System (ADS)

Khalid, N. H.; Ismail, Y. M. Baba; Mohamad, A. A.

Absorbency testing is used to determine the percentage of ZnCl 2 or NH 4Cl solution absorbed by a hydroponics gel (HPG). It is found that the absorbency of ZnCl 2 or NH 4Cl solution decreases with increasing solution concentration. The conductivity of ZnCl 2- and NH 4Cl-HPG electrolytes is dependent on the solution concentration. A mixture of salt solution with HPG yields excellent gel polymer electrolytes with conductivities of 0.026 and 0.104 S cm -1 at 3 M ZnCl 2 and 7 M NH 4Cl, respectively. These gel electrolytes are then used to produce zinc-carbon cells. The fabricated cells give capacities of 8.8 and 10.0 mAh, have an internal resistance of 25.4 and 19.8 Ω, a maximum power density of 12.7 and 12.2 mW cm -2, and a short-circuit current density of 29.1 and 33.9 mA cm -2 for ZnCl 2- and NH 4Cl-HPG electrolytes, respectively.

Negative Transference Numbers in Polymer Electrolytes

NASA Astrophysics Data System (ADS)

Pesko, Danielle; Timachova, Ksenia; Balsara, Nitash

Energy density and safety of conventional lithium-ion batteries is limited by the use of flammable organic liquids as a solvent for lithium salts. Polymer electrolytes have the potential to address both limitations. The poor performance of batteries with polymer electrolytes is generally attributed to low ionic conductivity. The purpose of our work is to show that another transport property, the cation transference number, t +, of polymer electrolytes is fundamentally different from that of conventional electrolytes. Our experimental approach, based on concentrated solution theory, indicates that t + of mixtures of poly(ethylene oxide) and LiTFSI salt are negative over most of the accessible concentration window. In contrast, approaches based on dilute solution theory suggest that t + in the same system is positive. In addition to presenting a new approach for determining t +, we also present data obtained from the steady-state current method, pulsed-field-gradient NMR, and the current-interrupt method. Discrepancies between different approaches are resolved. Our work implies that in the absence of concentration gradients, the net fluxes of both cations and anions are directed toward the positive electrode. Conventional liquid electrolytes do not suffer from this constraint.

A lithium superionic conductor.

PubMed

Kamaya, Noriaki; Homma, Kenji; Yamakawa, Yuichiro; Hirayama, Masaaki; Kanno, Ryoji; Yonemura, Masao; Kamiyama, Takashi; Kato, Yuki; Hama, Shigenori; Kawamoto, Koji; Mitsui, Akio

2011-07-31

Batteries are a key technology in modern society. They are used to power electric and hybrid electric vehicles and to store wind and solar energy in smart grids. Electrochemical devices with high energy and power densities can currently be powered only by batteries with organic liquid electrolytes. However, such batteries require relatively stringent safety precautions, making large-scale systems very complicated and expensive. The application of solid electrolytes is currently limited because they attain practically useful conductivities (10(-2) S cm(-1)) only at 50-80 °C, which is one order of magnitude lower than those of organic liquid electrolytes. Here, we report a lithium superionic conductor, Li(10)GeP(2)S(12) that has a new three-dimensional framework structure. It exhibits an extremely high lithium ionic conductivity of 12 mS cm(-1) at room temperature. This represents the highest conductivity achieved in a solid electrolyte, exceeding even those of liquid organic electrolytes. This new solid-state battery electrolyte has many advantages in terms of device fabrication (facile shaping, patterning and integration), stability (non-volatile), safety (non-explosive) and excellent electrochemical properties (high conductivity and wide potential window).

Recent advances in solid polymer electrolyte fuel cell technology with low platinum loading electrodes

NASA Technical Reports Server (NTRS)

Srinivasan, Supramaniam; Manko, David J.; Enayatullah, Mohammad; Appleby, A. John

1989-01-01

High power density fuel cell systems for defense and civilian applications are being developed. Taking into consideration the main causes for efficiency losses (activation, mass transport and ohmic overpotentials) the only fuel cell systems capable of achieving high power densities are the ones with alkaline and solid polymer electrolyte. High power densities (0.8 W/sq cm at 0.8 V and 1 A/sq cm with H2 and O2 as reactants), were already used in NASA's Apollo and Space Shuttle flights as auxiliary power sources. Even higher power densities (4 W/sq cm - i.e., 8 A sq cm at 0.5 V) were reported by the USAF/International Fuel Cells in advanced versions of the alkaline system. High power densities (approximately 1 watt/sq cm) in solid polymer electrolyte fuel cells with ten times lower platinum loading in the electrodes (i.e., 0.4 mg/sq cm) were attained. It is now possible to reach a cell potential of 0.620 V at a current density of 2 A/sq cm and at a temperature of 95 C and pressure of 4/5 atm with H2/O2 as reactants. The slope of the linear region of the potential-current density plot for this case is 0.15 ohm-sq cm. With H2/air as reactants and under the same operating conditions, mass transport limitations are encountered at current densities above 1.4 A/sq cm. Thus, the cell potential at 1 A/sq cm with H2/air as reactants is less than that with H2/O2 as reactants by 40 mV, which is the expected value based on electrode kinetics of the oxygen reduction reaction, and at 2 A/sq cm with H2/air as reactant is less than the corresponding value with H2/O2 as reactants by 250 mV, which is due to the considerably greater mass transport limitations in the former case.

Elucidating Solvation Structures for Rational Design of Multivalent Electrolytes-A Review.

PubMed

Rajput, Nav Nidhi; Seguin, Trevor J; Wood, Brandon M; Qu, Xiaohui; Persson, Kristin A

2018-04-26

Fundamental molecular-level understanding of functional properties of liquid solutions provides an important basis for designing optimized electrolytes for numerous applications. In particular, exhaustive knowledge of solvation structure, stability, and transport properties is critical for developing stable electrolytes for fast-charging and high-energy-density next-generation energy storage systems. Accordingly, there is growing interest in the rational design of electrolytes for beyond lithium-ion systems by tuning the molecular-level interactions of solvate species present in the electrolytes. Here we present a review of the solvation structure of multivalent electrolytes and its impact on the electrochemical performance of these batteries. A direct correlation between solvate species present in the solution and macroscopic properties of electrolytes is sparse for multivalent electrolytes and contradictory results have been reported in the literature. This review aims to illustrate the current understanding, compare results, and highlight future needs and directions to enable the deep understanding needed for the rational design of improved multivalent electrolytes.

Directing the Lithium–Sulfur Reaction Pathway via Sparingly Solvating Electrolytes for High Energy Density Batteries

PubMed Central

2017-01-01

The lithium–sulfur battery has long been seen as a potential next generation battery chemistry for electric vehicles owing to the high theoretical specific energy and low cost of sulfur. However, even state-of-the-art lithium–sulfur batteries suffer from short lifetimes due to the migration of highly soluble polysulfide intermediates and exhibit less than desired energy density due to the required excess electrolyte. The use of sparingly solvating electrolytes in lithium–sulfur batteries is a promising approach to decouple electrolyte quantity from reaction mechanism, thus creating a pathway toward high energy density that deviates from the current catholyte approach. Herein, we demonstrate that sparingly solvating electrolytes based on compact, polar molecules with a 2:1 ratio of a functional group to lithium salt can fundamentally redirect the lithium–sulfur reaction pathway by inhibiting the traditional mechanism that is based on fully solvated intermediates. In contrast to the standard catholyte sulfur electrochemistry, sparingly solvating electrolytes promote intermediate- and short-chain polysulfide formation during the first third of discharge, before disproportionation results in crystalline lithium sulfide and a restricted fraction of soluble polysulfides which are further reduced during the remaining discharge. Moreover, operation at intermediate temperatures ca. 50 °C allows for minimal overpotentials and high utilization of sulfur at practical rates. This discovery opens the door to a new wave of scientific inquiry based on modifying the electrolyte local structure to tune and control the reaction pathway of many precipitation–dissolution chemistries, lithium–sulfur and beyond. PMID:28691072

Directing the lithium–sulfur reaction pathway via sparingly solvating electrolytes for high energy density batteries

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lee, Chang -Wook; Pang, Quan; Ha, Seungbum

The lithium–sulfur battery has long been seen as a potential next generation battery chemistry for electric vehicles owing to the high theoretical specific energy and low cost of sulfur. However, even state-of-the-art lithium–sulfur batteries suffer from short lifetimes due to the migration of highly soluble polysulfide intermediates and exhibit less than desired energy density due to the required excess electrolyte. The use of sparingly solvating electrolytes in lithium–sulfur batteries is a promising approach to decouple electrolyte quantity from reaction mechanism, thus creating a pathway toward high energy density that deviates from the current catholyte approach. Herein, we demonstrate that sparinglymore » solvating electrolytes based on compact, polar molecules with a 2:1 ratio of a functional group to lithium salt can fundamentally redirect the lithium–sulfur reaction pathway by inhibiting the traditional mechanism that is based on fully solvated intermediates. In contrast to the standard catholyte sulfur electrochemistry, sparingly solvating electrolytes promote intermediate- and short-chain polysulfide formation during the first third of discharge, before disproportionation results in crystalline lithium sulfide and a restricted fraction of soluble polysulfides which are further reduced during the remaining discharge. Moreover, operation at intermediate temperatures ca. 50 °C allows for minimal overpotentials and high utilization of sulfur at practical rates. Finally, this discovery opens the door to a new wave of scientific inquiry based on modifying the electrolyte local structure to tune and control the reaction pathway of many precipitation–dissolution chemistries, lithium–sulfur and beyond.« less

Directing the lithium–sulfur reaction pathway via sparingly solvating electrolytes for high energy density batteries

DOE PAGES

Lee, Chang -Wook; Pang, Quan; Ha, Seungbum; ...

2017-05-25

The lithium–sulfur battery has long been seen as a potential next generation battery chemistry for electric vehicles owing to the high theoretical specific energy and low cost of sulfur. However, even state-of-the-art lithium–sulfur batteries suffer from short lifetimes due to the migration of highly soluble polysulfide intermediates and exhibit less than desired energy density due to the required excess electrolyte. The use of sparingly solvating electrolytes in lithium–sulfur batteries is a promising approach to decouple electrolyte quantity from reaction mechanism, thus creating a pathway toward high energy density that deviates from the current catholyte approach. Herein, we demonstrate that sparinglymore » solvating electrolytes based on compact, polar molecules with a 2:1 ratio of a functional group to lithium salt can fundamentally redirect the lithium–sulfur reaction pathway by inhibiting the traditional mechanism that is based on fully solvated intermediates. In contrast to the standard catholyte sulfur electrochemistry, sparingly solvating electrolytes promote intermediate- and short-chain polysulfide formation during the first third of discharge, before disproportionation results in crystalline lithium sulfide and a restricted fraction of soluble polysulfides which are further reduced during the remaining discharge. Moreover, operation at intermediate temperatures ca. 50 °C allows for minimal overpotentials and high utilization of sulfur at practical rates. Finally, this discovery opens the door to a new wave of scientific inquiry based on modifying the electrolyte local structure to tune and control the reaction pathway of many precipitation–dissolution chemistries, lithium–sulfur and beyond.« less

Layer by Layer Ex-Situ Deposited Cobalt-Manganese Oxide as Composite Electrode Material for Electrochemical Capacitor

PubMed Central

Rusi; Chan, P. Y.; Majid, S. R.

2015-01-01

The composite metal oxide electrode films were fabricated using ex situ electrodeposition method with further heating treatment at 300°C. The obtained composite metal oxide film had a spherical structure with mass loading from 0.13 to 0.21 mg cm-2. The structure and elements of the composite was investigated using X-ray diffraction (XRD) and energy dispersive X-ray (EDX). The electrochemical performance of different composite metal oxides was studied by cyclic voltammetry (CV) and galvanostatic charge-discharge (CD). As an active electrode material for a supercapacitor, the Co-Mn composite electrode exhibits a specific capacitance of 285 Fg-1 at current density of 1.85 Ag-1 in 0.5M Na2SO4 electrolyte. The best composite electrode, Co-Mn electrode was then further studied in various electrolytes (i.e., 0.5M KOH and 0.5M KOH/0.04M K3Fe(CN) 6 electrolytes). The pseudocapacitive nature of the material of Co-Mn lead to a high specific capacitance of 2.2 x 103 Fg-1 and an energy density of 309 Whkg-1 in a 0.5MKOH/0.04MK3Fe(CN) 6 electrolyte at a current density of 10 Ag-1. The specific capacitance retention obtained 67% of its initial value after 750 cycles. The results indicate that the ex situ deposited composite metal oxide nanoparticles have promising potential in future practical applications. PMID:26158447

Layer by Layer Ex-Situ Deposited Cobalt-Manganese Oxide as Composite Electrode Material for Electrochemical Capacitor.

PubMed

Rusi; Chan, P Y; Majid, S R

2015-01-01

The composite metal oxide electrode films were fabricated using ex situ electrodeposition method with further heating treatment at 300°C. The obtained composite metal oxide film had a spherical structure with mass loading from 0.13 to 0.21 mg cm(-2). The structure and elements of the composite was investigated using X-ray diffraction (XRD) and energy dispersive X-ray (EDX). The electrochemical performance of different composite metal oxides was studied by cyclic voltammetry (CV) and galvanostatic charge-discharge (CD). As an active electrode material for a supercapacitor, the Co-Mn composite electrode exhibits a specific capacitance of 285 Fg(-1) at current density of 1.85 Ag(-1) in 0.5 M Na2SO4 electrolyte. The best composite electrode, Co-Mn electrode was then further studied in various electrolytes (i.e., 0.5 M KOH and 0.5 M KOH/0.04 M K3Fe(CN) 6 electrolytes). The pseudocapacitive nature of the material of Co-Mn lead to a high specific capacitance of 2.2 x 10(3) Fg(-1) and an energy density of 309 Whkg(-1) in a 0.5 M KOH/0.04 M K3Fe(CN) 6 electrolyte at a current density of 10 Ag(-1). The specific capacitance retention obtained 67% of its initial value after 750 cycles. The results indicate that the ex situ deposited composite metal oxide nanoparticles have promising potential in future practical applications.

Study on electrochemically deposited Mg metal

NASA Astrophysics Data System (ADS)

Matsui, Masaki

An electrodeposition process of magnesium metal from Grignard reagent based electrolyte was studied by comparing with lithium. The electrodeposition of magnesium was performed at various current densities. The obtained magnesium deposits did not show dendritic morphologies while all the lithium deposits showed dendritic products. Two different crystal growth modes in the electrodeposition process of magnesium metal were confirmed by an observation using scanning electron micro scope (SEM) and a crystallographic analysis using X-ray diffraction (XRD). An electrochemical study of the deposition/dissolution process of the magnesium showed a remarkable dependency of the overpotential of magnesium deposition on the electrolyte concentration compared with lithium. This result suggests that the dependency of the overpotential on the electrolyte concentration prevent the locally concentrated current resulting to form very uniform deposits.

BDD anodic treatment of 6:2 fluorotelomer sulfonate (6:2 FTSA). Evaluation of operating variables and by-product formation.

PubMed

Urtiaga, Ane; Soriano, Alvaro; Carrillo-Abad, Jordi

2018-06-01

The concerns about the undesired impacts on human health and the environment of long chain perfluorinated alkyl substances (PFASs) have driven industrial initiatives to replace PFASs by shorter chain fluorinated homologues. 6:2 fluorotelomer sulfonic acid (6:2 FTSA) is applied as alternative to PFOS in metal plating and fluoropolymer manufacture. This study reports the electrochemical treatment of aqueous 6:2 FTSA solutions on microcrystalline BDD anodes. Bench scale batch experiments were performed, focused on assessing the effect of the electrolyte and the applied current density (5-600 A m -2 ) on the removal of 6:2 FTSA, the reduction of total organic carbon (TOC) and the fluoride release. Results showed that at the low range of applied current density (J = 50 A m -2 ), using NaCl, Na 2 SO 4 and NaClO 4 , the electrolyte exerted a minimal effect on removal rates. The formation of toxic inorganic chlorine species such as ClO 4 - was not observed. When using Na 2 SO 4 electrolyte, increasing the applied current density to 350-600 A m -2 promoted a notable enhancement of the 6:2 FTSA removal and defluorination rates, pointing to the positive contribution of electrogenerated secondary oxidants to the overall removal rate. 6:2 FTSA was transformed into shorter-chain PFCAs, and eventually into CO 2 and fluoride, as TOC reduction was >90%. Finally, it was demonstrated that diffusion in the liquid phase was controlling the overall kinetic rate, although with moderate improvements due to secondary oxidants at very high current densities. Copyright © 2018 Elsevier Ltd. All rights reserved.

Ambient-Pressure XPS Study of a Ni–Fe Electrocatalyst for the Oxygen Evolution Reaction

DOE PAGES

Ali-Löytty, Harri; Louie, Mary W.; Singh, Meenesh R.; ...

2016-01-05

Chemical analysis of solid–liquid interfaces under electrochemical conditions has recently become feasible due to the development of new synchrotron radiation techniques. In this paper, we report the use of “tender” X-ray ambient-pressure X-ray photoelectron spectroscopy (APXPS) to characterize a thin film of Ni–Fe oxyhydroxide electrodeposited on Au as the working electrode at different applied potentials in 0.1 M KOH as the electrolyte. Our results show that the as-prepared 7 nm thick Ni–Fe (50% Fe) film contains Fe and Ni in both their metallic as well as oxidized states, and undergoes further oxidation when the sample is subjected to electrochemical oxidation–reductionmore » cycles. Metallic Fe is oxidized to Fe 3+ and metallic Ni to Ni 2+/3+. This work shows that it is possible to monitor the chemical nature of the Ni–Fe catalyst as a function of potential when the corresponding current densities are small. This allows for operando measurements just above the onset of OER; however, current densities as they are desired in photoelectrochemical devices (~1–10 mA cm –2) could not be achieved in this work, due to ohmic losses in the thin electrolyte film. We use a two-dimensional model to describe the spatial distribution of the electrochemical potential, current density, and pH as a function of the position above the electrolyte meniscus, to provide guidance toward enabling the acquisition of operando APXPS at high current density. Finally, the shifts in binding energy of water with applied potential predicted by the model are in good agreement with the experimental values.« less

Symmetric supercapacitor: Sulphurized graphene and ionic liquid.

PubMed

Shaikh, Jasmin S; Shaikh, Navajsharif S; Kharade, Rohini; Beknalkar, Sonali A; Patil, Jyoti V; Suryawanshi, Mahesh P; Kanjanaboos, Pongsakorn; Hong, Chang Kook; Kim, Jin Hyeok; Patil, Pramod S

2018-10-01

Symmetric supercapacitor is advanced over simple supercapacitor device due to their stability over a large potential window and high energy density. Graphene is a desired candidate for supercapacitor application since it has a high surface area, good electronic conductivity and high electro chemical stability. There is a pragmatic use of ionic liquid electrolyte for supercapacitor due to its stability over a large potential window, good ionic conductivity and eco-friendly nature. For high performance supercapacitor, the interaction between ionic liquid electrolyte and graphene are crucial for better charge transportation. In respect of this, a three-dimensional (3D) nanoporous honeycomb shaped sulfur embedded graphene (S-graphene) has been synthesized by simple chemical method. Here, the fabrication of high performance symmetric supercapacitor is done by using S-graphene as an electrode and [BMIM-PF 6 ] as an electrolyte. The particular architecture of S-graphene benefited to reduce the ion diffusion resistance, providing the large surface area for charge transportation and efficient charge storage. The S-graphene and ionic liquid-based symmetric supercapacitor device showed the large potential window of 3.2 V with high energy density 124 Wh kg -1 at 0.2 A g -1 constant applied current density. Furthermore, this device shows good cycling performance (stability) with a capacitive retention of 95% over 20,000 cycles at a higher current density of 2 A g -1 . Copyright © 2018 Elsevier Inc. All rights reserved.

Treatment of synthetic arsenate wastewater with iron-air fuel cell electrocoagulation to supply drinking water and electricity in remote areas.

PubMed

Kim, Jung Hwan; Maitlo, Hubdar Ali; Park, Joo Yang

2017-05-15

Electrocoagulation with an iron-air fuel cell is an innovative arsenate removal system that can operate without an external electricity supply. Thus, this technology is advantageous for treating wastewater in remote regions where it is difficult to supply electricity. In this study, the possibility of real applications of this system for arsenate treatment with electricity production was verified through electrolyte effect investigations using a small-scale fuel cell and performance testing of a liter-scale fuel cell stack. The electrolyte species studied were NaCl, Na 2 SO 4 , and NaHCO 3 . NaCl was overall the most effective electrolyte for arsenate treatment, although Na 2 SO 4 produced the greatest electrical current and power density. In addition, although the current density and power density were proportional to the concentrations of NaCl and Na 2 SO 4 , the use of concentrations above 20 mM of NaCl and Na 2 SO 4 inhibited arsenate treatment due to competition effects between anions and arsenate in adsorption onto the iron hydroxide. The dominant iron hydroxide produced at the iron anode was found to be lepidocrocite by means of Raman spectroscopy. A liter-scale four-stack iron-air fuel cell with 10 mM NaCl electrolyte was found to be able to treat about 300 L of 1 ppm arsenate solution to below 10 ppb during 1 day, based on its 60-min treatment capacity, as well as produce the maximum power density of 250 mW/m 2 . Copyright © 2017 Elsevier Ltd. All rights reserved.

Polymer electrolyte membrane water electrolysis: Restraining degradation in the presence of fluctuating power

NASA Astrophysics Data System (ADS)

Rakousky, Christoph; Reimer, Uwe; Wippermann, Klaus; Kuhri, Susanne; Carmo, Marcelo; Lueke, Wiebke; Stolten, Detlef

2017-02-01

Polymer electrolyte membrane (PEM) water electrolysis generates 'green' hydrogen when conducted with electricity from renewable - but fluctuating - sources like wind or solar photovoltaic. Unfortunately, the long-term stability of the electrolyzer performance is still not fully understood under these input power profiles. In this study, we contrast the degradation behavior of our PEM water electrolysis single cells that occurs under operation with constant and intermittent power and derive preferable operating states. For this purpose, five different current density profiles are used, of which two were constant and three dynamic. Cells operated at 1 A cm-2 show no degradation. However, degradation was observed for the remaining four profiles, all of which underwent periods of high current density (2 A cm-2). Hereby, constant operation at 2 A cm-2 led to the highest degradation rate (194 μV h-1). Degradation can be greatly reduced when the cells are operated with an intermittent profile. Current density switching has a positive effect on durability, as it causes reversible parts of degradation to recover and results in a substantially reduced degradation per mole of hydrogen produced. Two general degradation phenomena were identified, a decreased anode exchange current density and an increased contact resistance at the titanium porous transport layer (Ti-PTL).

Formation of a Spinel Coating on AZ31 Magnesium Alloy by Plasma Electrolytic Oxidation

NASA Astrophysics Data System (ADS)

Sieber, Maximilian; Simchen, Frank; Scharf, Ingolf; Lampke, Thomas

2016-03-01

Plasma electrolytic oxidation (PEO) is a common means for the surface modification of light metals. However, PEO of magnesium substrates in dilute electrolytes generally leads to the formation of coatings consisting of unfavorable MgO magnesium oxide. By incorporation of electrolyte components, the phase constitution of the oxide coatings can be modified. Coatings consisting exclusively of MgAl2O4 magnesium-aluminum spinel are produced by PEO in an electrolyte containing hydroxide, aluminate, and phosphate anions. The hardness of the coatings is 3.5 GPa on Martens scale on average. Compared to the bare substrate, the coatings reduce the corrosion current density in dilute sodium chloride solution by approx. one order of magnitude and slightly shift the corrosion potential toward more noble values.

Investigation of electrolyte leaching in the performance degradation of phosphoric acid-doped polybenzimidazole membrane-based high temperature fuel cells

NASA Astrophysics Data System (ADS)

Jeong, Yeon Hun; Oh, Kyeongmin; Ahn, Sungha; Kim, Na Young; Byeon, Ayeong; Park, Hee-Young; Lee, So Young; Park, Hyun S.; Yoo, Sung Jong; Jang, Jong Hyun; Kim, Hyoung-Juhn; Ju, Hyunchul; Kim, Jin Young

2017-09-01

Precise monitoring of electrolyte leaching in high-temperature polymer electrolyte membrane fuel cell (HT-PEMFC) devices during lifetime tests is helpful in making a diagnosis of their quality changes and analyzing their electrochemical performance degradation. Here, we investigate electrolyte leaching in the performance degradation of phosphoric acid (PA)-doped polybenzimidazole (PBI) membrane-based HT-PEMFCs. We first perform quantitative analyses to measure PA leakage during cell operation by spectrophotometric means, and a higher PA leakage rate is detected when the current density is elevated in the cell. Second, long-term degradation tests under various current densities of the cells and electrochemical impedance spectroscopy (EIS) analysis are performed to examine the influence of PA loss on the membrane and electrodes during cell performance degradation. The combined results indicate that PA leakage affect cell performance durability, mostly due to an increase in charge transfer resistance and a decrease in the electrochemical surface area (ECSA) of the electrodes. Additionally, a three-dimensional (3-D) HT-PEMFC model is applied to a real-scale experimental cell, and is successfully validated against the polarization curves measured during various long-term experiments. The simulation results highlight that the PA loss from the cathode catalyst layer (CL) is a significant contributor to overall performance degradation.

Relation of morphology of electrodeposited zinc to ion concentration profile

NASA Technical Reports Server (NTRS)

May, C. E.; Kautz, H. E.; Sabo, B. B.

1977-01-01

The morphology of electrodeposited zinc was studied with special attention to the ion concentration profile. The initial concentrations were 9M hydroxide ion and 1.21M zincate. Current densities were 6.4 to 64 mA/sq cm. Experiments were run with a horizontal cathode which was observed in situ using a microscope. The morphology of the zinc deposit was found to be a function of time as well as current density; roughly, the log of the transition time from mossy to large crystalline type deposit is inversely proportional to current density. Probe electrodes indicated that the electrolyte in the cathode chamber was mixed by self inducted convection. However, relatively large concentration gradients of the involved species existed across the boundary layer of the cathode. Analysis of the data suggests that the morphology converts from mossy to large crystalline when the hydroxide activity on the cathode surface exceeds about 12 M. Other experiments show that the pulse discharge technique had no effect on the morphology in the system where the bulk concentration of the electrolyte was kept homogeneous via self induced convection.

Design of a microbial fuel cell and its transition to microbial electrolytic cell for hydrogen production by electrohydrogenesis.

PubMed

Gupta, Pratima; Parkhey, Piyush; Joshi, Komal; Mahilkar, Anjali

2013-10-01

Anaerobic bacteria were isolated from industrial wastewater and soil samples and tested for exoelectrogenic activity by current production in double chambered microbial fuel cell (MFC), which was further transitioned into a single chambered microbial electrolytic cell to test hydrogen production by electrohydrogenesis. Of all the cultures, the isolate from industrial water sample showed the maximum values for current = 0.161 mA, current density = 108.57 mA/m2 and power density = 48.85 mW/m2 with graphite electrode. Maximum voltage across the cell, however, was reported by the isolate from sewage water sample (506 mv) with copper as electrode. Tap water with KMnO4 was the best cathodic electrolyte as the highest values for all the measured MFC parameters were reported with it. Once the exoelectrogenic activity of the isolates was confirmed by current production, these were tested for hydrogen production in a single chambered microbial electrolytic cell (MEC) modified from the MFC. Hydrogen production was reported positive from co-culture of isolates of both the water samples and co-culture of one soil and one water sample. The maximum rate and yield of hydrogen production was 0.18 m3H2/m3/d and 3.2 mol H2/mol glucose respectively with total hydrogen production of 42.4 mL and energy recovery of 57.4%. Cumulative hydrogen production for a five day cycle of MEC operation was 0.16 m3H2/m3/d.

Calcium-bismuth electrodes for large-scale energy storage (liquid metal batteries)

NASA Astrophysics Data System (ADS)

Kim, Hojong; Boysen, Dane A.; Ouchi, Takanari; Sadoway, Donald R.

2013-11-01

Calcium is an attractive electrode material for use in grid-scale electrochemical energy storage due to its low electronegativity, earth abundance, and low cost. The feasibility of combining a liquid Ca-Bi positive electrode with a molten salt electrolyte for use in liquid metal batteries at 500-700 °C was investigated. Exhibiting excellent reversibility up to current densities of 200 mA cm-2, the calcium-bismuth liquid alloy system is a promising positive electrode candidate for liquid metal batteries. The measurement of low self-discharge current suggests that the solubility of calcium metal in molten salt electrolytes can be sufficiently suppressed to yield high coulombic efficiencies >98%. The mechanisms giving rise to Ca-Bi electrode overpotentials were investigated in terms of associated charge transfer and mass transport resistances. The formation of low density Ca11Bi10 intermetallics at the electrode-electrolyte interface limited the calcium deposition rate capability of the electrodes; however, the co-deposition of barium into bismuth from barium-containing molten salts suppressed Ca-Bi intermetallic formation thereby improving the discharge capacity.

Lithium electrodeposition dynamics in aprotic electrolyte observed in situ via transmission electron microscopy

DOE PAGES

Leenheer, Andrew Jay; Jungjohann, Katherine Leigh; Zavadil, Kevin Robert; ...

2015-03-18

Electrodeposited metallic lithium is an ideal negative battery electrode, but nonuniform microstructure evolution during cycling leads to degradation and safety issues. A better understanding of the Li plating and stripping processes is needed to enable practical Li-metal batteries. Here we use a custom microfabricated, sealed liquid cell for in situ scanning transmission electron microscopy (STEM) to image the first few cycles of lithium electrodeposition/dissolution in liquid aprotic electrolyte at submicron resolution. Cycling at current densities from 1 to 25 mA/cm 2 leads to variations in grain structure, with higher current densities giving a more needle-like, higher surface area deposit. Themore » effect of the electron beam was explored, and it was found that, even with minimal beam exposure, beam-induced surface film formation could alter the Li microstructure. The electrochemical dissolution was seen to initiate from isolated points on grains rather than uniformly across the Li surface, due to the stabilizing solid electrolyte interphase surface film. As a result, we discuss the implications for operando STEM liquid-cell imaging and Li-battery applications.« less

Treatment of winery wastewater by anodic oxidation using BDD electrode.

PubMed

Candia-Onfray, Christian; Espinoza, Nicole; Sabino da Silva, Evanimek B; Toledo-Neira, Carla; Espinoza, L Carolina; Santander, Rocío; García, Verónica; Salazar, Ricardo

2018-05-04

The effective removal of organics from winery wastewater was obtained in real residual effluents from the wine industry using anodic oxidation (AO). The effluent had an initial organic load of [COD] 0 of 3490 mg L -1 equal to [TOC] 0 of 1320 mg L -1 . In addition, more than 40 organic compounds were identified by means of GC-MS. Different density currents as well as the addition of electrolytes were tested during electrolysis. The results show the decay of [COD] t by 63.6% when no support electrolyte was added, whereas almost total mineralization and disinfection was reached after adding of 50 mM of sodium sulfate and sodium chloride and applying higher density currents. The presence of sulfate and chloride in large concentration favors the production of oxidants such as hydroxyl radicals and active chlorine species that react with organics in solution. Moreover, the addition of a supporting electrolyte to industrial wastewater increases conductivity, reduces cell potential and therefore, decreases the energy consumption of the AO process. Copyright © 2018 Elsevier Ltd. All rights reserved.

Usage of Neural Network to Predict Aluminium Oxide Layer Thickness

PubMed Central

Michal, Peter; Vagaská, Alena; Gombár, Miroslav; Kmec, Ján; Spišák, Emil; Kučerka, Daniel

2015-01-01

This paper shows an influence of chemical composition of used electrolyte, such as amount of sulphuric acid in electrolyte, amount of aluminium cations in electrolyte and amount of oxalic acid in electrolyte, and operating parameters of process of anodic oxidation of aluminium such as the temperature of electrolyte, anodizing time, and voltage applied during anodizing process. The paper shows the influence of those parameters on the resulting thickness of aluminium oxide layer. The impact of these variables is shown by using central composite design of experiment for six factors (amount of sulphuric acid, amount of oxalic acid, amount of aluminium cations, electrolyte temperature, anodizing time, and applied voltage) and by usage of the cubic neural unit with Levenberg-Marquardt algorithm during the results evaluation. The paper also deals with current densities of 1 A·dm−2 and 3 A·dm−2 for creating aluminium oxide layer. PMID:25922850

Usage of neural network to predict aluminium oxide layer thickness.

PubMed

Michal, Peter; Vagaská, Alena; Gombár, Miroslav; Kmec, Ján; Spišák, Emil; Kučerka, Daniel

2015-01-01

This paper shows an influence of chemical composition of used electrolyte, such as amount of sulphuric acid in electrolyte, amount of aluminium cations in electrolyte and amount of oxalic acid in electrolyte, and operating parameters of process of anodic oxidation of aluminium such as the temperature of electrolyte, anodizing time, and voltage applied during anodizing process. The paper shows the influence of those parameters on the resulting thickness of aluminium oxide layer. The impact of these variables is shown by using central composite design of experiment for six factors (amount of sulphuric acid, amount of oxalic acid, amount of aluminium cations, electrolyte temperature, anodizing time, and applied voltage) and by usage of the cubic neural unit with Levenberg-Marquardt algorithm during the results evaluation. The paper also deals with current densities of 1 A · dm(-2) and 3 A · dm(-2) for creating aluminium oxide layer.

A new ether-based electrolyte for dendrite-free lithium-metal based rechargeable batteries

PubMed Central

Miao, Rongrong; Yang, Jun; Xu, Zhixin; Wang, Jiulin; Nuli, Yanna; Sun, Limin

2016-01-01

A new ether-based electrolyte to match lithium metal electrode is prepared by introducing 1, 4-dioxane as co-solvent into lithium bis(fluorosulfonyl)imide/1,2-dimethoxyethane solution. Under the synergetic effect of solvents and salt, this simple liquid electrolyte presents stable Li cycling with dendrite-free Li deposition even at relatively high current rate, high coulombic efficiency of ca. 98%, and good anodic stability up to ~4.87 V vs Li RE. Its excellent performance will open up a new possibility for high energy-density rechargeable Li metal battery system. PMID:26878890

Plasma electrolytic oxidation treatment mode influence on corrosion properties of coatings obtained on Zr-1Nb alloy in silicate-phosphate electrolyte

NASA Astrophysics Data System (ADS)

Farrakhov, R. G.; Mukaeva, V. R.; Fatkullin, A. R.; Gorbatkov, M. V.; Tarasov, P. V.; Lazarev, D. M.; Babu, N. Ramesh; Parfenov, E. V.

2018-01-01

This research is aimed at improvement of corrosion properties for Zr-1Nb alloy via plasma electrolytic oxidation (PEO). The coatings obtained in DC, pulsed unipolar and pulsed bipolar modes were assessed using SEM, XRD, PDP and EIS techniques. It was shown that pulsed unipolar mode provides the PEO coatings having promising combination of the coating thickness, surface roughness, porosity, corrosion potential and current density, and charge transfer resistance, all contributing to corrosion protection of the zirconium alloy for advanced fuel cladding applications.

Fabrication, testing and simulation of all solid state three dimensional Li-ion batteries

DOE PAGES

Talin, Albert Alec; Ruzmetov, Dmitry; Kolmakov, Andrei; ...

2016-11-10

Realization of safe, long cycle life and simple to package solid-state rechargeable batteries with high energy and power density has been a long-standing goal of the energy storage community. [1,2] Much of the research activity has been focused on developing new solid electrolytes with high Li ionic conductivity. In addition, LiPON, the only solid electrolyte currently used in commercial thin film solid state Li-ion batteris (SSLIBs), has a conductivity of ~10 -6 S/cm, compared to ~0.01 S/cm typically observed for liquid organic electrolytes [3].

Manufacturing of Dysprosium-Iron Alloys by Electrolysis in Fluoride-Based Electrolytes. Electrolysis in a Laboratory-Scale Cell

NASA Astrophysics Data System (ADS)

Martinez, Ana Maria; Osen, Karen Sende; Støre, Anne; Gudbrandsen, Henrik; Kjos, Ole Sigmund; Solheim, Asbjørn; Wang, Zhaohui; Oury, Alexandre; Namy, Patrick

2018-04-01

Electrolytic production of light rare earth elements and rare earth alloys with transition elements takes place in a fluoride-based electrolyte using rare earth oxides as raw material. The optimization of this method, mainly in terms of the energy efficiency and environmental impact control, is rather challenging. Anode effects, evolution of fluorine-containing compounds and side cathode reactions could largely be minimized by good control of the amount of rare earth oxide species dissolved in the fluoride-based electrolyte and their dissolution rate. The Dy2O3 feed rate needed for stable cell operation was studied by following up the anode voltage and gas analysis. On-line analysis of the cell off-gases by FTIR showed that the electrochemical reaction for the formation of Dy-Fe alloy gives mainly CO gas and that CF4 is starting to evolve gradually at anode voltages of ca. 3.25 V. The limiting current density for the discharge of the oxide ions at the graphite anode was in the range of 0.1 to 0.18 A cm-2 at dissolved Dy2O3 contents of ca. 1 wt pct. Modeling of the laboratory cell reactor was also carried out by implementing two models, i.e., an electrical model simulating the current density distribution at the electrodes and a laminal bubbly flow model that explains the electrolyte velocity induced by gas bubble production at the anode.

Influence of the Oxygen Electrode Open Ratio and Electrolyte Evaporation on the Performance of Li-O2 Batteries.

PubMed

Mohazabrad, Farhad; Wang, Fangzhou; Li, Xianglin

2017-05-10

This study experimentally investigates and numerically simulates the influence of the cathode electrode open ratio (ratio of oxygen-opening area to the total electrode surface area) on the performance of Li-O 2 batteries at various discharge current densities. At the current density of 0.1 mA/cm 2 , the maximum discharge capacity is achieved at 25% open ratio among the tested open ratios (0-100%). As the open ratio increases from 25% to 100%, the specific discharge capacity decreases from 995 to 397 mA h/g carbon . A similar trend is observed at 0.3 mA/cm 2 , while the maximum discharge capacity is obtained at 3% open ratio among the tested open ratios. The model that assumes the electrode is always fully saturated by the electrolyte does not obtain similar trends with experimental results, while the model that considers electrolyte loss by evaporation and the volume change of the solid obtains the same trend with experimental observations. The open ratio governs not only availability of oxygen but also the evaporation of the electrolyte and the contact resistance. The faster evaporation of the electrolyte at a higher open ratio can be the main reason for the decrease of the discharge capacity, especially when the open ratio is relatively high (above 25%). Meanwhile, the contact resistance of the battery, measured by the electrochemical impedance spectroscopy (EIS), increases from 3.97 to 7.02 Ω when the open ratio increased from 3% to 95%. The increase of the Ohmic overpotential, however, is negligible (on the order of millivolts) because of the low discharge and charge current rates (on the order of 0.1 mA).

PVA:LiClO4: a robust, high Tg polymer electrolyte for adjustable ion gating of 2D materials

NASA Astrophysics Data System (ADS)

Kinder, Erich; Fullerton, Susan; CenterLow Energy Systems Technology Team

2015-03-01

Polymer electrolytes are an effective way to gate organic semiconductors and nanomaterials, such as nanotubes and 2D materials, by establishing an electrostatic double layer with large capacitance. Widely used solid electrolytes, such as those based on polyethylene oxide, have a glass transition temperature below room temperature. This permits relatively fast ion mobility at T = 23 °C, but requires a constant applied field to maintain a doping profile. Moreover, PEO-based electrolytes cannot withstand a variety of solvents, limiting its use. Here, we demonstrate a polymer electrolyte using polyvinyl alcohol (PVA) with Tg >23 °C, through which a doping profile can be defined by a potential applied when the polymer is heated above Tg, then ``locked-in'' by cooling the electrolyte to room temperature (

Characterization of poly methyl methaacrylate and reduced graphene oxide composite for application as electrolyte in dye sensitized solar cells

NASA Astrophysics Data System (ADS)

Shrivatsav, Roshan; Mahalingam, Vignesh; Lakshmi Narayanan, E. R.; Naveen Balaji, N.; Balu, Murali; Krishna Prasad, R.; Kumaresan, Duraisamy

2018-04-01

Quasi-solid state iodide/triiodide redox electrolyte containing reduced graphene oxide and poly (methyl methaacrylate) (RGO-PMMA) composites for the fabrication of more durable, high performance dye sensitized solar cells are prepared. The morphological analysis of prepared RGO-PMMA composites showed formation of spherical like morphologies of RGO dispersed PMMA particles with their macroscopic inter-particle networks having voids. The x ray diffraction and electrical conductivity studies showed the addition of 1 wt% of filler RGO into amorphous PMMA matrix increased the electrical conductivity of the polymer composite about three orders of magnitude from 10‑7 and 10‑4 S cm‑1. Further, the photovoltaic current-voltage analysis of DSSCs with different RGO-PMMA composite based iodide/triiodide redox electrolytes showed the highest power conversion efficiency of 5.38% and the fill factor 0.63 for 2% RGO-PMMA electrolyte. The EIS analysis showed an increased recombination resistance (Rct2) at TiO2 electrode/dye/electrolyte interface due to the better electrical conductivity of RGO with good ionic conductivity in 2% RGO-PMMA composite based redox electrolyte boosted the generation of a high current density and fill factor in their DSSCs.

High-Potential Metalless Nanocarbon Foam Supercapacitors Operating in Aqueous Electrolyte.

PubMed

Liu, Chueh; Li, Changling; Ahmed, Kazi; Mutlu, Zafer; Lee, Ilkeun; Zaera, Francisco; Ozkan, Cengiz S; Ozkan, Mihrimah

2018-04-01

Light-weight graphite foam decorated with carbon nanotubes (dia. 20-50 nm) is utilized as an effective electrode without binders, conductive additives, or metallic current collectors for supercapacitors in aqueous electrolyte. Facile nitric acid treatment renders wide operating potentials, high specific capacitances and energy densities, and long lifespan over 10 000 cycles manifested as 164.5 and 111.8 F g -1 , 22.85 and 12.58 Wh kg -1 , 74.6% and 95.6% capacitance retention for 2 and 1.8 V, respectively. Overcharge protection is demonstrated by repetitive cycling between 2 and 2.5 V for 2000 cycles without catastrophic structural demolition or severe capacity fading. Graphite foam without metallic strut possessing low density (≈0.4-0.45 g cm -3 ) further reduces the total weight of the electrode. The thorough investigation of the specific capacitances and coulombic efficiencies versus potential windows and current densities provides insights into the selection of operation conditions for future practical devices. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

High energy density aluminum-oxygen cell

NASA Technical Reports Server (NTRS)

Rudd, E. J.; Gibbons, D. W.

1993-01-01

An alternative to a secondary battery as the power source for vehicle propulsion is a fuel cell. An example of this is the metal-air fuel cell using metals such as aluminum, zinc, or iron. Aluminum is a particularly attractive candidate, having high energy and power densities, being environmentally acceptable, and having a large, established industrial base for production and distribution. An aluminum-oxygen system is currently under development for a UUV test vehicle, and recent work has focussed upon low corrosion aluminum alloys and an electrolyte management system for processing the by-products of the energy-producing reactions. This paper summarizes the progress made in both areas. Anode materials capable of providing high utilization factors over current densities ranging from S to 150 mA/sq cm have been identified. These materials are essential to realizing an acceptable mission life for the UUV. With respect to the electrolyte management system, a filter/precipitator unit has been successfully operated for over 250 hours in a large scale, half-cell system.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Esswein, AJ; Surendranath, Y; Reece, SY

A high surface area electrode is functionalized with cobalt-based oxygen evolving catalysts (Co-OEC = electrodeposited from pH 7 phosphate, Pi, pH 8.5 methylphosphonate, MePi, and pH 9.2 borate electrolyte, Bi). Co-OEC prepared from MePi and operated in Pi and Bi achieves a current density of 100 mA cm(-2) for water oxidation at 442 and 363 mV overpotential, respectively. The catalyst retains activity in near-neutral pH buffered electrolyte in natural waters such as those from the Charles River (Cambridge, MA) and seawater (Woods Hole, MA). The efficacy and ease of operation of anodes functionalized with Co-OEC at appreciable current density togethermore » with its ability to operate in near neutral pH buffered natural water sources bodes well for the translation of this catalyst to a viable renewable energy storage technology.« less

Role of perfluoropolyether-based electrolytes in lithium metal batteries: Implication for suppressed Al current collector corrosion and the stability of Li metal/electrolytes interfaces

NASA Astrophysics Data System (ADS)

Cong, Lina; Liu, Jia; Armand, Michel; Mauger, Alain; Julien, Christian M.; Xie, Haiming; Sun, Liqun

2018-03-01

The development of safe and high performance lithium metal batteries represents a major technological challenge for this new century. Historically, intrinsic instabilities of conventional liquid organic electrolytes induced battery failures and safety issues that hinder the practical utilization of advanced rechargeable lithium metal batteries. Herein, we report a multifunctional perfluoropolyether-based liquid polymer electrolyte (PFPE-MC/LiTFSI), presenting a unique "anion-solvent" interaction. This interaction optimizes the interfacial chemistry of lithium metal batteries, which effectively inhibits the corrosion of aluminum current collectors, suppresses lithium dendrite growth, and also facilitates the formation of a thin and stable SEI layer on Li anode. Even at a high current density of 0.7 mA cm-2, the lithium dendrites do not form after 1360 h of continuous operation. The LiFePO4|PFPE-MC/LiTFSI|Li cell delivers a stable cycling performance with over 99.9% columbic efficiency either at ambient temperature or high temperature, which is significantly superior to those using traditional carbonate electrolytes. In addition, PFPE-MC/LiTFSI electrolyte also possesses eye-catching properties, such as being non-flammable, non-volatile, non-hygroscopic, and existing in the liquid state between -90 °C and 200 °C, which further ensures the high safety of the lithium metal batteries, making this electrolyte promising for the development of high energy lithium metal batteries.

A zwitterionic gel electrolyte for efficient solid-state supercapacitors

PubMed Central

Peng, Xu; Liu, Huili; Yin, Qin; Wu, Junchi; Chen, Pengzuo; Zhang, Guangzhao; Liu, Guangming; Wu, Changzheng; Xie, Yi

2016-01-01

Gel electrolytes have attracted increasing attention for solid-state supercapacitors. An ideal gel electrolyte usually requires a combination of advantages of high ion migration rate, reasonable mechanical strength and robust water retention ability at the solid state for ensuring excellent work durability. Here we report a zwitterionic gel electrolyte that successfully brings the synergic advantages of robust water retention ability and ion migration channels, manifesting in superior electrochemical performance. When applying the zwitterionic gel electrolyte, our graphene-based solid-state supercapacitor reaches a volume capacitance of 300.8 F cm−3 at 0.8 A cm−3 with a rate capacity of only 14.9% capacitance loss as the current density increases from 0.8 to 20 A cm−3, representing the best value among the previously reported graphene-based solid-state supercapacitors, to the best of our knowledge. We anticipate that zwitterionic gel electrolyte may be developed as a gel electrolyte in solid-state supercapacitors. PMID:27225484

Safer Electrolytes for Lithium-Ion Cells

NASA Technical Reports Server (NTRS)

Kejha, Joe; Smith, Novis; McCloseky, Joel

2004-01-01

A number of nonvolatile, low-flammability liquid oligomers and polymers based on aliphatic organic carbonate molecular structures have been found to be suitable to be blended with ethylene carbonate to make electrolytes for lithium-ion electrochemical cells. Heretofore, such electrolytes have often been made by blending ethylene carbonate with volatile, flammable organic carbonates. The present nonvolatile electrolytes have been found to have adequate conductivity (about 2 mS/cm) for lithium ions and to remain liquid at temperatures down to -5 C. At normal charge and discharge rates, lithiumion cells containing these nonvolatile electrolytes but otherwise of standard design have been found to operate at current and energy densities comparable to those of cells now in common use. They do not perform well at high charge and discharge rates -- an effect probably attributable to electrolyte viscosity. Cells containing the nonvolatile electrolytes have also been found to be, variously, nonflammable or at least self-extinguishing. Hence, there appears to be a basis for the development of safer high-performance lithium-ion cells.

A salient effect of density on the dynamics of nonaqueous electrolytes.

PubMed

Han, Sungho

2017-04-24

The mobility and solvation of lithium ions in electrolytes are crucial for the performance and safety of lithium ion batteries. It has been known that a single type of solvent cannot satisfy the requirements of both mobility and solvation simultaneously for electrolytes. Therefore, complex solvent mixtures have been used to optimize both properties. Here we present the effects of density on the dynamics and solvation of organic liquid electrolytes via extensive molecular dynamics simulations. Our study finds that a small variation in density can induce a significant effect on the mobility of electrolytes but does not influence the solvation structure of a lithium ion. It turns out that an adjustment of the density of electrolytes could provide a more effective way to enhance mobility than a control of the solvent mixture ratio of electrolytes. Our study reveals that the density change of electrolytes mainly affects the residence time of solvents in the first solvation shell of a lithium ion rather than the structural change of the solvation sheath. Finally, our results suggest an intriguing point for understanding and designing electrolytes of lithium ion batteries for better performance and safety.

A salient effect of density on the dynamics of nonaqueous electrolytes

NASA Astrophysics Data System (ADS)

Han, Sungho

2017-04-01

The mobility and solvation of lithium ions in electrolytes are crucial for the performance and safety of lithium ion batteries. It has been known that a single type of solvent cannot satisfy the requirements of both mobility and solvation simultaneously for electrolytes. Therefore, complex solvent mixtures have been used to optimize both properties. Here we present the effects of density on the dynamics and solvation of organic liquid electrolytes via extensive molecular dynamics simulations. Our study finds that a small variation in density can induce a significant effect on the mobility of electrolytes but does not influence the solvation structure of a lithium ion. It turns out that an adjustment of the density of electrolytes could provide a more effective way to enhance mobility than a control of the solvent mixture ratio of electrolytes. Our study reveals that the density change of electrolytes mainly affects the residence time of solvents in the first solvation shell of a lithium ion rather than the structural change of the solvation sheath. Finally, our results suggest an intriguing point for understanding and designing electrolytes of lithium ion batteries for better performance and safety.

Impact of isoelectric points of nanopowders in electrolytes on electrochemical characteristics of dye sensitized solar cells

NASA Astrophysics Data System (ADS)

Mohanty, Shyama Prasad; Bhargava, Parag

2012-11-01

Nanoparticle loaded quasi solid electrolytes are important from the view point of developing electrolytes for dye sensitized solar cells (DSSCs) having long term stability. The present work shows the influence of isoelectric point of nanopowders in electrolyte on the photoelectrochemical characteristics of DSSCs. Electrolytes with nanopowders of silica, alumina and magnesia which have widely differing isoelectric points are used in the study. Adsorption of ions from the electrolyte on the nanopowder surface, characterized by zeta potential measurement, show that cations get adsorbed on silica, alumina surface while anions get adsorbed on magnesia surface. The electrochemical characteristics of nanoparticulate loaded electrolytes are examined through cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS). DSSCs fabricated using liquid, silica or alumina loaded electrolytes exhibit almost similar performance. But interestingly, the magnesia loaded electrolyte-based cell show lower short circuit current density (JSC) and much higher open circuit voltage (VOC), which is attributed to adsorption of anions. Such anionic adsorption prevents the dark reaction in magnesia loaded electrolyte-based cell and thus, enhances the VOC by almost 100 mV as compared to liquid electrolyte based cell. Also, higher electron life time at the titania/electrolyte interface is observed in magnesia loaded electrolyte-based cell as compared to others.

A bifunctional electrolyte additive for separator wetting and dendrite suppression in lithium metal batteries

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zheng, Hao; Xie, Yong; Xiang, Hongfa

Reformulation of electrolyte systems and improvement of separator wettability are vital to electrochemical performances of rechargeable lithium (Li) metal batteries, especially for suppressing Li dendrites. In this work we report a bifunctional electrolyte additive that improves separator wettability and suppresses Li dendrite growth in LMBs. A triblock polyether (Pluronic P123) was introduced as an additive into a commonly used carbonate-based electrolyte. It was found that addition of 0.2~1% (by weight) P123 into the electrolyte could effectively enhance the wettability of polyethylene separator. More importantly, the adsorption of P123 on Li metal surface can act as an artificial solid electrolyte interphasemore » layer and contribute to suppress the growth of Li dendrites. A smooth and dendritic-free morphology can be achieved in the electrolyte with 0.2% P123. The Li||Li symmetric cells with the 0.2% P123 containing electrolyte exhibit a relatively stable cycling stability at high current densities of 1.0 and 3.0 mA cm-2.« less

3D Fiber-Network-Reinforced Bicontinuous Composite Solid Electrolyte for Dendrite-free Lithium Metal Batteries.

PubMed

Li, Dan; Chen, Long; Wang, Tianshi; Fan, Li-Zhen

2018-02-28

Replacement of flammable organic liquid electrolytes with solid Li + conductors is a promising approach to realize excellent performance of Li metal batteries. However, ceramic electrolytes are either easily reduced by Li metal or penetrated by Li dendrites through their grain boundaries, and polymer electrolytes are also faced with instability on the electrode/electrolyte interface and weak mechanical property. Here, we report a three-dimensional fiber-network-reinforced bicontinuous solid composite electrolyte with flexible Li + -conductive network (lithium aluminum titanium phosphate (LATP)/polyacrylonitrile), which helps to enhance electrochemical stability on the electrode/electrolyte interface by isolating Li and LATP and suppress Li dendrites growth by mechanical reinforcement of fiber network for the composite solid electrolyte. The composite electrolyte shows an excellent electrochemical stability after 15 days of contact with Li metal and has an enlarged tensile strength (10.72 MPa) compared to the pure poly(ethylene oxide)-bistrifluoromethanesulfonimide lithium salt electrolyte, leading to a long-term stability and safety of the Li symmetric battery with a current density of 0.3 mA cm -2 for 400 h. In addition, the composite electrolyte also shows good electrochemical and thermal stability. These results provide such fiber-reinforced membranes that present stable electrode/electrolyte interface and suppress lithium dendrite growth for high-safety all-solid-state Li metal batteries.

Non-aqueous aluminium-air battery based on ionic liquid electrolyte

NASA Astrophysics Data System (ADS)

Revel, Renaud; Audichon, Thomas; Gonzalez, Serge

2014-12-01

A promising metal-air secondary battery based on aluminium-oxygen couple is described. In this paper, we observed that an aluminium-air battery employing EMImCl, AlCl3 room temperature ionic liquid (RTIL) as electrolyte and aluminium as negative electrode, has an exceptional reduced self-discharged rate. Due to its new and innovative type of electrolyte, this aluminium-air battery can support relatively high current densities (up to 0.6 mA cm-2) and an average voltage of 0.6-0.8 V. Such batteries may find immediate applications, as they can provide an internal, built-in autonomous and self-sustained energy source.

Preparation of aluminum-magnesium alloy from magnesium oxide in RECl3-KCl-MgCl2 electrolyte by molten salts electrolysis method

NASA Astrophysics Data System (ADS)

Yang, Shaohua; Wu, Lin; Yang, Fengli; Li, Mingzhou; Hu, Xianwei; Wang, Zhaowen; Shi, Zhongning; Gao, Bingliang

Aluminum-magnesium alloys were prepared from magnesium oxide by molten salt electrolysis method. 10w%RECl3-63.5w%KCl-23.5w%MgCl2-3w%MgO was taken as electrolyte. The results showed that RE could be attained in aluminum-magnesium alloy, and it was proved that the RE was reduced directly by aluminum. Magnesium in the alloy was produced by electrolysis on cathode. The content of RE in the alloy was about 0.8wt %-1.2wt%, and the content of Mg in the alloy was lwt%˜6wt% with electrolytic times. The highest current efficiency was 81.3% with 0.8A/cm2 current density. The process of electrolysis was controlled together by electrochemical polarization and concentration polarization.

Lithium thionyl chloride high rate discharge

NASA Technical Reports Server (NTRS)

Klinedinst, K. A.

1980-01-01

Improvements in high rate lithium thionyl chloride power technology achieved by varying the electrolyte composition, operating temperature, cathode design, and cathode composition are discussed. Discharge capacities are plotted as a function of current density, cell voltage, and temperature.

Design of bipolar, flowing-electrolyte zinc-bromine electric-vehicle battery systems

NASA Astrophysics Data System (ADS)

Malachesky, P. A.; Bellows, R. J.; Einstein, H. E.; Grimes, P. G.; Newby, K.; Young, A.

1983-01-01

The integration of bipolar, flowing electrolyte zinc-bromine technology into a viable electric vehicle battery system requires careful analysis of the requirements placed on the battery system by the EV power train. In addition to the basic requirement of an appropriate battery voltage and power density, overall battery system energy efficiency must also be considered and parasitic losses from auxiliaries such as pumps and shunt current protection minimized. An analysis of the influence of these various factors on zinc-bromine EV battery system design has been carried out for two types of EV propulsion systems. The first of these is a nominal 100V dc system, while the second is a high voltage (200V dc) system as might be used with an advanced design ac propulsion system. Battery performance was calculated using an experimentally determined relationship which expresses battery voltage as a function of current density and state-of-charge.

Increased fracture depth range in controlled spalling of (100)-oriented germanium via electroplating

DOE PAGES

Crouse, Dustin; Simon, John; Schulte, Kevin L.; ...

2018-01-31

Controlled spalling in (100)-oriented germanium using a nickel stressor layer shows promise for semiconductor device exfoliation and kerfless wafering. Demonstrated spall depths of 7-60 um using DC sputtering to deposit the stressor layer are appropriate for the latter application but spall depths < 5 um may be required to minimize waste for device applications. This work investigates the effect of tuning both electroplating current density and electrolyte chemistry on the residual stress in the nickel and on the achievable spall depth range for the Ni/Ge system as a lower-cost, higher-throughput alternative to sputtering. By tuning current density and electrolyte phosphorousmore » concentration, it is shown that electroplating can successfully span the same range of spalled thicknesses as has previously been demonstrated by sputtering and can reach sufficiently high stresses to enter a regime of thickness (<7 um) appropriate to minimize substrate consumption for device applications.« less

Effect of Hydrogen Charging on the Stress Corrosion Behavior of 2205 Duplex Stainless Steel Under 3.5 wt.% NaCl Thin Electrolyte Layer

NASA Astrophysics Data System (ADS)

Zhao, Tianliang; Liu, Zhiyong; Hu, Shanshan; Du, Cuiwei; Li, Xiaogang

2017-05-01

The effect of hydrogen charging on the stress corrosion cracking (SCC) behavior of 2205 duplex stainless steel (DSS) under 3.5 wt.% NaCl thin electrolyte layer was investigated on precharged samples through hydrogen determination, electrochemical measurement, and slow strain rate tensile test. Results show that hydrogen charging weakens the passive film without inducing any obvious trace of localized anodic dissolution. Therefore, hydrogen charging increases the SCC susceptibility of 2205 DSS mainly through mechanism of hydrogen embrittlement rather than mechanism of localized anodic dissolution. 2205 DSS shows a more susceptibility to hydrogen under the TEL when hydrogen charging current density (HCCD) is between 20 and 50 mA cm-2. The increasing trend is remarkable when hydrogen charging current density increases from 20 to 50 mA cm-2 and fades after 50 mA cm-2.

Improvement of the electrochemical properties via poly(3,4-ethylenedioxythiophene) oriented micro/nanorods

NASA Astrophysics Data System (ADS)

Li, Yu; Wang, Bichen; Chen, Huimin; Feng, Wei

Arrays of oriented poly(3,4-ethylenedioxythiophene) (PEDOT) micro/nanorods are synthesized by electrochemical galvanostatic method at the current density of 1 mA cm -2 in the cetyltrimethylammonium bromide (CTAB) aqueous solution whose pH value is 1. The CTAB is used both as the surfactant and the supporting salt in the electrolyte solution. The electrochemical properties of PEDOT films are characterized by cyclic voltammetry and galvanostatic charge/discharge techniques, which indicate that the arrays of oriented PEDOT micro/nanorods can be applied as the electrode materials of supercapacitors. In addition, the cycling performance of PEDOT micro/nanorods is much better than that of traditional PEDOT particles. The effects of the concentration of CTAB, the current density, and pH value of electrolyte solutions on the morphologies and electrochemical properties of PEDOT films are investigated. The mechanism of different morphologies formation is discussed in this study as well.

Increased fracture depth range in controlled spalling of (100)-oriented germanium via electroplating

DOE Office of Scientific and Technical Information (OSTI.GOV)

Crouse, Dustin; Simon, John; Schulte, Kevin L.

Controlled spalling in (100)-oriented germanium using a nickel stressor layer shows promise for semiconductor device exfoliation and kerfless wafering. Demonstrated spall depths of 7-60 um using DC sputtering to deposit the stressor layer are appropriate for the latter application but spall depths < 5 um may be required to minimize waste for device applications. This work investigates the effect of tuning both electroplating current density and electrolyte chemistry on the residual stress in the nickel and on the achievable spall depth range for the Ni/Ge system as a lower-cost, higher-throughput alternative to sputtering. By tuning current density and electrolyte phosphorousmore » concentration, it is shown that electroplating can successfully span the same range of spalled thicknesses as has previously been demonstrated by sputtering and can reach sufficiently high stresses to enter a regime of thickness (<7 um) appropriate to minimize substrate consumption for device applications.« less

Factors controlling charge recombination under dark and light conditions in dye sensitised solar cells.

PubMed

Barnes, Piers R F; Anderson, Assaf Y; Juozapavicius, Mindaugas; Liu, Lingxuan; Li, Xiaoe; Palomares, Emilio; Forneli, Amparo; O'Regan, Brian C

2011-02-28

A simple and powerful approach for assessing the recombination losses in dye sensitised solar cells (DSSCs) across the current voltage curve (j-V) as a function of TiO(2) electron concentration (n) is demonstrated. The total flux of electrons recombining with iodine species in the electrolyte and oxidised dye molecules can be thought of as a recombination current density, defined as j(rec) = j(inj)-j where j(inj) is the current of electrons injected from optically excited dye states and j is the current density collected at cell voltage (V). The electron concentration at any given operating conditions is determined by charge extraction. This allows comparison of factors influencing electron recombination rates at matched n. We show that j(rec) is typically 2-3 times higher under 1 sun equivalent illumination (j(inj) > 0) relative to dark (j(inj) = 0) conditions. This difference was increased by increasing light intensity, electrolyte iodine concentration and electrolyte solvent viscosity. The difference was reduced by increasing the electrolyte iodide concentration and increasing the temperature. These results allowed us to verify a numerical model of complete operational cells (Barnes et al., Phys. Chem. Chem. Phys., DOI: 10.1039/c0cp01554g) and to relate the differences in j(rec) to physical processes in the devices. The difference between j(rec) in the light and dark can be explained by two factors: (1) an increase in the concentration of electron acceptor species (I(3)(-) and/or I(2)) when current is flowing under illumination relative to dark conditions where the current is flowing in the opposite direction, and (2) a non-trivial contribution from electron recombination to oxidised dye molecules under light conditions. More generally, the technique helps to assign the observed relationship between the components, processing and performance of DSSCs to more fundamental physical processes.

Structure that encapsulates lithium metal for high energy density battery anode

DOE Office of Scientific and Technical Information (OSTI.GOV)

Cui, Yi; Yan, Kai; Chu, Steven

A battery includes 1) an anode, 2) a cathode, and 3) an electrolyte disposed between the anode and the cathode. The anode includes a current collector and an interfacial layer disposed over the current collector, and the interfacial layer includes an array of interconnected, protruding regions that define spaces.

Simulations of thermal Rayleigh-Marangoni convection in a three-layer liquid-metal-battery model

NASA Astrophysics Data System (ADS)

Köllner, Thomas; Boeck, Thomas; Schumacher, Jörg

2017-11-01

Operating a liquid-metal battery produces Ohmic losses in the electrolyte layer that separates both metal electrodes. As a consequence, temperature gradients establish which potentially cause thermal convection since density and interfacial tension depend on the local temperature. In our numerical investigations, we considered three plane, immiscible layers governed by the Navier-Stokes-Boussinesq equations held at a constant temperature of 500°C at the bottom and top. A homogeneous current is applied that leads to a preferential heating of the mid electrolyte layer. We chose a typical material combination of Li separated by LiCl-KCl (a molten salt) from Pb-Bi for which we analyzed the linear stability of pure thermal conduction and performed three-dimensional direct-numerical simulations by a pseudospectral method probing different: electrolyte layer heights, overall heights, and current densities. Four instability mechanisms are identified, which are partly coupled to each other: buoyant convection in the upper electrode, buoyant convection in the molten salt layer, and Marangoni convection at both interfaces between molten salt and electrode. The global turbulent heat transfer follows scaling predictions for internally heated buoyant convection. Financial support by the Deutsche Forschungsgemeinschaft under Grant No. KO 5515/1-1 is gratefully acknowledged.

Selection of new Kynar-based electrolytes for lithium-ion batteries

NASA Astrophysics Data System (ADS)

Christie, Alasdair M.; Christie, Lynn; Vincent, Colin A.

New electrolyte solution compositions have been identified for use in lithium-ion batteries after gelling with an appropriate quantity of Kynar polymer. Since the Li + conducting medium is largely the liquid electrolyte component, the assessment of these solutions as suitable lithium-ion cell candidates were investigated before adding the polymer. Selected electrolyte solutions were then used in the preparation of polymer gels. The specific conductivities of Kynar-based gels were determined as a function of salt concentration and polymer concentration. Optimised self-supporting polymer films, based on mixtures of ethylene carbonate (EC), ethylmethyl carbonate (EMC) and lithium hexafluorophosphate (LiPF 6) or lithium tetrafluoroborate (LiBF 4), showed good high current density cycling performance when used as separators in coke and Li 1- xMn 2O 4 (spinel) half-cells.

Robust High-performance Dye-sensitized Solar Cells Based on Ionic Liquid-sulfolane Composite Electrolytes.

PubMed

Lau, Genevieve P S; Décoppet, Jean-David; Moehl, Thomas; Zakeeruddin, Shaik M; Grätzel, Michael; Dyson, Paul J

2015-12-16

Novel ionic liquid-sulfolane composite electrolytes based on the 1,2,3-triazolium family of ionic liquids were developed for dye-sensitized solar cells. The best performing device exhibited a short-circuit current density of 13.4 mA cm(-2), an open-circuit voltage of 713 mV and a fill factor of 0.65, corresponding to an overall power conversion efficiency (PCE) of 6.3%. In addition, these devices are highly stable, retaining more than 95% of the initial device PCE after 1000 hours of light- and heat-stress. These composite electrolytes show great promise for industrial application as they allow for a 14.5% improvement in PCE, compared to the solvent-free eutectic ionic liquid electrolyte system, without compromising device stability.

Cascade redox flow battery systems

DOEpatents

Horne, Craig R.; Kinoshita, Kim; Hickey, Darren B.; Sha, Jay E.; Bose, Deepak

2014-07-22

A reduction/oxidation ("redox") flow battery system includes a series of electrochemical cells arranged in a cascade, whereby liquid electrolyte reacts in a first electrochemical cell (or group of cells) before being directed into a second cell (or group of cells) where it reacts before being directed to subsequent cells. The cascade includes 2 to n stages, each stage having one or more electrochemical cells. During a charge reaction, electrolyte entering a first stage will have a lower state-of-charge than electrolyte entering the nth stage. In some embodiments, cell components and/or characteristics may be configured based on a state-of-charge of electrolytes expected at each cascade stage. Such engineered cascades provide redox flow battery systems with higher energy efficiency over a broader range of current density than prior art arrangements.

Electrolytic decontamination of conductive materials for hazardous waste management

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wedman, D.E.; Martinez, H.E.; Nelson, T.O.

1996-12-31

Electrolytic removal of plutonium and americium from stainless steel and uranium surfaces has been demonstrated. Preliminary experiments were performed on the electrochemically based decontamination of type 304L stainless steel in sodium nitrate solutions to better understand the metal removal effects of varying cur-rent density, pH, and nitrate concentration parameters. Material removal rates and changes in surface morphology under these varying conditions are reported. Experimental results indicate that an electropolishing step before contamination removes surface roughness, thereby simplifying later electrolytic decontamination. Sodium nitrate based electrolytic decontamination produced the most uniform stripping of material at low to intermediate pH and at sodiummore » nitrate concentrations of 200 g L{sup -1} and higher. Stirring was also observed to increase the uniformity of the stripping process.« less

Three-Dimensional, Solid-State Mixed Electron-Ion Conductive Framework for Lithium Metal Anode.

PubMed

Xu, Shaomao; McOwen, Dennis W; Wang, Chengwei; Zhang, Lei; Luo, Wei; Chen, Chaoji; Li, Yiju; Gong, Yunhui; Dai, Jiaqi; Kuang, Yudi; Yang, Chunpeng; Hamann, Tanner R; Wachsman, Eric D; Hu, Liangbing

2018-06-13

Solid-state electrolytes (SSEs) have been widely considered as enabling materials for the practical application of lithium metal anodes. However, many problems inhibit the widespread application of solid state batteries, including the growth of lithium dendrites, high interfacial resistance, and the inability to operate at high current density. In this study, we report a three-dimensional (3D) mixed electron/ion conducting framework (3D-MCF) based on a porous-dense-porous trilayer garnet electrolyte structure created via tape casting to facilitate the use of a 3D solid state lithium metal anode. The 3D-MCF was achieved by a conformal coating of carbon nanotubes (CNTs) on the porous garnet structure, creating a composite mixed electron/ion conductor that acts as a 3D host for the lithium metal. The lithium metal was introduced into the 3D-MCF via slow electrochemical deposition, forming a 3D lithium metal anode. The slow lithiation leads to improved contact between the lithium metal anode and garnet electrolyte, resulting in a low resistance of 25 Ω cm 2 . Additionally, due to the continuous CNT coating and its seamless contact with the garnet we observed highly uniform lithium deposition behavior in the porous garnet structure. With the same local current density, the high surface area of the porous garnet framework leads to a higher overall areal current density for stable lithium deposition. An elevated current density of 1 mA/cm 2 based on the geometric area of the cell was demonstrated for continuous lithium cycling in symmetric lithium cells. For battery operation of the trilayer structure, the lithium can be cycled between the 3D-MCF on one side and the cathode infused into the porous structure on the opposite side. The 3D-MCF created by the porous garnet structure and conformal CNT coating provides a promising direction toward new designs in solid-state lithium metal batteries.

Complex hydrides as room-temperature solid electrolytes for rechargeable batteries

NASA Astrophysics Data System (ADS)

de Jongh, P. E.; Blanchard, D.; Matsuo, M.; Udovic, T. J.; Orimo, S.

2016-03-01

A central goal in current battery research is to increase the safety and energy density of Li-ion batteries. Electrolytes nowadays typically consist of lithium salts dissolved in organic solvents. Solid electrolytes could facilitate safer batteries with higher capacities, as they are compatible with Li-metal anodes, prevent Li dendrite formation, and eliminate risks associated with flammable organic solvents. Less than 10 years ago, LiBH4 was proposed as a solid-state electrolyte. It showed a high ionic conductivity, but only at elevated temperatures. Since then a range of other complex metal hydrides has been reported to show similar characteristics. Strategies have been developed to extend the high ionic conductivity of LiBH4 down to room temperature by partial anion substitution or nanoconfinement. The present paper reviews the recent developments in complex metal hydrides as solid electrolytes, discussing in detail LiBH4, strategies towards for fast room-temperature ionic conductors, alternative compounds, and first explorations of implementation of these electrolytes in all-solid-state batteries.

Engineering rheology of electrolytes using agar for improving the performance of bioelectrochemical systems.

PubMed

Rathinam, Navanietha Krishnaraj; Tripathi, Abhilash K; Smirnova, Alevtina; Beyenal, Haluk; Sani, Rajesh K

2018-04-24

The present study is focused on enhancing the rheological properties of the electrolyte and eliminating sedimentation of microorganisms/flocs without affecting the electron transfer kinetics for improved bioelectricity generation. Agar derived from polysaccharide agarose (0.05-0.2%, w/v) was chosen as a rheology modifying agent. Electroanalytical investigations showed that electrolytes modified with 0.15% agar display a nine-fold increase in current density (1.2 mA/cm 2 ) by a thermophilic strain (Geobacillus sp. 44C, 60 °C) when compared with the control. Sodium phosphate buffer (0.1 M, pH 7) electrolyte with riboflavin (0.1 mM) was used as the control. Electrolytes modified with 0.15% agar significantly improved chemical oxygen demand removal rates. This developed electrolyte will aid in improving bioelectricity generation in Bioelectrochemical Systems (BES). The developed strategy avoids the use of peristaltic pumps and magnetic stirrers, thereby improving the energy efficiency of the process. Copyright © 2018 Elsevier Ltd. All rights reserved.

Transforming from planar to three-dimensional lithium with flowable interphase for solid lithium metal batteries

PubMed Central

Liu, Yayuan; Lin, Dingchang; Jin, Yang; Liu, Kai; Tao, Xinyong; Zhang, Qiuhong; Zhang, Xiaokun; Cui, Yi

2017-01-01

Solid-state lithium (Li) metal batteries are prominent among next-generation energy storage technologies due to their significantly high energy density and reduced safety risks. Previously, solid electrolytes have been intensively studied and several materials with high ionic conductivity have been identified. However, there are still at least three obstacles before making the Li metal foil-based solid-state systems viable, namely, high interfacial resistance at the Li/electrolyte interface, low areal capacity, and poor power output. The problems are addressed by incorporating a flowable interfacial layer and three-dimensional Li into the system. The flowable interfacial layer can accommodate the interfacial fluctuation and guarantee excellent adhesion at all time, whereas the three-dimensional Li significantly reduces the interfacial fluctuation from the whole electrode level (tens of micrometers) to local scale (submicrometer) and also decreases the effective current density for high-capacity and high-power operations. As a consequence, both symmetric and full-cell configurations can achieve greatly improved electrochemical performances in comparison to the conventional Li foil, which are among the best reported values in the literature. Noticeably, solid-state full cells paired with high–mass loading LiFePO4 exhibited, at 80°C, a satisfactory specific capacity even at a rate of 5 C (110 mA·hour g−1) and a capacity retention of 93.6% after 300 cycles at a current density of 3 mA cm−2 using a composite solid electrolyte middle layer. In addition, when a ceramic electrolyte middle layer was adopted, stable cycling with greatly improved capacity could even be realized at room temperature. PMID:29062894

Transforming from planar to three-dimensional lithium with flowable interphase for solid lithium metal batteries

DOE Office of Scientific and Technical Information (OSTI.GOV)

Liu, Yayuan; Lin, Dingchang; Jin, Yang

Solid-state lithium (Li) metal batteries are prominent among next-generation energy storage technologies due to their significantly high energy density and reduced safety risks. Previously, solid electrolytes have been intensively studied and several materials with high ionic conductivity have been identified. However, there are still at least three obstacles before making the Li metal foil-based solid-state systems viable, namely, high interfacial resistance at the Li/electrolyte interface, low areal capacity, and poor power output. The problems are addressed by incorporating a flowable interfacial layer and three-dimensional Li into the system. The flowable interfacial layer can accommodate the interfacial fluctuation and guarantee excellentmore » adhesion at all time, whereas the three-dimensional Li significantly reduces the interfacial fluctuation from the whole electrode level (tens of micrometers) to local scale (submicrometer) and also decreases the effective current density for high-capacity and high-power operations. As a consequence, both symmetric and full-cell configurations can achieve greatly improved electrochemical performances in comparison to the conventional Li foil, which are among the best reported values in the literature. Noticeably, solid-state full cells paired with high–mass loading LiFePO4 exhibited, at 80°C, a satisfactory specific capacity even at a rate of 5 C (110 mA·hour g -1) and a capacity retention of 93.6% after 300 cycles at a current density of 3 mA cm -2 using a composite solid electrolyte middle layer. In addition, when a ceramic electrolyte middle layer was adopted, stable cycling with greatly improved capacity could even be realized at room temperature.« less

Transforming from planar to three-dimensional lithium with flowable interphase for solid lithium metal batteries

DOE PAGES

Liu, Yayuan; Lin, Dingchang; Jin, Yang; ...

2017-10-01

Solid-state lithium (Li) metal batteries are prominent among next-generation energy storage technologies due to their significantly high energy density and reduced safety risks. Previously, solid electrolytes have been intensively studied and several materials with high ionic conductivity have been identified. However, there are still at least three obstacles before making the Li metal foil-based solid-state systems viable, namely, high interfacial resistance at the Li/electrolyte interface, low areal capacity, and poor power output. The problems are addressed by incorporating a flowable interfacial layer and three-dimensional Li into the system. The flowable interfacial layer can accommodate the interfacial fluctuation and guarantee excellentmore » adhesion at all time, whereas the three-dimensional Li significantly reduces the interfacial fluctuation from the whole electrode level (tens of micrometers) to local scale (submicrometer) and also decreases the effective current density for high-capacity and high-power operations. As a consequence, both symmetric and full-cell configurations can achieve greatly improved electrochemical performances in comparison to the conventional Li foil, which are among the best reported values in the literature. Noticeably, solid-state full cells paired with high–mass loading LiFePO4 exhibited, at 80°C, a satisfactory specific capacity even at a rate of 5 C (110 mA·hour g -1) and a capacity retention of 93.6% after 300 cycles at a current density of 3 mA cm -2 using a composite solid electrolyte middle layer. In addition, when a ceramic electrolyte middle layer was adopted, stable cycling with greatly improved capacity could even be realized at room temperature.« less

Solid polymer electrolyte (SPE) fuel cell technology program, phase 2/2A. [testing and evaluations

NASA Technical Reports Server (NTRS)

1976-01-01

Test evaluations were performed on a fabricated single solid polymer electrolyte cell unit. The cell operated at increased current density and at higher performance levels. This improved performance was obtained through a combination of increased temperature, increased reactant pressures, improved activation techniques and improved thermal control over the baseline cell configuration. The cell demonstrated a higher acid content membrane which resulted in increased performance. Reduced catalyst loading and low cost membrane development showed encouraging results.

Efficiently dense hierarchical graphene based aerogel electrode for supercapacitors

NASA Astrophysics Data System (ADS)

Wang, Xin; Lu, Chengxing; Peng, Huifen; Zhang, Xin; Wang, Zhenkun; Wang, Gongkai

2016-08-01

Boosting gravimetric and volumetric capacitances simultaneously at a high rate is still a discrepancy in development of graphene based supercapacitors. We report the preparation of dense hierarchical graphene/activated carbon composite aerogels via a reduction induced self-assembly process coupled with a drying post treatment. The compact and porous structures of composite aerogels could be maintained. The drying post treatment has significant effects on increasing the packing density of aerogels. The introduced activated carbons play the key roles of spacers and bridges, mitigating the restacking of adjacent graphene nanosheets and connecting lateral and vertical graphene nanosheets, respectively. The optimized aerogel with a packing density of 0.67 g cm-3 could deliver maximum gravimetric and volumetric capacitances of 128.2 F g-1 and 85.9 F cm-3, respectively, at a current density of 1 A g-1 in aqueous electrolyte, showing no apparent degradation to the specific capacitance at a current density of 10 A g-1 after 20000 cycles. The corresponding gravimetric and volumetric capacitances of 116.6 F g-1 and 78.1 cm-3 with an acceptable cyclic stability are also achieved in ionic liquid electrolyte. The results show a feasible strategy of designing dense hierarchical graphene based aerogels for supercapacitors.

Improving the aluminum-air battery system for use in electrical vehicles

NASA Astrophysics Data System (ADS)

Yang, Shaohua

The objectives of this study include improvement of the efficiency of the aluminum/air battery system and demonstration of its ability for vehicle applications. The aluminum/air battery system can generate enough energy and power for driving ranges and acceleration similar to that of gasoline powered cars. Therefore has the potential to be a power source for electrical vehicles. Aluminum/air battery vehicle life cycle analysis was conducted and compared to that of lead/acid and nickel-metal hydride vehicles. Only the aluminum/air vehicles can be projected to have a travel range comparable to that of internal combustion engine vehicles (ICE). From this analysis, an aluminum/air vehicle is a promising candidate compared to ICE vehicles in terms of travel range, purchase price, fuel cost, and life cycle cost. We have chosen two grades of Al alloys (Al alloy 1350, 99.5% and Al alloy 1199, 99.99%) in our study. Only Al 1199 was studied extensively using Na 2SnO3 as an electrolyte additive. We then varied concentration and temperature, and determined the effects on the parasitic (corrosion) current density and open circuit potential. We also determined cell performance and selectivity curves. To optimize the performance of the cell based on our experiments, the recommended operating conditions are: 3--4 N NaOH, about 55°C, and a current density of 150--300 mA/cm2. We have modeled the cell performance using the equations we developed. The model prediction of cell performance shows good agreement with experimental data. For better cell performance, our model studies suggest use of higher electrolyte flow rate, smaller cell gap, higher conductivity and lower parasitic current density. We have analyzed the secondary current density distributions in a two plane, parallel Al/air cell and a wedge-type Al/air cell. The activity of the cathode has a large effect on the local current density. With increases in the cell gap, the local current density increases, but the increase is not as significant as the increase in the current density away from the entrance. By extending the cathode below the anode, the high local current density can be reduced.

High Temperature Polymers for use in Fuel Cells

NASA Technical Reports Server (NTRS)

Peplowski, Katherine M.

2004-01-01

NASA Glenn Research Center (GRC) is currently working on polymers for fuel cell and lithium battery applications. The desire for more efficient, higher power density, and a lower environmental impact power sources has led to interest in proton exchanges membrane fuels cells (PEMFC) and lithium batteries. A PEMFC has many advantages as a power source. The fuel cell uses oxygen and hydrogen as reactants. The resulting products are electricity, heat, and water. The PEMFC consists of electrodes with a catalyst, and an electrolyte. The electrolyte is an ion-conducting polymer that transports protons from the anode to the cathode. Typically, a PEMFC is operated at a temperature of about 80 C. There is intense interest in developing a fuel cell membrane that can operate at higher temperatures in the range of 80 C- 120 C. Operating the he1 cell at higher temperatures increases the kinetics of the fuel cell reaction as well as decreasing the susceptibility of the catalyst to be poisoned by impurities. Currently, Nafion made by Dupont is the most widely used polymer membrane in PEMFC. Nafion does not function well above 80 C due to a significant decrease in the conductivity of the membrane from a loss of hydration. In addition to the loss of conductivity at high temperatures, the long term stability and relatively high cost of Nafion have stimulated many researches to find a substitute for Nafion. Lithium ion batteries are popular for use in portable electronic devices, such as laptop computers and mobile phones. The high power density of lithium batteries makes them ideal for the high power demand of today s advanced electronics. NASA is developing a solid polymer electrolyte that can be used for lithium batteries. Solid polymer electrolytes have many advantages over the current gel or liquid based systems that are used currently. Among these advantages are the potential for increased power density and design flexibility. Automobiles, computers, and cell phones require highly efficient power density for lowering emissions and meeting increasing consumer demands. Many of the solutions can be provided by proton exchange membrane fuel cells and lithium batteries. NASA Glenn Research Center has recognized this need, and is presently engaged in a solution. The goals for the summer include mastering synthesis techniques, understanding the reactions occurring during the synthesis, and characterizing the resulting polymer membranes using NMR, DSC, and TGA for the PEMFC and lithium batteries.

Electrosynthesis of cerium hexaboride by the molten salt technique

NASA Astrophysics Data System (ADS)

Amalajyothi, K.; Berchmans, L. John; Angappan, S.; Visuvasam, A.

2008-07-01

Molten salts are well thought-out as the incredibly promising medium for chemical and electrochemical synthesis of compounds. Hence a stab has been made on the electrochemical synthesis of CeB 6 using molten salt technique. The electrolyte consisted of lithium fluoride (LiF), boron trioxide (B 2O 3) and cerium chloride (CeCl 3). Electrochemical experiments were carried out in an inconal reactor in an argon atmosphere. Electrolysis was executed in a high-density graphite crucible, which doles out as the electrolyte clutching vessel as well as the anode. The cathode was made up of a molybdenum rod. The electrolysis was carried out at 900 °C at different current densities intended for the synthesis of CeB 6 crystals. After the electrolysis, the cathode product was removed and cleaned using dilute HCl solution. The crystals were scrutinized by X-ray diffraction (XRD) to make out the phase and the purity. It has been observed that CeB 6 crystals are synthesized at all current densities and the product has traces of impurities.

Enhanced cycling performance of a Li metal anode in a dimethylsulfoxide-based electrolyte using highly concentrated lithium salt for a lithium-oxygen battery

NASA Astrophysics Data System (ADS)

Togasaki, Norihiro; Momma, Toshiyuki; Osaka, Tetsuya

2016-03-01

Stable charge-discharge cycling behavior for a lithium metal anode in a dimethylsulfoxide (DMSO)-based electrolyte is strongly desired of lithium-oxygen batteries, because the Li anode is rapidly exhausted as a result of side reactions during cycling in the DMSO solution. Herein, we report a novel electrolyte design for enhancing the cycling performance of Li anodes by using a highly concentrated DMSO-based electrolyte with a specific Li salt. Lithium nitrate (LiNO3), which forms an inorganic compound (Li2O) instead of a soluble product (Li2S) on a lithium surface, exhibits a >20% higher coulombic efficiency than lithium bis(trifluoromethanesulfonyl)imide, lithium bis(fluorosulfonyl)imide, and lithium perchlorate, regardless of the loading current density. Moreover, the stable cycling of Li anodes in DMSO-based electrolytes depends critically on the salt concentration. The highly concentrated electrolyte 4.0 M LiNO3/DMSO displays enhanced and stable cycling performance comparable to that of carbonate-based electrolytes, which had not previously been achieved. We suppose this enhancement is due to the absence of free DMSO solvent in the electrolyte and the promotion of the desolvation of Li ions on the solid electrolyte interphase surface, both being consequences of the unique structure of the electrolyte.

Ambient temperature secondary lithium cells containing inorganic electrolyte

NASA Astrophysics Data System (ADS)

Schlaikjer, Carl R.

The history and current status of rechargeable lithium cells using electrolytes based on liquid sulfur dioxide are reviewed. Three separate approaches currently under development include lithium/lithium dithionite/carbon cells with a supporting electrolyte salt; lithium/cupric chloride cells using sulfur dioxide/lithium tetrachloroaluminate; and several adaptations of a lithium/carbon cell using sulfur dioxide/lithium tetrachloroaluminate in which the discharge reaction involves the incorporation of aluminum into the positive electrode. The latter two chemistries have been studied in prototype hardware. For AA size cells with cupric chloride, 157 Whr/1 at 24 W/1 for 230 cycles was reported. For AA size cells containing 2LiCl-CaCl2-4AlCl3-12SO2, energy densities as high as 265 Whr/liter and 100 Whr/kg have been observed, but, at 26 W/1, for only 10 cycles. The advantages and remaining problems are discussed.

Efficiency and cost advantages of an advanced-technology nuclear electrolytic hydrogen-energy production facility

NASA Technical Reports Server (NTRS)

Donakowski, T. D.; Escher, W. J. D.; Gregory, D. P.

1977-01-01

The concept of an advanced-technology (viz., 1985 technology) nuclear-electrolytic water electrolysis facility was assessed for hydrogen production cost and efficiency expectations. The facility integrates (1) a high-temperature gas-cooled nuclear reactor (HTGR) operating a binary work cycle, (2) direct-current (d-c) electricity generation via acyclic generators, and (3) high-current-density, high-pressure electrolyzers using a solid polymer electrolyte (SPE). All subsystems are close-coupled and optimally interfaced for hydrogen production alone (i.e., without separate production of electrical power). Pipeline-pressure hydrogen and oxygen are produced at 6900 kPa (1000 psi). We found that this advanced facility would produce hydrogen at costs that were approximately half those associated with contemporary-technology nuclear electrolysis: $5.36 versus $10.86/million Btu, respectively. The nuclear-heat-to-hydrogen-energy conversion efficiency for the advanced system was estimated as 43%, versus 25% for the contemporary system.

Hybrid electrolytes for lithium metal batteries

NASA Astrophysics Data System (ADS)

Keller, Marlou; Varzi, Alberto; Passerini, Stefano

2018-07-01

This perspective article discusses the most recent developments in the field of hybrid electrolytes, here referred to electrolytes composed of two, well-defined ion-conducting phases, for high energy density lithium metal batteries. The two phases can be both solid, as e.g., two inorganic conductors or one inorganic and one polymer conductor, or, differently, one liquid and one inorganic conductor. In this latter case, they are referred as quasi-solid hybrid electrolytes. Techniques for the appropriate characterization of hybrid electrolytes are discussed emphasizing the importance of ionic conduction and interfacial properties. On this view, multilayer systems are also discussed in more detail. Investigations on Lewis acid-base interactions, activation energies for lithium-ion transfer between the phases, and the formation of an interphase between the components are reviewed and analyzed. The application of different hybrid electrolytes in lithium metal cells with various cathode compositions is also discussed. Fabrication methods for the feasibility of large-scale applications are briefly analyzed and different cell designs and configurations, which are most suitable for the integration of hybrid electrolytes, are determined. Finally, the specific energy of cells containing different hybrid electrolytes is estimated to predict possible enhancement in energy with respect to the current lithium-ion battery technology.

Zn-Mn alloy coatings from acidic chloride bath: Effect of deposition conditions on the Zn-Mn electrodeposition-morphological and structural characterization

NASA Astrophysics Data System (ADS)

Loukil, N.; Feki, M.

2017-07-01

Zn-Mn alloy electrodeposition on steel electrode in chloride bath was investigated using cyclic voltammetric, chronopotentiometric and chronoamperometric techniques. Cyclic voltammetries (CV) reveal a deep understanding of electrochemical behaviors of each metal Zn, Mn, proton discharge and Zn-Mn co-deposition. The electrochemical results show that with increasing Mn2+ ions concentration in the electrolytic bath, Mn2+ reduction occurs at lower over-potential leading to an enhancement of Mn content into the Zn-Mn deposits. A dimensionless graph model was used to analyze the effect of Mn2+ ions concentration on Zn-Mn nucleation process. It was found that the nucleation process is not extremely affected by Mn2+ concentration. Nevertheless, it significantly depends on the applied potential. Several parameters such as Mn2+ ions concentration, current density and stirring were investigated with regard to the Mn content into the final Zn-Mn coatings. It was found that the Mn content increases with increasing the applied current density jimp and Mn2+ ions concentration in the electrolytic bath. However, stirring of the solution decreases the Mn content in the Zn-Mn coatings. The phase structure and surface morphology of Zn-Mn deposits are characterized by means of X-ray diffraction analysis and Scanning Electron Microscopy (SEM), respectively. The Zn-Mn deposited at low current density is tri-phasic and consisting of η-Zn, ζ-MnZn13 and hexagonal close packed ε-Zn-Mn. An increase in current density leads to a transition from crystalline to amorphous structure, arising from the hydroxide inclusions in the Zn-Mn coating at high current density.

Inhibiting Polysulfide Shuttle in Lithium-Sulfur Batteries through Low-Ion-Pairing Salts and a Triflamide Solvent.

PubMed

Shyamsunder, Abhinandan; Beichel, Witali; Klose, Petra; Pang, Quan; Scherer, Harald; Hoffmann, Anke; Murphy, Graham K; Krossing, Ingo; Nazar, Linda F

2017-05-22

The step-change in gravimetric energy density needed for electrochemical energy storage devices to power unmanned autonomous vehicles, electric vehicles, and enable low-cost clean grid storage is unlikely to be provided by conventional lithium ion batteries. Lithium-sulfur batteries comprising lightweight elements provide a promising alternative, but the associated polysulfide shuttle in typical ether-based electrolytes generates loss in capacity and low coulombic efficiency. The first new electrolyte based on a unique combination of a relatively hydrophobic sulfonamide solvent and a low ion-pairing salt, which inhibits the polysulfide shuttle, is presented. This system behaves as a sparingly solvating electrolyte at slightly elevated temperatures, where it sustains reversible capacities as high as 1200-1500 mAh g -1 over a wide range of current density (2C-C/5, respectively) when paired with a lithium metal anode, with a coulombic efficiency of >99.7 % in the absence of LiNO 3 additive. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Nanoscaled Na3PS4 Solid Electrolyte for All-Solid-State FeS2/Na Batteries with Ultrahigh Initial Coulombic Efficiency of 95% and Excellent Cyclic Performances.

PubMed

Wan, Hongli; Mwizerwa, Jean Pierre; Qi, Xingguo; Xu, Xiaoxiong; Li, Hong; Zhang, Qiang; Cai, Liangting; Hu, Yong-Sheng; Yao, Xiayin

2018-04-18

Nanosized Na 3 PS 4 solid electrolyte with an ionic conductivity of 8.44 × 10 -5 S cm -1 at room temperature is synthesized by a liquid-phase reaction. The resultant all-solid-state FeS 2 /Na 3 PS 4 /Na batteries show an extraordinary high initial Coulombic efficiency of 95% and demonstrate high energy density of 611 Wh kg -1 at current density of 20 mA g -1 at room temperature. The outstanding performances of the battery can be ascribed to good interface compatibility and intimate solid-solid contact at FeS 2 electrode/nanosized Na 3 PS 4 solid electrolytes interface. Meanwhile, excellent cycling stability is achieved for the battery after cycling at 60 mA g -1 for 100 cycles, showing a high capacity of 287 mAh g -1 with the capacity retention of 80%.

The LiAl/FeS2 battery power source for the future

NASA Technical Reports Server (NTRS)

Briscoe, J. Douglass; Embrey, J.; Oweis, S.; Press, K.

1992-01-01

Advanced high power density rechargeable batteries are currently under development. These batteries have the potential of greatly increasing the power and energy densities available for space applications. Depending on whether the system is optimized for high power or high energy, values up to 150 Wh/kg and 2100 W/kg (including hardware) are projected. This is due to the fact that the system uses a high conductivity molten salt electrolyte. The electrolyte also serves as a separator layer with unlimited freeze thaw capabilities. Life of 1000 cycles and ten calendar years is projected. The electrochemistry consists of a lithium aluminum alloy negative electrode, iron disulfide positive electrode, and magnesium oxide powder immobilized molten salt electrolyte. Processed powders are cold compacted into circular discs which are assembled into bipolar cell hardware with peripheral ceramic salts. The culmination of the work will be a high energy battery of 40 kWh and a high power battery of 28 kWh.

Sodium-ion hybrid electrolyte battery for sustainable energy storage applications

NASA Astrophysics Data System (ADS)

Senthilkumar, S. T.; Abirami, Mari; Kim, Junsoo; Go, Wooseok; Hwang, Soo Min; Kim, Youngsik

2017-02-01

Sustainable, safe, and low-cost energy storage systems are essential for large-scale electrical energy storage. Herein, we report a sodium (Na)-ion hybrid electrolyte battery with a replaceable cathode system, which is separated from the Na metal anode by a Na superionic conducting ceramic. By using a fast Na-ion-intercalating nickel hexacyanoferrate (NiHCF) cathode along with an eco-friendly seawater catholyte, we demonstrate good cycling performance with an average discharge voltage of 3.4 V and capacity retention >80% over 100 cycles and >60% over 200 cycle. Remarkably, such high capacity retention is observed for both the initial as well as replaced cathodes. Moreover, a Na-metal-free hybrid electrolyte battery containing hard carbon as the anode exhibits an energy density of ∼146 Wh kg-1 at a current density of 10 mA g-1, which is comparable to that of lead-acid batteries and much higher than that of conventional aqueous Na-ion batteries. These results pave the way for further advances in sustainable energy storage technology.

Bulk-Type All-Solid-State Lithium-Ion Batteries: Remarkable Performances of a Carbon Nanofiber-Supported MgH2 Composite Electrode.

PubMed

Zeng, Liang; Ichikawa, Takayuki; Kawahito, Koji; Miyaoka, Hiroki; Kojima, Yoshitsugu

2017-01-25

Magnesium hydride, MgH 2 , a recently developed compound for lithium-ion batteries, is considered to be a promising conversion-type negative electrode material due to its high theoretical lithium storage capacity of over 2000 mA h g -1 , suitable working potential, and relatively small volume expansion. Nevertheless, it suffers from unsatisfactory cyclability, poor reversibility, and slow kinetics in conventional nonaqueous electrolyte systems, which greatly limit the practical application of MgH 2 . In this work, a vapor-grown carbon nanofiber was used to enhance the electrical conductivity of MgH 2 using LiBH 4 as the solid-state electrolyte. It shows that a reversible capacity of over 1200 mA h g -1 with an average voltage of 0.5 V (vs Li/Li + ) can be obtained after 50 cycles at a current density of 1000 mA g -1 . In addition, the capacity of MgH 2 retains over 1100 mA h g -1 at a high current density of 8000 mA g -1 , which indicates the possibility of using MgH 2 as a negative electrode material for high power and high capacity lithium-ion batteries in future practical applications. Moreover, the widely studied sulfide-based solid electrolyte was also used to assemble battery cells with MgH 2 electrode in the same system, and the electrochemical performance was as good as that using LiBH 4 electrolyte.

Reduction of capacity decay in vanadium flow batteries by an electrolyte-reflow method

NASA Astrophysics Data System (ADS)

Wang, Ke; Liu, Le; Xi, Jingyu; Wu, Zenghua; Qiu, Xinping

2017-01-01

Electrolyte imbalance is a major issue with Vanadium flow batteries (VFBs) as it has a significant impact on electrolyte utilization and cycle life over extended charge-discharge cycling. This work seeks to reduce capacity decay and prolong cycle life of VFBs by adopting a novel electrolyte-reflow method. Different current density and various start-up time of the method are investigated in the charge-discharge tests. The results show that the capacity decay rate is reduced markedly and the cycle life is prolonged substantially by this method. In addition, the coulomb efficiency, voltage efficiency and energy efficiency remain stable during the whole cycle life test, which indicates this method has little impact on the long lifetime performance of the VFBs. The method is low-cost, simple, effective, and can be applied in industrial VFB productions.

Cellulose nanofibril/reduced graphene oxide/carbon nanotube hybrid aerogels for highly flexible and all-solid-state supercapacitors.

PubMed

Zheng, Qifeng; Cai, Zhiyong; Ma, Zhenqiang; Gong, Shaoqin

2015-02-11

A novel type of highly flexible and all-solid-state supercapacitor that uses cellulose nanofibril (CNF)/reduced graphene oxide (RGO)/carbon nanotube (CNT) hybrid aerogels as electrodes and H2SO4/poly(vinyl alcohol) (PVA) gel as the electrolyte was developed and is reported here. These flexible solid-state supercapacitors were fabricated without any binders, current collectors, or electroactive additives. Because of the porous structure of the CNF/RGO/CNT aerogel electrodes and the excellent electrolyte absorption properties of the CNFs present in the aerogel electrodes, the resulting flexible supercapacitors exhibited a high specific capacitance (i.e., 252 F g(-1) at a discharge current density of 0.5 A g(-1)) and a remarkable cycle stability (i.e., more than 99.5% of the capacitance was retained after 1000 charge-discharge cycles at a current density of 1 A g(-1)). Furthermore, the supercapacitors also showed extremely high areal capacitance, areal power density, and energy density (i.e., 216 mF cm(-2), 9.5 mW cm(-2), and 28.4 μWh cm(-2), respectively). In light of its excellent electrical performance, low cost, ease of large-scale manufacturing, and environmental friendliness, the CNF/RGO/CNT aerogel electrodes may have a promising application in the development of flexible energy-storage devices.

Boron-doped diamond electrooxidation of ethyl paraben: The effect of electrolyte on by-products distribution and mechanisms.

PubMed

Frontistis, Zacharias; Antonopoulou, Maria; Yazirdagi, Melis; Kilinc, Zeynep; Konstantinou, Ioannis; Katsaounis, Alexandros; Mantzavinos, Dionissios

2017-06-15

Ethyl paraben (EP), a representative emerging pollutant of the parabens family, was subject to electrochemical oxidation over a boron-doped diamond (BDD) anode. Experiments were carried out in a single-compartment cell at 10-70 mA cm -2 current density, 200-600 μg L -1 EP concentration, initial solution pH 3-9 and 0.1 M electrolyte concentration. The degradation rate is favored at increased current densities and in the presence of NaCl as the supporting electrolyte, while the pH effect is inconsiderable. For instance, the first order rate constant for the degradation of 200 μg L -1 EP at 30 mA cm -2 was 0.25, 0.1 and 0.07 min -1 with NaCl, Na 2 SO 4 and HClO 4 , respectively. Degradation in secondary treated wastewater was faster than in pure water presumably due to the action of chloride ions present in the effluent. Liquid chromatography time-of-flight mass spectrometry (LC-TOF-MS) was employed to determine major transformation by-products (TBPs). The route of EP degradation with Na 2 SO 4 involves hydroxylation and demethylation reactions, signifying the role of electrogenerated hydroxyl radicals in the process. Twenty one TBPs were identified with NaCl as the electrolyte, including several chlorinated and non-chlorinated dimers and trimers; these findings suggest that indirect oxidation mediated by chlorine radicals and other chlorine active species also takes place. In this view, the role of the supporting electrolyte is crucial since it can influence both reaction kinetics and pathways. Copyright © 2016 Elsevier Ltd. All rights reserved.

The effects of electrolyte on the supercapacitive performance of activated calcium carbide-derived carbon

NASA Astrophysics Data System (ADS)

Wu, Hao; Wang, Xianyou; Jiang, Lanlan; Wu, Chun; Zhao, Qinglan; Liu, Xue; Hu, Ben'an; Yi, Lanhua

2013-03-01

Porous calcium carbide-derived carbon (CCDC) has been prepared by one-step route from CaC2 in a freshly prepared chlorine environment at lower temperature, and following activated by ZnCl2 to get activated CCDC. The performances of the supercapacitors based on activated CCDC as electrode active material in aqueous KOH, K2SO4, KCl and KNO3 electrolytes are studied by cyclic voltammetry, constant current charged/discharged, cyclic life and electrochemical impedance spectroscopy. It has been found that the supercapacitor using 6 M KOH as electrolyte shows an energy density of 8.3 Wh kg-1 and a power density of 1992 W kg-1 based on the total weight of the electrode active materials with a voltage range 0 V-1 V. Meanwhile, the specific capacitance of the supercapacitor in 6 M KOH electrolyte is 68 F g-1 at the scan rate of 1 mV s-1 in the voltage range of 0 V-1 V, the charge-transfer resistance is extremely low and the relaxation time is the least of all. The supercapacitor also exhibits a good cycling performance and keeps 95% of initial capacity over 5000 cycles.

Solid oxide MEMS-based fuel cells

DOEpatents

Jankowksi, Alan F.; Morse, Jeffrey D.

2007-03-13

A micro-electro-mechanical systems (MEMS) based thin-film fuel cells for electrical power applications. The MEMS-based fuel cell may be of a solid oxide type (SOFC), a solid polymer type (SPFC), or a proton exchange membrane type (PEMFC), and each fuel cell basically consists of an anode and a cathode separated by an electrolyte layer. The electrolyte layer can consist of either a solid oxide or solid polymer material, or proton exchange membrane electrolyte materials may be used. Additionally catalyst layers can also separate the electrodes (cathode and anode) from the electrolyte. Gas manifolds are utilized to transport the fuel and oxidant to each cell and provide a path for exhaust gases. The electrical current generated from each cell is drawn away with an interconnect and support structure integrated with the gas manifold. The fuel cells utilize integrated resistive heaters for efficient heating of the materials. By combining MEMS technology with thin-film deposition technology, thin-film fuel cells having microflow channels and full-integrated circuitry can be produced that will lower the operating temperature an will yield an order of magnitude greater power density than the currently known fuel cells.

Solid polymer MEMS-based fuel cells

DOEpatents

Jankowski, Alan F [Livermore, CA; Morse, Jeffrey D [Pleasant Hill, CA

2008-04-22

A micro-electro-mechanical systems (MEMS) based thin-film fuel cells for electrical power applications. The MEMS-based fuel cell may be of a solid oxide type (SOFC), a solid polymer type (SPFC), or a proton exchange membrane type (PEMFC), and each fuel cell basically consists of an anode and a cathode separated by an electrolyte layer. The electrolyte layer can consist of either a solid oxide or solid polymer material, or proton exchange membrane electrolyte materials may be used. Additionally catalyst layers can also separate the electrodes (cathode and anode) from the electrolyte. Gas manifolds are utilized to transport the fuel and oxidant to each cell and provide a path for exhaust gases. The electrical current generated from each cell is drawn away with an interconnect and support structure integrated with the gas manifold. The fuel cells utilize integrated resistive heaters for efficient heating of the materials. By combining MEMS technology with thin-film deposition technology, thin-film fuel cells having microflow channels and full-integrated circuitry can be produced that will lower the operating temperature an will yield an order of magnitude greater power density than the currently known fuel cells.

Ion distributions, exclusion coefficients, and separation factors of electrolytes in a charged cylindrical nanopore: a partially perturbative density functional theory study.

PubMed

Peng, Bo; Yu, Yang-Xin

2009-10-07

The structural and thermodynamic properties for charge symmetric and asymmetric electrolytes as well as mixed electrolyte system inside a charged cylindrical nanopore are investigated using a partially perturbative density functional theory. The electrolytes are treated in the restricted primitive model and the internal surface of the cylindrical nanopore is considered to have a uniform charge density. The proposed theory is directly applicable to the arbitrary mixed electrolyte solution containing ions with the equal diameter and different valences. Large amount of simulation data for ion density distributions, separation factors, and exclusion coefficients are used to determine the range of validity of the partially perturbative density functional theory for monovalent and multivalent counterion systems. The proposed theory is found to be in good agreement with the simulations for both mono- and multivalent counterion systems. In contrast, the classical Poisson-Boltzmann equation only provides reasonable descriptions of monovalent counterion system at low bulk density, and is qualitatively and quantitatively wrong in the prediction for the multivalent counterion systems due to its neglect of the strong interionic correlations in these systems. The proposed density functional theory has also been applied to an electrolyte absorbed into a pore that is a model of the filter of a physiological calcium channel.

Effect of conductive additives to gel electrolytes on activated carbon-based supercapacitors

NASA Astrophysics Data System (ADS)

Barzegar, Farshad; Dangbegnon, Julien K.; Bello, Abdulhakeem; Momodu, Damilola Y.; Johnson, A. T. Charlie; Manyala, Ncholu

2015-09-01

This article is focused on polymer based gel electrolyte due to the fact that polymers are cheap and can be used to achieve extended potential window for improved energy density of the supercapacitor devices when compared to aqueous electrolytes. Electrochemical characterization of a symmetric supercapacitor devices based on activated carbon in different polyvinyl alcohol (PVA) based gel electrolytes was carried out. The device exhibited a maximum energy density of 24 Wh kg-1 when carbon black was added to the gel electrolyte as conductive additive. The good energy density was correlated with the improved conductivity of the electrolyte medium which is favorable for fast ion transport in this relatively viscous environment. Most importantly, the device remained stable with no capacitance lost after 10,000 cycles.

Principles and Applications of Solid Polymer Electrolyte Reactors for Electrochemical Hydrodehalogenation of Organic Pollutants

NASA Astrophysics Data System (ADS)

Cheng, Hua; Scott, Keith

The ability to re-cycle halogenated liquid wastes, based on electrochemical hydrodehalogenation (EHDH), will provide a significant economic advantage and will reduce the environmental burden in a number of processes. The use of a solid polymer electrolyte (SPE) reactor is very attractive for this purpose. Principles and features of electrochemical HDH technology and SPE EHDH reactors are described. The SPE reactor enables selective dehalogenation of halogenated organic compounds in both aqueous and non-aqueous media with high current efficiency and low energy consumption. The influence of operating conditions, including cathode material, current density, reactant concentration and temperature on the HDH process and its stability are examined.

Mechanistic Study of Electrolyte Additives to Stabilize High-Voltage Cathode-Electrolyte Interface in Lithium-Ion Batteries.

PubMed

Gao, Han; Maglia, Filippo; Lamp, Peter; Amine, Khalil; Chen, Zonghai

2017-12-27

Current developments of electrolyte additives to stabilize electrode-electrolyte interface in lithium-ion batteries highly rely on a trial-and-error search, which involves repetitive testing and intensive amount of resources. The lack of understandings on the fundamental protection mechanisms of the additives significantly increases the difficulty for the transformational development of new additives. In this study, we investigated two types of individual protection routes to build a robust cathode-electrolyte interphase at high potentials: (i) a direct reduction in the catalytic decomposition of the electrolyte solvent; and (ii) formation of a "corrosion inhibitor film" that prevents severely attack and passivation from protons that generated from the solvent oxidation, even the decomposition of solvent cannot be mitigated. Effect of two exemplary electrolyte additives, lithium difluoro(oxalato)borate (LiDFOB) and 3-hexylthiophene (3HT), on LiNi 0.6 Mn 0.2 Co 0.2 O 2 (NMC 622) cathode were investigated to validate our hypothesis. It is demonstrated that understandings of both electrolyte additives and solvent are essential and careful balance between the cathode protection mechanism of additives and their side effects is critical to obtain optimum results. More importantly, this study opens up new directions of rational design of functional electrolyte additives for the next-generation high-energy-density lithium-ion chemistries.

Effect of some operational parameters on the arsenic removal by electrocoagulation using iron electrodes

PubMed Central

2014-01-01

Arsenic contamination of drinking water is a global problem that will likely become more apparent in future years as scientists and engineers measure the true extent of the problem. Arsenic poisoning is preventable though as there are several methods for easily removing even trace amounts of arsenic from drinking water. In the present study, electrocoagulation was evaluated as a treatment technology for arsenic removal from aqueous solutions. The effects of parameters such as initial pH, current density, initial concentration, supporting electrolyte type and stirring speed on removal efficiency were investigated. It has been observed that initial pH was highly effective on the arsenic removal efficiency. The highest removal efficiency was observed at initial pH = 4. The obtained experimental results showed that the efficiency of arsenic removal increased with increasing current density and decreased with increasing arsenic concentration in the solution. Supporting electrolyte had not significant effects on removal, adding supporting electrolyte decreased energy consumption. The effect of stirring speed on removal efficiency was investigated and the best removal efficiency was at the 150 rpm. Under the optimum conditions of initial pH 4, current density of 0.54 mA/cm2, stirring speed of 150 rpm, electrolysis time of 30 minutes, removal was obtained as 99.50%. Energy consumption in the above conditions was calculated as 0.33 kWh/m3. Electrocoagulation with iron electrodes was able to bring down 50 mg/L arsenic concentration to less than 10 μg/L at the end of electrolysis time of 45 minutes with low electrical energy consumption as 0.52 kWh/m3. PMID:24991426

Anomalies in the equilibrium and nonequilibrium properties of correlated ions in complex molecular environments

NASA Astrophysics Data System (ADS)

Mahakrishnan, Sathiya; Chakraborty, Subrata; Vijay, Amrendra

2017-11-01

Emergent statistical attributes, and therefore the equations of state, of an assembly of interacting charge carriers embedded within a complex molecular environment frequently exhibit a variety of anomalies, particularly in the high-density (equivalently, the concentration) regime, which are not well understood, because they do not fall under the low-concentration phenomenologies of Debye-Hückel-Onsager and Poisson-Nernst-Planck, including their variants. To go beyond, we here use physical concepts and mathematical tools from quantum scattering theory, transport theory with the Stosszahlansatz of Boltzmann, and classical electrodynamics (Lorentz gauge) and obtain analytical expressions both for the average and the frequency-wave vector-dependent longitudinal and transverse current densities, diffusion coefficient, and the charge density, and therefore the analytical expressions for (a) the chemical potential, activity coefficient, and the equivalent conductivity for strong electrolytes and (b) the current-voltage characteristics for ion-transport processes in complex molecular environments. Using a method analogous to the notion of Debye length and thence the electrical double layer, we here identify a pair of characteristic length scales (longitudinal and the transverse), which, being wave vector and frequency dependent, manifestly exhibit nontrivial fluctuations in space-time. As a unifying theme, we advance a quantity (inverse length dimension), gscat(a ), which embodies all dynamical interactions, through various quantum scattering lengths, relevant to molecular species a, and the analytical behavior which helps us to rationalize the properties of strong electrolytes, including anomalies, in all concentration regimes. As an example, the behavior of gscat(a ) in the high-concentration regime explains the anomalous increase of the Debye length with concentration, as seen in a recent experiment on electrolyte solutions. We also put forth an extension of the standard diffusion equation, which manifestly incorporates the effects arising from the underlying microscopic collisions among constituent molecular species. Furthermore, we show a nontrivial connection between the current-voltage characteristics of electrolyte solutions and the Landauer's approach to electrical conduction in mesoscopic solids and thereby establish a definite conceptual bridge between the two disjoint subjects. For numerical insight, we present results on the aqueous solution of KCl as an example of strong electrolyte, and the transport (conduction as well as diffusion) of K+ ions in water, as an example of ion transport across the voltage-gated channels in biological cells.

Anomalies in the equilibrium and nonequilibrium properties of correlated ions in complex molecular environments.

PubMed

Mahakrishnan, Sathiya; Chakraborty, Subrata; Vijay, Amrendra

2017-11-01

Emergent statistical attributes, and therefore the equations of state, of an assembly of interacting charge carriers embedded within a complex molecular environment frequently exhibit a variety of anomalies, particularly in the high-density (equivalently, the concentration) regime, which are not well understood, because they do not fall under the low-concentration phenomenologies of Debye-Hückel-Onsager and Poisson-Nernst-Planck, including their variants. To go beyond, we here use physical concepts and mathematical tools from quantum scattering theory, transport theory with the Stosszahlansatz of Boltzmann, and classical electrodynamics (Lorentz gauge) and obtain analytical expressions both for the average and the frequency-wave vector-dependent longitudinal and transverse current densities, diffusion coefficient, and the charge density, and therefore the analytical expressions for (a) the chemical potential, activity coefficient, and the equivalent conductivity for strong electrolytes and (b) the current-voltage characteristics for ion-transport processes in complex molecular environments. Using a method analogous to the notion of Debye length and thence the electrical double layer, we here identify a pair of characteristic length scales (longitudinal and the transverse), which, being wave vector and frequency dependent, manifestly exhibit nontrivial fluctuations in space-time. As a unifying theme, we advance a quantity (inverse length dimension), g_{scat}^{(a)}, which embodies all dynamical interactions, through various quantum scattering lengths, relevant to molecular species a, and the analytical behavior which helps us to rationalize the properties of strong electrolytes, including anomalies, in all concentration regimes. As an example, the behavior of g_{scat}^{(a)} in the high-concentration regime explains the anomalous increase of the Debye length with concentration, as seen in a recent experiment on electrolyte solutions. We also put forth an extension of the standard diffusion equation, which manifestly incorporates the effects arising from the underlying microscopic collisions among constituent molecular species. Furthermore, we show a nontrivial connection between the current-voltage characteristics of electrolyte solutions and the Landauer's approach to electrical conduction in mesoscopic solids and thereby establish a definite conceptual bridge between the two disjoint subjects. For numerical insight, we present results on the aqueous solution of KCl as an example of strong electrolyte, and the transport (conduction as well as diffusion) of K^{+} ions in water, as an example of ion transport across the voltage-gated channels in biological cells.

A hydrogen-ferric ion rebalance cell operating at low hydrogen concentrations for capacity restoration of iron-chromium redox flow batteries

NASA Astrophysics Data System (ADS)

Zeng, Y. K.; Zhao, T. S.; Zhou, X. L.; Zou, J.; Ren, Y. X.

2017-06-01

To eliminate the adverse impacts of hydrogen evolution on the capacity of iron-chromium redox flow batteries (ICRFBs) during the long-term operation and ensure the safe operation of the battery, a rebalance cell that reduces the excessive Fe(III) ions at the positive electrolyte by using the hydrogen evolved from the negative electrolyte is designed, fabricated and tested. The effects of the flow field, hydrogen concentration and H2/N2 mixture gas flow rate on the performance of the hydrogen-ferric ion rebalance cell have been investigated. Results show that: i) an interdigitated flow field based rebalance cell delivers higher limiting current densities than serpentine flow field based one does; ii) the hydrogen utilization can approach 100% at low hydrogen concentrations (≤5%); iii) the apparent exchange current density of hydrogen oxidation reaction in the rebalance cell is proportional to the square root of the hydrogen concentration at the hydrogen concentration from 1.3% to 50%; iv) a continuous rebalance process is demonstrated at the current density of 60 mA cm-2 and hydrogen concentration of 2.5%. Moreover, the cost analysis shows that the rebalance cell is just approximately 1% of an ICRFB system cost.

Dendritic Zinc Growth in Acid Electrolyte: Effect of the pH

NASA Astrophysics Data System (ADS)

Bengoa, Leandro N.; Pary, Paola; Seré, Pablo R.; Conconi, M. Susana; Egli, Walter A.

2018-03-01

In this paper, dendritic growth at the edges of electrogalvanized steel strip has been studied using a specially designed rotating washer electrode which simulates the fluid dynamic conditions and the current density distribution at the steel strip edge found in a production line. The effect of electrolyte pH and current density on dendritic growth in an acidic zinc plating bath (ZnSO4 and H2SO4) was addressed. The temperature was kept constant at 60 °C. Solution pH was adjusted to 1, 2 or 3 using different amounts of H2SO4. In addition, the influence of temperature on the pH of the solution was determined. The current density was set at 40 or 60 A/dm2, similar to that used in the industry. Deposits were characterized using SEM and XRD. The results showed that pH strongly affects dendrites shape, length and texture. Furthermore, the morphology of dendrites at the washer edge and of deposits on the flat portion of the washer changed considerably as solution pH was increased from 1 to 3. It was found that the morphology of dendrites at the washer edge stems from the morphology of the deposit on its flat portion, which in turn determines their shape.

The recovery of zinc from hot galvanizing slag in an anion-exchange membrane electrolysis reactor.

PubMed

Ren, Xiulian; Wei, Qifeng; Hu, Surong; Wei, Sijie

2010-09-15

This paper reports the optimization of the process parameters for recovery of zinc from hot galvanizing slag in an anion-exchange membrane electrolysis reactor. The experiments were carried out in an ammoniacal ammonium chloride system. The influence of composition of electrolytes, pH, stirring rate, current density and temperature, on cathodic current efficiency, specific power consumption and anodic dissolution of Zn were investigated. The results indicate that the cathode current efficiency increases and the hydrogen evolution decreased with increasing the cathode current density. The partial current for electrodeposition of Zn has liner relationship with omega(1/2) (omega: rotation rate). The highest current efficiency for dissolving zinc was obtained when NH(4)Cl concentration was 53.46 g L(-1) and the anodic dissolution of zinc was determined by mass transfer rate at stirring rate 0-300 r min(-1). Increase in temperature benefits to improve CE and dissolution of Zn, and reduce cell voltage. Initial pH of electrolytes plays an important role in the deposition and anodic dissolution of Zn. The results of single factor experiment show that about 50% energy consumption was saved for electrodeposition of Zn in the anion-exchange membrane electrolysis reactor. Copyright 2010 Elsevier B.V. All rights reserved.

Template-assisted fabrication of tin and antimony based nanowire arrays

NASA Astrophysics Data System (ADS)

Zaraska, Leszek; Kurowska, Elżbieta; Sulka, Grzegorz D.; Jaskuła, Marian

2012-10-01

Antimony nanowires with diameters ranging from 35 nm to 320 nm were successfully prepared by simple, galvanostatic electrodeposition inside the pores of anodic alumina membranes from a citrate based electrolyte. The use of the potassium antimonyl tartrate electrolyte for electrodeposition results in the formation of Sb/Sb2O3 nanowires. The structural features of the nanowire arrays were investigated by FE-SEM, and the nanowire composition was confirmed by EDS and XRD measurements. A distinct peak at about 27.5° in the XRD pattern recorded for nanowires formed in the tartrate electrolyte was attributed to the presence of co-deposited Sb2O3. Three types of dense arrays of Sn-SnSb nanowires with diameters ranging from 82 nm to 325 nm were also synthesized by DC galvanostatic electrodeposition into the anodic aluminum oxide (AAO) membranes for the first time. Only Sn and SnSb peaks appeared in the XRD pattern and both phases seem to have a relatively high degree of crystallinity. The influence of current density applied during electrodeposition on the composition of nanowires was investigated. It was found that the Sb content in fabricated nanowires decreases with increasing current density. The diameters of all synthesized nanowires roughly correspond to the dimensions of the nanochannels of AAO templates used for electrodeposition.

Organosulfide-plasticized solid-electrolyte interphase layer enables stable lithium metal anodes for long-cycle lithium-sulfur batteries

DOE Office of Scientific and Technical Information (OSTI.GOV)

Li, Guoxing; Gao, Yue; He, Xin

Lithium metal is a promising anode candidate for the next-generation rechargeable battery due to its highest specific capacity (3860 mA h g -1) and lowest potential, but low Coulombic efficiency and formation of lithium dendrites hinder its practical application. Here, we report a self-formed flexible hybrid solid-electrolyte interphase layer through co-deposition of organosulfides/organopolysulfides and inorganic lithium salts using sulfur-containing polymers as an additive in the electrolyte. The organosulfides/organopolysulfides serve as “plasticizer” in the solid-electrolyte interphase layer to improve its mechanical flexibility and toughness. The as-formed robust solid-electrolyte interphase layers enable dendrite-free lithium deposition and significantly improve Coulombic efficiency (99% overmore » 400 cycles at a current density of 2mAcm -2). A lithium-sulfur battery based on this strategy exhibits long cycling life (1000 cycles) and good capacity retention. This study reveals an avenue to effectively fabricate stable solid-electrolyte interphase layer for solving the issues associated with lithium metal anodes.« less

Organosulfide-plasticized solid-electrolyte interphase layer enables stable lithium metal anodes for long-cycle lithium-sulfur batteries

DOE PAGES

Li, Guoxing; Gao, Yue; He, Xin; ...

2017-10-11

Lithium metal is a promising anode candidate for the next-generation rechargeable battery due to its highest specific capacity (3860 mA h g -1) and lowest potential, but low Coulombic efficiency and formation of lithium dendrites hinder its practical application. Here, we report a self-formed flexible hybrid solid-electrolyte interphase layer through co-deposition of organosulfides/organopolysulfides and inorganic lithium salts using sulfur-containing polymers as an additive in the electrolyte. The organosulfides/organopolysulfides serve as “plasticizer” in the solid-electrolyte interphase layer to improve its mechanical flexibility and toughness. The as-formed robust solid-electrolyte interphase layers enable dendrite-free lithium deposition and significantly improve Coulombic efficiency (99% overmore » 400 cycles at a current density of 2mAcm -2). A lithium-sulfur battery based on this strategy exhibits long cycling life (1000 cycles) and good capacity retention. This study reveals an avenue to effectively fabricate stable solid-electrolyte interphase layer for solving the issues associated with lithium metal anodes.« less

Transparent, flexible supercapacitors from nano-engineered carbon films.

PubMed

Jung, Hyun Young; Karimi, Majid B; Hahm, Myung Gwan; Ajayan, Pulickel M; Jung, Yung Joon

2012-01-01

Here we construct mechanically flexible and optically transparent thin film solid state supercapacitors by assembling nano-engineered carbon electrodes, prepared in porous templates, with morphology of interconnected arrays of complex shapes and porosity. The highly textured graphitic films act as electrode and current collector and integrated with solid polymer electrolyte, function as thin film supercapacitors. The nanostructured electrode morphology and the conformal electrolyte packaging provide enough energy and power density for the devices in addition to excellent mechanical flexibility and optical transparency, making it a unique design in various power delivery applications.

Transparent, flexible supercapacitors from nano-engineered carbon films

PubMed Central

Jung, Hyun Young; Karimi, Majid B.; Hahm, Myung Gwan; Ajayan, Pulickel M.; Jung, Yung Joon

2012-01-01

Here we construct mechanically flexible and optically transparent thin film solid state supercapacitors by assembling nano-engineered carbon electrodes, prepared in porous templates, with morphology of interconnected arrays of complex shapes and porosity. The highly textured graphitic films act as electrode and current collector and integrated with solid polymer electrolyte, function as thin film supercapacitors. The nanostructured electrode morphology and the conformal electrolyte packaging provide enough energy and power density for the devices in addition to excellent mechanical flexibility and optical transparency, making it a unique design in various power delivery applications. PMID:23105970

Transparent, flexible supercapacitors from nano-engineered carbon films

NASA Astrophysics Data System (ADS)

Jung, Hyun Young; Karimi, Majid B.; Hahm, Myung Gwan; Ajayan, Pulickel M.; Jung, Yung Joon

2012-10-01

Here we construct mechanically flexible and optically transparent thin film solid state supercapacitors by assembling nano-engineered carbon electrodes, prepared in porous templates, with morphology of interconnected arrays of complex shapes and porosity. The highly textured graphitic films act as electrode and current collector and integrated with solid polymer electrolyte, function as thin film supercapacitors. The nanostructured electrode morphology and the conformal electrolyte packaging provide enough energy and power density for the devices in addition to excellent mechanical flexibility and optical transparency, making it a unique design in various power delivery applications.

Stack developments in a kW class all vanadium mixed acid redox flow battery at the Pacific Northwest National Laboratory

DOE PAGES

Reed, David M.; Thomsen, Edwin C.; Li, Bin; ...

2015-11-21

Over the past several years, efforts have been focused on improving the performance of kW class stacks with increasing current density. The influence of the Nafion membrane resistance, an interdigitated design to reduce the pressure drop in the electrolyte circuit, the temperature of the electrolyte, and the electrode structure will be discussed and correlated to the electrical performance. Furthermore, improvements to the stack energy efficiency and how those translate to the overall system efficiency will also be discussed.

Electrochemical synthesis of binary molybdenum-tungsten carbides (Mo,W)2C from tungstate-molybdate-carbonate melts

NASA Astrophysics Data System (ADS)

Kushkhov, Kh. B.; Kardanov, A. L.; Adamokova, M. N.

2013-02-01

Nanopowders of binary tungsten-molybdenum carbide are fabricated by high-temperature electrochemical synthesis. The optimum concentration relations between electrolyte components, the current density, and the quantity of electricity are determined to synthesize binary tungsten-molybdenum carbides.

Energy-density enhancement of carbon-nanotube-based supercapacitors with redox couple in organic electrolyte.

PubMed

Park, Jinwoo; Kim, Byungwoo; Yoo, Young-Eun; Chung, Haegeun; Kim, Woong

2014-11-26

We demonstrate for the first time that the incorporation of a redox-active molecule in an organic electrolyte can increase the cell voltage of a supercapacitor. The redox molecule also contributes to increasing the cell capacitance by a faradaic redox reaction, and therefore the energy density of the supercapacitor can be significantly increased. More specifically, the addition of redox-active decamethylferrocene in an organic electrolyte results in an approximately 27-fold increase in the energy density of carbon-nanotube-based supercapacitors. The resulting high energy density (36.8 Wh/kg) stems from the increased cell voltage (1.1 V→2.1 V) and cell capacitance (8.3 F/g→61.3 F/g) resulting from decamethylferrocene addition. We found that the voltage increase is associated with the potential of the redox species relative to the electrochemical stability window of the supporting electrolyte. These results will be useful in identifying new electrolytes for high-energy-density supercapacitors.

Influence of lead ions on the macromorphology of electrodeposited zinc

DOE Office of Scientific and Technical Information (OSTI.GOV)

Tsuda, Tetsuaki; Tobias, Charles W.

1981-09-01

The morphology of zinc as it is electrodeposited from acid solutions demonstrates a remarkable imprint of electrolyte flow conditions. The development of macromorphology of zinc deposits has been investigated under galvanostatic conditions on a rotating plantinum disk electrode by use of photomacrography, scanning electron microscopy, electron probe microanalysis and Auger microprobe analysis. Logarithmic spiral markings, which reflect the hydrodynamic flow on a rotating disk, appear in a certain region of current density well below the limiting current density. Morphological observations revealed the major influence of trace lead ions on the amplifications of surface roughness through coalescence and preferred growth ofmore » initial protrusions. Results obtained from ultra-pure electrolyte suggest preferred crystal growth towards well-mixed orientation in the concentration field caused by slight differences in crystallization overpotential. A qualitative model involving a coupling mechanism between the evolving surface roughness and instability phenomena in the boundary layer is advanced to explain the formation of spiral patterns.« less

Nano ZnO-activated carbon composite electrodes for supercapacitors

NASA Astrophysics Data System (ADS)

Selvakumar, M.; Krishna Bhat, D.; Manish Aggarwal, A.; Prahladh Iyer, S.; Sravani, G.

2010-05-01

A symmetrical (p/p) supercapacitor has been fabricated by making use of nanostructured zinc oxide (ZnO)-activated carbon (AC) composite electrodes for the first time. The composites have been characterized by field emission scanning electron microscopy (FESEM) and X-ray diffraction analysis (XRD). Electrochemical properties of the prepared nanocomposite electrodes and the supercapacitor have been studied using cyclic voltammetry (CV) and AC impedance spectroscopy in 0.1 M Na 2SO 4 as electrolyte. The ZnO-AC nanocomposite electrode showed a specific capacitance of 160 F/g for 1:1 composition. The specific capacitance of the electrodes decreased with increase in zinc oxide content. Galvanostatic charge-discharge measurements have been done at various current densities, namely 2, 4, 6 and 7 mA/cm 2. It has been found that the cells have excellent electrochemical reversibility and capacitive characteristics in 0.1 M Na 2SO 4 electrolyte. It has also been observed that the specific capacitance is constant up to 500 cycles at all current densities.

Treatment of oily wastewater of a gas refinery by electrocoagulation using aluminum electrodes.

PubMed

Saeedi, Mohesn; Khalvati-Fahlyani, Amin

2011-03-01

Oily wastewaters are the most important discharges of gas refineries from an environmental point-of-view. In the present study, treatment of gas refinery oily wastewater by electrocoagulation using aluminum electrodes was investigated. The effects of electrode distance, initial pH, sodium sulfate (Na2SO4) as a supporting electrolyte, polyaluminum chloride dosage as a coagulant aid, and current density on the efficiency of chemical oxygen demand (COD) removal were examined. The results revealed that the COD removal rate increases by applying more current density and polyaluminum chloride and, to a lesser extent, Na2SO4 dosage. The results also showed that 97% COD can be removed at optimum operational conditions. Specific electrical energy consumption could be reduced from 19.48 kWh (kg COD removal)(-1) to 11.057 kWh (kg COD removal)(-1) using Na2SO4 as a supporting electrolyte. Gas chromatographic analysis of raw and treated wastewater also revealed that most normal hydrocarbons (nearly 99%) were removed during the electrocoagulation process.

Facile electrodeposition of reduced graphene oxide hydrogels for high-performance supercapacitors

NASA Astrophysics Data System (ADS)

Pham, Viet Hung; Gebre, Tesfaye; Dickerson, James H.

2015-03-01

We report both a facile, scalable method to prepare reduced graphene oxide hydrogels through the electrodeposition of graphene oxide and its use as an electrode for high-performance supercapacitors. Such systems exhibited specific capacitances of 147 and 223 F g-1 at a current density of 10 A g-1 when using H2SO4 and H2SO4 + hydroquinone redox electrolytes, respectively.We report both a facile, scalable method to prepare reduced graphene oxide hydrogels through the electrodeposition of graphene oxide and its use as an electrode for high-performance supercapacitors. Such systems exhibited specific capacitances of 147 and 223 F g-1 at a current density of 10 A g-1 when using H2SO4 and H2SO4 + hydroquinone redox electrolytes, respectively. Electronic supplementary information (ESI) available: GO synthesis, characterization, fabrication of ERGO supercapacitor and electrochemical measurement, elemental composition, TGA and XRD of GO and ERGO. See DOI: 10.1039/c4nr07508k

Study on Self-start up of Polymer Electrolyte Fuel Cell Stack at Subzero Temperature

NASA Astrophysics Data System (ADS)

Shirato, Hiroyasu; Hoshina, Hideo; Yamakoshi, Yukiyasu; Tomita, Kazuhiko; Oka, Yoshiaki

This paper aims to boot up polymer electrolyte fuel cells at subzero temperature without energy from outside and compass the conditions. Visualization tests of water drainage and voltage-current density characteristics provided the selection of a serpentine type as a channel of a fuel cell separator for cold region. The successful start-up of the cell at subzero temperature requires suitable current densities corresponding to the ambient temperature since the lower the temperature is, the lower the cell voltage soon after the start-up is. Suitable amount of exhausted energy is also necessary for the successful self start-up. Humidification using potassium acetate 30 mass% solution provides increased impedance of the cell and inhibits the water freezing owing to its dispersal to the electrode compared to no humidification. A stack laminated 25 sheets of the serpentine type separators enables stabilized power generation at normal temperature. The stack is also bootable with no energy from outside at 263K.

Advances in the electrodeposition of aluminum from ionic liquid based electrolytes

NASA Astrophysics Data System (ADS)

Leadbetter, Kirt C.

Aluminum plating is of considerable technical and economic interest because it provides an eco-friendly substitute for cadmium coatings used on many military systems. However, cadmium has been determined to be a significant environmental safety and occupational health (ESOH) hazard because of its toxicity and carcinogenic nature. Furthermore, the cost of treating and disposing of generated wastes, which often contain cyanide, is costly and is becoming prohibitive in the face of increasingly stringent regulatory standards. The non-toxic alternative aluminum is equivalent or superior in performance to cadmium. In addition, it could serve to provide an alternative to hexavalent chromium coatings used on military systems for similar reasons to that of cadmium. Aluminum is a beneficial alternative in that it demonstrates self-healing corrosion resistance in the form of a tightly-bound, impervious oxide layer. A successfully plated layer would be serviceable over a wider temperature range, 925 °F for aluminum compared to 450 oF for cadmium. In addition, an aluminum layer can be anodized to make it non-conducting and colorable. In consideration of the plating process, aluminum cannot be deposited from aqueous solutions because of its reduction potential. Therefore, nonaqueous electrolytes are required for deposition. Currently, aluminum can be electrodeposited in nonaqueous processes that use hazardous chemicals such as toluene and pyrophoric aluminum alkyls. Electrodeposition from ionic liquids provides the potential for a safer method that could be easily scaled up for industrial application. The plating process could be performed at a lower temperature and higher current density than other commercially available aluminum electrodeposition processes; thus a reduced process cost could be possible. The current ionic liquid based electrolytes are more expensive; however production on a larger scale and a long electrolyte lifetime are associated with a reduction in price. Advancements of this nonaqueous aluminum plating process have the potential to lead to a novel and competitive commercial aluminum deposition process. In this investigation aluminum electrodeposition from ionic liquid based electrolytes onto steel, copper and magnesium substrates without conversion coatings or strike layers was evaluated in six different ionic liquid based electrolytes in two technical setups. Three of which are commercially available aluminum plating electrolytes, three of which, discussed in literature were created on site by research personnel in the laboratory. The three commercially available electrolytes were: 1-Butyl-3-methylimidazolium chloride ([BMIm]Cl) * 1.5 AlCl3 with proprietary additives from IoLiTec, 1-Ethyl-3-methylimidazolium chloride ([EMIm]Cl) * 1.5 AlCl3 with proprietary additives from IoLiTec, and BasionicsTM AL-02, an aluminum plating electrolyte containing [EMIm]Cl * 1.5 AlCl3 with additives from BASF. The three electrolytes created on site were based on the 1-ethyl-3-methylimidazolium chloride ionic liquid with added 1.5 AlCl3 and one with added sodium dodecyl sulfate. Small scale plating tests in a 25-mL plating cell were conducted to provide a comparative analysis of the six different electrolytes considered. From these investigations, two were chosen to be evaluated in a larger 1-liter plating cell; designed and constructed to provide a more realistic evaluation of plating parameters with selected electrolytes to better portray industrial electroplating conditions. The effect of current density (10-40 mA/cm 2), temperature (30-90° Celsius) and plating bath agitation on current efficiency, corrosion resistance by the ASTM B117 method, adhesion, microstructure, and chemical composition (evaluated with energy-dispersive x-ray spectroscopy) of the plated Al-layer was explored in both the 25-mL and 1-L plating cell investigations. In addition development of pre- and post-treatment processes for the metal substrates was attempted. While previous investigations focused on one or two of these topics, this research seeks to investigate all discussed phenomena and characteristics. Additionally, there is little research that reports on the adhesion performance of aluminum coatings from ionic liquids. Also, corrosion investigations are limited to all but a few publications. So too, the deposition of aluminum in a larger, more realistic plating cell has never been thoroughly investigated. This is key if a practical application of the technology is ever to be realized. In sum, correlations were drawn between electrolyte, current density, temperature and bath agitation with quality and characteristic of electrodeposited aluminum layers. The overriding goal to create an acceptably competitive aluminum coating process to replace cadmium and compete with other commercial aluminum deposition processes was not successful. Competitiveness was evaluated as per the discussed characteristics and so also, by a comparison to physical samples created in a more realistic plating cell to AlumiPlate aluminum coatings.

Allotropic control: How certain fluorinated carbonate electrolytes protect aluminum current collectors by promoting the formation of insoluble coordination polymers

DOE PAGES

Shkrob, Ilya A.; Pupek, Krzysztof Z.; Abraham, Daniel P.

2016-07-28

Here, there is a strong incentive for increasing the operation voltage of Li-ion cells above 4.5 V in order to increase the density of stored energy. Aluminum is an inexpensive, lightweight metal that is commonly used as a positive electrode current collector in these cells. Imide LiX salts, such as lithium bis(trifluoromethylsulfonyl)imide (X = TFSI), and lithium bis(fluorosulfonyl)imide (X = FSI), are chemically stable on the energized lithiated transition metal oxide electrodes, but their presence in the electrolyte causes rapid anodic dissolution and pitting of Al current collectors at potentials exceeding 4.0 V versus Li/Li +. For LiBF 4 andmore » LiPF 6, the release of HF near the energized surfaces passivates the exposed Al metal, inhibiting this pitting corrosion, but it also causes the gradual degradation of the cathode active material, negating this important advantage. Here we report that in certain electrolytes containing fluorinated carbonate solvents and LiX salts, the threshold voltage for safe operation of Al current collectors can be increased to 5.5 V versus Li/Li +. Interestingly, the most efficient solvent also facilitates the formation of an insoluble gel when AlX 3 is introduced into this solvent. We suggest that this solvent promotes the aggregation of coordination polymers of AlX 3 at the exposed Al surface that isolate this surface from the electrolyte, thereby preventing further Al dissolution and corrosion. Other examples of Al collector protection may also involve this mechanism. Our study suggests that such “allotropic control” could be a way of widening the operation window of Li-ion cells without electrode deterioration, Al current collector corrosion, and electrolyte breakdown.« less

Allotropic control: How certain fluorinated carbonate electrolytes protect aluminum current collectors by promoting the formation of insoluble coordination polymers

DOE Office of Scientific and Technical Information (OSTI.GOV)

Shkrob, Ilya A.; Pupek, Krzysztof Z.; Abraham, Daniel P.

Here, there is a strong incentive for increasing the operation voltage of Li-ion cells above 4.5 V in order to increase the density of stored energy. Aluminum is an inexpensive, lightweight metal that is commonly used as a positive electrode current collector in these cells. Imide LiX salts, such as lithium bis(trifluoromethylsulfonyl)imide (X = TFSI), and lithium bis(fluorosulfonyl)imide (X = FSI), are chemically stable on the energized lithiated transition metal oxide electrodes, but their presence in the electrolyte causes rapid anodic dissolution and pitting of Al current collectors at potentials exceeding 4.0 V versus Li/Li +. For LiBF 4 andmore » LiPF 6, the release of HF near the energized surfaces passivates the exposed Al metal, inhibiting this pitting corrosion, but it also causes the gradual degradation of the cathode active material, negating this important advantage. Here we report that in certain electrolytes containing fluorinated carbonate solvents and LiX salts, the threshold voltage for safe operation of Al current collectors can be increased to 5.5 V versus Li/Li +. Interestingly, the most efficient solvent also facilitates the formation of an insoluble gel when AlX 3 is introduced into this solvent. We suggest that this solvent promotes the aggregation of coordination polymers of AlX 3 at the exposed Al surface that isolate this surface from the electrolyte, thereby preventing further Al dissolution and corrosion. Other examples of Al collector protection may also involve this mechanism. Our study suggests that such “allotropic control” could be a way of widening the operation window of Li-ion cells without electrode deterioration, Al current collector corrosion, and electrolyte breakdown.« less

Ionic Liquid Catalyzed Electrolyte for Electrochemical Polyaniline Supercapacitors

NASA Astrophysics Data System (ADS)

Inamdar, A. I.; Im, Hyunsik; Jung, Woong; Kim, Hyungsang; Kim, Byungchul; Yu, Kook-Hyun; Kim, Jin-Sang; Hwang, Sung-Min

2013-05-01

The effect of different wt.% of ionic liquid "1,6-bis (trimethylammonium-1-yl) hexane tetrafluoroborate" in 0.5 M LiClO4+PC electrolyte on the supercapacitor properties of polyaniline (PANI) thin film are investigated. The PANI film is synthesized using electropolymerization of aniline in the presence of sulfuric acid. The electrochemical properties of the PANI thin film are studied by cyclic voltammetry, galvanostatic charge-discharge and electrochemical impedance spectroscopy (EIS) measurements. The optimum amount of the ionic liquid is found to be 2 wt.% which provides better ionic conductivity of the electrolyte. The highest specific capacitance of 259 F/g is obtained using the 2 wt.% electrolyte. This capacitance remains at up to 208 F/g (80% capacity retention) after 1000 charge-discharge cycles at a current density of 0.5 mA/g. The PANI film in the 2 wt.% ionic liquid catalyzed 0.5 M LiClO4+PC electrolyte shows small electrochemical resistance, better rate performance and higher cyclability. The increased ionic conductivity of the 2 wt.% ionic liquid catalyzed electrolyte causes a reduction in resistance at the electrode/electrolyte interface, which can be useful in electrochemically-preferred power devices for better applicability.

Evaluation of double-layer density modulated Si thin films as Li-ion battery anodes

NASA Astrophysics Data System (ADS)

Taha Demirkan, Muhammed; Yurukcu, Mesut; Dursun, Burcu; Demir-Cakan, Rezan; Karabacak, Tansel

2017-10-01

Double-layer density modulated silicon thin films which contain alternating low and high density Si film layers were fabricated by magnetron sputtering. Two different samples consisting of alternating layers of high-density/low-density and low-density/high-density Si thin film layers were investigated as anode electrodes in Li-ion batteries. Si thin film in which the terminating layer at the top is low density Si layer-quoted as low-density/high-density film (LD/HD)- exhibits better performance than Si thin film that has high density layer at the top, -quoted as high-density/low-density (HD/LD). A highly stabilized cycling performance with the specific charge capacities of 2000 mAh g-1 at the 150th cycle at C/2 current density, and 1200 mAh g-1 at the 240th cycle at 10 C current density were observed for the LD/HD Si anode in the presence of fluoroethylene carbonate (FEC) electrolyte additive.

The electrochemical oxide growth behaviour on titanium in acid and alkaline electrolytes.

PubMed

Sul, Y T; Johansson, C B; Jeong, Y; Albrektsson, T

2001-06-01

Titanium implants have a thin oxide surface layer. The properties of this oxide layer may explain the good biocompatibility of titanium implants. Anodic oxidation results in a thickening of the oxide film, with possible improved biocompatability of anodized implants. The aim of the present study was twofold: (1) firstly, to characterize the growth behaviour of galvanostatically prepared anodic oxide films on commercially pure (c.p.) titanium and (2) secondly, to establish a better understanding of the electroche0mical growth behaviour of anodic oxide on commercially pure titanium (ASTM grade 1) after changes of the electrochemical parameters in acetic acid, phosphoric acid, calcium hydroxide, and sodium hydroxide under galvanostatic anodizing mode. The oxide thickness was measured by Ar sputter etching in Auger Electron spectroscopy (AES) and the colours were estimated by an L*a*b* system (lightness, hue and saturation) using a spectrophotometer. In the first part of our study, it was demonstrated that the interference colours were useful to identify the thickness of titanium oxide. It was also found that the anodic forming voltages with slope (dV/dt) in acid electrolytes were higher than in alkaline electrolytes. Each of the used electrolytes demonstrates an intrinsically specific growth constant (nm/V) in the range of 1.4--2.78 nm/V. In the second part of our study we found, as a general trend, that an increase of electrolyte concentration and electrolyte temperature respectively decreases the anodic forming voltage, the anodic forming rate (nm/s) and the current efficiency (nm.cm(2)/C), while an increase of the current density and the surface area ratio of the anode to cathode increase the anodic forming voltage, the anodic forming rate and the current efficiency. The effects of electrolyte concentration, electrolyte temperature, and agitation speed were explained on the basis of the model of the electrical double layer.

Borohydride electro-oxidation in a molten alkali hydroxide eutectic mixture and a novel borohydride-periodate battery

NASA Astrophysics Data System (ADS)

Wang, Andrew; Gyenge, Előd L.

2015-05-01

The electrochemical oxidation of BH4- in a molten NaOH-KOH eutectic mixture (0.515:0.485 mole fractions), is investigated for the first time by cyclic voltammetry and electrochemical impedance spectroscopy. Anodically oxidized Ni is electrocatalytically more active than Pt for BH4- oxidation in the molten alkali electrolyte as shown by the more than three times higher exchange current density (i.e. 15.8 mA cm-2 vs. 4.6 mA cm-2 at 185 °C). Next the proof-of-concept for a novel BH4-/IO4- molten alkali electrolyte battery is presented. Using oxidized Ni mesh anode and Pt mesh cathode a maximum power density of 63 mW cm-2 is achieved at 185 °C.

Fabrication of titanium dioxide nanotube arrays using organic electrolytes

NASA Astrophysics Data System (ADS)

Yoriya, Sorachon

This dissertation focuses on fabrication and improvement of morphological features of TiO2 nanotube arrays in the selected organic electrolytes including dimethyl sulfoxide (DMSO; see Chapter 4) and diethylene glycol (DEG; see Chapter 5). Using a polar dimethyl sulfoxide containing hydrofluoric acid, the vertically oriented TiO2 nanotube arrays with well controlled morphologies, i.e. tube lengths ranging from few microns up to 101 microm, pore diameters from 100 nm to 150 nm, and wall thicknesses from 15 nm to 50 nm were achieved. Various anodization variables including fluoride ion concentration, voltage, anodization time, water content, and reuse of the anodized electrolyte could be manipulated under proper conditions to control the nanotube array morphology. Anodization current behaviors associated with evolution of nanotube length were analyzed in order to clarify and better understand the formation mechanism of nanotubes grown in the organic electrolytes. Typically observed for DMSO electrolyte, the behavior that anodization current density gradually decreases with time is a reflection of a constant growth rate of nanotube arrays. Large fluctuation of anodization current was significantly observed probably due to the large change in electrolyte properties during anodization, when anodizing in high conductivity electrolytes such as using high HF concentration and reusing the anodized electrolyte as a second time. It is believed that the electrolyte properties such as conductivity and polarity play important role in affecting ion solvation and interactions in the solution consequently determining the formation of oxide film. Fabrication of the TiO2 nanotube array films was extended to study in the more viscous diethylene glycol (DEG) electrolyte. The arrayed nanotubes achieved from DEG electrolytes containing either HF or NH4 F are fully separated, freely self-standing structure with open pores and a wide variation of tube-to-tube spacing ranging from < 100 nm to ~2 microm. In comparison to DMSO electrolyte, the electrochemical anodization rates are relatively slower in DEG electrolyte; as a result, the nanotube length is typically less than 10 microm. Pore size of nanotubes grown in DEG has been extended from 150 nm up to approximately 400 nm. The approach to pore widening could be achieved by using a specific condition of low HF concentration and prolonged anodization time. The study of evolution of nanotubes grown in DEG electrolytes showed that a fibrous layer was formed in the early growth stages and then was chemically and gradually removed after a long duration, leaving behind the nanotubes with large pore size. In DEG electrolyte, the closer spacing between Ti and Pt electrodes resulted in the larger nanotube morphological parameters due to the enhanced electrode kinetics facilitating the electrode reactions. Furthermore, this dissertation showed possibilities to crystallize the titania nanotube array films at room temperature via anodization in either DMSO or DEG electrolytes. The partially crystallized films could be achieved specifically in the optimum slow growth process conditions. Due to partial crystallization of the as-anodized samples, the high temperature annealing study revealed that the temperatures of phase transformation are 260 ºC and 430°C for respectively amorphous to anatase and anatase to rutile, which are accounted as the lowest phase transformation temperatures reported to date (2010). Finally, the photoelectrochemical properties of the DMSO fabricated nanotubes were investigated. The maximum photocurrent density of ~ 11 mA cm--2 was achieved by using the 46-microm long nanotube array sample with completely open pores, and photoconversion efficiencies of 5.425 % (+/- 0.087) (under UV light) and 0.197 % (+/- 0.001) (under solar spectrum AM 1.5) have been demonstrated. Biomedical applications of the DEG fabricated nanotube arrays films such as blood clotting, hemocompatibility, and drug delivery were investigated. The titania nanotube arrays showed a significant platelet adhesion and activation, a higher viability, and a greater capability in blood clotting compared to a smooth Ti surface. In drug delivery application, the drug elution kinetics, behavior and diffusion of drug molecules were most profoundly affected by the nanotube architectures such as the pore packing density and the gap or separation between the tubes, the nanotube length, and especially the nanotube pore diameter. (Abstract shortened by UMI.)

Zn/gelled 6 M KOH/O 2 zinc-air battery

NASA Astrophysics Data System (ADS)

Mohamad, A. A.

The gel electrolyte for the zinc-air cell was prepared by mixing hydroponics gel with a 6 M potassium hydroxide aqueous solution. The self-discharge of cells was characterized by measuring the open-circuit voltage. The effect of a discharge rate of 50 mA constant current on cell voltage and plateau hour, as well as the voltage-current and current density-power density were measured and analysed. The electrode degradation after discharge cycling was characterized by structural and surface methods. The oxidation of the electrode surface further blocked the utilization of the Zn anode and was identified as a cause for the failure of the cell.

Electrochemical treatment of anti-cancer drug carboplatin on mixed-metal oxides and boron doped diamond electrodes: Density functional theory modelling and toxicity evaluation.

PubMed

Barışçı, Sibel; Turkay, Ozge; Ulusoy, Ebru; Soydemir, Gülfem; Seker, Mine Gul; Dimoglo, Anatoli

2018-02-15

This study represents the electrooxidation of anti-cancer drug carboplatin (CrbPt) with different mixed metal oxide (MMO) and boron doped diamond (BDD) electrodes. The most effective anode was found as Ti/RuO 2 with the complete degradation of CrbPt in just 5min. The effect of applied current density, pH and electrolyte concentration on CrbPt degradation has been studied. The degradation of CrbPt significantly increased at the initial stages of the process with increasing current density. However, further increase in current density did not affect the degradation rate. While complete degradation of CrbPt was provided at pH 7, the degradation rates were 49% and 75% at pH 9 and 4, respectively. Besides, increasing supporting electrolyte (Na 2 SO 4 ) concentration provided higher degradation rate but further increase in Na 2 SO 4 concentration did not provide higher degradation rate due to excess amount of SO 4 -2 . According to the DFT calculations, the formation of [Pt(NH 3 ) 2 (H 2 O) 2 ] 2+ and [Pt(NH 3 ) 2 (OH) 2 ] takes place with molecular weights of 265 and 263gmol -1 , respectively. Toxicity of treated samples at BDD and Ti/RuO 2 electrodes has been also evaluated in this study. The results showed that Ti/RuO 2 anode provided zero toxicity at the end of the process. Copyright © 2017 Elsevier B.V. All rights reserved.

Mechanistic Study of Electrolyte Additives to Stabilize High-Voltage Cathode–Electrolyte Interface in Lithium-Ion Batteries

DOE Office of Scientific and Technical Information (OSTI.GOV)

Gao, Han; Maglia, Filippo; Lamp, Peter

Current developments of electrolyte additives to stabilize electrode-electrolyte interface in Li-ion batteries highly rely on a trial-and-error search, which involves repetitive testing and intensive amount of resources. The lack of understandings on the fundamental protection mechanisms of the additives significantly increases the difficulty for the transformational development of new additives. In this study, we investigated two types of individual protection routes to build a robust cathode-electrolyte interphase at high potentials: (i) a direct reduction in the catalytic decomposition of the electrolyte solvent; and (ii) formation of a “corrosion inhibitor film” that prevents severely attack and passivation from protons that generatedmore » from the solvent oxidation, even the decomposition of solvent cannot not mitigated. Effect of three exemplary electrolyte additives: (i) lithium difluoro(oxalato)borate (LiDFOB); (ii) 3-hexylthiophene (3HT); and (iii) tris(hexafluoro-iso-propyl)phosphate (HFiP), on LiNi0.6Mn0.2Co0.2O2 (NMC 622) cathode were investigated to validate our hypothesis. It is demonstrated that understandings of both electrolyte additives and solvent are essential and careful balance between the cathode protection mechanism of additives and their side effects is critical to obtain optimum results. More importantly, this study opens up new directions of rational design of functional electrolyte additives for the next generation high-energy density lithium-ion chemistries.« less

Facile preparation of graphene by high-temperature electrolysis and its application in supercapacitor.

PubMed

Jiao, Chen-Xu; Xing, Bao-Yan; Zhao, Jian-Guo; Geng, Yu; Li, Zuo-Peng

2014-01-01

Graphene is well known owing to its astonishing properties: stronger than diamond, more conductive than copper and more flexible than rubber. Because of its potential uses in industry, researchers have been searching for less toxicity ways to make graphene in large amount with lower cost. We demonstrated an efficient method to prepare graphene by high temperature electrolysis technique. High resolution scanning electron microscopy and raman spectroscopy were used to characterize the microstructure of graphene. Graphene was assembled into the supercapacitor and its performance of electrochemical capacitor was investigated by constant current charge and discharge, cyclic voltammetry and AC impedance. The results showed that the micro-morphology of the prepared graphene was multilayer and it was favorable when the electrolytic voltage was 1.5 V. When the current density is 1 mA/cm(2), the specific capacitance of the graphene supercapacitor can reach 78.01 F/g in 6 mol/L KOH electrolyte, which was an increase of 114% compared with 36.43 F/g of conventional KOH electrolyte.

Nickel electroplating on copper pre-activated Al alloy in the electrolyte containing PEG1000 as an additive

NASA Astrophysics Data System (ADS)

Guan, Jie; Wang, Jinwei; Zhang, Dawei

2018-06-01

Ni coatings are prepared on Cu-pretreated anodic Al alloy by electroplating technique in environment-friendly electrolytes with PEG1000 as an additive. Some defects like pores, cracks and even uncovered areas are observed for the sample of the Cu-pretreated anodic Al alloy, and these defects seem to be remedied with the following Ni electroplating as observed from their SEM images; while the covering effect of Ni onto the Cu layer is rather limited as judged by their corrosion current data of polarization test. After adding PEG1000 in the Ni electroplating electrolyte, the obtained coating surfaces are seen smoother and thicker; and most of the tiny particles are seen closely packed together with some bigger particles on them. The diffusion of nickel particles into copper layer are confirmed by the line and mapping mode of EDS element analysis for the Ni-Cu composite coating. Their much lower corrosion current density ( I corr) and higher micro-hardness support the fact that the addition of PEG1000 in Ni plating electrolyte has a function of promoting the refinement of Ni particles and the formation of more compacter, thicker and smoother Ni-Cu composite coating.

ELECTRODEPOSITION OF PLUTONIUM

DOEpatents

Wolter, F.J.

1957-09-10

A process of electrolytically recovering plutonium from dilute aqueous solutions containing plutonium ions comprises electrolyzing the solution at a current density of about 0.44 ampere per square centimeter in the presence of an acetate-sulfate buffer while maintaining the pH of the solution at substantially 5 and using a stirred mercury cathode.

Decorating Graphene Oxide with Ionic Liquid Nanodroplets: An Approach Leading to Energy-Dense, High-Voltage Supercapacitors.

PubMed

She, Zimin; Ghosh, Debasis; Pope, Michael A

2017-10-24

A major stumbling block in the development of high energy density graphene-based supercapacitors has been maintaining high ion-accessible surface area combined with high electrode density. Herein, we develop an ionic liquid (IL)-surfactant microemulsion system that is found to facilitate the spontaneous adsorption of IL-filled micelles onto graphene oxide (GO). This adsorption distributes the IL over all available surface area and provides an aqueous formulation that can be slurry cast onto current collectors, leaving behind a dense nanocomposite film of GO/IL/surfactant. By removing the surfactant and reducing the GO through a low-temperature (360 °C) heat treatment, the IL plays a dual role of spacer and electrolyte. We study the effect of IL content and operating temperature on the performance, demonstrating a record high gravimetric capacitance (302 F/g at 1 A/g) for 80 wt % IL composites. At 60 wt % IL, combined high capacitance and bulk density (0.76 g/cm 3 ), yields one of the highest volumetric capacitances (218 F/cm 3 , at 1 A/g) ever reported for a high-voltage IL-based supercapacitor. While achieving promising rate performance and cycle-life, the approach also eliminates the long and costly electrolyte imbibition step of cell assembly as the electrolyte is cast directly with the electrode material.

Synthesis of and characterization of lithium ceramic electrolytes

NASA Astrophysics Data System (ADS)

Rangasamy, Ezhiylmurugan

The depleting fossil fuel reserves, rising oil prices and the need for reduction in CO2 emissions have created an unprecedented impetus for vehicle electrification. Lithium batteries have the highest energy density of the various available battery technologies. They are the most promising battery candidate to enable Hybrid Electric Vehicles (HEVs) and Plug-in Electric Vehicles (PEVs). However, current Li-ion current battery technology is costly and requires a significant increase in energy density to achieve range comparable to conventional gasoline-powered vehicles. Advanced lithium battery technologies such as Li-S and Li-O2 could potentially offer significant improvements in energy density to address the limitations with current Li-ion technology. The implementation of these advanced battery technologies, however, has been limited by the lack of electrolyte technology to enable the use of metallic lithium anodes. Thus, there is a clear and compelling need to develop new electrolyte materials that exhibit the unique combination of fast ion conductivity, stability against lithium, air and moisture. Lithium Lanthanum Titanium Oxide (LLTO) and Lithium Lanthanum Zirconium Oxide (LLZO) have been identified as viable candidates for the advanced battery technologies. However, issues concerning phase purity and densification warrant developing new and novel synthetic techniques. A single step procedure has been developed for the synthesis of Lithium Lanthanum Titanium Oxide (LLTO) membranes. The single step procedure combines phase formation and densification of the ceramic electrolyte in a hot pressing technique. The effect of synthetic technique on relative density, grain structure and ionic conductivity of the LLTO membranes has been explored in detail. The critical step of synthesizing cubic Lithium Lanthanum Zirconium Oxide (LLZO) has been systematically studied through the controlled doping of Al, using X-Ray Diffraction (XRD) analysis. Effects of Li and Al concentration on the crystal structure of LLZO were also studied in detail. Critical dopant concentration of Al to stabilize cubic LLZO was established during the course of this study. Systematic doping studies on the 24c site of La3+ in the primary lattice have also been explored in detail using XRD analysis to improve the ionic conductivity by maintaining the Li sub-lattice free of dopants. It is hypothesized that the supervalent substitutions create Li vacancies in the sub-lattice promoting disorder, thereby stabilizing cubic LLZO. While Ce4+ substitution for La3+ proved to be effective in synthesizing cubic LLZO, precipitation of Ce4+ observed under Backscattered electron (BSE) imaging limited its ionic conductivity. In an effort to develop flexible, solution-based synthetic techniques, two novel processes were established to prepare low dimensional, cubic LLZO powders. Hot pressing of the synthesized LLZO samples yielded high relative density (>95%) ceramic electrolyte membranes. Arrhenius studies using EIS to measure activation energy revealed and empirical relationship between the grain size and activation energy for dense LLZO membranes.

Current status of solid-state lithium batteries employing solid redox polymerization cathodes

NASA Astrophysics Data System (ADS)

Visco, S. J.; Doeff, M. M.; Dejonghe, L. C.

1991-03-01

The rapidly growing demand for secondary batteries having high specific energy and power has naturally led to increased efforts in lithium battery technology. Still, the increased safety risks associated with high energy density systems has tempered the enthusiasm of proponents of such systems for use in the consumer marketplace. The inherent advantages of all-solid-state batteries in regards to safety and reliability are strong factors in advocating their introduction to the marketplace. However, the low ionic conductivity of solid electrolytes relative to nonaqueous liquid electrolytes implies low power densities for solid state systems operating at ambient temperatures. Recent advances in polymer electrolytes have led to the introduction of solid electrolytes having conductivities in the range of 10(exp -4)/ohm cm at room temperature; this is still two orders of magnitude lower than liquid electrolytes. Although these improved ambient conductivities put solid state batteries in the realm of practical devices, it is clear that solid state batteries using such polymeric separators will be thin film devices. Fortunately, thin film fabrication techniques are well established in the plastics and paper industry, and present the possibility of continuous web-form manufacturing. This style of battery manufacture should make solid polymer batteries very cost-competitive with conventional secondary cells. In addition, the greater geometric flexibility of thin film solid state cells should provide benefits in terms of the end-use form factor in device design. This work discusses the status of solid redox polymerization cathodes.

Influence of anodization parameters on the morphology of TiO 2 nanotube arrays

NASA Astrophysics Data System (ADS)

Omidvar, Hamid; Goodarzi, Saba; Seif, Ahmad; Azadmehr, Amir R.

2011-07-01

TiO 2 nanotube arrays can be fabricated by electrochemical anodization in organic and inorganic electrolytes. Morphology of these nanotube arrays changes when anodization parameters such as applied voltage, type of electrolyte, time and temperature are varied. Nanotube arrays fabricated by anodization of commercial titanium in electrolytes containing NH 4F solution and either sulfuric or phosphoric acid were studied at room temperature; time of anodization was kept constant. Applied voltage, fluoride ion concentration, and acid concentrations were varied and their influences on TiO 2 nanotubes were investigated. The current density of anodizing was recorded by computer controlled digital multimeter. The surface morphology (top-view) of nanotube arrays were observed by SEM. The nanotube arrays in this study have inner diameters in range of 40-80 nm.

The contribution of mediated oxidation mechanisms in the electrolytic degradation of cyanuric acid using diamond anodes.

PubMed

Bensalah, Nasr; Dbira, Sondos; Bedoui, Ahmed

2016-07-01

In this work, the contribution of mediated oxidation mechanisms in the electrolytic degradation of cyanuric acid using boron-doped diamond (BDD) anodes was investigated in different electrolytes. A complete mineralization of cyanuric acid was obtained in NaCl; however lower degrees of mineralization of 70% and 40% were obtained in Na2SO4 and NaClO4, respectively. This can be explained by the nature of the oxidants electrogenerated in each electrolyte. It is clear that the contribution of active chlorine (Cl2, HClO, ClO(-)) electrogenerated from oxidation of chlorides on BDD is much more important in the electrolytic degradation of cyanuric acid than the persulfate and hydroxyl radicals produced by electro-oxidation of sulfate and water on BDD anodes. This could be explained by the high affinity of active chlorine towards nitrogen compounds. No organic intermediates were detected during the electrolytic degradation of cyanuric acid in any the electrolytes, which can be explained by their immediate depletion by hydroxyl radicals produced on the BDD surface. Nitrates and ammonium were the final products of electrolytic degradation of cyanuric acid on BDD anodes in all electrolytes. In addition, small amounts of chloramines were formed in the chloride medium. Low current density (≤10mA/cm(2)) and neutral medium (pH in the range 6-9) should be used for high efficiency electrolytic degradation and negligible formation of hazardous chlorate and perchlorate. Copyright © 2016. Published by Elsevier B.V.

All-Fullerene-Based Cells for Nonaqueous Redox Flow Batteries.

PubMed

Friedl, Jochen; Lebedeva, Maria A; Porfyrakis, Kyriakos; Stimming, Ulrich; Chamberlain, Thomas W

2018-01-10

Redox flow batteries have the potential to revolutionize our use of intermittent sustainable energy sources such as solar and wind power by storing the energy in liquid electrolytes. Our concept study utilizes a novel electrolyte system, exploiting derivatized fullerenes as both anolyte and catholyte species in a series of battery cells, including a symmetric, single species system which alleviates the common problem of membrane crossover. The prototype multielectron system, utilizing molecular based charge carriers, made from inexpensive, abundant, and sustainable materials, principally, C and Fe, demonstrates remarkable current and energy densities and promising long-term cycling stability.

Electrocatalytic performances of LaNi1-xMgxO3 perovskite oxides as bi-functional catalysts for lithium air batteries

NASA Astrophysics Data System (ADS)

Du, Zhenzhen; Yang, Peng; Wang, Long; Lu, Yuhao; Goodenough, J. B.; Zhang, Jian; Zhang, Dawei

2014-11-01

Mg-doped perovskite oxides LaNi1-xMgxO3 (x = 0, 0.08, 0.15) electrocatalysts are synthesized by a sol-gel method using citric acid as complex agent and ethylene glycol as thickening agent. The intrinsic oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) activity of as-prepared perovskite oxides in aqueous electrolyte are examined on a rotating disk electrode (RDE) set up. Li-air primary batteries on the basis of Mg-doped perovskite oxides LaNi1-xMgxO3 (x = 0, 0.08, 0.15) and nonaqueous electrolyte are also fabricated and tested. In terms of the ORR current densities and OER current densities, the performance is enhanced in the order of LaNiO3, LaNi0.92Mg0.08O3 and LaNi0.85Mg0.15O3. Most notably, partially substituting nickel with magnesium suppresses formation of Ni2+ and ensures high concentration of both OER and ORR reaction energy favorable Ni3+ (eg = 1) on the surface of perovskite catalysts. Nonaqueous Li-air primary battery using LaNi0.92Mg0.08O3 and LaNi0.85Mg0.15O3 as the cathode catalysts exhibit improved performances compared with LaNiO3 catalyst, which are consistent with the ORR current densities.

Complexing agent and heavy metal removals from metal plating effluent by electrocoagulation with stainless steel electrodes.

PubMed

Kabdaşli, Işik; Arslan, Tülin; Olmez-Hanci, Tuğba; Arslan-Alaton, Idil; Tünay, Olcay

2009-06-15

In the present study, the treatability of a metal plating wastewater containing complexed metals originating from the nickel and zinc plating process by electrocoagulation using stainless steel electrodes was experimentally investigated. The study focused on the effect of important operation parameters on electrocoagulation process performance in terms of organic complex former, nickel and zinc removals as well as sludge production and specific energy consumption. The results indicated that increasing the applied current density from 2.25 to 9.0 mA/cm(2) appreciably enhanced TOC removal efficiency from 20% to 66%, but a further increase in the applied current density to 56.25 mA/cm(2) did not accelerate TOC removal rates. Electrolyte concentration did not affect the process performance significantly and the highest TOC reduction (66%) accompanied with complete heavy metal removals were achieved at the original chloride content ( approximately 1500 mg Cl/L) of the wastewater sample. Nickel removal performance was adversely affected by the decrease of initial pH from its original value of 6. Optimum working conditions for electrocoagulation of metal plating effluent were established as follows: an applied current density of 9 mA/cm(2), the effluent's original electrolyte concentration and pH of the composite sample. TOC removal rates obtained for all electrocoagulation runs fitted pseudo-first-order kinetics very well (R(2)>92-99).

Sulfone-carbonate ternary electrolyte with further increased capacity retention and burn resistance for high voltage lithium ion batteries

NASA Astrophysics Data System (ADS)

Xue, Leigang; Lee, Seung-Yul; Zhao, Zuofeng; Angell, C. Austen

2015-11-01

Safety and high energy density are the two focus issues for current lithium ion batteries. For safety, it has been demonstrated that sulfone electrolytes are much less flammable than the prevailing all-carbonate type, and they are also promising for high voltage batteries due to the high oxidization resistance. However, the high melting points and viscosities greatly restricted their application. Based on our previous work on use of fluidity-enhancing cosolvents to make binary sulfone-carbonate electrolytes, we report here a three-component system that is more conductive and should be even less flammable while additionally having better low temperature stability. The conductivity-viscosity relations have been determined for this electrolyte and are comparable to those of the "standard" carbonate electrolyte. The additional component also produces much improved capacity retention for the LiNi0.5Mn1.5O4 cathode. As with carbonate electrolytes, increase of temperature to 55 °C leads to rapid capacity decrease during cycling, but the capacity loss is due to the salt, not the solvent. The high discharge capacity observed at 25 °C when LiBF4 replaces LiPF6, is fully retained at 55 °C.

Restricting the Solubility of Polysulfides in Li-S Batteries Via Electrolyte Salt Selection

DOE Office of Scientific and Technical Information (OSTI.GOV)

Chen, Junzheng; Han, Kee Sung; Henderson, Wesley A.

2016-03-29

Polysulfide solubility in the electrolyte has a critical role to the Li-S battery but the mechanism study on the solubility needs to be carefully carried out. In this paper we found that lithium 2-trifluoromethyl-4,5-dicyanoimidazole (LiTDI) reveals a suppression of the polysulfide solubility in electrolytes (relative to the most widely used electrolyte formulation) and the Li-S cells achieved homogeneous stable capacity retention upon extensive cycling and Li metal deposition on the anode. Combined experimental, simulation and calculation methods suggest the dominate disproportionation product of Li2S8 is Li2S4 in the LiTDI electrolyte due to a different interaction between lithium ion and TDImore » anion. The Li2S4 would continuesly form a Li4S8 dimer and be fully locallized to precipitate out. The use of the electrolyte with the LiTDI salt (with polysulfide and LiNO3 additives) enabled a cell with a high sulfur (3 mg-S cm-2) loading to deliver a 1.67 mAh cm-2 areal capacity after 300 stable cycles at a high current (2.4 mA cm-2) density.« less

Electrolytic treatment of Standard Malaysian Rubber process wastewater.

PubMed

Vijayaraghavan, Krishnan; Ahmad, Desa; Yazid, Ahmad Yuzri Ahmad

2008-01-31

A new method of Standard Malaysian Rubber (SMR) process wastewater treatment was developed based on in situ hypochlorous acid generation. The hypochlorous acid was generated in an undivided electrolytic cell consisting of two sets of graphite as anode and stainless sheets as cathode. The generated hypochlorous acid served as an oxidizing agent to destroy the organic matter present in the SMR wastewater. For an influent COD concentration of 2960 mg/L at an initial pH 4.5+/-0.1, current density 74.5 mA/cm(2), sodium chloride content 3% and electrolysis period of 75 min, resulted in the following residual values pH 7.5, COD 87 mg/L, BOD(5) 60 mg/L, TOC 65 mg/L, total chlorine 146 mg/L, turbidity 7 NTU and temperature 48 degrees C, respectively. In the case of 2% sodium chloride as an electrolyte for the above said operating condition resulted in the following values namely: pH 7.2, COD 165 mg/L, BOD(5) 105 mg/L, TOC 120 mg/L, total chlorine 120 mg/L, turbidity 27 NTU and temperature 53 degrees C, respectively. The energy requirement were found to be 30 and 46 Wh/L, while treating 24 L of SMR wastewater at 2 and 3% sodium chloride concentration at a current density 74.5 mA/cm(2). The observed energy difference was due to the improved conductivity at high sodium chloride content.

Poly(vinyl Alcohol) Borate Gel Polymer Electrolytes Prepared by Electrodeposition and Their Application in Electrochemical Supercapacitors.

PubMed

Jiang, Mengjin; Zhu, Jiadeng; Chen, Chen; Lu, Yao; Ge, Yeqian; Zhang, Xiangwu

2016-02-10

Gel polymer electrolytes (GPEs) have been studied for preparing flexible and compact electrochemical energy storage devices. However, the preparation and use of GPEs are complex, and most GPEs prepared through traditional methods do not have good wettability with the electrodes, which retard them from achieving their performance potential. In this study, these problems are addressed by conceiving and implementing a simple, but effective, method of electrodepositing poly(vinyl alcohol) potassium borate (PVAPB) GPEs directly onto the surfaces of active carbon electrodes for electrochemical supercapacitors. PVAPB GPEs serve as both the electrolyte and the separator in the assembled supercapacitors, and their scale and shape are determined solely by the geometry of the electrodes. PVAPB GPEs have good bonding to the active electrode materials, leading to excellent and stable electrochemical performance of the supercapacitors. The electrochemical performance of PVAPB GPEs and supercapacitors can be manipulated simply by adjusting the concentration of KCl salt used during the electrodeposition process. With a 0.9 M KCl concentration, the as-prepared supercapacitors deliver a specific capacitance of 65.9 F g(-1) at a current density of 0.1 A g(-1) and retain more than 95% capacitance after 2000 charge/discharge cycles at a current density of 1 A g(-1). These supercapacitors also exhibit intelligent high voltage self-protection function due to the electrolysis-induced cross-linking effect of PVAPB GPEs.

Electrolyte additive enabled fast charging and stable cycling lithium metal batteries

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zheng, Jianming; Engelhard, Mark H.; Mei, Donghai

2017-03-01

Lithium (Li) metal battery is an attractive energy storage system owing to the ultrahigh specific capacity and the lowest redox potential of Li metal anode. However, safety concern associated with dendrite growth and limited cycle life especially at a high charge current density are two critical challenges hindering the practical applications of rechargeable Li metal batteries. Here, we report for the first time that an optimal amount (0.05 M) of LiPF6 as additive in the LiTFSI-LiBOB dual-salt/carbonate-based electrolyte can significantly enhance the charging capability and the long-term cycle life of Li metal batteries with a moderately high cathode loading ofmore » 1.75 mAh cm-2. Unprecedented stable-cycling (97.1% capacity retention after 500 cycles) along with very limited increase in electrode over-potential has been achieved at a high current density of 1.75 mA cm-2. This unparalleled fast charging and stable cycling performance is contributed from both the stabilized Al cathode current collector, and, more importantly, the robust and conductive SEI layer formed on Li metal anode in the presence of the LiPF6 additive.« less

Photolithographically Patterned TiO2 Films for Electrolyte-Gated Transistors.

PubMed

Valitova, Irina; Kumar, Prajwal; Meng, Xiang; Soavi, Francesca; Santato, Clara; Cicoira, Fabio

2016-06-15

Metal oxides constitute a class of materials whose properties cover the entire range from insulators to semiconductors to metals. Most metal oxides are abundant and accessible at moderate cost. Metal oxides are widely investigated as channel materials in transistors, including electrolyte-gated transistors, where the charge carrier density can be modulated by orders of magnitude upon application of relatively low electrical bias (2 V). Electrolyte gating offers the opportunity to envisage new applications in flexible and printed electronics as well as to improve our current understanding of fundamental processes in electronic materials, e.g. insulator/metal transitions. In this work, we employ photolithographically patterned TiO2 films as channels for electrolyte-gated transistors. TiO2 stands out for its biocompatibility and wide use in sensing, electrochromics, photovoltaics and photocatalysis. We fabricated TiO2 electrolyte-gated transistors using an original unconventional parylene-based patterning technique. By using a combination of electrochemical and charge carrier transport measurements we demonstrated that patterning improves the performance of electrolyte-gated TiO2 transistors with respect to their unpatterned counterparts. Patterned electrolyte-gated (EG) TiO2 transistors show threshold voltages of about 0.9 V, ON/OFF ratios as high as 1 × 10(5), and electron mobility above 1 cm(2)/(V s).

Nanoporous Hybrid Electrolytes for High-Energy Batteries Based on Reactive Metal Anodes

DOE Office of Scientific and Technical Information (OSTI.GOV)

Tu, Zhengyuan; Zachman, Michael J.; Choudhury, Snehashis

2017-01-06

Successful strategies for stabilizing electrodeposition of reactive metals, including lithium, sodium, and aluminum are a requirement for safe, high-energy electrochemical storage technologies that utilize these metals as anodes. Unstable deposition produces high-surface area dendritic structures at the anode/electrolyte interface, which causes premature cell failure by complex physical and chemical processes that have presented formidable barriers to progress. Here, it is reported that hybrid electrolytes created by infusing conventional liquid electrolytes into nanoporous membranes provide exceptional ability to stabilize Li. Electrochemical cells based on γ-Al2O3 ceramics with pore diameters below a cut-off value above 200 nm exhibit long-term stability even atmore » a current density of 3 mA cm-2. The effect is not limited to ceramics; similar large enhancements in stability are observed for polypropylene membranes with less monodisperse pores below 450 nm. These findings are critically assessed using theories for ion rectification and electrodeposition reactions in porous solids and show that the source of stable electrodeposition in nanoporous electrolytes is fundamental.« less

Lithium dendrite growth through solid polymer electrolyte membranes

NASA Astrophysics Data System (ADS)

Harry, Katherine; Schauser, Nicole; Balsara, Nitash

2015-03-01

Replacing the graphite-based anode in current batteries with a lithium foil will result in a qualitative increase in the energy density of lithium batteries. The primary reason for not adopting lithium-foil anodes is the formation of dendrites during cell charging. In this study, stop-motion X-ray microtomography experiments were used to directly monitor the growth of lithium dendrites during electrochemical cycling of symmetric lithium-lithium cells with a block copolymer electrolyte. In an attempt to understand the relationship between viscoelastic properties of the electrolyte on dendrite formation, a series of complementary experiments including cell cycling, tomography, ac impedance, and rheology, were conducted above and below the glass transition temperature of the non-conducting poly(styrene) block; the conducting phase is a mixture of rubbery poly(ethylene oxide) and a lithium salt. The tomography experiments enable quantification of the evolution of strain in the block copolymer electrolyte. Our work provides fundamental insight into the dynamics of electrochemical deposition of metallic films in contact with high modulus polymer electrolytes. Rational approaches for slowing down and, perhaps, eliminating dendrite growth are proposed.

Differential geometry-based solvation and electrolyte transport models for biomolecular modeling: a review

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wei, Guowei; Baker, Nathan A.

2016-11-11

This chapter reviews the differential geometry-based solvation and electrolyte transport for biomolecular solvation that have been developed over the past decade. A key component of these methods is the differential geometry of surfaces theory, as applied to the solvent-solute boundary. In these approaches, the solvent-solute boundary is determined by a variational principle that determines the major physical observables of interest, for example, biomolecular surface area, enclosed volume, electrostatic potential, ion density, electron density, etc. Recently, differential geometry theory has been used to define the surfaces that separate the microscopic (solute) domains for biomolecules from the macroscopic (solvent) domains. In thesemore » approaches, the microscopic domains are modeled with atomistic or quantum mechanical descriptions, while continuum mechanics models (including fluid mechanics, elastic mechanics, and continuum electrostatics) are applied to the macroscopic domains. This multiphysics description is integrated through an energy functional formalism and the resulting Euler-Lagrange equation is employed to derive a variety of governing partial differential equations for different solvation and transport processes; e.g., the Laplace-Beltrami equation for the solvent-solute interface, Poisson or Poisson-Boltzmann equations for electrostatic potentials, the Nernst-Planck equation for ion densities, and the Kohn-Sham equation for solute electron density. Extensive validation of these models has been carried out over hundreds of molecules, including proteins and ion channels, and the experimental data have been compared in terms of solvation energies, voltage-current curves, and density distributions. We also propose a new quantum model for electrolyte transport.« less

High Packing Density Unidirectional Arrays of Vertically Aligned Graphene with Enhanced Areal Capacitance for High-Power Micro-Supercapacitors.

PubMed

Zheng, Shuanghao; Li, Zhilin; Wu, Zhong-Shuai; Dong, Yanfeng; Zhou, Feng; Wang, Sen; Fu, Qiang; Sun, Chenglin; Guo, Liwei; Bao, Xinhe

2017-04-25

Interfacial integration of a shape-engineered electrode with a strongly bonded current collector is the key for minimizing both ionic and electronic resistance and then developing high-power supercapacitors. Herein, we demonstrated the construction of high-power micro-supercapacitors (VG-MSCs) based on high-density unidirectional arrays of vertically aligned graphene (VG) nanosheets, derived from a thermally decomposed SiC substrate. The as-grown VG arrays showed a standing basal plane orientation grown on a (0001̅) SiC substrate, tailored thickness (3.5-28 μm), high-density structurally ordering alignment of graphene consisting of 1-5 layers, vertically oriented edges, open intersheet channels, high electrical conductivity (192 S cm -1 ), and strong bonding of the VG edges to the SiC substrate. As a result, the demonstrated VG-MSCs displayed a high areal capacitance of ∼7.3 mF cm -2 and a fast frequency response with a short time constant of 9 ms. Furthermore, VG-MSCs in both an aqueous polymer gel electrolyte and nonaqueous ionic liquid of 1-ethyl-3-methylimidazolium tetrafluoroborate operated well at high scan rates of up to 200 V s -1 . More importantly, VG-MSCs offered a high power density of ∼15 W cm -3 in gel electrolyte and ∼61 W cm -3 in ionic liquid. Therefore, this strategy of producing high-density unidirectional VG nanosheets directly bonded on a SiC current collector demonstrated the feasibility of manufacturing high-power compact supercapacitors.

Microfluidic platform for studying the electrochemical reduction of carbon dioxide

NASA Astrophysics Data System (ADS)

Whipple, Devin Talmage

Diminishing supplies of conventional energy sources and growing concern over greenhouse gas emissions present significant challenges to supplying the world's rapidly increasing demand for energy. The electrochemical reduction of carbon dioxide has the potential to address many of these issues by providing a means of storing electricity in chemical form. Storing electrical energy as chemicals is beneficial for leveling the output of clean, but intermittent renewable energy sources such as wind and solar. Electrical energy stored as chemicals can also be used as carbon neutral fuels for portable applications allowing petroleum derived fuels in the transportation sector to be replaced by more environmentally friendly energy sources. However, to be a viable technology, the electrochemical reduction of carbon dioxide needs to have both high current densities and energetic efficiencies (Chapter 1). Although many researchers have studied the electrochemical reduction of CO2 including parameters such as catalysts, electrolytes and temperature, further investigation is needed to improve the understanding of this process and optimize the performance (Chapter 2). This dissertation reports the development and validation of a microfluidic reactor for the electrochemical reduction of CO2 (Chapter 3). The design uses a flowing liquid electrolyte instead of the typical polymer electrolyte membrane. In addition to other benefits, this flowing electrolyte gives the reactor great flexibility, allowing independent analysis of each electrode and the testing of a wide variety of conditions. In this work, the microfluidic reactor has been used in the following areas: • Comparison of different metal catalysts for the reduction of CO2 to formic acid and carbon monoxide (Chapter 4). • Investigation of the effects of the electrolyte pH on the reduction of CO2 to formic acid and carbon monoxide (Chapter 5). • Study of amine based electrolytes for lowering the overpotentials for CO2 reduction and suppressing undesirable hydrogen evolution (Chapter 6). • Investigation of the effects of reaction temperature on the Faradaic efficiency and current density for CO2 reduction on several catalysts (Chapter 7). These studies demonstrate the utility of this flexible reactor design and provide increased understanding of the electrochemical reduction of CO2 and the critical parameters for optimization of this process.

In-depth porosity control of mesoporous silicon layers by an anodization current adjustment

NASA Astrophysics Data System (ADS)

Lascaud, J.; Defforge, T.; Certon, D.; Valente, D.; Gautier, G.

2017-12-01

The formation of thick mesoporous silicon layers in P+-type substrates leads to an increase in the porosity from the surface to the interface with silicon. The adjustment of the current density during the electrochemical etching of porous silicon is an intuitive way to control the layer in-depth porosity. The duration and the current density during the anodization were varied to empirically model porosity variations with layer thickness and build a database. Current density profiles were extracted from the model in order to etch layer with in-depth control porosity. As a proof of principle, an 80 μm-thick porous silicon multilayer was synthetized with decreasing porosities from 55% to 35%. The results show that the assessment of the in-depth porosity could be significantly enhanced by taking into account the pure chemical etching of the layer in the hydrofluoric acid-based electrolyte.

Microstructure and properties of ceramic coatings prepared by micro-arc oxidation on 7075 aluminum alloy

NASA Astrophysics Data System (ADS)

Cao, G. P.; Song, R. G.

2018-02-01

Micro-arc oxidation (MAO) ceramic coatings were prepared in silicate-based electrolyte on 7075 aluminum alloy. The effects of current density on microstructure and properties of the MAO coatings were studied by scanning electron microscopy (SEM), stereoscopic microscopy, x-ray diffraction (XRD), electrochemical tests as well as tribological and wear tests. The results showed that the current density plays an important role in affecting the quality of the MAO coatings. XRD results showed that the α-Al2O3 phase first increased then decreased with increasing the current density, which matched well with the micro-hardness test and the wearing test results. On the other hand, the coalescent strength measurements revealed that the coating prepared at the current density of 12 A dm-2 is of the highest adhesion force. The potentiodynamic polarization test proved that the coating obtained under 10 A dm-2 exhibits the best corrosion resistance, which is directly related to the morphology of coating.

Flute type micropores activated carbon from cotton stalk for high performance supercapacitors

NASA Astrophysics Data System (ADS)

Tian, Xun; Ma, Hongru; Li, Zhe; Yan, Shaocun; Ma, Lei; Yu, Feng; Wang, Gang; Guo, Xuhong; Ma, Yanqing; Wong, Chingping

2017-08-01

Flute type micropores activated carbon (FTMAC) has been successfully obtained from cotton stalk via KOH-chemical activation method. The synthesized carbon material exhibits an ordered pore structure with high specific surface area of 1964.46 m2 g-1 and pore volume of 1.03 m3 g-1. The assembled FTMAC-based electrode delivers a high specific capacitance of 254 F g-1 at a current density of 0.2 A g-1 in 1 M H2SO4 aqueous electrolyte. It still can maintain 221 F g-1at a current density of 10 A g-1, demonstrating a good rate capacity (87% retention), as well as long cyclic stability of 96% capacitance retention after 10000 charging and discharging cycles at current density of 1 A g-1. Moreover, the symmetric supercapacitor can deliver a high energy density of 18.14 W h kg-1 and a power density of 450.37 W kg-1 which is operated in the voltage range of 0-1.8 V.

Transport dynamics of a high-power-density matrix-type hydrogen-oxygen fuel cell

NASA Technical Reports Server (NTRS)

Prokopius, P. R.; Hagedorn, N. H.

1974-01-01

Experimental transport dynamics tests were made on a space power fuel cell of current design. Various operating transients were introduced and transport-related response data were recorded with fluidic humidity sensing instruments. Also, sampled data techniques were developed for measuring the cathode-side electrolyte concentration during transient operation.

Electrodes of carbonized MWCNT-cellulose paper for supercapacitor

NASA Astrophysics Data System (ADS)

Sun, Xiaogang; Cai, Manyuan; Chen, Long; Qiu, Zhiwen; Liu, Zhenghong

2017-07-01

A flexible composite paper of multi-walled carbon nanotube (MWCNT) and cellulose fiber (CF) were fabricated by traditional paper-making method. Then, the MWCNT/CF papers were carbonized at high temperature in vacuum to remove organic component. The carbonized MWCNT/CF (MWCNT/CCF) papers are consisted of MWCNT and carbon fiber. The papers were characterized by scanning electron microscope (SEM), X-ray diffraction (XRD), and four-point probe resistance meter. The electrochemical performances of the supercapacitors were tested by cyclic voltammetry and galvanostatic charge/discharge >with 1 moL/L LiPF6 as electrolyte. The MWCNT/CCF electrode yielded a specific capacitance of 156F/g at a current density of 50 mA/g by galvanostatic charge/discharge measurement, which is 1.29 times higher than MWCNT/CF electrode of 68F/g. The MWCNT/CCF electrodes also displayed an excellent specific capacitance retention of 84% after 2000 continuous charge/discharge cycles at a current density of 400 mA/g. The increase of specific capacitance can be attributed to enhanced electrical conductivity of MWCNT/CCF papers and improved contact interface between electrolyte and electrodes.

Electrochemical oxidation of ampicillin antibiotic at boron-doped diamond electrodes and process optimization using response surface methodology.

PubMed

Körbahti, Bahadır K; Taşyürek, Selin

2015-03-01

Electrochemical oxidation and process optimization of ampicillin antibiotic at boron-doped diamond electrodes (BDD) were investigated in a batch electrochemical reactor. The influence of operating parameters, such as ampicillin concentration, electrolyte concentration, current density, and reaction temperature, on ampicillin removal, COD removal, and energy consumption was analyzed in order to optimize the electrochemical oxidation process under specified cost-driven constraints using response surface methodology. Quadratic models for the responses satisfied the assumptions of the analysis of variance well according to normal probability, studentized residuals, and outlier t residual plots. Residual plots followed a normal distribution, and outlier t values indicated that the approximations of the fitted models to the quadratic response surfaces were very good. Optimum operating conditions were determined at 618 mg/L ampicillin concentration, 3.6 g/L electrolyte concentration, 13.4 mA/cm(2) current density, and 36 °C reaction temperature. Under response surface optimized conditions, ampicillin removal, COD removal, and energy consumption were obtained as 97.1 %, 92.5 %, and 71.7 kWh/kg CODr, respectively.

Characterization of Nanocrystalline Nickel-Cobalt Alloys Synthesized by Direct and Pulse Electrodeposition

NASA Astrophysics Data System (ADS)

Salehi, M.; Saidi, A.; Ahmadian, M.; Raeissi, K.

2014-01-01

Nanocrystalline Ni-Co alloys are electrodeposited by direct (DC) and pulse current (PC) in an electrolyte solution which consisted of nickel sulfate, cobalt sulfate and boric acid. Electrodeposition parameters including current density, electrolyte pH and pulse times in a single electrolyte bath were changed. XRD pattern showed that the structure of the alloys depends on Co content and the synthesis parameter and changed from single phase structure (fcc) to dual phase structure (fcc + hcp). The Co content in the deposited alloys declined from 70 at.% to 50 at.% by increasing in direct current from 70 mA/cm2 to 115 mA/cm2 and also decreased from 75 at.% to 33 at.% with decrease in pH values from 4 to 2. By applying PC the Co content changed from 76 at.% to 41 at.%. Magnetic properties measurements showed the saturation magnetization (Ms) increased with increasing the Co content. There was no significant effect on coercivity values (Hc) with change in Co content and about 40 Oe was obtained for all samples. The grain size of deposited alloys obtained between 24-58 nm and 15-21 nm by applying DC and PC, respectively.

Designable ultra-smooth ultra-thin solid-electrolyte interphases of three alkali metal anodes.

PubMed

Gu, Yu; Wang, Wei-Wei; Li, Yi-Juan; Wu, Qi-Hui; Tang, Shuai; Yan, Jia-Wei; Zheng, Ming-Sen; Wu, De-Yin; Fan, Chun-Hai; Hu, Wei-Qiang; Chen, Zhao-Bin; Fang, Yuan; Zhang, Qing-Hong; Dong, Quan-Feng; Mao, Bing-Wei

2018-04-09

Dendrite growth of alkali metal anodes limited their lifetime for charge/discharge cycling. Here, we report near-perfect anodes of lithium, sodium, and potassium metals achieved by electrochemical polishing, which removes microscopic defects and creates ultra-smooth ultra-thin solid-electrolyte interphase layers at metal surfaces for providing a homogeneous environment. Precise characterizations by AFM force probing with corroborative in-depth XPS profile analysis reveal that the ultra-smooth ultra-thin solid-electrolyte interphase can be designed to have alternating inorganic-rich and organic-rich/mixed multi-layered structure, which offers mechanical property of coupled rigidity and elasticity. The polished metal anodes exhibit significantly enhanced cycling stability, specifically the lithium anodes can cycle for over 200 times at a real current density of 2 mA cm -2 with 100% depth of discharge. Our work illustrates that an ultra-smooth ultra-thin solid-electrolyte interphase may be robust enough to suppress dendrite growth and thus serve as an initial layer for further improved protection of alkali metal anodes.

The lithium storage performance of electrolytic-carbon from CO2

NASA Astrophysics Data System (ADS)

Tang, Juanjuan; Deng, Bowen; Xu, Fei; Xiao, Wei; Wang, Dihua

2017-02-01

Sustainable and affordable energy resources are urgently demanded to mitigate environmental issues. Herein, carbon materials, prepared by electrochemical reduction of greenhouse gas, CO2, in Li-Na-K carbonate molten salts (electrolytic-carbon), are tested as negative electrode materials for Li-ion batteries. Owing to the small particle size and suitable surface area, the electrolytic-carbon exhibits a high reversible capacity of 798 mAh g-1 (more than two times of graphites' theoretical capacity) at 50 mA g-1 and 266 mAh g-1 with a stable cyclability over 500 cycles at a current density up to 500 mA g-1, as well as remarkable rate performance. Furthermore, a comprehensively study was conducted to investigate the effects of electrolysis temperature and cell voltage on the electrochemical performance of the electrolytic-carbon. These results demonstrate a promising strategy to develop renewable high-performance carbon negative electrode materials for Li-ion batteries by molten salt capture and electrochemical reduction of CO2.

A numerical study on electrochemical transport of ions in calcium fluoride slag

NASA Astrophysics Data System (ADS)

Karimi-Sibaki, E.; Kharicha, A.; Wu, M.; Ludwig, A.

2016-07-01

Electrically resistive CaF 2-based slags are widely used in electroslag remelting (ESR) process to generate Joule heat for the melting of electrode. The electric current is conducted by ions (electrolyte) such as Ca +2 or F -, thus it is necessary to establish electrochemical models to study electrical behavior of slag. This paper presents a numerical model on electrochemical transport of ions in an arbitrary symmetrical (ZZ) and non-symmetrical (CaF2) stagnant electrolytes blocked by two parallel, planar electrodes. The dimensionless Poisson-Nernst-Planck (PNP) equations are solved to model electro-migration and diffusion of ions. The ions are considered to be inert that no Faradic reactions occur. Spatial variations of concentrations of ions, charge density and electric potential across the electrolyte are analyzed. It is shown that the applied potential has significant influence on the system response. At high applied voltage, the anodic potential drop near the electrode is significantly larger than cathodic potential drop in fully dissociated CaF2 electrolyte.

Micropore engineering of carbonized porous aromatic framework (PAF-1) for supercapacitors application.

PubMed

Li, Yanqiang; Roy, Soumyajit; Ben, Teng; Xu, Shixian; Qiu, Shilun

2014-07-07

Micropore engineering of porous carbons on the effect of capacitance was explored using a carbonized porous aromatic framework (PAF-1). The porous carbons obtained through different carbonization methods show different pore structures enabling us to do this. The capacitance was measured both in aqueous electrolyte and different organic electrolytes. The porous carbons prepared by KOH activation show both high microporous volume, which is beneficial for charge storage, and mesoporous volume, which is devoted to fast ion diffusion in the pores; properties which are highly desirable. It shows a capacitance as high as 280 F g(-1) and 203 F g(-1) at a current density of 1 A g(-1) in 6.0 M KOH and 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide (EMImTFSI), respectively. We also demonstrate the effect of diffusion and that of geometric packing of the electrolyte ions in the pores, where a commensurate match of the electrolyte ions with the pores of carbonized materials control and influence significantly the capacitance of these materials.

Study of the mechanism for electrodeposition of dendrite-free zinc in an alkaline electrolyte modified with 1-ethyl-3-methylimidazolium dicyanamide

NASA Astrophysics Data System (ADS)

Xu, M.; Ivey, D. G.; Qu, W.; Xie, Z.

2015-01-01

Electrodeposition of Zn was conducted in a new electrolyte system composed of an alkaline solution (9 M KOH + 5 wt% ZnO) modified with a small amount (0.5 wt%) of room temperature ionic liquid 1-ethyl-3-methylimidazolium dicyanamide (EMI-DCA). At a high deposition current density of 80 mA cm-2, a porous, dendrite-free Zn film characterized by clusters of small Zn particles was obtained. The mechanism for the modified Zn morphology in the EMI-DCA containing electrolyte was studied by cyclic voltammetry, chronoamperometry, electrochemical impedance spectroscopy (EIS) and scanning electron microscopy. It was found that the addition of EMI-DCA changed the Zn nucleation process and reduced the potential variation during electrodeposition, which suppressed the uneven growth of Zn deposits and the formation of Zn dendrites. EIS results indicated that there was adsorption of EMI+ cations at the Zn film/electrolyte interface, which may have contributed to suppressed dendritic Zn growth.

Effects of cathode electrolyte interfacial (CEI) layer on long term cycling of all-solid-state thin-film batteries

DOE PAGES

Wang, Ziying; Lee, Jungwoo Z.; Xin, Huolin L.; ...

2016-05-30

All-solid-state lithium-ion batteries have the potential to not only push the current limits of energy density by utilizing Li metal, but also improve safety by avoiding flammable organic electrolyte. However, understanding the role of solid electrolyte – electrode interfaces will be critical to improve performance. In this paper, we conducted long term cycling on commercially available lithium cobalt oxide (LCO)/lithium phosphorus oxynitride (LiPON)/lithium (Li) cells at elevated temperature to investigate the interfacial phenomena that lead to capacity decay. STEM-EELS analysis of samples revealed a previously unreported disordered layer between the LCO cathode and LiPON electrolyte. This electrochemically inactive layer grewmore » in thickness leading to loss of capacity and increase of interfacial resistance when cycled at 80 °C. Finally, the stabilization of this layer through interfacial engineering is crucial to improve the long term performance of thin-film batteries especially under thermal stress.« less

Engineering of highly ordered TiO2 nanopore arrays by anodization

NASA Astrophysics Data System (ADS)

Wang, Huijie; Huang, Zhennan; Zhang, Li; Ding, Jie; Ma, Zhaoxia; Liu, Yong; Kou, Shengzhong; Yang, Hangsheng

2016-07-01

Finite element analysis was used to simulate the current density distributions in the TiO2 barrier layer formed at the initial stage of Ti anodization. The morphology modification of the barrier layer was found to induce current density distribution change. By starting the anodization with proper TiO2 barrier layer morphology, the current density distribution can be adjusted to favor the formation of either nanotube arrays or nanopore arrays of anodic TiO2. We also found that the addition of sodium acetate into the electrolyte suppressed both the field-assisted chemical dissolution of TiO2 and the TiF62- hydrolysis induced TiO2 deposition during anodization, and thus further favored the nanopore formation. Accordingly, highly ordered anodic TiO2 nanopore arrays, similar to anodic aluminum oxide nanopore arrays, were successfully prepared.

All-Solid-State High-Energy Asymmetric Supercapacitors Enabled by Three-Dimensional Mixed-Valent MnOx Nanospike and Graphene Electrodes.

PubMed

Yang, Jie; Li, Guizhu; Pan, Zhenghui; Liu, Meinan; Hou, Yuan; Xu, Yijun; Deng, Hong; Sheng, Leimei; Zhao, Xinluo; Qiu, Yongcai; Zhang, Yuegang

2015-10-14

Three-dimensional (3D) nanostructures enable high-energy storage devices. Here we report a 3D manganese oxide nanospike (NSP) array electrode fabricated by anodization and subsequent electrodeposition. All-solid-state asymmetric supercapacitors were assembled with the 3D Al@Ni@MnOx NSP as the positive electrode, chemically converted graphene (CCG) as the negative electrode, and Na2SO4/poly(vinyl alcohol) (PVA) as the polymer gel electrolyte. Taking advantage of the different potential windows of Al@Ni@MnOx NSP and CCG electrodes, the asymmetric supercapacitor showed an ideal capacitive behavior with a cell voltage up to 1.8 V, capable of lighting up a red LED indicator (nominal voltage of 1.8 V). The device could deliver an energy density of 23.02 W h kg(-1) at a current density of 1 A g(-1). It could also preserve 96.3% of its initial capacitance at a current density of 2 A g(-1) after 10000 charging/discharging cycles. The remarkable performance is attributed to the unique 3D NSP array structure that could play an important role in increasing the effective electrode surface area, facilitating electrolyte permeation, and shortening the electron pathway in the active materials.

Negative differential electrolyte resistance in a solid-state nanopore resulting from electroosmotic flow bistability.

PubMed

Luo, Long; Holden, Deric A; White, Henry S

2014-03-25

A solid-state nanopore separating two aqueous solutions containing different concentrations of KCl is demonstrated to exhibit negative differential resistance (NDR) when a constant pressure is applied across the nanopore. NDR refers to a decrease in electrical current when the voltage applied across the nanopore is increased. NDR results from the interdependence of solution flow (electroosmotic and pressure-engendered) with the distributions of K+ and Cl- within the nanopore. A switch from a high-conductivity state to a low-conductivity state occurs over a very narrow voltage window (<2 mV) that depends on the nanopore geometry, electrolyte concentration, and nanopore surface charge density. Finite element simulations based on a simultaneous solution of the Navier-Stokes, Poisson, and Nernst-Planck equations demonstrate that NDR results from a positive feedback mechanism between the ion distributions and electroosmotic flow, yielding a true bistability in fluid flow and electrical current at a critical applied voltage, i.e., the NDR "switching potential". Solution pH and Ca2+ were separately employed as chemical stimuli to investigate the dependence of the NDR on the surface charge density. The NDR switching potential is remarkably sensitive to the surface charge density, and thus to pH and the presence of Ca2+, suggesting possible applications in chemical sensing.

Charged plate in asymmetric electrolytes: One-loop renormalization of surface charge density and Debye length due to ionic correlations.

PubMed

Ding, Mingnan; Lu, Bing-Sui; Xing, Xiangjun

2016-10-01

Self-consistent field theory (SCFT) is used to study the mean potential near a charged plate inside a m:-n electrolyte. A perturbation series is developed in terms of g=4πκb, where band1/κ are Bjerrum length and bare Debye length, respectively. To the zeroth order, we obtain the nonlinear Poisson-Boltzmann theory. For asymmetric electrolytes (m≠n), the first order (one-loop) correction to mean potential contains a secular term, which indicates the breakdown of the regular perturbation method. Using a renormalizaton group transformation, we remove the secular term and obtain a globally well-behaved one-loop approximation with a renormalized Debye length and a renormalized surface charge density. Furthermore, we find that if the counterions are multivalent, the surface charge density is renormalized substantially downwards and may undergo a change of sign, if the bare surface charge density is sufficiently large. Our results agrees with large MC simulation even when the density of electrolytes is relatively high.

Structure of spherical electric double layers with fully asymmetric electrolytes: a systematic study by Monte Carlo simulations and density functional theory.

PubMed

Patra, Chandra N

2014-11-14

A systematic investigation of the spherical electric double layers with the electrolytes having size as well as charge asymmetry is carried out using density functional theory and Monte Carlo simulations. The system is considered within the primitive model, where the macroion is a structureless hard spherical colloid, the small ions as charged hard spheres of different size, and the solvent is represented as a dielectric continuum. The present theory approximates the hard sphere part of the one particle correlation function using a weighted density approach whereas a perturbation expansion around the uniform fluid is applied to evaluate the ionic contribution. The theory is in quantitative agreement with Monte Carlo simulation for the density and the mean electrostatic potential profiles over a wide range of electrolyte concentrations, surface charge densities, valence of small ions, and macroion sizes. The theory provides distinctive evidence of charge and size correlations within the electrode-electrolyte interface in spherical geometry.

Second harmonic generation study of malachite green adsorption at the interface between air and an electrolyte solution: observing the effect of excess electrical charge density at the interface.

PubMed

Song, Jinsuk; Kim, Mahn Won

2010-03-11

Understanding the differential adsorption of ions at the interface of an electrolyte solution is very important because it is closely related, not only to the fundamental aspects of biological systems, but also to many industrial applications. We have measured the excess interfacial negative charge density at air-electrolyte solution interfaces by using resonant second harmonic generation of oppositely charged probe molecules. The excess charge density increased with the square root of the bulk electrolyte concentration. A new adsorption model that includes the electrostatic interaction between adsorbed molecules is proposed to explain the measured adsorption isotherm, and it is in good agreement with the experimental results.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wei, Xiaoliang; Xu, Wu; Huang, Jinhua

Nonaqueous redox flow batteries hold the promise to achieve higher energy density ascribed to the broader voltage window than their aqueous counterparts, but their current performance is limited by low redox material concentration, poor cell efficiency, and inferior cycling stability. We report a new nonaqueous total-organic flow battery based on high concentrations of 9-fluorenone as negative and 2,5-di-tert-butyl-1-methoxy-4-[2’-methoxyethoxy]benzene as positive redox materials. The supporting electrolytes are found to greatly affect the cycling stability of flow cells through varying chemical stabilities of the charged radical species, especially the 9-fluorenone radical anions, as confirmed by electron spin resonance. Such an electrolyte optimizationmore » sheds light on mechanistic understandings of capacity fading in flow batteries employing organic radical-based redox materials and demonstrates that rational design of supporting electrolyte is vital for stable cyclability.« less

Behavior of Lithium Metal Anodes under Various Capacity Utilization and High Current Density in Lithium Metal Batteries

DOE Office of Scientific and Technical Information (OSTI.GOV)

Jiao, Shuhong; Zheng, Jianming; Li, Qiuyan

Lithium (Li) metal batteries (LMBs) are regarded as the most promising power sources for electric vehicles. Besides the Li dendrite growth and low Li Coulombic efficiency, how to well match Li metal anode with a high loading (normally over 3.0 mAh cm-2) cathode is another key challenge to achieve the real high energy density battery. In this work, we systematically investigate the effects of the Li metal capacity usage in each cycle, manipulated by varying the cathode areal loading, on the stability of Li metal anode and the cycling performance of LMBs using the LiNi1/3Mn1/3Co1/3O2 (NMC) cathode and an additive-containingmore » dual-salt/carbonate-solvent electrolyte. It is demonstrated that the Li||NMC cells show decent long-term cycling performance even with NMC areal capacity loading up to ca. 4.0 mAh cm-2 and at a charge current density of 1.0 mA cm-2. The increase of the Li capacity usage in each cycle causes variation in the components of the solid electrolyte interphase (SEI) layer on Li metal anode and generates more ionic conductive species from this electrolyte. Further study reveals for the first time that the degradation of Li metal anode and the thickness of SEI layer on Li anode show linear relationship with the areal capacity of NMC cathode. Meanwhile, the expansion rate of consumed Li and the ratio of SEI thickness to NMC areal loading are kept almost the same value with increasing cathode loading, respectively. These fundamental findings provide new perspectives on the rational evaluation of Li metal anode stability for the development of rechargeable LMBs.« less

Electrochemical behavior of high performance on-chip porous carbon films for micro-supercapacitors applications in organic electrolytes

NASA Astrophysics Data System (ADS)

Brousse, K.; Huang, P.; Pinaud, S.; Respaud, M.; Daffos, B.; Chaudret, B.; Lethien, C.; Taberna, P. L.; Simon, P.

2016-10-01

Carbide derived carbons (CDCs) are promising materials for preparing integrated micro-supercapacitors, as on-chip CDC films are prepared via a process fully compatible with current silicon-based device technology. These films show good adherence on the substrate and high capacitance thanks to their unique nanoporous structure which can be fine-tuned by adjusting the synthesis parameters during chlorination of the metallic carbide precursor. The carbon porosity is mostly related to the synthesis temperature whereas the thickness of the films depends on the chlorination duration. Increasing the pore size allows the adsorption of large solvated ions from organic electrolytes and leads to higher energy densities. Here, we investigated the electrochemical behavior and performance of on-chip TiC-CDC in ionic liquid solvent mixtures of 1-ethyl-3-methylimidazolium tetrafluoroborate (EMIBF4) diluted in either acetonitrile or propylene carbonate via cyclic voltammetry and electrochemical impedance spectroscopy. Thin CDC films exhibited typical capacitive signature and achieved 169 F cm-3 in both electrolytes; 65% of the capacitance was still delivered at 1 V s-1. While increasing the thickness of the films, EMI+ transport limitation was observed in more viscous PC-based electrolyte. Nevertheless, the energy density reached 90 μW h cm-2 in 2M EMIBF4/ACN, confirming the interest of these CDC films for micro-supercapacitors applications.

Curvature in solid oxide fuel cells

NASA Astrophysics Data System (ADS)

Li, Wenxia; Hasinska, Kathy; Seabaugh, Matt; Swartz, Scott; Lannutti, John

At this point in history, curvature is inherent to the laminated components that comprise solid oxide fuel cells (SOFCs). Surprisingly, however, this fact has never been previously quantified in the literature. In addition, potential curvature changes associated with NiO reduction and re-oxidation during operation have not been investigated. In this report, an optical profilometer was employed to non-destructively quantify the surface curvature or cracking behavior observed on a large scale in industrially manufactured cells. This provides insights into the challenges that the component materials face as well as additional appreciation for why, in spite of a concerted effort to commercialize SOFC power generation, all currently manufactured SOFC stacks fail. Our results demonstrate that cracked electrolyte areas (caused by differential sintering) are flatter than uncracked regions. The height of the electrolyte surface ranged from 86 to 289 μm above the baseline following sintering. Reduction typically results in increases in curvature of up to 214 μm. Initial crack density appears to affect curvature evolution during reduction; the higher the crack density, the smaller the curvature increase following reduction at 600 °C. In general, however, we observed that the electrolyte layer is remarkably resistant to further cracking during these typographic changes. Following oxidation at 750 °C, large changes in curvature (up to 280 μm) are noted that appear to be related to the strength of the bond between the electrolyte and the underlying anode.

Design and Processing of Electret Structures

DTIC Science & Technology

2009-10-31

and width as a function of time. ( d ) Estimated current density j of dissolving copper disk as a function of time. (e) Total current I of dissolving...effect leading to a higher corrosion rate in the galvanic microreactor . Because of the small scale of our galvanic system, the dissolving copper disk is...estimated by focusing with a calibrated microscope stage.   Figure 5: Particle separation and electrolyte convection. Scale bars in ( A , D ) are 100 µm

Carbon treated commercial aluminium alloys as anodes for aluminium-air batteries in sodium chloride electrolyte

NASA Astrophysics Data System (ADS)

Pino, M.; Herranz, D.; Chacón, J.; Fatás, E.; Ocón, P.

2016-09-01

An easy treatment based in carbon layer deposition into aluminium alloys is presented to enhance the performance of Al-air primary batteries with neutral pH electrolyte. The jellification of aluminate in the anode surface is described and avoided by the carbon covering. Treated commercial Al alloys namely Al1085 and Al7475 are tested as anodes achieving specific capacities above 1.2 Ah g-1vs 0.5 Ah g-1 without carbon covering. The influence of the binder proportion in the treatment as well as different carbonaceous materials, Carbon Black, Graphene and Pyrolytic Graphite are evaluated as candidates for the covering. Current densities of 1-10 mA cm-2 are measured and the influence of the alloy explored. A final battery design of 4 cells in series is presented for discharges with a voltage plateau of 2 V and 1 Wh g-1 energy density.

Synthesis of homogeneous CaMoO4 microspheres with nanopits for high-capacity anode material in Li-ion battery

NASA Astrophysics Data System (ADS)

You, Jiangfeng; Xin, Ling; Yu, Xiao; Zhou, Xiang; Liu, Yong

2018-03-01

Homogeneous CaMoO4 microspheres with interesting nanopit morphology were prepared by a simple one-step hydrothermal method. These microspheres had a very promising alternative structure for application in Li-ion batteries (LIBs), because they combined the advantages of both the primary nanosized and secondary microsized structures. The nanopits distributed on CaMoO4 material can accommodate volume change, increase their contacting surface and wetting property with electrolyte, and improve wetting contact between CaMoO4 material and electrolyte, leading to enhanced cycling stability and electrochemical performance. Meanwhile, the robust microsphere structure can both prevent aggregation and provide high tap density. When used as an anode in LIBs, the electrodes delivered a high discharge capacity of 434 mAh/g after 50 charge-discharge cycles at a current density of 200 mA/g, showing good cycling performance.

The electrochemical generation of useful chemical species from lunar materials

NASA Technical Reports Server (NTRS)

Tsai, Kan J.; Kuchynka, Daniel J.; Sammells, Anthony F.

1990-01-01

Electrochemical cells have been fabricated for the simultaneous generation of oxygen and lithium from a Li2O-containing molten salt (Li2O-LiCl-LiF). The cell utilizes an oxygen vacancy conducting solid electrolyte, yttria-stabilized zirconia (YSZ), to effect separation between oxygen evolving and lithium reduction half-cell reactions. The cell, which operates at 700-850 C, possesses rapid electrode kinetics at the lithium-alloy electrode with exchange current density values being greater than 60 mA/sq cm. When used in the electrolytic mode, lithium produced at the negative electrode would be continuously removed from the cell for later use (under lunar conditions) as an easily storable reducing agent for the chemical refining of lunar ores. Because of the high reversibility of this electrochemical system, it has also formed the basis for the lithium-oxygen secondary battery system which possesses the highest theoretical energy density yet investigated.

The electrochemical generation of useful chemical species from lunar materials

NASA Astrophysics Data System (ADS)

Tsai, Kan J.; Kuchynka, Daniel J.; Sammells, Anthony F.

Electrochemical cells have been fabricated for the simultaneous generation of oxygen and lithium from a Li2O-containing molten salt (Li2O-LiCl-LiF). The cell utilizes an oxygen vacancy conducting solid electrolyte, yttria-stabilized zirconia (YSZ), to effect separation between oxygen evolving and lithium reduction half-cell reactions. The cell, which operates at 700-850 C, possesses rapid electrode kinetics at the lithium-alloy electrode with exchange current density values being greater than 60 mA/sq cm. When used in the electrolytic mode, lithium produced at the negative electrode would be continuously removed from the cell for later use (under lunar conditions) as an easily storable reducing agent for the chemical refining of lunar ores. Because of the high reversibility of this electrochemical system, it has also formed the basis for the lithium-oxygen secondary battery system which possesses the highest theoretical energy density yet investigated.

Performance of Liquid Phase Exfoliated Graphene As Electrochemical Double Layer Capacitors Electrodes

NASA Astrophysics Data System (ADS)

Huffstutler, Jacob; Wasala, Milinda; Richie, Julianna; Winchester, Andrew; Ghosh, Sujoy; Kar, Swastik; Talapatra, Saikat

2014-03-01

We will present the results of our investigations of electrochemical double layer capacitors (EDLCs) or supercapacitors (SC) fabricated using liquid-phase exfoliated graphene. Several electrolytes, such as aqueous potassium hydroxide KOH (6M), ionic 1-Butyl-3-methylimidazolium hexafluorophosphate [BMIM][PF6], and ionic 1-butyl-1-methylpyrrolidinium tris(pentafluoroethyl)trifluorophosphate[BMP][FAP] were used. These EDLC's show good performance compared to other carbon nanomaterials based EDLC's devices. We found that the liquid phase exfoliated graphene based devices possess specific capacitance values as high as 262 F/g, when used with ionic liquid electrolyte[BMP][FAP], with power densities (~ 454 W/kg) and energy densities (~ 0.38Wh/kg). Further, these devices indicated rapid charge transfer response even without the use of any binders or specially prepared current collectors. A detailed electrochemical impedance spectroscopy analysis in order to understand the phenomenon of charge storage in these materials will be presented.

Sparingly Solvating Electrolytes for High Energy Density Lithium-Sulfur Batteries

DOE Office of Scientific and Technical Information (OSTI.GOV)

Cheng, Lei; Curtiss, Larry A.; Zavadil, Kevin R.

2016-07-11

Moving to lighter and less expensive battery chemistries compared to lithium-ion requires the control of energy storage mechanisms based on chemical transformations rather than intercalation. Lithium sulfur (Li/S) has tremendous theoretical specific energy, but contemporary approaches to control this solution-mediated, precipitation-dissolution chemistry requires using large excesses of electrolyte to fully solubilize the polysulfide intermediate. Achieving reversible electrochemistry under lean electrolyte operation is the only path for Li/S to move beyond niche applications to potentially transformational performance. An emerging topic for Li/S research is the use of sparingly solvating electrolytes and the creation of design rules for discovering new electrolyte systemsmore » that fundamentally decouple electrolyte volume from reaction mechanism. This perspective presents an outlook for sparingly solvating electrolytes as the key path forward for longer-lived, high-energy density Li/S batteries including an overview of this promising new concept and some strategies for accomplishing it.« less

Sparingly solvating electrolytes for high energy density Lithium–sulfur batteries

DOE PAGES

Cheng, Lei; Curtiss, Larry A.; Zavadil, Kevin R.; ...

2016-07-11

Moving to lighter and less expensive battery chemistries compared to lithium-ion requires the control of energy storage mechanisms based on chemical transformations rather than intercalation. Lithium sulfur (Li/S) has tremendous theoretical specific energy, but contemporary approaches to control this solution-mediated, precipitation-dissolution chemistry requires using large excesses of electrolyte to fully solubilize the polysulfide intermediate. Achieving reversible electrochemistry under lean electrolyte operation is the only path for Li/S to move beyond niche applications to potentially transformational performance. An emerging topic for Li/S research is the use of sparingly solvating electrolytes and the creation of design rules for discovering new electrolyte systemsmore » that fundamentally decouple electrolyte volume from reaction mechanism. Furthermore, this perspective presents an outlook for sparingly solvating electrolytes as the key path forward for longer-lived, high-energy density Li/S batteries including an overview of this promising new concept and some strategies for accomplishing it.« less

Comparative analysis of 2D and 3D model of a PEMFC in COMSOL

NASA Astrophysics Data System (ADS)

Lakshmi, R. Bakiya; Harikrishnan, N. P.; Juliet, A. Vimala

2017-10-01

In this article, 2D and 3D model of a PEMFC has been simulated in order to study their performance when subjected to similar operating conditions. The comparison reveals interesting phenomena of performance enhancement of the fuel cell. Design of fuel cell channel and stationary studies were done in COMSOL. Variations in current density and electrolyte potential from simulation results were observed when operated at a temperature of 120 °C. The electrolyte potential was found to have increased from 1 to 2.5 V and the surface pressure due to fluid flow was found to have increased from 3 to 9.58 Pa.

Solid Polymer Electrolyte Fuel Cell Technology Program

NASA Technical Reports Server (NTRS)

1980-01-01

Work is reported on phase 5 of the Solid Polymer Electrolyte (SPE) Fuel Cell Technology Development program. The SPE fuel cell life and performance was established at temperatures, pressures, and current densities significantly higher than those previously demonstrated in sub-scale hardware. Operation of single-cell Buildup No. 1 to establish life capabilities of the full-scale hardware was continued. A multi-cell full-scale unit (Buildup No. 2) was designed, fabricated, and test evaluated laying the groundwork for the construction of a reactor stack. A reactor stack was then designed, fabricated, and successfully test-evaluated to demonstrate the readiness of SPE fuel cell technology for future space applications.

Effect of silicate ions on electrode overvoltage

NASA Technical Reports Server (NTRS)

Gras, J. M.; Seite, C.

1979-01-01

The influence of the addition of a silicate to a caustic solution (KOH) is studied in order to determine the degree to which silicates inhibit the corrosion of chrysotile under conditions of electrolysis at working temperatures of 100 C and above. In an alkaline solution containing various silicate concentrations, current density was increased and electrode overvoltage was measured. Results show that silicate ion concentrations in the electrolyte increase with temperature without effecting electrochemical performance up to 115 C at 700 MA/sqcm. At this point the concentration is about 0.5 g Si/100 g KOH. Beyond this limit, electrolytic performance rapidly degenerates due to severe oxidation of the electrodes.

Vertically-aligned Co(OH)2 Nanosheet Films for Flexible All-solid-state Electrochemical Supercapacitor

NASA Astrophysics Data System (ADS)

Tian, Yazhou; Gong, Jiangfeng; Zhu, Weihua

2017-11-01

Vertically-aligned Co(OH)2 nanosheets were cathodically electrodeposited on a piece of gold coated polyethylene terephthalate (Au-PET) as an electrode material for supercapacitor. The Co(OH)2 electrode showed a high capacitance of 2695 F g-1 at 8 A g-1 in 1 M KOH aqueous electrolyte. Besides, the films were employed to assemble symmetric all-solid-state supercapacitors with PVA/LiCl gel served as solid electrolyte. The device exhibits an areal capacitance of 50.5 μF cm-2 at the current density of 2 μA cm-2 accompanied by excellent cycle stability.

A High-Energy-Density Potassium Battery with a Polymer-Gel Electrolyte and a Polyaniline Cathode.

PubMed

Gao, Hongcai; Xue, Leigang; Xin, Sen; Goodenough, John B

2018-05-04

A safe, rechargeable potassium battery of high energy density and excellent cycling stability has been developed. The anion component of the electrolyte salt is inserted into a polyaniline cathode upon charging and extracted from it during discharging while the K + ion of the KPF 6 salt is plated/stripped on the potassium-metal anode. The use of a p-type polymer cathode increases the cell voltage. By replacing the organic-liquid electrolyte in a glass-fiber separator with a polymer-gel electrolyte of cross-linked poly(methyl methacrylate), a dendrite-free potassium anode can be plated/stripped, and the electrode/electrolyte interface is stabilized. The potassium anode wets the polymer, and the cross-linked architecture provides small pores of adjustable sizes to stabilize a solid-electrolyte interphase formed at the anode/electrolyte interface. This alternative electrolyte/cathode strategy offers a promising new approach to low-cost potassium batteries for the stationary storage of electric power. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Symmetric redox supercapacitor based on micro-fabrication with three-dimensional polypyrrole electrodes

NASA Astrophysics Data System (ADS)

Sun, Wei; Zheng, Ruilin; Chen, Xuyuan

To achieve higher energy density and power density, we have designed and fabricated a symmetric redox supercapacitor based on microelectromechanical system (MEMS) technologies. The supercapacitor consists of a three-dimensional (3D) microstructure on silicon substrate micromachined by high-aspect-ratio deep reactive ion etching (DRIE) method, two sputtered Ti current collectors and two electrochemical polymerized polypyrrole (PPy) films as electrodes. Electrochemical tests, including cyclic voltammetry (CV), electrochemical impedance spectroscopy (EIS) and galvanostatical charge/discharge methods have been carried out on the single PPy electrodes and the symmetric supercapacitor in different electrolytes. The specific capacitance (capacitance per unit footprint area) and specific power (power per unit footprint area) of the PPy electrodes and symmetric supercapacitor can be calculated from the electrochemical test data. It is found that NaCl solution is a good electrolyte for the polymerized PPy electrodes. In NaCl electrolyte, single PPy electrodes exhibit 0.128 F cm -2 specific capacitance and 1.28 mW cm -2 specific power at 20 mV s -1 scan rate. The symmetric supercapacitor presents 0.056 F cm -2 specific capacitance and 0.56 mW cm -2 specific power at 20 mV s -1 scan rate.

Mass transport enhancement in redox flow batteries with corrugated fluidic networks

NASA Astrophysics Data System (ADS)

Lisboa, Kleber Marques; Marschewski, Julian; Ebejer, Neil; Ruch, Patrick; Cotta, Renato Machado; Michel, Bruno; Poulikakos, Dimos

2017-08-01

We propose a facile, novel concept of mass transfer enhancement in flow batteries based on electrolyte guidance in rationally designed corrugated channel systems. The proposed fluidic networks employ periodic throttling of the flow to optimally deflect the electrolytes into the porous electrode, targeting enhancement of the electrolyte-electrode interaction. Theoretical analysis is conducted with channels in the form of trapezoidal waves, confirming and detailing the mass transport enhancement mechanism. In dilute concentration experiments with an alkaline quinone redox chemistry, a scaling of the limiting current with Re0.74 is identified, which compares favourably against the Re0.33 scaling typical of diffusion-limited laminar processes. Experimental IR-corrected polarization curves are presented for high concentration conditions, and a significant performance improvement is observed with the narrowing of the nozzles. The adverse effects of periodic throttling on the pumping power are compared with the benefits in terms of power density, and an improvement of up to 102% in net power density is obtained in comparison with the flow-by case employing straight parallel channels. The proposed novel concept of corrugated fluidic networks comes with facile fabrication and contributes to the improvement of the transport characteristics and overall performance of redox flow battery systems.

Optimizing photovoltaic performance in CuInS 2 and CdS quantum dot-sensitized solar cells by using an agar-based gel polymer electrolyte

DOE PAGES

Raphael, E.; Jara, D. H.; Schiavon, M. A.

2017-01-19

Quantum dot-sensitized solar cells (QDSSCs) offer new opportunities to address the clean energy challenge, being one of the top candidates for third generation photovoltaics. Like dye-sensitized solar cells (DSSCs), QDSSCs normally use liquid electrolytes that suffer from issues such as evaporation or leakage. In this study a gel polysulfide electrolyte was prepared containing a natural polymer, agar, and was used as a quasi-solid-state electrolyte in solar cells to replace the conventional liquid electrolytes. This gel electrolyte shows almost the same conductivity as the liquid one. The solar cells were fabricated using CuInS 2 quantum dots (QDs), previously synthesized, deposited onmore » TiO 2 photoanodes by electrophoretic deposition (EPD). CdS was deposited on TiO 2 by successive ionic layer adsorption and reaction (SILAR). Reduced graphene oxide (RGO)–Cu 2S, brass, and thin film CuxS were used as counter electrodes. Compared to a liquid polysulfide water based electrolyte, solar cells based on CuInS 2 and CdS using gel polymer electrolyte (GPE) exhibit greater incident photon to current conversion efficiency (IPCE = 51.7% at 520 nm and 72.7% at 440 nm), photocurrent density (J sc = 10.75 and 13.51 mA cm -2), and power conversion efficiency (η = 2.97 and 2.98%) while exhibiting significantly enhanced stability. The solar cells employing the agar-based gel polymeric electrolyte are about a factor of 0.20 more stable than using a liquid electrolyte. The higher photovoltaic performance is due to the good conductivity and high wettability as well as the superior permeation capability of the gel electrolyte into the mesoporous matrix of a TiO 2 film« less

Optimizing photovoltaic performance in CuInS 2 and CdS quantum dot-sensitized solar cells by using an agar-based gel polymer electrolyte

DOE Office of Scientific and Technical Information (OSTI.GOV)

Raphael, E.; Jara, D. H.; Schiavon, M. A.

Quantum dot-sensitized solar cells (QDSSCs) offer new opportunities to address the clean energy challenge, being one of the top candidates for third generation photovoltaics. Like dye-sensitized solar cells (DSSCs), QDSSCs normally use liquid electrolytes that suffer from issues such as evaporation or leakage. In this study a gel polysulfide electrolyte was prepared containing a natural polymer, agar, and was used as a quasi-solid-state electrolyte in solar cells to replace the conventional liquid electrolytes. This gel electrolyte shows almost the same conductivity as the liquid one. The solar cells were fabricated using CuInS 2 quantum dots (QDs), previously synthesized, deposited onmore » TiO 2 photoanodes by electrophoretic deposition (EPD). CdS was deposited on TiO 2 by successive ionic layer adsorption and reaction (SILAR). Reduced graphene oxide (RGO)–Cu 2S, brass, and thin film CuxS were used as counter electrodes. Compared to a liquid polysulfide water based electrolyte, solar cells based on CuInS 2 and CdS using gel polymer electrolyte (GPE) exhibit greater incident photon to current conversion efficiency (IPCE = 51.7% at 520 nm and 72.7% at 440 nm), photocurrent density (J sc = 10.75 and 13.51 mA cm -2), and power conversion efficiency (η = 2.97 and 2.98%) while exhibiting significantly enhanced stability. The solar cells employing the agar-based gel polymeric electrolyte are about a factor of 0.20 more stable than using a liquid electrolyte. The higher photovoltaic performance is due to the good conductivity and high wettability as well as the superior permeation capability of the gel electrolyte into the mesoporous matrix of a TiO 2 film« less

Electrochemical Approach for Analyzing Electrolyte Transport Properties and Their Effect on Protonic Ceramic Fuel Cell Performance.

PubMed

Danilov, Nikolay; Lyagaeva, Julia; Vdovin, Gennady; Medvedev, Dmitry; Demin, Anatoly; Tsiakaras, Panagiotis

2017-08-16

The design and development of highly conductive materials with wide electrolytic domain boundaries are among the most promising means of enabling solid oxide fuel cells (SOFCs) to demonstrate outstanding performance across low- and intermediate-temperature ranges. While reducing the thickness of the electrolyte is an extensively studied means for diminishing the total resistance of SOFCs, approaches involving an improvement in the transport behavior of the electrolyte membranes have been less-investigated. In the present work, a strategy for analyzing the electrolyte properties and their effect on SOFC output characteristics is proposed. To this purpose, a SOFC based on a recently developed BaCe 0.5 Zr 0.3 Dy 0.2 O 3-δ proton-conducting ceramic material was fabricated and tested. The basis of the strategy consists of the use of traditional SOFC testing techniques combined with the current interruption method and electromotive force measurements with a modified polarization-correction assessment. This allows one to determine simultaneously such important parameters as maximal power density; ohmic and polarization resistances; average ion transport numbers; and total, ionic, and electronic film conductivities and their activation energies. The proposed experimental procedure is expected to expand both fundamental and applied basics that could be further adopted to improve the technology of electrochemical devices based on proton-conducting electrolytes.

Superior Conductive Solid-like Electrolytes: Nanoconfining Liquids within the Hollow Structures

DOE Office of Scientific and Technical Information (OSTI.GOV)

Zhang, Jinshui; Bai, Ying; Sun, Xiao-Guang

2015-01-01

The growth and proliferation of lithium (Li) dendrites during cell recharge is unavoidable, which seriously hinders the development and application of rechargeable Li metal batteries. Solid electrolytes with robust mechanical modulus are regarded as a promising approach to overcome the dendrite problems. However, their room-temperature ionic conductivities are usually too low to reach the level required for normal battery operation. Here, a class of novel solid electrolytes with liquid-like room-temperature ionic conductivities (> 1 mS cm-1) has been successfully synthesized by taking advantage of the unique nanoarchitectures of hollow silica (HS) spheres to confine liquid electrolytes in hollow space tomore » afford high conductivities. In a symmetric lithium/lithium cell, such kind of solid-like electrolytes demonstrates a robust performance against Li dendrite problems, well stabilizing the cell system from short circuiting in a long-time operation at current densities ranging from 0.16 to 0.32 mA cm-2. Moreover, the high flexibility and compatibility of HS nanoarchitectures, in principle, enables broad tunability to choose desired liquids for the fabrication of other kinds of solid-like electrolytes, such as those containing Na+, Mg2+ or Al3+ as conductive media, providing a useful alternative strategy for the development of next generation rechargeable batteries.« less

Enhanced supercapacitance of activated vertical graphene nanosheets in hybrid electrolyte

NASA Astrophysics Data System (ADS)

Ghosh, Subrata; Sahoo, Gopinath; Polaki, S. R.; Krishna, Nanda Gopala; Kamruddin, M.; Mathews, Tom

2017-12-01

Supercapacitors are becoming the workhorse for emerging energy storage applications due to their higher power density and superior cycle life compared to conventional batteries. The performance of supercapacitors depends on the electrode material, type of electrolyte, and interaction between them. Owing to the beneficial interconnected porous structure with multiple conducting channels, vertical graphene nanosheets (VGN) have proved to be leading supercapacitor electrode materials. Herein, we demonstrate a novel approach based on the combination of surface activation and a new organo-aqueous hybrid electrolyte, tetraethylammonium tetrafluoroborate in H2SO4, to achieve significant enhancement in supercapacitor performance of VGN. As-synthesized VGN exhibits an excellent supercapacitance of 0.64 mF/cm2 in H2SO4. However, identification of a novel electrolyte for performance enhancement is the subject of current research. The present manuscript demonstrates the potential of the hybrid electrolyte in enhancing the areal capacitance (1.99 mF/cm2) with excellent retention (only 5.4% loss after 5000 cycles) and Coulombic efficiency (93.1%). In addition, a five-fold enhancement in the capacitance of VGNs (0.64 to 3.31 mF/cm2) with a reduced internal resistance is achieved by the combination of KOH activation and the hybrid electrolyte.

Hybrid capacitors utilizing halogen-based redox reactions at interface between carbon positive electrode and aqueous electrolytes

NASA Astrophysics Data System (ADS)

Yamazaki, Shigeaki; Ito, Tatsuya; Murakumo, Yuka; Naitou, Masashi; Shimooka, Toshiharu; Yamagata, Masaki; Ishikawa, Masashi

2016-09-01

We propose novel hybrid capacitors (HCs) with electrolyte-involved redox reactions of bromide or iodide species by pretreatment of an activated carbon positive electrode. The treatment is simple; impregnation of pores at an activated carbon fiber cloth (ACFC) as a positive electrode with bromine- or iodine-containing water before cell assembly. The treated positive electrode is applied to a HC cell with a non-treated negative electrode of ACFC and its electrochemical performance is investigated by galvanostatic cycling and leakage current tests. Few studies on such "electrolytic" charge storage systems have provided acceptable capacitor performance because of inevitable self-discharge caused by diffusion of charged species form an electrode to the other one through an electrolyte. Nevertheless, our electrolyte-redox-based HCs show excellent performance without undesirable diffusion of charged species. Moreover, the present HC utilizing a bromide redox system fulfills a practical cell voltage of 1.8 V in spite of an aqueous electrolyte system. This high voltage provides excellent energy density, which is 5 times higher than that in a conventional aqueous electric double-layer capacitor (EDLC), and 1.2 times higher even than that in a 2.7 V-class non-aqueous EDLC, while keeping high charge-discharge rate capability.

Nitrogen-Doped Porous Carbon Nanosheets from Eco-Friendly Eucalyptus Leaves as High Performance Electrode Materials for Supercapacitors and Lithium Ion Batteries.

PubMed

Mondal, Anjon Kumar; Kretschmer, Katja; Zhao, Yufei; Liu, Hao; Wang, Chengyin; Sun, Bing; Wang, Guoxiu

2017-03-13

Nitrogen-doped porous carbon nanosheets were prepared from eucalyptus tree leaves by simply mixing the leaf powders with KHCO 3 and subsequent carbonisation. Porous carbon nanosheets with a high specific surface area of 2133 m 2  g -1 were obtained and applied as electrode materials for supercapacitors and lithium ion batteries. For supercapacitor applications, the porous carbon nanosheet electrode exhibited a supercapacitance of 372 F g -1 at a current density of 500 mA g -1 in 1 m H 2 SO 4 aqueous electrolyte and excellent cycling stability over 15 000 cycles. In organic electrolyte, the nanosheet electrode showed a specific capacitance of 71 F g -1 at a current density of 2 Ag -1 and stable cycling performance. When applied as the anode material for lithium ion batteries, the as-prepared porous carbon nanosheets also demonstrated a high specific capacity of 819 mA h g -1 at a current density of 100 mA g -1 , good rate capability, and stable cycling performance. The outstanding electrochemical performances for both supercapacitors and lithium ion batteries are derived from the large specific surface area, porous nanosheet structure and nitrogen doping effects. The strategy developed in this paper provides a novel route to utilise biomass-derived materials for low-cost energy storage systems. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Composite cathode materials development for intermediate temperature solid oxide fuel cell systems

NASA Astrophysics Data System (ADS)

Qin, Ya

Solid oxide fuel cell (SOFC) systems are of particular interest as electrochemical power systems that can operate on various hydrocarbon fuels with high fuel-to-electrical energy conversion efficiency. Within the SOFC stack, La0.8Sr 0.2Ga0.8Mg0.115Co0.085O3-delta (LSGMC) has been reported as an optimized composition of lanthanum gallate based electrolytes to achieve higher oxygen ionic conductivity at intermediate temperatures, i.e., 500-700°C. The electrocatalytic properties of interfaces between LSGMC electrolytes and various candidate intermediate-temperature SOFC cathodes have been investigated. Sm0.5Sr0.5CoO 3-delta (SSC), and La0.6Sr0.4Co0.2Fe 0.8O3-delta (LSCF), in both pure and composite forms with LSGMC, were investigated with regards to both oxygen reduction and evolution, A range of composite cathode compositions, having ratios of SSC (in wt.%) with LSGMC (wt.%) spanning the compositions 9:1, 8:2, 7:3, 6:4 and 5:5, were investigated to determine the optimal cathode-electrolyte interface performance at intermediate temperatures. All LSGMC electrolyte and cathode powders were synthesized using the glycine-nitrate process (GNP). Symmetrical electrochemical cells were investigated with three-electrode linear dc polarization and ac impedance spectroscopy to characterize the kinetics of the interfacial reactions in detail. Composite cathodes were found to perform better than the single phase cathodes due to significantly reduced polarization resistances. Among those composite SSC-LSGMC cathodes, the 7:3 composition has demonstrated the highest current density at the equivalent overpotential values, indicating that 7:3 is an optimal mixing ratio of the composite cathode materials to achieve the best performance. For the composite SC-LSGMC cathode/LSGMC interface, the cathodic overpotential under 1 A/cm2 current density was as low as 0.085 V at 700°C, 0.062V at 750°C and 0.051V at 800°C in air. Composite LSCF-LSGMC cathode/LSGMC interfaces were found to have about twice the exchange current density of composite SSC-LSGMC/LSGMC interfaces at 700°C. In this research effort, it has been found that: (1) the glycine-nitrate combustion process is favorable to produce perovskite-type oxide powders with good phase purity and negligible intermediate or contaminant phases; (2) The electrochemical performance for both the SSC-LSGMC and LSCF-LSGMC composite electrode materials on LSGMC confirm their potential for use in intermediate temperature SOFC applications; (3) The composite LSCF-LSGMC electrode exhibited much higher current density than the composite SSC-LSGMC electrode in the current dc polarization measurements; and (4) Primary market study results showed promising commercialization feasibility of these new materials sets, provided production is scaled up (with dramatic cost reductions).

Influence of temperature and electrolyte on the performance of activated-carbon supercapacitors

NASA Astrophysics Data System (ADS)

Liu, Ping; Verbrugge, Mark; Soukiazian, Souren

For hybrid electric vehicle traction applications, energy storage devices with high power density and energy efficiency are required. A primary attribute of supercapacitors is that they retain their high power density and energy efficiency even at -30 °C, the lowest temperature at which unassisted starting must be provided to customers. More abuse-tolerant electrolytes are preferred to the high-conductivity acetonitrile-based systems commonly employed. Propylene carbonate based electrolytes are a promising alternative. In this work, we compare the electrochemical performance of two high-power density electrical double layer supercapacitors employing acetonitrile and propylene carbonate as solvents. From this study, we are able to elucidate phenomena that control the resistance of supercapacitor at lower temperatures, and quantify the difference in performance associated with the two electrolytes.

Transport studies in polymer electrolyte fuel cell with porous metallic flow field at ultra high current density

NASA Astrophysics Data System (ADS)

Srouji, Abdul-Kader

Achieving cost reduction for polymer electrolyte fuel cells (PEFC) requires a simultaneous effort in increasing power density while reducing precious metal loading. In PEFCs, the cathode performance is often limiting due to both the slow oxygen reduction reaction (ORR), and mass transport limitation caused by limited oxygen diffusion and liquid water flooding at high current density. This study is motivated by the achievement of ultra-high current density through the elimination of the channel/land (C/L) paradigm in PEFC flow field design. An open metallic element (OME) flow field capable of operating at unprecedented ultra-high current density (3 A/cm2) introduces new advantages and limitations for PEFC operation. The first part of this study compares the OME with a conventional C/L flow field, through performance and electrochemical diagnostic tools such as electrochemical impedance spectroscopy (EIS). The results indicate the uniqueness of the OME's mass transport improvement. No sign of operation limitation due to flooding is noted. The second part specifically examines water management at high current density using the OME flow field. A unique experimental setup is developed to measure steady-state and transient net water drag across the membrane, in order to characterize the fundamental aspects of water transport at high current density with the OME. Instead of flooding, the new limitation is identified to be anode side dry-out of the membrane, caused by electroosmotic drag. The OME improves water removal from the cathode, which immediately improves oxygen transport and performance. However, the low water content in the cathode reduces back diffusion of water to the membrane, and electroosmotic drag dominates at high current density, leading to dry-out. The third part employs the OME flow field as a tool that avoids C/L effects endemic to a typical flow field, in order to study oxygen transport resistance at the catalyst layer of a PEFC. In open literature, a resistance of unknown origin, was shown to directly or indirectly scale with Pt loading. A lack of understanding of the mechanism responsible for such resistance is noted, and several possible theories have been proposed. This lack of fundamental understanding of the origins of this resistance adds complexity to computational models which are designed to capture performance behavior with ultra-low loading electrodes. By employing the OME flow field as a tool to study this phenomena, the origins of the transport resistance appearing at ultra-low Platinum (Pt) loading is proposed to be an increase in oxygen dilution resistance through water film.

Equilibrium lithium-ion transport between nanocrystalline lithium-inserted anatase TiO2 and the electrolyte.

PubMed

Ganapathy, Swapna; van Eck, Ernst R H; Kentgens, Arno P M; Mulder, Fokko M; Wagemaker, Marnix

2011-12-23

The power density of lithium-ion batteries requires the fast transfer of ions between the electrode and electrolyte. The achievable power density is directly related to the spontaneous equilibrium exchange of charged lithium ions across the electrolyte/electrode interface. Direct and unique characterization of this charge-transfer process is very difficult if not impossible, and consequently little is known about the solid/liquid ion transfer in lithium-ion-battery materials. Herein we report the direct observation by solid-state NMR spectroscopy of continuous lithium-ion exchange between the promising nanosized anatase TiO(2) electrode material and the electrolyte. Our results reveal that the energy barrier to charge transfer across the electrode/electrolyte interface is equal to or greater than the barrier to lithium-ion diffusion through the solid anatase matrix. The composition of the electrolyte and in turn the solid/electrolyte interface (SEI) has a significant effect on the electrolyte/electrode lithium-ion exchange; this suggests potential improvements in the power of batteries by optimizing the electrolyte composition. Copyright © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Degradation of dye Procion Red MX-5B by electrolytic and electro-irradiated technologies using diamond electrodes.

PubMed

Cotillas, Salvador; Clematis, Davide; Cañizares, Pablo; Carpanese, Maria Paola; Rodrigo, Manuel A; Panizza, Marco

2018-05-01

This work focuses on the treatment of synthetic wastewater polluted with dye Procion Red MX-5B by different Electrochemical Advanced Oxidation Processes (EAOP) based on diamond anodes. The influence of the current density and the supporting electrolyte has been studied on dye removal and total mineralization of the organic matter. Results show that electrolysis with diamond electrodes is a suitable technology for an efficient degradation of dye. Nonetheless, the process efficiency increases when using chloride as supporting electrolyte because of the electrochemical generation of hypochlorite in wastewater which significantly contribute to dye removal. On the contrary, the total mineralization of the organic matter is more efficient in sulfate media. In this case, large amounts of peroxodisulfate are electrogenerated, favoring the complete removal of total organic carbon (TOC). On the other hand, lower current densities (10 mA cm -2 ) lead to a more efficient removal of both dye and TOC due to the mass transfer limitations of the technology. Finally, the coupling of UV light irradiation or ultrasound to electrolysis significantly improves the process performance, being photoelectrolysis the most efficient technology for the treatment of wastewater polluted with Procion Red MX-5B. This fact is due to the potential production of free chlorine or sulfate radicals that takes place by the activation of the electrogenerated oxidants. These species are more reactive than oxidants and, therefore, they quickly attack the organic matter present in wastewater. Copyright © 2018 Elsevier Ltd. All rights reserved.

Dimensionless numbers and correlating equations for the analysis of the membrane-gas diffusion electrode assembly in polymer electrolyte fuel cells

NASA Astrophysics Data System (ADS)

Gyenge, E. L.

The Quraishi-Fahidy method [Can. J. Chem. Eng. 59 (1981) 563] was employed to derive characteristic dimensionless numbers for the membrane-electrolyte, cathode catalyst layer and gas diffuser, respectively, based on the model presented by Bernardi and Verbrugge for polymer electrolyte fuel cells [AIChE J. 37 (1991) 1151]. Monomial correlations among dimensionless numbers were developed and tested against experimental and mathematical modeling results. Dimensionless numbers comparing the bulk and surface-convective ionic conductivities, the electric and viscous forces and the current density and the fixed surface charges, were employed to describe the membrane ohmic drop and its non-linear dependence on current density due to membrane dehydration. The analysis of the catalyst layer yielded electrode kinetic equivalents of the second Damköhler number and Thiele modulus, influencing the penetration depth of the oxygen reduction front based on the pseudohomogeneous film model. The correlating equations for the catalyst layer could describe in a general analytical form, all the possible electrode polarization scenarios such as electrode kinetic control coupled or not with ionic and/or oxygen mass transport limitation. For the gas diffusion-backing layer correlations are presented in terms of the Nusselt number for mass transfer in electrochemical systems. The dimensionless number-based correlating equations for the membrane electrode assembly (MEA) could provide a practical approach to quantify single-cell polarization results obtained under a variety of experimental conditions and to implement them in models of the fuel cell stack.

Effects of anodic oxidation parameters on a modified titanium surface.

PubMed

Park, Il Song; Lee, Min Ho; Bae, Tae Sung; Seol, Kyeong Won

2008-02-01

Anodic oxidation is an electrochemical treatment that can be used to control the thickness of an oxide layer formed on a titanium surface. This procedure has the advantage of allowing the ions contained in an electrolyte to deposit onto the oxide layer. The characteristics of a layer treated with anodic oxidation can vary according to the type and concentration of the electrolytes as well as the processing variables used during anodic oxidation. In this study, the constant electrolyte for anodic oxidation was a mixed solution containing 0.02 M DL-alpha-glycerophosphate disodium salt and 0.2M calcium acetate. Anodic oxidation was carried out at different voltages, current densities, and duration of anodic oxidation. The results showed that the current density and variation in the duration of anodic oxidation did not have a large effect on the change in the characteristics of the layer. On the other hand, the size of the micropores was increased with increasing voltage of anodic oxidation, and anatase and rutile phases were found to co-exist in the porous titanium dioxide layer. In addition, the thickness of the oxide layer on titanium and the characteristic of corrosion resistance increased with increasing voltage. The MTT test showed that the cell viability was increased considerably as a result of anodic oxidation. The anodizing voltage is an important parameter that determines the characteristics of the anodic oxide layer of titanium. (c) 2007 Wiley Periodicals, Inc.

The Li-ion rechargeable battery: a perspective.

PubMed

Goodenough, John B; Park, Kyu-Sung

2013-01-30

Each cell of a battery stores electrical energy as chemical energy in two electrodes, a reductant (anode) and an oxidant (cathode), separated by an electrolyte that transfers the ionic component of the chemical reaction inside the cell and forces the electronic component outside the battery. The output on discharge is an external electronic current I at a voltage V for a time Δt. The chemical reaction of a rechargeable battery must be reversible on the application of a charging I and V. Critical parameters of a rechargeable battery are safety, density of energy that can be stored at a specific power input and retrieved at a specific power output, cycle and shelf life, storage efficiency, and cost of fabrication. Conventional ambient-temperature rechargeable batteries have solid electrodes and a liquid electrolyte. The positive electrode (cathode) consists of a host framework into which the mobile (working) cation is inserted reversibly over a finite solid-solution range. The solid-solution range, which is reduced at higher current by the rate of transfer of the working ion across electrode/electrolyte interfaces and within a host, limits the amount of charge per electrode formula unit that can be transferred over the time Δt = Δt(I). Moreover, the difference between energies of the LUMO and the HOMO of the electrolyte, i.e., electrolyte window, determines the maximum voltage for a long shelf and cycle life. The maximum stable voltage with an aqueous electrolyte is 1.5 V; the Li-ion rechargeable battery uses an organic electrolyte with a larger window, which increase the density of stored energy for a given Δt. Anode or cathode electrochemical potentials outside the electrolyte window can increase V, but they require formation of a passivating surface layer that must be permeable to Li(+) and capable of adapting rapidly to the changing electrode surface area as the electrode changes volume during cycling. A passivating surface layer adds to the impedance of the Li(+) transfer across the electrode/electrolyte interface and lowers the cycle life of a battery cell. Moreover, formation of a passivation layer on the anode robs Li from the cathode irreversibly on an initial charge, further lowering the reversible Δt. These problems plus the cost of quality control of manufacturing plague development of Li-ion rechargeable batteries that can compete with the internal combustion engine for powering electric cars and that can provide the needed low-cost storage of electrical energy generated by renewable wind and/or solar energy. Chemists are contributing to incremental improvements of the conventional strategy by investigating and controlling electrode passivation layers, improving the rate of Li(+) transfer across electrode/electrolyte interfaces, identifying electrolytes with larger windows while retaining a Li(+) conductivity σ(Li) > 10(-3) S cm(-1), synthesizing electrode morphologies that reduce the size of the active particles while pinning them on current collectors of large surface area accessible by the electrolyte, lowering the cost of cell fabrication, designing displacement-reaction anodes of higher capacity that allow a safe, fast charge, and designing alternative cathode hosts. However, new strategies are needed for batteries that go beyond powering hand-held devices, such as using electrode hosts with two-electron redox centers; replacing the cathode hosts by materials that undergo displacement reactions (e.g. sulfur) by liquid cathodes that may contain flow-through redox molecules, or by catalysts for air cathodes; and developing a Li(+) solid electrolyte separator membrane that allows an organic and aqueous liquid electrolyte on the anode and cathode sides, respectively. Opportunities exist for the chemist to bring together oxide and polymer or graphene chemistry in imaginative morphologies.

Redox-Active Hydrogel Polymer Electrolytes with Different pH Values for Enhancing the Energy Density of the Hybrid Solid-State Supercapacitor.

PubMed

Tang, Xiaohui; Lui, Yu Hui; Merhi, Abdul Rahman; Chen, Bolin; Ding, Shaowei; Zhang, Bowei; Hu, Shan

2017-12-27

To enhance the energy density of solid-state supercapacitors, a novel solid-state cell, made of redox-active poly(vinyl alcohol) (PVA) hydrogel electrolytes and functionalized carbon nanotube-coated cellulose paper electrodes, was investigated in this work. Briefly, acidic PVA-[BMIM]Cl-lactic acid-LiBr and neutral PVA-[BMIM]Cl-sodium acetate-LiBr hydrogel polymer electrolytes are used as catholyte and anolyte, respectively. The acidic condition of the catholyte contributes to suppression of the undesired irreversible reaction of Br - and extension of the oxygen evolution reaction potential to a higher value than that of the redox potential of Br - /Br 3 - reaction. The observed Br - /Br 3 - redox activity at the cathode contributes to enhance the cathode capacitance. The neutral condition of the anolyte helps extend the operating voltage window of the supercapacitor by introducing hydrogen evolution reaction overpotential to the anode. The electrosorption of nascent H on the negative electrode also increases the anode capacitance. As a result, the prepared solid-state hybrid supercapacitor shows a broad voltage window of 1.6 V, with a high Coulombic efficiency of 97.6% and the highest energy density of 16.3 Wh/kg with power density of 932.6 W/kg at 2 A/g obtained. After 10 000 cycles of galvanostatic charge and discharge tests at the current density of 10 A/g, it exhibits great cyclic stability with 93.4% retention of the initial capacitance. In addition, a robust capacitive performance can also be observed from the solid-state supercapacitor at different bending angles, indicating its great potential as a flexible energy storage device.

Method for providing uranium articles with a corrosion resistant anodized coating

DOEpatents

Waldrop, Forrest B.; Washington, Charles A.

1982-01-01

Uranium articles are provided with anodized oxide coatings in an aqueous solution of an electrolyte selected from the group consisting of potassium phosphate, potassium hydroxide, ammonium hydroxide, and a mixture of potassium tetraborate and boric acid. The uranium articles are anodized at a temperature greater than about 75.degree. C. with a current flow of less than about 0.036 A/cm.sup.2 of surface area while the pH of the solution is maintained in a range of about 2 to 11.5. The pH values of the aqueous solution and the low current density utilized during the electrolysis prevent excessive dissolution of the uranium and porosity in the film or watering. The relatively high temperature of the electrolyte bath inhibits hydration and the attendant deleterious pitting so as to enhance corrosion resistance of the anodized coating.

High capacity of lithium-sulfur batteries at low electrolyte/sulfur ratio enabled by an organosulfide containing electrolyte

DOE PAGES

Chen, Shuru; Gao, Yue; Yu, Zhaoxin; ...

2016-11-30

We present that lithium-sulfur (Li-S) battery is a promising energy storage technology to replace lithium ion batteries for higher energy density and lower cost. Dissolution of lithium polysulfide intermediates in conventional Li-S electrolytes is known as one of the key technical barriers to the development of Li-S, because it promotes redistribution and irreversible deposition of Li 2S, and also forces large amounts of electrolyte to be used, shortening cycling life and driving down cell energy density. Recently, dimethyl disulfide as a functional co-solvent has been demonstrated to show an alternate electrochemical reaction pathway for sulfur cathodes by the formation ofmore » dimethyl polysulfides and lithium organosulfides as intermediates and reduction products. In this work, comprehensive studies show that this new pathway not only provides high capacity but also enables excellent capacity retention through a built-in automatic discharge shutoff mechanism by tuning carbon/sulfur ratio in sulfur cathodes to reduce unfavorable Li 2S formation. Furthermore, this new electrolyte system is also found to enable high capacity of high-sulfur-loading cathodes with low electrolyte/sulfur (E/S) ratios, such as a stable specific capacity of around 1000 mAh g -1 using a low electrolyte amount (i.e, E/S ratio of 5 mL g -1) and highsulfur-loading (4 mg cm -2) cathodes. This electrolyte system almost doubles the capacity obtained with conventional electrolytes under the same harsh conditions. In conclusion, these results highlight the practical potential of this electrolyte system to enable high-energy-density Li-S batteries.« less

Enhanced performance of ultracapacitors using redox additive-based electrolytes

NASA Astrophysics Data System (ADS)

Jain, Dharmendra; Kanungo, Jitendra; Tripathi, S. K.

2018-05-01

Different concentrations of potassium iodide (KI) as redox additive had been added to 1 M sulfuric acid (H2SO4) electrolyte with an aim of enhancing the capacitance and energy density of ultracapacitors via redox reactions at the interfaces of electrode-electrolyte. Ultracapacitors were fabricated using chemically treated activated carbon as electrode with H2SO4 and H2SO4-KI as an electrolyte. The electrochemical performances of fabricated supercapacitors were investigated by impedance spectroscopy, cyclic voltammetry and charge-discharge techniques. The maximum capacitance ` C' was observed with redox additives-based electrolyte system comprising 1 M H2SO4-0.3 M KI (1072 F g- 1), which is very much higher than conventional 1 M H2SO4 (61.3 F g- 1) aqueous electrolyte-based ultracapacitors. It corresponds to an energy density of 20.49 Wh kg- 1 at 2.1 A g- 1 for redox additive-based electrolyte, which is six times higher as compared to that of pristine electrolyte (1 M H2SO4) having energy density of only 3.36 Wh kg- 1. The temperature dependence behavior of fabricated cell was also analyzed, which shows increasing pattern in its capacitance values in a temperature range of 5-70 °C. Under cyclic stability test, redox electrolyte-based system shows almost 100% capacitance retention up to 5000 cycles and even more. For comparison, ultracapacitors based on polymer gel electrolyte polyvinyl alcohol (PVA) (10 wt%)—{H2SO4 (1 M)-KI (0.3 M)} (90 wt%) have been fabricated and characterized with the same electrode materials.

High capacity of lithium-sulfur batteries at low electrolyte/sulfur ratio enabled by an organosulfide containing electrolyte

DOE Office of Scientific and Technical Information (OSTI.GOV)

Chen, Shuru; Gao, Yue; Yu, Zhaoxin

We present that lithium-sulfur (Li-S) battery is a promising energy storage technology to replace lithium ion batteries for higher energy density and lower cost. Dissolution of lithium polysulfide intermediates in conventional Li-S electrolytes is known as one of the key technical barriers to the development of Li-S, because it promotes redistribution and irreversible deposition of Li 2S, and also forces large amounts of electrolyte to be used, shortening cycling life and driving down cell energy density. Recently, dimethyl disulfide as a functional co-solvent has been demonstrated to show an alternate electrochemical reaction pathway for sulfur cathodes by the formation ofmore » dimethyl polysulfides and lithium organosulfides as intermediates and reduction products. In this work, comprehensive studies show that this new pathway not only provides high capacity but also enables excellent capacity retention through a built-in automatic discharge shutoff mechanism by tuning carbon/sulfur ratio in sulfur cathodes to reduce unfavorable Li 2S formation. Furthermore, this new electrolyte system is also found to enable high capacity of high-sulfur-loading cathodes with low electrolyte/sulfur (E/S) ratios, such as a stable specific capacity of around 1000 mAh g -1 using a low electrolyte amount (i.e, E/S ratio of 5 mL g -1) and highsulfur-loading (4 mg cm -2) cathodes. This electrolyte system almost doubles the capacity obtained with conventional electrolytes under the same harsh conditions. In conclusion, these results highlight the practical potential of this electrolyte system to enable high-energy-density Li-S batteries.« less

Rational Development of Neutral Aqueous Electrolytes for Zinc–Air Batteries

PubMed Central

Clark, Simon; Latz, Arnulf

2017-01-01

Abstract Neutral aqueous electrolytes have been shown to extend both the calendar life and cycling stability of secondary zinc–air batteries (ZABs). Despite this promise, there are currently no modeling studies investigating the performance of neutral ZABs. Traditional continuum models are numerically insufficient to simulate the dynamic behavior of these complex systems because of the rapid, orders‐of‐magnitude concentration shifts that occur. In this work, we present a novel framework for modeling the cell‐level performance of pH‐buffered aqueous electrolytes. We apply our model to conduct the first continuum‐scale simulation of secondary ZABs using aqueous ZnCl2–NH4Cl as electrolyte. We first use our model to interpret the results of two recent experimental studies of neutral ZABs, showing that the stability of the pH value is a significant factor in cell performance. We then optimize the composition of the electrolyte and the design of the cell considering factors including pH stability, final discharge product, and overall energy density. Our simulations predict that the effectiveness of the pH buffer is limited by slow mass transport and that chlorine‐containing solids may precipitate in addition to ZnO. PMID:28898553

Highly uniform and monodisperse carbon nanospheres enriched with cobalt-nitrogen active sites as a potential oxygen reduction electrocatalyst

NASA Astrophysics Data System (ADS)

Wan, Xing; Wang, Hongjuan; Yu, Hao; Peng, Feng

2017-04-01

Uniform cobalt and nitrogen co-doped carbon nanospheres (CoN-CNS) with high specific surface area (865 m2 g-1) have been prepared by a simple but efficient method. The prepared CoN-CNS catalyst exhibits outstanding catalytic performance for the oxygen reduction reaction (ORR) in both alkaline and acidic electrolytes. In alkaline electrolyte, the prepared CoN-CNS has more positive half-wave potential and larger kinetic current density than commercial Pt/C. In acidic electrolyte, CoN-CNS also shows good ORR activity with high electron transfer number, its onset and half-wave potentials are all close to those of commercial carbon supported platinum catalyst (Pt/C). CoN-CNS catalyst shows more superior stability and higher methanol-tolerance than commercial Pt/C both in alkaline and in acidic electrolytes. The potassium thiocyanate-poisoning test further confirms that the cobalt-nitrogen active sites exist in CoN-CNS, which are dominating to endow high ORR catalytic activity in acidic electrolyte. This study develops a new method to prepare non-precious metal catalyst with excellent ORR performances for direct methanol fuel cells.

Dendrite Suppression by Synergistic Combination of Solid Polymer Electrolyte Crosslinked with Natural Terpenes and Lithium-Powder Anode for Lithium-Metal Batteries.

PubMed

Shim, Jimin; Lee, Jae Won; Bae, Ki Yoon; Kim, Hee Joong; Yoon, Woo Young; Lee, Jong-Chan

2017-05-22

Lithium-metal anode has fundamental problems concerning formation and growth of lithium dendrites, which prevents practical applications of next generation of high-capacity lithium-metal batteries. The synergistic combination of solid polymer electrolyte (SPE) crosslinked with naturally occurring terpenes and lithium-powder anode is promising solution to resolve the dendrite issues by substituting conventional liquid electrolyte/separator and lithium-foil anode system. A series of SPEs based on polysiloxane crosslinked with natural terpenes are prepared by facile thiol-ene click reaction under mild condition and the structural effect of terpene crosslinkers on electrochemical properties is studied. Lithium powder with large surface area is prepared by droplet emulsion technique (DET) and used as anode material. The effect of the physical state of electrolyte (solid/liquid) and morphology of lithium-metal anode (powder/foil) on dendrite growth behavior is systematically studied. The synergistic combination of SPE and lithium-powder anode suggests an effective solution to suppress the dendrite growth owing to the formation of a stable solid-electrolyte interface (SEI) layer and delocalized current density. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Composite electrolyte with proton conductivity for low-temperature solid oxide fuel cell

DOE Office of Scientific and Technical Information (OSTI.GOV)

Raza, Rizwan, E-mail: razahussaini786@gmail.com; Department of Energy Technology, Royal Institute of Technology, KTH, Stockholm 10044; Ahmed, Akhlaq

In the present work, cost-effective nanocomposite electrolyte (Ba-SDC) oxide is developed for efficient low-temperature solid oxide fuel cells (LTSOFCs). Analysis has shown that dual phase conduction of O{sup −2} (oxygen ions) and H{sup +} (protons) plays a significant role in the development of advanced LTSOFCs. Comparatively high proton ion conductivity (0.19 s/cm) for LTSOFCs was achieved at low temperature (460 °C). In this article, the ionic conduction behaviour of LTSOFCs is explained by carrying out electrochemical impedance spectroscopy measurements. Further, the phase and structure analysis are investigated by X-ray diffraction and scanning electron microscopy techniques. Finally, we achieved an ionic transport numbermore » of the composite electrolyte for LTSOFCs as high as 0.95 and energy and power density of 90% and 550 mW/cm{sup 2}, respectively, after sintering the composite electrolyte at 800 °C for 4 h, which is promising. Our current effort toward the development of an efficient, green, low-temperature solid oxide fuel cell with the incorporation of high proton conductivity composite electrolyte may open frontiers in the fields of energy and fuel cell technology.« less

Micro-tubular solid oxide fuel cell based on a porous yttria-stabilized zirconia support

NASA Astrophysics Data System (ADS)

Panthi, Dhruba; Tsutsumi, Atsushi

2014-08-01

Solid oxide fuel cells (SOFCs) are promising electrochemical energy conversion devices owing to their high power generation efficiency and environmentally benign operation. Micro-tubular SOFCs, which have diameters ranging from a few millimeters to the sub-millimeter scale, offer several advantages over competing SOFCs such as high volumetric power density, good endurance against thermal cycling, and flexible sealing between fuel and oxidant streams. Herein, we successfully realized a novel micro-tubular SOFC design based on a porous yttria-stabilized zirconia (YSZ) support using multi-step dip coating and co-sintering methods. The micro-tubular SOFC consisted of Ni-YSZ, YSZ, and strontium-doped lanthanum manganite (LSM)-YSZ as the anode, electrolyte, and cathode, respectively. In addition, to facilitate current collection from the anode and cathode, Ni and LSM were applied as an anode current collector and cathode current collector, respectively. Micro-crystalline cellulose was selected as a pore former to achieve better shrinkage behavior of the YSZ support so that the electrolyte layer could be densified at a co-sintering temperature of 1300°C. The developed micro-tubular design showed a promising electrochemical performance with maximum power densities of 525, 442, and 354 mW cm-2 at 850, 800, and 750°C, respectively.

Dynamic behaviour of interphases and its implication on high-energy-density cathode materials in lithium-ion batteries

PubMed Central

Li, Wangda; Dolocan, Andrei; Oh, Pilgun; Celio, Hugo; Park, Suhyeon; Cho, Jaephil; Manthiram, Arumugam

2017-01-01

Undesired electrode–electrolyte interactions prevent the use of many high-energy-density cathode materials in practical lithium-ion batteries. Efforts to address their limited service life have predominantly focused on the active electrode materials and electrolytes. Here an advanced three-dimensional chemical and imaging analysis on a model material, the nickel-rich layered lithium transition-metal oxide, reveals the dynamic behaviour of cathode interphases driven by conductive carbon additives (carbon black) in a common nonaqueous electrolyte. Region-of-interest sensitive secondary-ion mass spectrometry shows that a cathode-electrolyte interphase, initially formed on carbon black with no electrochemical bias applied, readily passivates the cathode particles through mutual exchange of surface species. By tuning the interphase thickness, we demonstrate its robustness in suppressing the deterioration of the electrode/electrolyte interface during high-voltage cell operation. Our results provide insights on the formation and evolution of cathode interphases, facilitating development of in situ surface protection on high-energy-density cathode materials in lithium-based batteries. PMID:28443608

A high-mobility electronic system at an electrolyte-gated oxide surface

DOE PAGES

Gallagher, Patrick; Lee, Menyoung; Petach, Trevor A.; ...

2015-03-12

Electrolyte gating is a powerful technique for accumulating large carrier densities at a surface. Yet this approach suffers from significant sources of disorder: electrochemical reactions can damage or alter the sample, and the ions of the electrolyte and various dissolved contaminants sit Angstroms from the electron system. Accordingly, electrolyte gating is well suited to studies of superconductivity and other phenomena robust to disorder, but of limited use when reactions or disorder must be avoided. Here we demonstrate that these limitations can be overcome by protecting the sample with a chemically inert, atomically smooth sheet of hexagonal boron nitride. We illustratemore » our technique with electrolyte-gated strontium titanate, whose mobility when protected with boron nitride improves more than 10-fold while achieving carrier densities nearing 10 14 cm –2. In conclusion, our technique is portable to other materials, and should enable future studies where high carrier density modulation is required but electrochemical reactions and surface disorder must be minimized.« less

Dynamic behaviour of interphases and its implication on high-energy-density cathode materials in lithium-ion batteries

NASA Astrophysics Data System (ADS)

Li, Wangda; Dolocan, Andrei; Oh, Pilgun; Celio, Hugo; Park, Suhyeon; Cho, Jaephil; Manthiram, Arumugam

2017-04-01

Undesired electrode-electrolyte interactions prevent the use of many high-energy-density cathode materials in practical lithium-ion batteries. Efforts to address their limited service life have predominantly focused on the active electrode materials and electrolytes. Here an advanced three-dimensional chemical and imaging analysis on a model material, the nickel-rich layered lithium transition-metal oxide, reveals the dynamic behaviour of cathode interphases driven by conductive carbon additives (carbon black) in a common nonaqueous electrolyte. Region-of-interest sensitive secondary-ion mass spectrometry shows that a cathode-electrolyte interphase, initially formed on carbon black with no electrochemical bias applied, readily passivates the cathode particles through mutual exchange of surface species. By tuning the interphase thickness, we demonstrate its robustness in suppressing the deterioration of the electrode/electrolyte interface during high-voltage cell operation. Our results provide insights on the formation and evolution of cathode interphases, facilitating development of in situ surface protection on high-energy-density cathode materials in lithium-based batteries.

A Long Cycle Life, Self-Healing Zinc-Iodine Flow Battery with High Power Density.

PubMed

Xie, Congxin; Zhang, Huamin; Xu, Wenbin; Wang, Wei; Li, Xianfeng

2018-05-01

A zinc-iodine flow battery (ZIFB) with long cycle life, high energy, high power density, and self-healing behavior is prepared. The long cycle life was achieved by employing a low-cost porous polyolefin membrane and stable electrolytes. The pores in the membrane can be filled with a solution containing I 3 - that can react with zinc dendrite. Therefore, by consuming zinc dendrite, the battery can self-recover from micro-short-circuiting resulting from overcharging. By using KI, ZnBr 2 , and KCl as electrolytes and a high ion-conductivity porous membrane, a very high power density can be achieved. As a result, a ZIFB exhibits an energy efficiency (EE) of 82 % at 80 mA cm -2 , which is 8 times higher than the currently reported ZIFBs. Furthermore, a stack with an output of 700 W was assembled and continuously run for more than 300 cycles. We believe this ZIFB can lead the way to development of new-generation, high-performance flow batteries. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Nitrogen and sulfur co-doped porous graphene aerogel as an efficient electrode material for high performance supercapacitor in ionic liquid electrolyte

NASA Astrophysics Data System (ADS)

Chen, Yujuan; Liu, Zhaoen; Sun, Li; Lu, Zhiwei; Zhuo, Kelei

2018-06-01

Nitrogen and sulfur co-doped graphene aerogel (NS-GA) is prepared by one-pot process. The as-prepared materials are investigated as supercapacitors electrodes in an ionic liquid (1-ethyl-3-methylimidazolium tetrafluoroborate, EMIMBF4) electrolyte. The NS-GA is characterized using X-ray diffraction, X-ray photoelectron spectroscopy, and Raman spectroscopy scanning electron microscopy. The results show that the NS-GA has hierarchical porous structure. Electrochemical performance is investigated by cycle voltammetry and galvanostatic charge-discharge. Notably, the supercapacitor based on the NS-GA-5 possesses a maximum energy density of 100.7 Wh kg-1 at power density of 0.94 kW kg-1. The electrode materials also offer a large specific capacitance of 203.2 F g-1 at a current density of 1 A g-1 and the capacitance retention of NS-GA-5 is 90% after 3000 cycles at a scan rate of 2 A g-1. The NS-GA-5 with numerous advantages including low cost and remarkable electrochemical behaviors can be a promising electrode material for the application of supercapacitors.

Dedicated nuclear facilities for electrolytic hydrogen production

NASA Technical Reports Server (NTRS)

Foh, S. E.; Escher, W. J. D.; Donakowski, T. D.

1979-01-01

An advanced technology, fully dedicated nuclear-electrolytic hydrogen production facility is presented. This plant will produce hydrogen and oxygen only and no electrical power will be generated for off-plant use. The conceptual design was based on hydrogen production to fill a pipeline at 1000 psi and a 3000 MW nuclear base, and the base-line facility nuclear-to-shaftpower and shaftpower-to-electricity subsystems, the water treatment subsystem, electricity-to-hydrogen subsystem, hydrogen compression, efficiency, and hydrogen production cost are discussed. The final conceptual design integrates a 3000 MWth high-temperature gas-cooled reactor operating at 980 C helium reactor-out temperature, direct dc electricity generation via acyclic generators, and high-current density, high-pressure electrolyzers based on the solid polymer electrolyte approach. All subsystems are close-coupled and optimally interfaced and pipeline hydrogen is produced at 1000 psi. Hydrogen costs were about half of the conventional nuclear electrolysis process.

Corrosion evaluation of zirconium doped oxide coatings on aluminum formed by plasma electrolytic oxidation.

PubMed

Bajat, Jelena; Mišković-Stanković, Vesna; Vasilić, Rastko; Stojadinović, Stevan

2014-01-01

The plasma electrolytic oxidation (PEO) of aluminum in sodium tungstate (Na(2)WO(4) · (2)H(2)O) and Na(2)WO(4) · (2)H(2)O doped with Zr was analyzed in order to obtain oxide coatings with improved corrosion resistance. The influence of current density in PEO process and anodization time was investigated, as well as the influence of Zr, with the aim to find out how they affect the chemical content, morphology, surface roughness, and corrosion stability of oxide coatings. It was shown that the presence of Zr increases the corrosion stability of oxide coatings for all investigated PEO times. Evolution of EIS spectra during the exposure to 3% NaCl, as a strong corrosive agent, indicated the highest corrosion stability for PEO coating formed on aluminum at 70 mA/cm(2) for 2 min in a zirconium containing electrolyte.

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wang, Ziying; Lee, Jungwoo Z.; Xin, Huolin L.

All-solid-state lithium-ion batteries have the potential to not only push the current limits of energy density by utilizing Li metal, but also improve safety by avoiding flammable organic electrolyte. However, understanding the role of solid electrolyte – electrode interfaces will be critical to improve performance. In this paper, we conducted long term cycling on commercially available lithium cobalt oxide (LCO)/lithium phosphorus oxynitride (LiPON)/lithium (Li) cells at elevated temperature to investigate the interfacial phenomena that lead to capacity decay. STEM-EELS analysis of samples revealed a previously unreported disordered layer between the LCO cathode and LiPON electrolyte. This electrochemically inactive layer grewmore » in thickness leading to loss of capacity and increase of interfacial resistance when cycled at 80 °C. Finally, the stabilization of this layer through interfacial engineering is crucial to improve the long term performance of thin-film batteries especially under thermal stress.« less

Resolution in QCM sensors for the viscosity and density of liquids: application to lead acid batteries.

PubMed

Cao-Paz, Ana María; Rodríguez-Pardo, Loreto; Fariña, José; Marcos-Acevedo, Jorge

2012-01-01

In battery applications, particularly in automobiles, submarines and remote communications, the state of charge (SoC) is needed in order to manage batteries efficiently. The most widely used physical parameter for this is electrolyte density. However, there is greater dependency between electrolyte viscosity and SoC than that seen for density and SoC. This paper presents a Quartz Crystal Microbalance (QCM) sensor for electrolyte density-viscosity product measurements in lead acid batteries. The sensor is calibrated in H(2)SO(4) solutions in the battery electrolyte range to obtain sensitivity, noise and resolution. Also, real-time tests of charge and discharge are conducted placing the quartz crystal inside the battery. At the same time, the present theoretical "resolution limit" to measure the square root of the density-viscosity product [Formula: see text] of a liquid medium or best resolution achievable with a QCM oscillator is determined. Findings show that the resolution limit only depends on the characteristics of the liquid to be studied and not on frequency. The QCM resolution limit for [Formula: see text] measurements worsens when the density-viscosity product of the liquid is increased, but it cannot be improved by elevating the work frequency.

Resolution in QCM Sensors for the Viscosity and Density of Liquids: Application to Lead Acid Batteries

PubMed Central

Cao-Paz, Ana María; Rodríguez-Pardo, Loreto; Fariña, José; Marcos-Acevedo, Jorge

2012-01-01

In battery applications, particularly in automobiles, submarines and remote communications, the state of charge (SoC) is needed in order to manage batteries efficiently. The most widely used physical parameter for this is electrolyte density. However, there is greater dependency between electrolyte viscosity and SoC than that seen for density and SoC. This paper presents a Quartz Crystal Microbalance (QCM) sensor for electrolyte density-viscosity product measurements in lead acid batteries. The sensor is calibrated in H2SO4 solutions in the battery electrolyte range to obtain sensitivity, noise and resolution. Also, real-time tests of charge and discharge are conducted placing the quartz crystal inside the battery. At the same time, the present theoretical “resolution limit” to measure the square root of the density-viscosity product (ρη) of a liquid medium or best resolution achievable with a QCM oscillator is determined. Findings show that the resolution limit only depends on the characteristics of the liquid to be studied and not on frequency. The QCM resolution limit for ρη measurements worsens when the density-viscosity product of the liquid is increased, but it cannot be improved by elevating the work frequency. PMID:23112618

Incorporation of Ca and P on anodized titanium surface: Effect of high current density.

PubMed

Laurindo, Carlos A H; Torres, Ricardo D; Mali, Sachin A; Gilbert, Jeremy L; Soares, Paulo

2014-04-01

This study systematically evaluated the surface and corrosion characteristics of commercially pure titanium (grade 2) modified by plasma electrolytic oxidation (PEO) with high current density. The anodization process was carried out galvanostatically (constant current density) using a solution containing calcium glycerophosphate (0.02mol/L) and calcium acetate (0.15mol/L). The current densities applied were 400, 700, 1000 and 1200mA/cm(2) for a period of 15s. Composition, crystalline structure, morphology, roughness, wettability and "in-vitro" bioactivity test in SBF of the anodized layer were evaluated by X-ray diffraction, scanning electron microscopy, energy dispersive spectroscopy, profilometry and contact angle measurements. Corrosion properties were evaluated by open circuit potential, electrochemical impedance spectroscopy (EIS) and potentiodynamic polarization measurements. The results show that the TiO2 oxide layers present an increase of thickness, porosity, roughness, wettability, Ca/P ratio, and bioactivity, with the applied current density up to 1000mA/cm(2). Corrosion resistance also increases with applied current density. It is observed that for 1200mA/cm(2), there is a degradation of the oxide layer. In general, the results suggest that the anodized TiO2 layer with better properties is formed with an applied current of 1000mA/cm(2). Copyright © 2014 Elsevier B.V. All rights reserved.

Correlating Microstructural Lithium Metal Growth with Electrolyte Salt Depletion in Lithium Batteries Using ⁷Li MRI.

PubMed

Chang, Hee Jung; Ilott, Andrew J; Trease, Nicole M; Mohammadi, Mohaddese; Jerschow, Alexej; Grey, Clare P

2015-12-09

Lithium dendrite growth in lithium ion and lithium rechargeable batteries is associated with severe safety concerns. To overcome these problems, a fundamental understanding of the growth mechanism of dendrites under working conditions is needed. In this work, in situ (7)Li magnetic resonance (MRI) is performed on both the electrolyte and lithium metal electrodes in symmetric lithium cells, allowing the behavior of the electrolyte concentration gradient to be studied and correlated with the type and rate of microstructure growth on the Li metal electrode. For this purpose, chemical shift (CS) imaging of the metal electrodes is a particularly sensitive diagnostic method, enabling a clear distinction to be made between different types of microstructural growth occurring at the electrode surface and the eventual dendrite growth between the electrodes. The CS imaging shows that mossy types of microstructure grow close to the surface of the anode from the beginning of charge in every cell studied, while dendritic growth is triggered much later. Simple metrics have been developed to interpret the MRI data sets and to compare results from a series of cells charged at different current densities. The results show that at high charge rates, there is a strong correlation between the onset time of dendrite growth and the local depletion of the electrolyte at the surface of the electrode observed both experimentally and predicted theoretical (via the Sand's time model). A separate mechanism of dendrite growth is observed at low currents, which is not governed by salt depletion in the bulk liquid electrolyte. The MRI approach presented here allows the rate and nature of a process that occurs in the solid electrode to be correlated with the concentrations of components in the electrolyte.

Electrochemical characterization of p(+)n and n(+)p diffused InP structures

NASA Technical Reports Server (NTRS)

Wilt, David M.; Faur, Maria; Faur, Mircea; Goradia, M.; Vargas-Aburto, Carlos

1993-01-01

The relatively well documented and widely used electrolytes for characterization and processing of Si and GaAs-related materials and structures by electrochemical methods are of little or no use with InP because the electrolytes presently used either dissolve the surface preferentially at the defect areas or form residual oxides and introduce a large density of surface states. Using an electrolyte which was newly developed for anodic dissolution of InP, and was named the 'FAP' electrolyte, accurate characterization of InP related structures including nature and density of surface states, defect density, and net majority carrier concentration, all as functions of depth was performed. A step-by-step optimization of n(+)p and p(+)n InP structures made by thermal diffusion was done using the electrochemical techniques, and resulted in high performance homojunction InP structures.

Influence of electric current on bacterial viability in wastewater treatment.

PubMed

Wei, V; Elektorowicz, M; Oleszkiewicz, J A

2011-10-15

Minimizing the influence of electric current on bacterial viability in the electro-technologies such as electrophoresis and electrocoagulation is crucial in designing and operating the electric hybrid wastewater treatment system. In this study the biomass from a membrane bioreactor (MBR) was subjected to constant direct current and the bacterial viability was monitored against electrical intensity, duration as well as the spatial vicinity related to the electrodes. It was found that the bacterial viability was not significantly affected (less than 10% of death percentage) when the applied electric current density (CD) was less than 6.2 A/m2 after 4 h. The percentage of live cell dropped by 15% and 29% at CD of 12.3 A/m2 and 24.7 A/m2, respectively. The pH of electrolytic biomass fluid has shifted to alkaline (from nearly neutral to around pH 10) at CD above 12.3 A/m2, which could have been the contributing factor for the bacterial inactivation. The temperature change in the electrolytic media at all current densities during 4 h of experiment was less than 2 °C, thus temperature effects were negligible. Bacteria experienced different micro-environments in the electrochemical reactor. Bacterial cells on the cathode surface exhibited highest death rate, whereas bacteria outside the space between electrodes were the least affected. It was concluded that in an electro-technology integrated wastewater treatment process, sufficient mixing should be used to avoid localized inactivation of bacterial cells. Copyright © 2011 Elsevier Ltd. All rights reserved.

First-principles estimates of free energy barriers for Mg desolvation and intercalation at electrolyte/electrode interfaces

NASA Astrophysics Data System (ADS)

Wan, Liwen; Prendergast, David

2014-03-01

There is a growing interest in developing multivalent ion batteries that could, in principle, double or triple the energy density compared to the monovalent Li-ion batteries. However, the strong electrostatic interaction caused by the extra charge also makes it very challenging to find appropriate intercalation compounds that allow for relatively fast and reversible ion transport. An established working multivalent battery is comprised of Mg(AlCl2BuEt)2 salts in THF solution as the electrolyte, and Mg metal and Mo6S8 Chevrel phase as the anode and cathode, respectively. Currently, we lack a clear understanding of the mechanism for Mg desolvation and intercalation at the interface between the electrolyte and Chevrel phase surfaces, which is critical in designing new advanced battery systems with improved ion diffusion rate. Here, we present a theoretical investigation of the dynamics and kinetics of the Mg desolvation/intercalation process. The surface properties of Mo6S8 are studied for the first time using density functional theory (DFT) and its interaction with the electrolyte is simulated via an ab initio molecular dynamics (AIMD) approach. The free energy barrier for Mg diffusing through the interface is then calculated by performing a set of biased AIMD simulations. This work is supported as part of the Joint Center for Energy Storage Research (JCESR), an Energy Innovation Hub funded by the U.S. Department of Energy, Office of Science, Basic Energy Sciences.

Nanoporous graphene obtained by hydrothermal process in H2O2 and its application for supercapacitors

NASA Astrophysics Data System (ADS)

Lv, Jinlong; Liang, Tongxiang

2016-08-01

Nanohole graphene oxide (NHGO) was obtained in a homogeneous aqueous mixture of graphene oxide (GO) and H2O2 at 120 °C. Supercapacitors were fabricated as the electrode material by using NHGO. A specific capacitance of 240.1 F g-1 was obtained at a current density of 1 A g-1 in 6 m KOH electrolyte and specific capacitance remained 193.6 F g-1 at the current density of 20 A g-1. This was attributed to reducing the inner space between the double-layers, enhanced ion diffusion and large specific surface area. Supercapacitor prepared with NHGO electrodes also exhibited an excellent cycle stability.

Lithium Dendrite Suppression and Enhanced Interfacial Compatibility Enabled by an Ex Situ SEI on Li Anode for LAGP-Based All-Solid-State Batteries.

PubMed

Hou, Guangmei; Ma, Xiaoxin; Sun, Qidi; Ai, Qing; Xu, Xiaoyan; Chen, Lina; Li, Deping; Chen, Jinghua; Zhong, Hai; Li, Yang; Xu, Zhibin; Si, Pengchao; Feng, Jinkui; Zhang, Lin; Ding, Fei; Ci, Lijie

2018-06-06

The electrode-electrolyte interface stability is a critical factor influencing cycle performance of All-solid-state lithium batteries (ASSLBs). Here, we propose a LiF- and Li 3 N-enriched artificial solid state electrolyte interphase (SEI) protective layer on metallic lithium (Li). The SEI layer can stabilize metallic Li anode and improve the interface compatibility at the Li anode side in ASSLBs. We also developed a Li 1.5 Al 0.5 Ge 1.5 (PO 4 ) 3 -poly(ethylene oxide) (LAGP-PEO) concrete structured composite solid electrolyte. The symmetric Li/LAGP-PEO/Li cells with SEI-protected Li anodes have been stably cycled with small polarization at a current density of 0.05 mA cm -2 at 50 °C for nearly 400 h. ASSLB-based on SEI-protected Li anode, LAGP-PEO electrolyte, and LiFePO 4 (LFP) cathode exhibits excellent cyclic stability with an initial discharge capacity of 147.2 mA h g -1 and a retention of 96% after 200 cycles.

LiCl-LiI molten salt electrolyte with bismuth-lead positive electrode for liquid metal battery

NASA Astrophysics Data System (ADS)

Kim, Junsoo; Shin, Donghyeok; Jung, Youngjae; Hwang, Soo Min; Song, Taeseup; Kim, Youngsik; Paik, Ungyu

2018-02-01

Liquid metal batteries (LMBs) are attractive energy storage device for large-scale energy storage system (ESS) due to the simple cell configuration and their high rate capability. The high operation temperature caused by high melting temperature of both the molten salt electrolyte and metal electrodes can induce the critical issues related to the maintenance cost and degradation of electrochemical properties resulting from the thermal corrosion of materials. Here, we report a new chemistry of LiCl-LiI electrolyte and Bi-Pb positive electrode to lower the operation temperature of Li-based LMBs and achieve the long-term stability. The cell (Li|LiCl-LiI|Bi-Pb) is operated at 410 °C by employing the LiCl-LiI (LiCl:LiI = 36:64 mol %) electrolyte and Bi-Pb alloy (Bi:Pb = 55.5:44.5 mol %) positive electrode. The cell shows excellent capacity retention (86.5%) and high Coulombic efficiencies over 99.3% at a high current density of 52 mA cm-2 during 1000th cycles.

Electrochemical properties of lithium iron phosphate cathode material using polymer electrolyte

NASA Astrophysics Data System (ADS)

Kim, Jae-Kwang; Choi, Jae-Won; Cheruvally, Gouri; Shin, Yong-Jo; Ahn, Jou-Hyeon; Cho, Kwon-Koo; Ahn, Hyo-Jun; Kim, Ki-Won

2007-12-01

Carbon-coated lithium iron phosphate (LiFePO4/C) cathode material was synthesized by mechano-chemical activation method. The performance of LiFePO4/C in lithium battery was tested with an electrospun polymer-based electrolyte. Liquid electrolyte of 1M lithium hexafluorophosphate (LiPF6) in ethylene carbonate/dimethyl carbonate (EC/DMC) (1 : 1vol) was incorporated in electrospun poly(vinylidene fluoride-co-hexafluoropropylene) (P(VdF-HFP)) microfibrous membrane to prepare the polymer electrolyte (PE). The cell based on Li|PE|Li FePO4/C exhibited an initial discharge capacity of 142 mAh g-1 at 0.1 C-rate at room temperature. Good cycling performance even under the high current density of 2 C could be obtained. Impedance spectroscopy was applied to investigate the material behavior during 0.1 C-rate charge-discharge cycling. When the fresh cell and the cell after different cycles were compared, impedance resistance was found to decrease with cycling. Impedance study indicated good cycle life for the cell when tested at room temperature.

Micrographic detection of plastic deformation in nickel base alloys

DOEpatents

Steeves, Arthur F.; Bibb, Albert E.

1984-01-01

A method for detecting low levels of plastic deformation in metal articles comprising electrolytically etching a flow free surface of the metal article with nital at a current density of less than about 0.1 amp/cm.sup.2 and microscopically examining the etched surface to determine the presence of alternating striations. The presence of striations indicates plastic deformation in the article.

Micrographic detection of plastic deformation in nickel-base alloys

DOEpatents

Steeves, A.F.; Bibb, A.E.

1980-09-20

A method for detecting low levels of plastic deformation in metal articles comprising electrolytically etching a flow free surface of the metal article with nital at a current density of less than about 0.1 amp/cm/sup 2/ and microscopically examining the etched surface to determine the presence of alternating striations. The presence of striations indicates plastic deformation in the article.

An alternative to hydrogenation processes. Electrocatalytic hydrogenation of benzophenone.

PubMed

Mozo Mulero, Cristina; Sáez, Alfonso; Iniesta, Jesús; Montiel, Vicente

2018-01-01

The electrocatalytic hydrogenation of benzophenone was performed at room temperature and atmospheric pressure using a polymer electrolyte membrane electrochemical reactor (PEMER). Palladium (Pd) nanoparticles were synthesised and supported on a carbonaceous matrix (Pd/C) with a 28 wt % of Pd with respect to carbon material. Pd/C was characterised by transmission electron microscopy (TEM), and thermogravimetric analysis (TGA). Cathodes were prepared using Pd electrocatalytic loadings (L Pd ) of 0.2 and 0.02 mg cm -2 . The anode consisted of hydrogen gas diffusion for the electrooxidation of hydrogen gas, and a 117 Nafion exchange membrane acted as a cationic polymer electrolyte membrane. Benzophenone solution was electrochemically hydrogenated in EtOH/water (90/10 v/v) plus 0.1 M H 2 SO 4 . Current densities of 10, 15 and 20 mA cm -2 were analysed for the preparative electrochemical hydrogenation of benzophenone and such results led to the highest fractional conversion (X R ) of around 30% and a selectivity over 90% for the synthesis of diphenylmethanol upon the lowest current density. With regards to an increase by ten times the Pd electrocatalytic loading the electrocatalytic hydrogenation led neither to an increase in fractional conversion nor to a change in selectivity.

An alternative to hydrogenation processes. Electrocatalytic hydrogenation of benzophenone

PubMed Central

Mozo Mulero, Cristina; Iniesta, Jesús; Montiel, Vicente

2018-01-01

The electrocatalytic hydrogenation of benzophenone was performed at room temperature and atmospheric pressure using a polymer electrolyte membrane electrochemical reactor (PEMER). Palladium (Pd) nanoparticles were synthesised and supported on a carbonaceous matrix (Pd/C) with a 28 wt % of Pd with respect to carbon material. Pd/C was characterised by transmission electron microscopy (TEM), and thermogravimetric analysis (TGA). Cathodes were prepared using Pd electrocatalytic loadings (LPd) of 0.2 and 0.02 mg cm−2. The anode consisted of hydrogen gas diffusion for the electrooxidation of hydrogen gas, and a 117 Nafion exchange membrane acted as a cationic polymer electrolyte membrane. Benzophenone solution was electrochemically hydrogenated in EtOH/water (90/10 v/v) plus 0.1 M H2SO4. Current densities of 10, 15 and 20 mA cm−2 were analysed for the preparative electrochemical hydrogenation of benzophenone and such results led to the highest fractional conversion (XR) of around 30% and a selectivity over 90% for the synthesis of diphenylmethanol upon the lowest current density. With regards to an increase by ten times the Pd electrocatalytic loading the electrocatalytic hydrogenation led neither to an increase in fractional conversion nor to a change in selectivity. PMID:29623115

Anodic oxidation of slaughterhouse wastewater on boron-doped diamond: process variables effect.

PubMed

Abdelhay, Arwa; Jum'h, Inshad; Abdulhay, Enas; Al-Kazwini, Akeel; Alzubi, Mashael

2017-12-01

A non-sacrificial boron-doped diamond electrode was prepared in the laboratory and used as a novel anode for electrochemical oxidation of poultry slaughterhouse wastewater. This wastewater poses environmental threats as it is characterized by a high content of recalcitrant organics. The influence of several process variables, applied current density, initial pH, supporting electrolyte nature, and concentration of electrocoagulant, on chemical oxygen demand (COD) removal, color removal, and turbidity removal was investigated. Results showed that raising the applied current density to 3.83 mA/cm 2 has a positive effect on COD removal, color removal, and turbidity removal. These parameters increased to 100%, 90%, and 80% respectively. A low pH of 5 favored oxidants generation and consequently increased the COD removal percentage to reach 100%. Complete removal of COD had occurred in the presence of NaCl (1%) as supporting electrolyte. Na 2 SO 4 demonstrated lower efficiency than NaCl in terms of COD removal. The COD decay kinetics follows the pseudo-first-order reaction. The simultaneous use of Na 2 SO 4 and FeCl 3 decreased the turbidity in wastewater by 98% due to electrocoagulation.

Low-cost flexible supercapacitors based on laser reduced graphene oxide supported on polyethylene terephthalate substrate

NASA Astrophysics Data System (ADS)

Ghoniem, Engy; Mori, Shinsuke; Abdel-Moniem, Ahmed

2016-08-01

A controlled high powered CO2 laser system is used to reduce and pattern graphene oxide (GO) film supported onto a flexible polyethylene terephthalate (PET) substrate. The laser reduced graphene oxide (rGO) film is characterized and evaluated electrochemically in the absence and presence of an overlying anodicaly deposited thin film of pseuodcapactive MnO2 as electrodes for supercapacitor applications using aqueous electrolyte. The laser treatment of the GO film leads to an overlapped structure of defective multi-layer rGO sheets with an electrical conductivity of 273 S m-1. The rGO and MnO2/rGO electrodes exhibit specific capacitance in the range of 82-107 and 172-368 Fg-1 at applied current range of 0.1-1.0 mA cm-2 and retain 98 and 95% of their initial capacitances after 2000 cycles at a current density of 1.0 mA cm-2, respectively. Also, the rGO is assigned as an electrode material for flexible conventionally stacked and interdigitated in-plane supercapacitor structures using gel electrolyte. Three electrode architectures of 2, 4, and 6 sub-electrodes are studied for the interdigital in-plane design. The device with interdigital 6 sub-electrodes architecture I-PS(6) delivers power density of 537.1 Wcm-3 and an energy density of 0.45 mWh cm-3.

Rechargeable Al/Cl2 battery with molten AlCl4/-/ electrolyte.

NASA Technical Reports Server (NTRS)

Holleck, G. L.; Giner, J.; Burrows, B.

1972-01-01

A molten salt system based on Al- and Cl2 carbon electrodes, with an AlCl3 alkali chloride eutectic as electrolyte, offers promise as a rechargeable, high energy density battery which can operate at a relatively low temperature. Electrode kinetic studies showed that the electrode reactions at the Al anode were rapid and that the observed passivation phenomena were due to the formation at the electrode surface of a solid salt layer resulting from concentration changes on anodic or cathodic current flow. It was established that carbon electrodes were intrinsically active for chlorine reduction in AlCl3-alkali chloride melts. By means of a rotating vitreous carbon disk electrode, the kinetic parameters were determined.

Contribution of mesopores in MgO-templated mesoporous carbons to capacitance in non-aqueous electrolytes

NASA Astrophysics Data System (ADS)

Kado, Yuya; Soneda, Yasushi; Yoshizawa, Noriko

2015-02-01

MgO-templated mesoporous carbons were fabricated by annealing trimagnesium dicitrate nonahydrate at various temperatures from 700 to 1000 °C with subsequent acid leaching of MgO. The obtained carbons contained a large amount of mesopores. Performances of electric double-layer capacitors using these carbons were examined for propylene carbonate electrolyte containing 1 M tetraethylammonium tetrafluoroborate. The mesoporous carbons synthesized at higher temperatures showed better rate capabilities. AC impedance measurements indicated that high-temperature annealing of the carbon precursors and the presence of mesopores were important for high rate performance. In addition, the contribution of mesopores to capacitance was more significant at higher current densities of 30 A g-1.

Two dimensional distribution measurement of electric current generated in a polymer electrolyte fuel cell using 49 NMR surface coils.

PubMed

Ogawa, Kuniyasu; Sasaki, Tatsuyoshi; Yoneda, Shigeki; Tsujinaka, Kumiko; Asai, Ritsuko

2018-05-17

In order to increase the current density generated in a PEFC (polymer electrolyte fuel cell), a method for measuring the spatial distribution of both the current and the water content of the MEA (membrane electrode assembly) is necessary. Based on the frequency shifts of NMR (nuclear magnetic resonance) signals acquired from the water contained in the MEA using 49 NMR coils in a 7 × 7 arrangement inserted in the PEFC, a method for measuring the two-dimensional spatial distribution of electric current generated in a unit cell with a power generation area of 140 mm × 160 mm was devised. We also developed an inverse analysis method to determine the two-dimensional electric current distribution that can be applied to actual PEFC connections. Two analytical techniques, namely coarse graining of segments and stepwise search, were used to shorten the calculation time required for inverse analysis of the electric current map. Using this method and techniques, spatial distributions of electric current and water content in the MEA were obtained when the PEFC generated electric power at 100 A. Copyright © 2018 Elsevier Inc. All rights reserved.

Heat transfer and thermal management studies of lithium polymer batteries for electric vehicle applications

NASA Astrophysics Data System (ADS)

Song, Li

The thermal conductivities of the polymer electrolyte and composite cathode are important parameters characterizing heat transport in lithium polymer batteries. The thermal conductivities of lithium polymer electrolytes, including poly-ethylene oxide (PEO), PEO-LiClO4, PEO-LiCF3SO 3, PEO-LiN(CF3SO2)2, PEO-LiC(CF 3SO2)3, and the thermal conductivities of TiS 2 and V6O13 composite cathodes, were measured over the temperature range from 25°C to 150°C by a guarded heat flow meter. The thermal conductivities of the electrolytes were found to be relatively constant for the temperature and for electrolytes with various concentrations of the lithium salt. The thermal conductivities of the composite cathodes were found to increase with the temperature below the melting temperature of the polymer electrolyte and only slightly increase above the melting temperature. Three different lithium polymer cells, including Li/PEO-LiCF3 S O3/TiS2, Li/PEO-LiC(CF3 S O2)3/V6 O13, and Li/PEO-LiN(CF3 S O2)2/ Li1+x Mn2 O4 were prepared and their discharge curves, along with heat generation rates, were measured at various galvanostatic discharge current densities, and at different temperature (70°C, 80°C and 90°C), by a potentiostat/galvanostat and an isothermal microcalorimeter. The thermal stability of a lithium polymer battery was examined by a linear perturbation analysis. In contrast to the thermal conductivity, the ionic conductivity of polymer electrolytes for lithium-polymer cell increases greatly with increasing temperature, an instability could arise from this temperature dependence. The numerical calculations, using a two dimensional thermal model, were carried out for constant potential drop across the electrolyte, for constant mean current density and for constant mean cell output power. The numerical calculations were approximately in agreement with the linear perturbation analysis. A coupled mathematical model, including electrochemical and thermal components, was developed to study the heat transfer and thermal management of lithium polymer batteries. The results calculated from the model, including temperature distributions, and temperatures at different stages of discharge are significantly different from those calculated from the thermal model. The discharge curves and heat generation rates calculated by the electrochemical-thermal model were in agreement with the experimental results. Different thermal management approaches, including a variable conductance insulation enclosure were studied.

Manufacturing and characterization of magnesium alloy foils for use as anode materials in rechargeable magnesium ion batteries

NASA Astrophysics Data System (ADS)

Schloffer, Daniel; Bozorgi, Salar; Sherstnev, Pavel; Lenardt, Christian; Gollas, Bernhard

2017-11-01

The fabrication of thin foils of magnesium for use as anode material in rechargeable magnesium ion batteries is described. In order to improve its workability, the magnesium was alloyed by melting metallurgy with zinc and/or gadolinium, producing saturated solid solutions. The material was extruded to thin foils and rolled to a thickness of approximately 100 μm. The electrochemical behavior of Mg-1.63 wt% Zn, Mg-1.55 wt% Gd and Mg-1.02 wt% Zn-1.01 wt% Gd was studied in (PhMgCl)2-AlCl3/THF electrolyte by cyclic voltammetry and galvanostatic cycling in symmetrical cells. Analysis of the current-potential curves in the Tafel region and the linear region close to the equilibrium potential show almost no effect of the alloying elements on the exchange current densities (5-45 μA/cm2) and the transfer coefficients. Chemical analyses of the alloy surfaces and the electrolyte demonstrate that the alloying elements not only dissolve with the magnesium during the anodic half-cycles, but also re-deposit during the cathodic half-cycles together with the magnesium and aluminum from the electrolyte. Given the negligible corrosion rate in aprotic electrolytes under such conditions, no adverse effects of alloying elements are expected for the performance of magnesium anodes in secondary batteries.

Electrolytes Based on TEMPO–Co Tandem Redox Systems Outperform Single Redox Systems in Dye‐sensitized Solar Cells

PubMed Central

Cong, Jiayan; Hao, Yan; Boschloo, Gerrit

2014-01-01

Abstract A new TEMPO–Co tandem redox system with TEMPO and Co(bpy)3 2+/3+ has been investigated for the use in dye‐sensitized solar cells (DSSCs). A large open‐circuit voltage (V OC) increase, from 862 mV to 965 mV, was observed in the tandem redox system, while the short‐circuit current density (J SC) was maintained. The conversion efficiency was observed to increase from 7.1 % for cells containing the single Co(bpy)3 2+/3+ redox couple, to 8.4 % for cells containing the TEMPO–Co tandem redox system. The reason for the increase in V OC and overall efficiency is ascribed to the involvement of partial regeneration of the sensitizing dye molecules by TEMPO. This assumption can be verified through the observed much faster regeneration dynamics exhibited in the presence of the tandem system. Using the tandem redox system, the faster recombination problem of the single TEMPO redox couple is resolved and the mass‐transport of the metal‐complex‐based electrolyte is also improved. This TEMPO–Co tandem system is so far the most effienct tandem redox electrolyte reported not involving iodine. The current results show a promising future for tandem system as replacements for single redox systems in electrolytes for DSSCs. PMID:25504818

Manganese dioxide decoration of macroscopic carbon nanotube fibers: From high-performance liquid-based to all-solid-state supercapacitors

NASA Astrophysics Data System (ADS)

Pendashteh, Afshin; Senokos, Evgeny; Palma, Jesus; Anderson, Marc; Vilatela, Juan J.; Marcilla, Rebeca

2017-12-01

Supercapacitors capable of providing high voltage, energy and power density but yet light, low volume occupying, flexible and mechanically robust are highly interesting and demanded for portable applications. Herein, freestanding flexible hybrid electrodes based on MnO2 nanoparticles grown on macroscopic carbon nanotube fibers (CNTf-MnO2) were fabricated, without the need of any metallic current collector. The CNTf, a support with excellent electrical conductivity, mechanical stability, and appropriate pore structure, was homogeneously decorated with porous akhtenskite ɛ-MnO2 nanoparticles produced via electrodeposition in an optimized organic-aqueous mixture. Electrochemical properties of these decorated fibers were evaluated in different electrolytes including a neutral aqueous solution and a pure 1-butyl-3-methylpyrrolidinium bis(trifluoromethylsulfonyl)imide ionic liquid (PYR14TFSI). This comparison helps discriminate the various contributions to the total capacitance: (surface) Faradaic and non-Faradaic processes, improved wetting by aqueous electrolytes. Accordingly, symmetric supercapacitors with PYR14TFSI led to a high specific energy of 36 Wh· kgMnO2-1 (16 Wh·kg-1 including the weight of CNTf) and real specific power of 17 kW· kgMnO2-1 (7.5 kW kg-1) at 3.0 V with excellent cycling stability. Moreover, flexible all solid-state supercapacitors were fabricated using PYR14TFSI-based polymer electrolyte, exhibiting maximum energy density of 21 Wh·kg-1 and maximum power density of 8 kW kg-1 normalized by total active material.

Garnet-type solid-state fast Li ion conductors for Li batteries: critical review.

PubMed

Thangadurai, Venkataraman; Narayanan, Sumaletha; Pinzaru, Dana

2014-07-07

Batteries are electrochemical devices that store electrical energy in the form of chemical energy. Among known batteries, Li ion batteries (LiBs) provide the highest gravimetric and volumetric energy densities, making them ideal candidates for use in portable electronics and plug-in hybrid and electric vehicles. Conventional LiBs use an organic polymer electrolyte, which exhibits several safety issues including leakage, poor chemical stability and flammability. The use of a solid-state (ceramic) electrolyte to produce all-solid-state LiBs can overcome all of the above issues. Also, solid-state Li batteries can operate at high voltage, thus, producing high power density. Various types of solid Li-ion electrolytes have been reported; this review is focused on the most promising solid Li-ion electrolytes based on garnet-type metal oxides. The first studied Li-stuffed garnet-type compounds are Li5La3M2O12 (M = Nb, Ta), which show a Li-ion conductivity of ∼10(-6) at 25 °C. La and M sites can be substituted by various metal ions leading to Li-rich garnet-type electrolytes, such as Li6ALa2M2O12, (A = Mg, Ca, Sr, Ba, Sr0.5Ba0.5) and Li7La3C2O12 (C = Zr, Sn). Among the known Li-stuffed garnets, Li6.4La3Zr1.4Ta0.6O12 exhibits the highest bulk Li-ion conductivity of 10(-3) S cm(-1) at 25 °C with an activation energy of 0.35 eV, which is an order of magnitude lower than that of the currently used polymer, but is chemically stable at higher temperatures and voltages compared to polymer electrolytes. Here, we discuss the chemical composition-structure-ionic conductivity relationship of the Li-stuffed garnet-type oxides, as well as the Li ion conduction mechanism.

Bioactivity and biocompatibility of hydroxyapatite-based bioceramic coatings on zirconium by plasma electrolytic oxidation.

PubMed

Aktuğ, Salim Levent; Durdu, Salih; Yalçın, Emine; Çavuşoğlu, Kültigin; Usta, Metin

2017-02-01

In the present work, hydroxyapatite (HAP)-based plasma electrolytic oxide (PEO) coatings were produced on zirconium at different current densities in a solution containing calcium acetate and β-calcium glycerophosphate by a single step. The phase structure, surface morphology, functional groups, thickness and roughness of the coatings were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), attenuated total reflectance-Fourier transform infrared spectroscopy (ATR-FTIR), eddy current method and surface profilometer, respectively. The phases of cubic-zirconia, calcium zirconate and HAP were detected by XRD. The amount of HAP and calcium zirconate increased with increasing current density. The surface of the coatings was very porous and rough. Moreover, bioactivity and biocompatibility of the coatings were analyzed in vitro immersion simulated body fluid (SBF) and MTT (3-(4,5-dimethyl thiazol-2yl)-2,5-diphenyl tetrazolium bromide) assay, hemolysis assay and bacterial formation. The apatite-forming ability of the coatings was evaluated after immersion in SBF up to 28days. After immersion, the bioactivity of HAP-based coatings on zirconium was greater than the ones of uncoated zirconium and zirconium oxide-based surface. The bioactivity of PEO surface on zirconium was significantly improved under SBF conditions. The bacterial adhesion of the coatings decreased with increasing current density. The bacterial adhesion of the coating produced at 0.370A/cm 2 was minimum compared to uncoated zirconium coated at 0.260 and 0.292A/cm 2 . The hemocompatibility of HAP-based surfaces was improved by PEO. The cell attachment and proliferation of the PEO coatings were better than the one of uncoated zirconium according to MTT assay results. Copyright © 2016 Elsevier B.V. All rights reserved.

The effect of grain size on aluminum anodes for Al-air batteries in alkaline electrolytes

NASA Astrophysics Data System (ADS)

Fan, Liang; Lu, Huimin

2015-06-01

Aluminum is an ideal material for metallic fuel cells. In this research, different grain sizes of aluminum anodes are prepared by equal channel angular pressing (ECAP) at room temperature. Microstructure of the anodes is examined by electron backscatter diffraction (EBSD) in scanning electron microscope (SEM). Hydrogen corrosion rates of the Al anodes in 4 mol L-1 NaOH are determined by hydrogen collection method. The electrochemical properties of the aluminum anodes are investigated in the same electrolyte using electrochemical impedance spectroscopy (EIS) and polarization curves. Battery performance is also tested by constant current discharge at different current densities. Results confirm that the electrochemical properties of the aluminum anodes are related to grain size. Finer grain size anode restrains hydrogen evolution, improves electrochemical activity and increases anodic utilization rate. The proposed method is shown to effectively improve the performance of Al-air batteries.

Method for providing uranium articles with a corrosion-resistant anodized coating

DOEpatents

Waldrop, F.B.; Washington, C.A.

1981-01-07

Uranium articles are provided with anodized oxide coatings in an aqueous solution of an electrolyte selected from the group consisting of potassium phosphate, potassium hydroxide, ammonium hydroxide, and a mixture of potassium tetraborate and boric acid. The uranium articles are anodized at a temperature greater than about 75/sup 0/C with a current flow of less than about 0.036 A/cm/sup 2/ of surface area while the pH of the solution is maintained in a range of about 2 to 11.5. The pH values of the aqueous solution and the low current density utilized during the electrolysis prevent excessive dissolution of the uranium and porosity in the film or watering. The relatively high temperature of the electrolyte bath inhibits hydration and the attendant deleterious pitting so as to enhance corrosion resistance of the anodized coating.

Liquid Water Saturation and Oxygen Transport Resistance in Polymer Electrolyte Membrane Fuel Cell Gas Diffusion Layers

NASA Astrophysics Data System (ADS)

Muirhead, Daniel

In this thesis, the relative humidity (RH) of the cathode reactant gas was investigated as a factor which influences gas diffusion layer (GDL) liquid water accumulation and mass transport-related efficiency losses over a range of operating current densities in a polymer electrolyte membrane (PEM) fuel cell. Limiting current measurements were used to characterize fuel cell oxygen transport resistance while simultaneous measurements of liquid water accumulation were conducted using synchrotron X-ray radiography. GDL porosity distributions were characterized with micro-computed tomography (microCT). The work presented here can be used by researchers to develop improved numerical models to predict GDL liquid water accumulation and to inform the design of next-generation GDL materials to mitigate mass transport-related efficiency losses. This work also contributes an extensive set of concurrent performance and liquid water visualization data to the PEM fuel cell field that can be used for validating multiphase transport models.

Redox flow batteries having multiple electroactive elements

DOE Office of Scientific and Technical Information (OSTI.GOV)

Wang, Wei; Li, Liyu; Yang, Zhenguo

Introducing multiple redox reactions with a suitable voltage range can improve the energy density of redox flow battery (RFB) systems. One example includes RFB systems utilizing multiple redox pairs in the positive half cell, the negative half cell, or in both. Such RFB systems can have a negative electrolyte, a positive electrolyte, and a membrane between the negative electrolyte and the positive electrolyte, in which at least two electrochemically active elements exist in the negative electrolyte, the positive electrolyte, or both.

High-performance supercapacitors based on vertically aligned carbon nanotubes and nonaqueous electrolytes

NASA Astrophysics Data System (ADS)

Kim, Byungwoo; Chung, Haegeun; Kim, Woong

2012-04-01

We demonstrate the high performance of supercapacitors fabricated with vertically aligned carbon nanotubes and nonaqueous electrolytes such as ionic liquids and conventional organic electrolytes. Specific capacitance, maximum power and energy density of the supercapacitor measured in ionic liquid were ˜75 F g-1, ˜987 kW kg-1 and ˜27 W h kg-1, respectively. The high power performance was consistently indicated by a fast relaxation time constant of 0.2 s. In addition, electrochemical oxidation of the carbon nanotubes improved the specific capacitance (˜158 F g-1) and energy density (˜53 W h kg-1). Both high power and energy density could be attributed to the fast ion transport realized by the alignment of carbon nanotubes and the wide operational voltage defined by the ionic liquid. The demonstrated carbon-nanotube- and nonaqueous-electrolyte-based supercapacitors show great potential for the development of high-performance energy storage devices.

All Solid State Rechargeable Lithium Batteries using Block Copolymers

NASA Astrophysics Data System (ADS)

Hallinan, Daniel; Balsara, Nitash

2011-03-01

The growing need for alternative energy and increased demand for mobile technology require higher density energy storage. Existing battery technologies, such as lithium ion, are limited by theoretical energy density as well as safety issues. Other battery chemistries are promising options for dramatically increasing energy density. Safety can be improved by replacing the flammable, reactive liquids used in existing lithium-ion battery electrolytes with polymer electrolytes. Block copolymers are uniquely suited for this task because ionic conductivity and mechanical strength, both important properties in battery formulation, can be independently controlled. In this study, lithium batteries were assembled using lithium metal as negative electrode, polystyrene-b-poly(ethylene oxide) copolymer with lithium salt as electrolyte, and a positive electrode. The positive electrode consisted of polymer electrolyte for ion conduction, carbon for electron conduction, and an active material. Batteries were charged and discharged over many cycles. The battery cycling results were compared to a conventional battery chemistry.

High-performance supercapacitors based on vertically aligned carbon nanotubes and nonaqueous electrolytes.

PubMed

Kim, Byungwoo; Chung, Haegeun; Kim, Woong

2012-04-20

We demonstrate the high performance of supercapacitors fabricated with vertically aligned carbon nanotubes and nonaqueous electrolytes such as ionic liquids and conventional organic electrolytes. Specific capacitance, maximum power and energy density of the supercapacitor measured in ionic liquid were ~75 F g(-1), ~987 kW kg(-1) and ~27 W h kg(-1), respectively. The high power performance was consistently indicated by a fast relaxation time constant of 0.2 s. In addition, electrochemical oxidation of the carbon nanotubes improved the specific capacitance (~158 F g(-1)) and energy density (~53 W h kg(-1)). Both high power and energy density could be attributed to the fast ion transport realized by the alignment of carbon nanotubes and the wide operational voltage defined by the ionic liquid. The demonstrated carbon-nanotube- and nonaqueous-electrolyte-based supercapacitors show great potential for the development of high-performance energy storage devices. © 2012 IOP Publishing Ltd

Recent advances in solid polymer electrolyte fuel cell technology with low platinum loading electrodes

NASA Technical Reports Server (NTRS)

Srinivasan, Supramaniam; Manko, David J.; Koch, Hermann; Enayetullah, Mohammad A.; Appleby, A. John

1989-01-01

Of all the fuel cell systems only alkaline and solid polymer electrolyte fuel cells are capable of achieving high power densities (greater than 1 W/sq cm) required for terrestrial and extraterrestrial applications. Electrode kinetic criteria for attaining such high power densities are discussed. Attainment of high power densities in solid polymer electrolyte fuel cells has been demonstrated earlier by different groups using high platinum loading electrodes (4 mg/sq cm). Recent works at Los Alamos National Laboratory and at Texas A and M University (TAMU) demonstrated similar performance for solid polymer electrolyte fuel cells with ten times lower platinum loading (0.45 mg/sq cm) in the electrodes. Some of the results obtained are discussed in terms of the effects of type and thickness of membrane and of the methods platinum localization in the electrodes on the performance of a single cell.

Rechargeable Ni-Li battery integrated aqueous/nonaqueous system.

PubMed

Li, Huiqiao; Wang, Yonggang; Na, Haitao; Liu, Haimei; Zhou, Haoshen

2009-10-28

A rechargeable Ni-Li battery, in which nickel hydroxide serving as a cathode in an aqueous electrolyte and Li metal serving as an anode in an organic electrolyte were integrated by a superionic conductor glass ceramic film (LISICON), was proposed with the expectation to combine the advantages of both a Li-ion battery and Ni-MH battery. It has the potential for an ultrahigh theoretical energy density of 935 Wh/kg, twice that of a Li-ion battery (414 Wh/kg), based on the active material in electrodes. A prototype Ni-Li battery fabricated in the present work demonstrated a cell voltage of 3.47 V and a capacity of 264 mAh/g with good retention during 50 cycles of charge/discharge. This battery system with a hybrid electrolyte provides a new avenue for the best combination of electrode/electrolyte/electrode to fulfill the potential of high energy density as well as high power density.

Oxygen Reduction Reaction Activity of Platinum Thin Films with Different Densities

DOE Office of Scientific and Technical Information (OSTI.GOV)

Ergul, Busra; Begum, Mahbuba; Kariuki, Nancy

Platinum thin films with different densities were grown on glassy carbon electrodes by high pressure sputtering deposition and evaluated as oxygen reduction reaction catalysts for polymer electrolyte fuel cells using cyclic voltammetry and rotating disk electrode techniques in aqueous perchloric acid electrolyte. The electrochemically active surface area, ORR mass activity (MA) and specific activity (SA) of the thin film electrodes were obtained. MA and SA were found to be higher for low-density films than for high-density film.

Dynamic behaviour of interphases and its implication on high-energy-density cathode materials in lithium-ion batteries

DOE Office of Scientific and Technical Information (OSTI.GOV)

Li, Wangda; Dolocan, Andrei; Oh, Pilgun

Undesired electrode–electrolyte interactions prevent the use of many high-energy-density cathode materials in practical lithium-ion batteries. Efforts to address their limited service life have predominantly focused on the active electrode materials and electrolytes. Here an advanced three-dimensional chemical and imaging analysis on a model material, the nickel-rich layered lithium transition-metal oxide, reveals the dynamic behaviour of cathode interphases driven by conductive carbon additives (carbon black) in a common nonaqueous electrolyte. Region-of-interest sensitive secondary-ion mass spectrometry shows that a cathode-electrolyte interphase, initially formed on carbon black with no electrochemical bias applied, readily passivates the cathode particles through mutual exchange of surface species.more » By tuning the interphase thickness, we demonstrate its robustness in suppressing the deterioration of the electrode/electrolyte interface during high-voltage cell operation. Finally, our results provide insights on the formation and evolution of cathode interphases, facilitating development of in situ surface protection on high-energy-density cathode materials in lithium-based batteries.« less

Dynamic behaviour of interphases and its implication on high-energy-density cathode materials in lithium-ion batteries

DOE PAGES

Li, Wangda; Dolocan, Andrei; Oh, Pilgun; ...

2017-04-26

Undesired electrode–electrolyte interactions prevent the use of many high-energy-density cathode materials in practical lithium-ion batteries. Efforts to address their limited service life have predominantly focused on the active electrode materials and electrolytes. Here an advanced three-dimensional chemical and imaging analysis on a model material, the nickel-rich layered lithium transition-metal oxide, reveals the dynamic behaviour of cathode interphases driven by conductive carbon additives (carbon black) in a common nonaqueous electrolyte. Region-of-interest sensitive secondary-ion mass spectrometry shows that a cathode-electrolyte interphase, initially formed on carbon black with no electrochemical bias applied, readily passivates the cathode particles through mutual exchange of surface species.more » By tuning the interphase thickness, we demonstrate its robustness in suppressing the deterioration of the electrode/electrolyte interface during high-voltage cell operation. Finally, our results provide insights on the formation and evolution of cathode interphases, facilitating development of in situ surface protection on high-energy-density cathode materials in lithium-based batteries.« less

Mechanism and kinetics of electrochemical degradation of uric acid using conductive-diamond anodes.

PubMed

Dbira, Sondos; Bensalah, Nasr; Bedoui, Ahmed

2016-12-01

Uric acid (UA) is one of the principal effluents of urine wastewaters, widely used in agriculture as fertilizer, which is potentially dangerous and biorefractory. Hence, the degradation of UA (2,6,8-trihydroxy purine) in aqueous solution of pH 3.0 has been studied by conductive-diamond electrochemical oxidation. Hydroxyl radicals formed from water oxidation at the surface of boron-doped diamond anodes were the main oxidizing agents. Effects of current density and supporting electrolyte on the degradation rate and process efficiency are assessed. Results show that the increase of current density from 20 to 60 mA cm(-2) leads to a decrease in the efficiency of the electrochemical process. In addition, the best degradation occurred in the presence of NaCl as conductive electrolyte. Interestingly, an almost total mineralization of 50 ppm UA was obtained when anodic oxidation was performed at low current densities (20 mA cm(-2)) and in the presence of NaCl. This result confirmed that the electrolysis using diamond anodes is a very interesting technology for the treatment of UA. The identification of UA transformation products was performed by high-performance liquid chromatography (HPLC). HPLC analysis of treated solutions revealed that oxalic acid and urea were the two intermediates found. Oxalic acid was the most persistent product. Based on detected intermediates and bibliographic research, a mechanism of UA mineralization by anodic oxidation has been proposed. Ionic chromatography analysis confirmed the release of [Formula: see text] and [Formula: see text] ions during UA mineralization.

Engineering the electrochemical capacitive properties of graphene sheets in ionic-liquid electrolytes by correct selection of anions.

PubMed

Shi, Minjie; Kou, Shengzhong; Yan, Xingbin

2014-11-01

Graphene sheet (GS)-ionic liquid (IL) supercapacitors are receiving intense interest because their specific energy density far exceeds that of GS-aqueous electrolytes supercapacitors. The electrochemical properties of ILs mainly depend on their diverse ions, especially anions. Therefore, identifying suitable IL electrolytes for GSs is currently one of the most important tasks. The electrochemical behavior of GSs in a series of ILs composed of 1-ethyl-3-methylimidazolium cation (EMIM(+)) with different anions is systematically studied. Combined with the formula derivation and building models, it is shown that the viscosity, ion size, and molecular weight of ILs affect the electrical conductivity of ILs, and thus, determine the electrochemical performances of GSs. Because the EMIM-dicyanamide IL has the lowest viscosity, ion size, and molecular weight, GSs in it exhibit the highest specific capacitance, smallest resistance, and best rate capability. In addition, because the tetrafluoroborate anion (BF4(-)) has the best electrochemical stability, the GS-[EMIM][BF4] supercapacitor has the widest potential window, and thus, displays the largest energy density. These results may provide valuable information for selecting appropriate ILs and designing high-performance GS-IL supercapacitors to meet different needs. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Design of an artificial photosynthetic system for production of alcohols in high concentration from CO 2

DOE PAGES

Singh, Meenesh R.; Bell, Alexis T.

2015-11-06

Artificial photosynthesis of liquid fuels is a potential source for clean energy. Alcohols are particularly attractive products because of their high energy density and market value per amount of energy input. The major challenges in photo/electrochemical synthesis of alcohols from sunlight, water and CO 2 are low product selectivity, high membrane fuel-crossover losses, and high cost of product separation from the electrolyte. Here we propose an artificial photosynthesis scheme for direct synthesis and separation to almost pure ethanol with minimum product crossover using saturated salt electrolytes. The ethanol produced in the saturated salt electrolytes can be readily phase separated intomore » a microemulsion, which can be collected as pure products in a liquid–liquid extractor. A novel design of an integrated artificial photosynthetic system is proposed that continuously produces >90 wt% pure ethanol using a polycrystalline copper cathode at a current density of 0.85 mA cm -2. The annual production rate of >90 wt% ethanol using such a photosynthesis system operating at 10 mA cm -2 (12% solar-to-fuel (STF) efficiency) can be 15.27 million gallons per year per square kilometer, which corresponds to 7% of the industrial ethanol production capacity of California.« less

Betavoltaic Enhancement Using Defect-Engineered TiO2 Nanotube Arrays through Electrochemical Reduction in Organic Electrolytes.

PubMed

Ma, Yang; Wang, Na; Chen, Jiang; Chen, Changsong; San, Haisheng; Chen, Jige; Cheng, Zhengdong

2018-06-19

Utilizing high-energy beta particles emitted from radioisotopes for long-lifetime betavoltaic cells is a great challenge due to low energy conversion efficiency. Here, we report a betavoltaic cell fabricated using TiO 2 nanotube arrays (TNTAs) electrochemically reduced in ethylene glycol electrolyte (EGECR-TNTAs) for the enhancement of the betavoltaic effect. The electrochemical reduction of TNTAs using high cathodic bias in organic electrolytes is indeed a facile and effective strategy to induce in situ self-doping of oxygen vacancy (OV) and Ti 3+ defects. The black EGECR-TNTAs are highly stable with a significantly narrower band gap and higher electrical conductivity as well as UV-vis-NIR light absorption. A 20 mCi of 63 Ni betavoltaic cell based on the reduced TNTAs exhibits a maximum ECE of 3.79% with open-circuit voltage of 1.04 V, short-circuit current density of 117.5 nA cm -2 , and a maximum power density of 39.2 nW cm -2 . The betavoltaic enhancement can be attributed to the enhanced charge carrier transport and separation as well as multiple exciton generation of electron-hole pairs due the generation of OV and Ti 3+ interstitial bands below the conductive band of TiO 2.

Design of an artificial photosynthetic system for production of alcohols in high concentration from CO 2

DOE Office of Scientific and Technical Information (OSTI.GOV)

Singh, Meenesh R.; Bell, Alexis T.

Artificial photosynthesis of liquid fuels is a potential source for clean energy. Alcohols are particularly attractive products because of their high energy density and market value per amount of energy input. The major challenges in photo/electrochemical synthesis of alcohols from sunlight, water and CO 2 are low product selectivity, high membrane fuel-crossover losses, and high cost of product separation from the electrolyte. Here we propose an artificial photosynthesis scheme for direct synthesis and separation to almost pure ethanol with minimum product crossover using saturated salt electrolytes. The ethanol produced in the saturated salt electrolytes can be readily phase separated intomore » a microemulsion, which can be collected as pure products in a liquid–liquid extractor. A novel design of an integrated artificial photosynthetic system is proposed that continuously produces >90 wt% pure ethanol using a polycrystalline copper cathode at a current density of 0.85 mA cm -2. The annual production rate of >90 wt% ethanol using such a photosynthesis system operating at 10 mA cm -2 (12% solar-to-fuel (STF) efficiency) can be 15.27 million gallons per year per square kilometer, which corresponds to 7% of the industrial ethanol production capacity of California.« less

Effect of Initial State of Lithium on the Propensity for Dendrite Formation: A Theoretical Study

DOE PAGES

Barai, Pallab; Higa, Kenneth; Srinivasan, Venkat

2016-12-17

Mechanical constraints have been widely used experimentally to prevent the growth of dendrites within lithium metal. The only article known to the authors that tries to theoretically understand how mechanical forces prevent dendrite growth was published by Monroe and Newman [J. Electrochem. Soc., 150 (10) A1377 (2005)]. Based on the assumption that surface tension prevents the growth of interfacial roughness, Monroe and Newman considered pre-stressed conditions of the lithium electrodes. This scenario indicates that prevention of dendrite growth by mechanical means is only possible by using electrolytes with shear modulus at least two times larger than that of lithium metal.more » Here, a different scenario of relaxed lithium metal (without any pre-existing surface stresses) has been considered in the present analysis. Deposition of lithium due to electrochemical reaction at the lithium/electrolyte interface induces compressive stress at the electrode, the electrolyte, and the newly deposited lithium metal. Present simulations indicate that during operation at low current densities, the scenario of relaxed lithium leads to no dendrites. Rather, the present study points to the importance of including the effect of current distribution to accurately capture the mechanical forces needed to prevent dendrite growth.« less

Effect of Initial State of Lithium on the Propensity for Dendrite Formation: A Theoretical Study

DOE Office of Scientific and Technical Information (OSTI.GOV)

Barai, Pallab; Higa, Kenneth; Srinivasan, Venkat

Mechanical constraints have been widely used experimentally to prevent the growth of dendrites within lithium metal. The only article known to the authors that tries to theoretically understand how mechanical forces prevent dendrite growth was published by Monroe and Newman [J. Electrochem. Soc., 150 (10) A1377 (2005)]. Based on the assumption that surface tension prevents the growth of interfacial roughness, Monroe and Newman considered pre-stressed conditions of the lithium electrodes. This scenario indicates that prevention of dendrite growth by mechanical means is only possible by using electrolytes with shear modulus at least two times larger than that of lithium metal.more » Here, a different scenario of relaxed lithium metal (without any pre-existing surface stresses) has been considered in the present analysis. Deposition of lithium due to electrochemical reaction at the lithium/electrolyte interface induces compressive stress at the electrode, the electrolyte, and the newly deposited lithium metal. Present simulations indicate that during operation at low current densities, the scenario of relaxed lithium leads to no dendrites. Rather, the present study points to the importance of including the effect of current distribution to accurately capture the mechanical forces needed to prevent dendrite growth.« less

High-Energy-Density Electrolytic Capacitors

NASA Technical Reports Server (NTRS)

Yen, Shiao-Ping S.; Lewis, Carol R.

1993-01-01

Reductions in weight and volume make new application possible. Supercapacitors and improved ultracapacitors advanced electrolytic capacitors developed for use as electric-load-leveling devices in such applications as electric vehicle propulsion systems, portable power tools, and low-voltage pulsed power supplies. One primary advantage: offer power densities much higher than storage batteries. Capacitors used in pulse mode, with short charge and discharge times. Derived from commercially available ultracapacitors. Made of lightweight materials; incorporate electrode/electrolyte material systems capable of operation at voltages higher than previous electrode/electrolyte systems. By use of innovative designs and manufacturing processes, made in wide range of rated capacitances and in rated operating potentials ranging from few to several hundred volts.

Cathode Characterization with Steel and Copper Collector Bars in an Electrolytic Cell

NASA Astrophysics Data System (ADS)

Das, Subrat; Morsi, Yos; Brooks, Geoffrey

2013-12-01

This article presents finite-element method simulation results of current distribution in an aluminum electrolytic cell. The model uses one quarter of the cell as a computational domain assuming longitudinal (along the length of the cell) and transverse axes of symmetries. The purpose of this work is to closely examine the impact of steel and copper collector bars on the cell current distribution. The findings indicated that an inclined steel collector bar (φ = 1°) can save up to 10-12 mV from the cathode lining in comparison to a horizontal 100 mm × 150-mm steel collector bar. It is predicted that a copper collector bar has a much higher potential of saving cathode voltage drop (CVD) and has a greater impact on the overall current distribution in the cell. A copper collector bar with 72% of cathode length and size of 100 mm × 150 mm is predicted to have more than 150 mV savings in cathode lining. In addition, a significant improvement in current distribution over the entire cathode surface is achieved when compared with a similar size of steel collector bar. There is a reduction of more than 70% in peak current density value due to the higher conductivity of copper. Comparisons between steel and copper collector bars with different sizes are discussed in terms CVD and current density distribution. The most important aspect of the findings is to recognize the influence of copper collector bars on the current distribution in molten metal. Lorentz fields are evaluated at different sizes of steel and copper collector bars. The simulation predicts that there is 50% decrease in Lorentz force due to the improvement in current distribution in the molten metal.

The electrochemical generation of useful chemical species from lunar materials

NASA Technical Reports Server (NTRS)

Tsai, Kan J.; Kuchynka, Daniel J.; Sammells, Anthony F.

1989-01-01

Electrochemical cells have been fabricated for the simultaneous generation of oxygen and lithium from a Li2O containing molten salt (Li2O-LiCl-LiF). The cell utilizes an oxygen vacancy conducting solid electrolyte, yttria-stabilized zirconia (YSZ), to effect separation between oxygen evolving and lithium reduction half-cell reactions. The cell, which operates at 700 to 850 C, possesses rapid electrode kinetics at the lithium-alloy electrode with exchange current density (i sub o) values being greater than 60mA sq cm. When used in the electrolytic mode, lithium produced at the negative electrode would be continuously removed from the cell for later use (under lunar conditions) as an easily storable reducing agent (compared to H2) for the chemical refining of lunar ores. Because of the high reversibility of this electrochemical system, it has also formed tha basis for the lithium oxygen secondary battery system which possesses the highest theoretical energy density yet investigated.

Nitrogen-doped three-dimensional graphene-supported platinum catalysts for polymer electrolyte membrane fuel cells application

NASA Astrophysics Data System (ADS)

Chu, Fuqiang; Li, Xingxing; Yuan, Wensen; Zhu, Huanhuan; Qin, Yong; Zhang, Shuai; Yuan, Ningyi; Lin, Bencai; Ding, Jianning

Catalysts are a key component of polymer electrolyte membrane fuel cells (PEMFCs). In this work, nitrogen-doped three-dimensional graphene-supported platinum (Pt-3DNG) catalysts are successfully prepared and characterized. SEM and TEM images show the Pt nanoparticles are uniformly dispersed in the sheets of nitrogen-doped 3DNG. Compared with that of the commercial Pt/C catalysts, Pt-3DNG show much better oxygen reduction reaction (ORR) activity and cycling stability, and the reduction in limit current density after 1000 cycles is only about 1.6% for the Pt-3DNG catalysts, whereas 7.2% for the commercial Pt/C catalysts. The single cell using Pt-3DNG catalysts in both the anode and the cathode show a higher peak power density (21.47mW cm-2) than that using commercial Pt/C catalysts (20.17mW cm-2) under the same conditions. These properties make this type of catalyst suitable for the application in PEMFCs.

Nickel supported on nitrogen-doped carbon nanotubes as hydrogen oxidation reaction catalyst in alkaline electrolyte

DOE PAGES

Zhuang, Zhongbin; Giles, Stephen A.; Zheng, Jie; ...

2016-01-14

The development of a low-cost, high-performance platinum-group-metal-free hydroxide exchange membrane fuel cell is hindered by the lack of a hydrogen oxidation reaction catalyst at the anode. Here we report that a composite catalyst, nickel nanoparticles supported on nitrogen-doped carbon nanotubes, has hydrogen oxidation activity similar to platinum-group metals in alkaline electrolyte. Although nitrogen-doped carbon nanotubes are a very poor hydrogen oxidation catalyst, as a support, it increases the catalytic performance of nickel nanoparticles by a factor of 33 (mass activity) or 21 (exchange current density) relative to unsupported nickel nanoparticles. Density functional theory calculations indicate that the nitrogen-doped support stabilizesmore » the nanoparticle against reconstruction, while nitrogen located at the edge of the nanoparticle tunes local adsorption sites by affecting the d-orbitals of nickel. Here, owing to its high activity and low cost, our catalyst shows significant potential for use in low-cost, high-performance fuel cells.« less

Nickel supported on nitrogen-doped carbon nanotubes as hydrogen oxidation reaction catalyst in alkaline electrolyte

PubMed Central

Zhuang, Zhongbin; Giles, Stephen A.; Zheng, Jie; Jenness, Glen R.; Caratzoulas, Stavros; Vlachos, Dionisios G.; Yan, Yushan

2016-01-01

The development of a low-cost, high-performance platinum-group-metal-free hydroxide exchange membrane fuel cell is hindered by the lack of a hydrogen oxidation reaction catalyst at the anode. Here we report that a composite catalyst, nickel nanoparticles supported on nitrogen-doped carbon nanotubes, has hydrogen oxidation activity similar to platinum-group metals in alkaline electrolyte. Although nitrogen-doped carbon nanotubes are a very poor hydrogen oxidation catalyst, as a support, it increases the catalytic performance of nickel nanoparticles by a factor of 33 (mass activity) or 21 (exchange current density) relative to unsupported nickel nanoparticles. Density functional theory calculations indicate that the nitrogen-doped support stabilizes the nanoparticle against reconstruction, while nitrogen located at the edge of the nanoparticle tunes local adsorption sites by affecting the d-orbitals of nickel. Owing to its high activity and low cost, our catalyst shows significant potential for use in low-cost, high-performance fuel cells. PMID:26762466

The electrochemical generation of useful chemical species from lunar materials

NASA Astrophysics Data System (ADS)

Tsai, Kan J.; Kuchynka, Daniel J.; Sammells, Anthony F.

1989-12-01

Electrochemical cells have been fabricated for the simultaneous generation of oxygen and lithium from a Li2O containing molten salt (Li2O-LiCl-LiF). The cell utilizes an oxygen vacancy conducting solid electrolyte, yttria-stabilized zirconia (YSZ), to effect separation between oxygen evolving and lithium reduction half-cell reactions. The cell, which operates at 700 to 850 C, possesses rapid electrode kinetics at the lithium-alloy electrode with exchange current density (i sub o) values being greater than 60mA sq cm. When used in the electrolytic mode, lithium produced at the negative electrode would be continuously removed from the cell for later use (under lunar conditions) as an easily storable reducing agent (compared to H2) for the chemical refining of lunar ores. Because of the high reversibility of this electrochemical system, it has also formed tha basis for the lithium oxygen secondary battery system which possesses the highest theoretical energy density yet investigated.

Ambipolar zinc-polyiodide electrolyte for a high-energy density aqueous redox flow battery

PubMed Central

Li, Bin; Nie, Zimin; Vijayakumar, M.; Li, Guosheng; Liu, Jun; Sprenkle, Vincent; Wang, Wei

2015-01-01

Redox flow batteries are receiving wide attention for electrochemical energy storage due to their unique architecture and advantages, but progress has so far been limited by their low energy density (~25 Wh l−1). Here we report a high-energy density aqueous zinc-polyiodide flow battery. Using the highly soluble iodide/triiodide redox couple, a discharge energy density of 167 Wh l−1 is demonstrated with a near-neutral 5.0 M ZnI2 electrolyte. Nuclear magnetic resonance study and density functional theory-based simulation along with flow test data indicate that the addition of an alcohol (ethanol) induces ligand formation between oxygen on the hydroxyl group and the zinc ions, which expands the stable electrolyte temperature window to from −20 to 50 °C, while ameliorating the zinc dendrite. With the high-energy density and its benign nature free from strong acids and corrosive components, zinc-polyiodide flow battery is a promising candidate for various energy storage applications. PMID:25709083

Ambipolar zinc-polyiodide electrolyte for a high-energy density aqueous redox flow battery.

PubMed

Li, Bin; Nie, Zimin; Vijayakumar, M; Li, Guosheng; Liu, Jun; Sprenkle, Vincent; Wang, Wei

2015-02-24

Redox flow batteries are receiving wide attention for electrochemical energy storage due to their unique architecture and advantages, but progress has so far been limited by their low energy density (~25 Wh l(-1)). Here we report a high-energy density aqueous zinc-polyiodide flow battery. Using the highly soluble iodide/triiodide redox couple, a discharge energy density of 167 Wh l(-1) is demonstrated with a near-neutral 5.0 M ZnI2 electrolyte. Nuclear magnetic resonance study and density functional theory-based simulation along with flow test data indicate that the addition of an alcohol (ethanol) induces ligand formation between oxygen on the hydroxyl group and the zinc ions, which expands the stable electrolyte temperature window to from -20 to 50 °C, while ameliorating the zinc dendrite. With the high-energy density and its benign nature free from strong acids and corrosive components, zinc-polyiodide flow battery is a promising candidate for various energy storage applications.

Rational Development of Neutral Aqueous Electrolytes for Zinc-Air Batteries.

PubMed

Clark, Simon; Latz, Arnulf; Horstmann, Birger

2017-12-08

Neutral aqueous electrolytes have been shown to extend both the calendar life and cycling stability of secondary zinc-air batteries (ZABs). Despite this promise, there are currently no modeling studies investigating the performance of neutral ZABs. Traditional continuum models are numerically insufficient to simulate the dynamic behavior of these complex systems because of the rapid, orders-of-magnitude concentration shifts that occur. In this work, we present a novel framework for modeling the cell-level performance of pH-buffered aqueous electrolytes. We apply our model to conduct the first continuum-scale simulation of secondary ZABs using aqueous ZnCl 2 -NH 4 Cl as electrolyte. We first use our model to interpret the results of two recent experimental studies of neutral ZABs, showing that the stability of the pH value is a significant factor in cell performance. We then optimize the composition of the electrolyte and the design of the cell considering factors including pH stability, final discharge product, and overall energy density. Our simulations predict that the effectiveness of the pH buffer is limited by slow mass transport and that chlorine-containing solids may precipitate in addition to ZnO. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Developing High-Performance Lithium Metal Anode in Liquid Electrolytes: Challenges and Progress.

PubMed

Li, Sa; Jiang, Mengwen; Xie, Yong; Xu, Hui; Jia, Junyao; Li, Ju

2018-04-01

Lithium metal anodes are potentially key for next-generation energy-dense batteries because of the extremely high capacity and the ultralow redox potential. However, notorious safety concerns of Li metal in liquid electrolytes have significantly retarded its commercialization: on one hand, lithium metal morphological instabilities (LMI) can cause cell shorting and even explosion; on the other hand, breaking of the grown Li arms induces the so-called "dead Li"; furthermore, the continuous consumption of the liquid electrolyte and cycleable lithium also shortens cell life. The research community has been seeking new strategies to protect Li metal anodes and significant progress has been made in the last decade. Here, an overview of the fundamental understandings of solid electrolyte interphase (SEI) formation, conceptual models, and advanced real-time characterizations of LMI are presented. Instructed by the conceptual models, strategies including increasing the donatable fluorine concentration (DFC) in liquid to enrich LiF component in SEI, increasing salt concentration (ionic strength) and sacrificial electrolyte additives, building artificial SEI to boost self-healing of natural SEI, and 3D electrode frameworks to reduce current density and delay Sand's extinction are summarized. Practical challenges in competing with graphite and silicon anodes are outlined. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Critical rate of electrolyte circulation for preventing zinc dendrite formation in a zinc-bromine redox flow battery

NASA Astrophysics Data System (ADS)

Yang, Hyeon Sun; Park, Jong Ho; Ra, Ho Won; Jin, Chang-Soo; Yang, Jung Hoon

2016-09-01

In a zinc-bromine redox flow battery, a nonaqueous and dense polybromide phase formed because of bromide oxidation in the positive electrolyte during charging. This formation led to complicated two-phase flow on the electrode surface. The polybromide and aqueous phases led to different kinetics of the Br/Br- redox reaction; poor mixing of the two phases caused uneven redox kinetics on the electrode surface. As the Br/Br- redox reaction was coupled with the zinc deposition reaction, the uneven redox reaction on the positive electrode was accompanied by nonuniform zinc deposition and zinc dendrite formation, which degraded battery stability. A single-flow cell was operated at varying electrolyte circulation rates and current densities. Zinc dendrite formation was observed after cell disassembly following charge-discharge testing. In addition, the flow behavior in the positive compartment was observed by using a transparent version of the cell. At low rate of electrolyte circulation, the polybromide phase clearly separated from the aqueous phase and accumulated at the bottom of the flow frame. In the corresponding area on the negative electrode, a large amount of zinc dendrites was observed after charge-discharge testing. Therefore, a minimum circulation rate should be considered to avoid poor mixing of the positive electrolyte.

Influence of Electrode Design and Contacting Layers on Performance of Electrolyte Supported SOFC/SOEC Single Cells.

PubMed

Kusnezoff, Mihails; Trofimenko, Nikolai; Müller, Martin; Michaelis, Alexander

2016-11-08

The solid oxide cell is a basis for highly efficient and reversible electrochemical energy conversion. A single cell based on a planar electrolyte substrate as support (ESC) is often utilized for SOFC/SOEC stack manufacturing and fulfills necessary requirements for application in small, medium and large scale fuel cell and electrolysis systems. Thickness of the electrolyte substrate, and its ionic conductivity limits the power density of the ESC. To improve the performance of this cell type in SOFC/SOEC mode, alternative fuel electrodes, on the basis of Ni/CGO as well as electrolytes with reduced thickness, have been applied. Furthermore, different interlayers on the air side have been tested to avoid the electrode delamination and to reduce the cell degradation in electrolysis mode. Finally, the influence of the contacting layer on cell performance, especially for cells with an ultrathin electrolyte and thin electrode layers, has been investigated. It has been found that Ni/CGO outperform traditional Ni/8YSZ electrodes and the introduction of a ScSZ interlayer substantially reduces the degradation rate of ESC in electrolysis mode. Furthermore, it was demonstrated that, for thin electrodes, the application of contacting layers with good conductivity and adhesion to current collectors improves performance significantly.

A rechargeable Li-O2 battery using a lithium nitrate/N,N-dimethylacetamide electrolyte.

PubMed

Walker, Wesley; Giordani, Vincent; Uddin, Jasim; Bryantsev, Vyacheslav S; Chase, Gregory V; Addison, Dan

2013-02-13

A major challenge in the development of rechargeable Li-O(2) batteries is the identification of electrolyte materials that are stable in the operating environment of the O(2) electrode. Straight-chain alkyl amides are one of the few classes of polar, aprotic solvents that resist chemical degradation in the O(2) electrode, but these solvents do not form a stable solid-electrolyte interphase (SEI) on the Li anode. The lack of a persistent SEI leads to rapid and sustained solvent decomposition in the presence of Li metal. In this work, we demonstrate for the first time successful cycling of a Li anode in the presence of the solvent, N,N-dimethylacetamide (DMA), by employing a salt, lithium nitrate (LiNO(3)), that stabilizes the SEI. A Li-O(2) cell containing this electrolyte composition is shown to cycle for more than 2000 h (>80 cycles) at a current density of 0.1 mA/cm(2) with a consistent charging profile, good capacity retention, and O(2) detected as the primary gaseous product formed during charging. The discovery of an electrolyte system that is compatible with both electrodes in a Li-O(2) cell may eliminate the need for protecting the anode with a ceramic membrane.

Optimization of Design Parameters and Operating Conditions of Electrochemical Capacitors for High Energy and Power Performance

NASA Astrophysics Data System (ADS)

Ike, Innocent S.; Sigalas, Iakovos; Iyuke, Sunny E.

2017-03-01

Theoretical expressions for performance parameters of different electrochemical capacitors (ECs) have been optimized by solving them using MATLAB scripts as well as via the MATLAB R2014a optimization toolbox. The performance of the different kinds of ECs under given conditions was compared using theoretical equations and simulations of various models based on the conditions of device components, using optimal values for the coefficient associated with the battery-kind material ( K BMopt) and the constant associated with the electrolyte material ( K Eopt), as well as our symmetric electric double-layer capacitor (EDLC) experimental data. Estimation of performance parameters was possible based on values for the mass ratio of electrodes, operating potential range ratio, and specific capacitance of electrolyte. The performance of asymmetric ECs with suitable electrode mass and operating potential range ratios using aqueous or organic electrolyte at appropriate operating potential range and specific capacitance was 2.2 and 5.56 times greater, respectively, than for the symmetric EDLC and asymmetric EC using the same aqueous electrolyte, respectively. This enhancement was accompanied by reduced cell mass and volume. Also, the storable and deliverable energies of the asymmetric EC with suitable electrode mass and operating potential range ratios using the proper organic electrolyte were 12.9 times greater than those of the symmetric EDLC using aqueous electrolyte, again with reduced cell mass and volume. The storable energy, energy density, and power density of the asymmetric EDLC with suitable electrode mass and operating potential range ratios using the proper organic electrolyte were 5.56 times higher than for a similar symmetric EDLC using aqueous electrolyte, with cell mass and volume reduced by a factor of 1.77. Also, the asymmetric EDLC with the same type of electrode and suitable electrode mass ratio, working potential range ratio, and proper organic electrolyte showed enhanced performance compared with the conventional symmetric EDLC using aqueous electrolyte, with reduced cell mass and volume. These results can obviously reduce the number of experiments required to determine the optimum manufacturing design for ECs and also demonstrate that use of an asymmetric electrode and organic electrolyte was very successful for improving the performance of the EC, with reduced cell mass and volume. These results can also act as guidelines for design, fabrication, and operation of electrochemical capacitors with outstanding storable energy, energy density, and power density.

Graphene oxide quantum dot-derived nitrogen-enriched hybrid graphene nanosheets by simple photochemical doping for high-performance supercapacitors

NASA Astrophysics Data System (ADS)

Xu, Yongjie; Li, Xinyu; Hu, Guanghui; Wu, Ting; Luo, Yi; Sun, Lang; Tang, Tao; Wen, Jianfeng; Wang, Heng; Li, Ming

2017-11-01

Nitrogen-enriched graphene was fabricated via a facile strategy. Graphene oxide (GO) nanosheets and graphene oxide quantum dots (GQDs) were used as a structure-directing agent and in situ activating agent, respectively, after photoreduction under NH3 atmosphere. The combination of photoreduction and NH3 not only reduced GO and GQD composites (GO/GQDs) within a shorter duration but also doped a high level of nitrogen on the composites (NrGO/GQDs). The nitrogen content of NrGO/GQDs reached as high as 18.86 at% within 5 min of irradiation. Benefiting from the nitrogen-enriched GO/GQDs hybrid structure, GQDs effectively prevent the agglomeration of GO sheets and increased the numbers of ion channels in the material. Meanwhile, the high levels of nitrogen improved electrical conductivity and strengthened the binding energy between GQD and GO sheets. Compared with reduced GO and low nitrogen-doped reduced GO, NrGO/GQD electrodes exhibited better electrochemical characteristics with a high specific capacitance of 344 F g-1 at a current density of 0.25 A g-1. Moreover, the NrGO/GQD electrodes exhibited 82% capacitance retention after 3000 cycles at a current density of 0.8 A g-1 in 6 M KOH electrolyte. More importantly, the NrGO/GQD electrodes deliver a high energy density of 43 Wh kg-1 at a power density of 417 W kg-1 in 1 M Li2SO4 electrolyte. The nitrogen-doped graphene and corresponding supercapacitor presented in this study are novel materials with potential applications in advanced energy storage systems.

Charge regulation at semiconductor-electrolyte interfaces.

PubMed

Fleharty, Mark E; van Swol, Frank; Petsev, Dimiter N

2015-07-01

The interface between a semiconductor material and an electrolyte solution has interesting and complex electrostatic properties. Its behavior will depend on the density of mobile charge carriers that are present in both phases as well as on the surface chemistry at the interface through local charge regulation. The latter is driven by chemical equilibria involving the immobile surface groups and the potential determining ions in the electrolyte solution. All these lead to an electrostatic potential distribution that propagate such that the electrolyte and the semiconductor are dependent on each other. Hence, any variation in the charge density in one phase will lead to a response in the other. This has significant implications on the physical properties of single semiconductor-electrolyte interfaces and on the electrostatic interactions between semiconductor particles suspended in electrolyte solutions. The present paper expands on our previous publication (Fleharty et al., 2014) and offers new results on the electrostatics of single semiconductor interfaces as well as on the interaction of charged semiconductor colloids suspended in electrolyte solution. Copyright © 2014 Elsevier Inc. All rights reserved.

Alkaline polymer electrolyte fuel cells stably working at 80 °C

NASA Astrophysics Data System (ADS)

Peng, Hanqing; Li, Qihao; Hu, Meixue; Xiao, Li; Lu, Juntao; Zhuang, Lin

2018-06-01

Alkaline polymer electrolyte fuel cells are a new class of polymer electrolyte fuel cells that fundamentally enables the use of nonprecious metal catalysts. The cell performance mostly relies on the quality of alkaline polymer electrolytes, including the ionic conductivity and the chemical/mechanical stability. For a long time, alkaline polymer electrolytes are thought to be too weak in stability to allow the fuel cell to be operated at elevated temperatures, e.g., above 60 °C. In the present work, we report a progress in the state-of-the-art alkaline polymer electrolyte fuel cell technology. By using a newly developed alkaline polymer electrolyte, quaternary ammonia poly (N-methyl-piperidine-co-p-terphenyl), which simultaneously possesses high ionic conductivity and excellent chemical/mechanical stability, the fuel cell can now be stably operated at 80 °C with high power density. The peak power density reaches ca. 1.5 W/cm2 at 80 °C with Pt/C catalysts used in both the anode and the cathode. The cell works stably in a period of study over 100 h.

Modeling the effect of shunt current on the charge transfer efficiency of an all-vanadium redox flow battery

NASA Astrophysics Data System (ADS)

Chen, Yong-Song; Ho, Sze-Yuan; Chou, Han-Wen; Wei, Hwa-Jou

2018-06-01

In an all-vanadium redox flow battery (VRFB), a shunt current is inevitable owing to the electrically conductive electrolyte that fills the flow channels and manifolds connecting cells. The shunt current decreases the performance of a VRFB stack as well as the energy conversion efficiency of a VRFB system. To understand the shunt-current loss in a VRFB stack with various designs and operating conditions, a mathematical model is developed to investigate the effects of the shunt current on battery performance. The model is calibrated with experimental data under the same operating conditions. The effects of the battery design, including the number of cells, state of charge (SOC), operating current, and equivalent resistance of the electrolytes in the flow channels and manifolds, on the shunt current are analyzed and discussed. The charge-transfer efficiency is calculated to investigate the effects of the battery design parameters on the shunt current. When the cell number is increased from 5 to 40, the charge transfer efficiency is decreased from 0.99 to a range between 0.76 and 0.88, depending on operating current density. The charge transfer efficiency can be maintained at higher than 0.9 by limiting the cell number to less than 20.

“Rocking-Chair”-Type Metal Hybrid Supercapacitors

DOE PAGES

Yoo, Hyun Deog; Han, Sang-Don; Bayliss, Ryan D.; ...

2016-10-24

Hybrid supercapacitors that follow a “rocking-chair”-type mechanism were developed by coupling divalent metal and activated carbon electrodes in nonaqueous electrolytes. Conventional supercapacitors require a large amount of electrolyte to provide a sufficient quantity of ions to the electrodes, due to their Daniell-type mechanism that depletes the ions from the electrolyte while charging. The alternative “rocking-chair”-type mechanism effectively enhances the energy density of supercapacitors by minimizing the necessary amount of electrolyte, because the ion is replenished from the metal anode while it is adsorbed to the cathode. Newly developed nonaqueous electrolytes for Mg and Zn electrochemistry, based on bis(trifluoromethylsulfonyl)imide (TFSI) salts,more » made the metal hybrid supercapacitors possible by enabling reversible deposition on the metal anodes and reversible adsorption on an activated carbon cathode. Factoring in gains through the cell design, the energy density of the metal hybrid supercapacitors is projected to be a factor of 7 higher than conventional devices thanks to both the “rocking-chair”-type mechanism that minimizes total electrolyte volume and the use of metal anodes, which have substantial merits in capacity and voltage. Self-discharge was also substantially alleviated compared to conventional supercapacitors. This concept offers a route to build supercapacitors that meet dual criteria of power and energy densities with a simple cell design.« less

"Rocking-Chair"-Type Metal Hybrid Supercapacitors.

PubMed

Yoo, Hyun Deog; Han, Sang-Don; Bayliss, Ryan D; Gewirth, Andrew A; Genorio, Bostjan; Rajput, Nav Nidhi; Persson, Kristin A; Burrell, Anthony K; Cabana, Jordi

2016-11-16

Hybrid supercapacitors that follow a "rocking-chair"-type mechanism were developed by coupling divalent metal and activated carbon electrodes in nonaqueous electrolytes. Conventional supercapacitors require a large amount of electrolyte to provide a sufficient quantity of ions to the electrodes, due to their Daniell-type mechanism that depletes the ions from the electrolyte while charging. The alternative "rocking-chair"-type mechanism effectively enhances the energy density of supercapacitors by minimizing the necessary amount of electrolyte, because the ion is replenished from the metal anode while it is adsorbed to the cathode. Newly developed nonaqueous electrolytes for Mg and Zn electrochemistry, based on bis(trifluoromethylsulfonyl)imide (TFSI) salts, made the metal hybrid supercapacitors possible by enabling reversible deposition on the metal anodes and reversible adsorption on an activated carbon cathode. Factoring in gains through the cell design, the energy density of the metal hybrid supercapacitors is projected to be a factor of 7 higher than conventional devices thanks to both the "rocking-chair"-type mechanism that minimizes total electrolyte volume and the use of metal anodes, which have substantial merits in capacity and voltage. Self-discharge was also substantially alleviated compared to conventional supercapacitors. This concept offers a route to build supercapacitors that meet dual criteria of power and energy densities with a simple cell design.

The Role of Air-Electrode Structure on the Incorporation of Immiscible PFCs in Nonaqueous Li-O2 Battery.

PubMed

Balaish, Moran; Ein-Eli, Yair

2017-03-22

Perfluorocarbons (PFCs) are considered advantageous additives to nonaqueous Li-O 2 battery due to their superior oxygen solubility and diffusivity compared to common battery electrolytes. Up to now, the main focus was concentrated on PFCs-electrolyte investigation; however, no special attention was granted to the role of carbon structure in the PFCs-Li-O 2 system. In our current research, immiscible PFCs, rather than miscible fluorinated ethers, were added to activated carbon class air electrode due to their higher susceptibility toward O 2 •- attack and to their ability to shift the reaction from two-phase to an artificial three-phase reaction zone. The results showed superior battery performance upon PFCs addition at lower current density (0.05 mA cm -2 ) but unexpectedly failed to do so at higher current density (0.1 and 0.2 mA cm -2 ), where oxygen transport limitation is best illustrated. The last was a direct result of liquid-liquid displacement phenomenon occurring when the two immiscible liquids were introduced into the porous carbon medium. The investigation and role of carbon structure on the mechanism upon PFCs addition to Li-O 2 system are suggested based on electrochemical characterization, wettability behavior studies, and the physical adsorption technique. Finally, we suggest an optimum air-electrode structure enabling the incorporation of immiscible PFCs in a nonaqueous Li-O 2 battery.

Practical stability limits of magnesium electrolytes

DOE Office of Scientific and Technical Information (OSTI.GOV)

Lipson, Albert L.; Han, Sang -Don; Pan, Baofei

2016-08-13

The development of a Mg ion based energy storage system could provide several benefits relative to today's Li-ion batteries, such as improved energy density. The electrolytes for Mg batteries, which are typically designed to efficiently plate and strip Mg, have not yet been proven to work with high voltage cathode materials that are needed to achieve high energy density. One possibility is that these electrolytes are inherently unstable on porous electrodes. To determine if this is indeed the case, the electrochemical properties of a variety of electrolytes were tested using a porous carbon coating on graphite foil and stainless steelmore » electrodes. It was determined that the oxidative stability limit on these porous electrodes is considerably reduced as compared to those found using polished platinum electrodes. Furthermore, the voltage stability was found to be about 3 V vs. Mg metal for the best performing electrolytes. In conclusion, these results imply the need for further research to improve the stability of Mg electrolytes to enable high voltage Mg batteries.« less

TEMPO-based catholyte for high-energy density nonaqueous redox flow batteries.

PubMed

Wei, Xiaoliang; Xu, Wu; Vijayakumar, Murugesan; Cosimbescu, Lelia; Liu, Tianbiao; Sprenkle, Vincent; Wang, Wei

2014-12-03

A TEMPO-based non-aqueous electrolyte with the TEMPO concentration as high as 2.0 m is demonstrated as a high-energy-density catholyte for redox flow battery applications. With a hybrid anode, Li|TEMPO flow cells using this electrolyte deliver an energy efficiency of ca. 70% and an impressively high energy density of 126 W h L(-1) . © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Core-Shell Fe1- xS@Na2.9PS3.95Se0.05 Nanorods for Room Temperature All-Solid-State Sodium Batteries with High Energy Density.

PubMed

Wan, Hongli; Mwizerwa, Jean Pierre; Qi, Xingguo; Liu, Xin; Xu, Xiaoxiong; Li, Hong; Hu, Yong-Sheng; Yao, Xiayin

2018-03-27

High ionic conductivity electrolyte and intimate interfacial contact are crucial factors to realize high-performance all-solid-state sodium batteries. Na 2.9 PS 3.95 Se 0.05 electrolyte with reduced particle size of 500 nm is first synthesized by a simple liquid-phase method and exhibits a high ionic conductivity of 1.21 × 10 -4 S cm -1 , which is comparable with that synthesized with a solid-state reaction. Meanwhile, a general interfacial architecture, that is, Na 2.9 PS 3.95 Se 0.05 electrolyte uniformly anchored on Fe 1- x S nanorods, is designed and successfully prepared by an in situ liquid-phase coating approach, forming core-shell structured Fe 1- x S@Na 2.9 PS 3.95 Se 0.05 nanorods and thus realizing an intimate contact interface. The Fe 1- x S@Na 2.9 PS 3.95 Se 0.05 /Na 2.9 PS 3.95 Se 0.05 /Na all-solid-state sodium battery demonstrates high specific capacity and excellent rate capability at room temperature, showing reversible discharge capacities of 899.2, 795.5, 655.1, 437.9, and 300.4 mAh g -1 at current densities of 20, 50, 100, 150, and 200 mA g -1 , respectively. The obtained all-solid-state sodium batteries show very high energy and power densities up to 910.6 Wh kg -1 and 201.6 W kg -1 based on the mass of Fe 1- x S at current densities of 20 and 200 mA g -1 , respectively. Moreover, the reaction mechanism of Fe 1- x S is confirmed by means of ex situ X-ray diffraction techniques, showing that partially reversible reaction occurs in the Fe 1- x S electrode after the second cycle, which gives the obtained all-solid-state sodium battery an exceptional cycling stability, exhibiting a high capacity of 494.3 mAh g -1 after cycling at 100 mA g -1 for 100 cycles. This contribution provides a strategy for designing high-performance room temperature all-solid-state sodium battery.

A novel carbon electrode material for highly improved EDLC performance.

PubMed

Fang, Baizeng; Binder, Leo

2006-04-20

Porous materials, developed by grafting functional groups through chemical surface modification with a surfactant, represent an innovative concept in energy storage. This work reports, in detail, the first practical realization of a novel carbon electrode based on grafting of vinyltrimethoxysilane (vtmos) functional group for energy storage in electric double layer capacitor (EDLC). Surface modification with surfactant vtmos enhances the hydrophobisation of activated carbon and the affinity toward propylene carbonate (PC) solvent, which improves the wettability of activated carbon in the electrolyte solution based on PC solvent, resulting in not only a lower resistance to the transport of electrolyte ions within micropores of activated carbon but also more usable surface area for the formation of electric double layer, and accordingly, higher specific capacitance, energy density, and power capability available from the capacitor based on modified carbon. Especially, the effects from surface modification become superior at higher discharge rate, at which much better EDLC performance (i.e., much higher energy density and power capability) has been achieved by the modified carbon, suggesting that the modified carbon is a novel and very promising electrode material of EDLC for large current applications where both high energy density and power capability are required.

Differential electrolytic potentiometric titration method for the determination of ciprofloxacin in drug formulations.

PubMed

Abulkibash, Abdalla M; Sultan, Salah M; Al-Olyan, Abeer M; Al-Ghannam, Sheikha M

2003-10-17

A simple and rapid differential electrolytic potentiometric titration method for the determination of ciprofloxacin was developed. The work is based on the fast complexation reaction between iron(III) and ciprofloxacin in a ratio of 1:3, respectively, in sulfuric acid media of 0.09 mol dm(-3). Among the electrodes tested silver amalgam electrodes were found to be a suitable indicating system. By applying a current density of 0.5 muA cm(-2) to these electrodes and using iron(III) solution of 0.097 mol dm(-3) as a titrant, normal titration curves were obtained. The method was successfully applied for the determination of ciprofloxacin in drug formulations as low as 4.0 ppm.

Dual membrane hollow fiber fuel cell and method of operating same

NASA Technical Reports Server (NTRS)

Ingham, J. D.; Lawson, D. D. (Inventor)

1978-01-01

A gaseous fuel cell is described which includes a pair of electrodes formed by open-ended, ion-exchange hollow fibers, each having a layer of metal catalyst deposited on the inner surface and large surface area current collectors such as braided metal mesh in contact with the metal catalyst layer. A fuel cell results when the electrodes are immersed in electrolytes and electrically connected. As hydrogen and oxygen flow through the bore of the fibers, oxidation and reduction reactions develop an electrical potential. Since the hollow fiber configuration provides large electrode area per unit volume and intimate contact between fuel and oxidizer at the interface, and due to the low internal resistance of the electrolyte, high power densities can be obtained.

A novel process of electroless Ni-P plating with plasma electrolytic oxidation pretreatment

NASA Astrophysics Data System (ADS)

Liu, Zhenmin; Gao, Wei

2006-12-01

A novel Ni based coating - plasma electrolytic oxidation (PEO) pre-treatment followed by electroless nickel (EN) plating - has been developed to produce pore free Ni coatings on AZ91 magnesium alloy. The application of the PEO film between the nickel coating and the substrate acts as an effective barrier and catalytic layer for the subsequent nickel plating. The potentiodynamic tests indicated that the corrosion current density of the PEO + EN plating on AZ91 decreased by almost two orders of magnitudes compared to the traditional EN coating. Salt fog spray testing further proved this improvement. More importantly, the new technique does not use Cr +6 and HF in its pretreatment, therefore is a much environmentally friendlier process.

Mesoporous NiCo2O4 nano-needles supported by 3D interconnected carbon network on Ni foam for electrochemical energy storage

NASA Astrophysics Data System (ADS)

Lu, Congxiang; Liu, Wen-wen; Pan, Hui; Tay, Beng Kang; Wang, Xingli; Liang, Kun; Wei, Xuezhe

2018-05-01

In this work, a three dimensional (3D) interconnected carbon network consisting of ultrathin graphite (UG) and carbon nanotubes (CNTs) on Ni foam is fabricated and employed as a novel type of substrate for mesoporous NiCo2O4 nano-needles. The successfully synthesized NiCo2O4 nano-needles/CNTs/UG on Ni foam has many advantages including facile electrolyte access and direct conducting pathways towards current collectors, which enable it to be a promising electrode material in battery-like electrochemical energy storage. Encouragingly, a high capacity of 135.1 mAh/g at the current density of 1 A/g, superior rate performance and also stable cycling for 1200 cycles at the current density of 5 A/g have been demonstrated in this novel material.

Organic pollutant removal from edible oil process wastewater using electrocoagulation

NASA Astrophysics Data System (ADS)

Sharma, S.; Can, O. T.; Hammed, M.; Nawarathna, D.; Simsek, H.

2018-03-01

Wastewaters generated from vegetable oil industries contain a high concentration of organic pollutants that are detrimental to the aquatic ecosystem. Electrochemical processes are gaining importance in the treatment of inorganic and resistant organic pollutants in wastewaters. In this study, electrocoagulation (EC) was applied to remove organic pollutants and oil and grease from canola oil wastewater using aluminum (Al) and iron (Fe) electrodes. The application of EC in the wastewater achieved more than 80% removal of organic carbon and nearly 100% removal of suspended solids (SS). The effectiveness of EC is influenced mainly by current density, pH, electrolyte (NaCl), electrode contact time and electrode type. It was observed that Al electrode combination yielded better removal at a lesser time compared to that of Fe electrodes. However, varying current densities had its significance in terms of coagulation time only. Increase in current density achieved decrease in coagulation time. Both Al and Fe could remove between 52-59% of oil and grease from canola oil wastewater

A porous carbon material from pyrolysis of fructus cannabis’s shells for supercapacitor electrode application

NASA Astrophysics Data System (ADS)

Li, Kai; Zhang, Wei-Bin; Zhao, Zhi-Yun; Zhao, Yue; Chen, Xi-Wen; Kong, Ling-Bin

2018-02-01

The porous carbon material is obtained via pyrolysis and activation of fructus cannabis’s shells, an easy-to-get biomass source, and is used as an active electrode material for supercapacitors. The obtained carbon exhibit a high specific surface area of 2389 m2 g-1. And the result of x-ray photoelectron spectroscopy (XPS) shows that the obtained porous carbon possess numerous oxygen groups, which can facilitate the wettability of the electrode. The prepared porous carbon also exhibit remarkable electrochemical properties, such as high specific capacitance of 357 F g-1 at a current density of 0.5 A g-1 in 6 mol L-1 aqueous KOH electrolyte, good rate capability of 77% capacitance retention as the current density increase from 0.5 A g-1 to 10 A g-1. In addition, it also presents a superior cycling stability of 100% capacitance retention after 10 000 cycles at the current density of 1 A g-1.

Maximizing fluid delivered by bubble-free electroosmotic pump with optimum pulse voltage waveform.

PubMed

Tawfik, Mena E; Diez, Francisco J

2017-03-01

In generating high electroosmotic (EO) flows for use in microfluidic pumps, a limiting factor is faradaic reactions that are more pronounced at high electric fields. These reactions lead to bubble generation at the electrodes and pump efficiency reduction. The onset of gas generation for high current density EO pumping depends on many parameters including applied voltage, working fluid, and pulse duration. The onset of gas generation can be delayed and optimized for maximum volume pumped in the minimum time possible. This has been achieved through the use of a novel numerical model that predicts the onset of gas generation during EO pumping using an optimized pulse voltage waveform. This method allows applying current densities higher than previously reported. Optimal pulse voltage waveforms are calculated based on the previous theories for different current densities and electrolyte molarity. The electroosmotic pump performance is investigated by experimentally measuring the fluid volume displaced and flow rate. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

One step shift towards flexible supercapacitors based on carbon nanotubes - A review

NASA Astrophysics Data System (ADS)

Yar, A.; Dennis, J. O.; Mohamed, N. M.; Mumtaz, A.; Irshad, M. I.; Ahmad, F.

2014-10-01

Supercapacitors have emerged as prominent energy storage devices that offer high energy density compared to conventional capacitors and high power density which is not found in batteries. Carbon nanotubes (CNTs) because of their high surface area and tremendous electrical properties are used as electrode material for supercapacitors. In this review we focused on the factors like surface area, role of the electrolyte and techniques adopted to improve performance of CNTs based supercapacitors. The supercapacitors are widely tested in liquid electrolytes which are normally hazardous in nature, toxic, flammable and their leakage has safety concerns. This review also focuses on research which is replacing these unsafe electrolytes by solid electrolytes with the combination of low cost CNTs deposited flexible supports for supercapacitors.

Oxygen concentration sensor for an internal combustion engine

DOE Office of Scientific and Technical Information (OSTI.GOV)

Nakajima, T.; Okada, Y.; Mieno, T.

1988-09-29

This patent describes an oxygen concentration sensor, comprising: an oxygen ion conductive solid electrolyte member forming a gas diffusion restricted region into which a measuring gas is introduced; a pair of electrodes sandwiching the solid electrolyte member; pump current supply means applying a pump voltage to the pair of electrodes through a current detection element to generate a pump current; and a heater element connected to the solid electrolyte member for heating the solid electrolyte member for heating the solid electrolyte member when a heater current is supplied from a heater current source; wherein the oxygen concentration sensor detects anmore » oxygen concentration in the measuring gas in terms of a current value of the pump current supplied through the current detection element and controls oxygen concentration in the gas diffusion restricted region by conducting oxygen ions through the solid electrolyte member in accordance to the flow of the pump current; and wherein the current detection element is connected to the electrode of the pair of electrodes facing the gas diffusion restricted region for insuring that the current value is representative of the pump current and possible leakage current from the heater current.« less

Comparative study of Ce0.80Sm0.20 Ba0.80Y0.20O3-δ (YB-SDC) electrolyte by various chemical synthesis routes

NASA Astrophysics Data System (ADS)

Tariq, Sana; Marium, Aniqa; Raza, Rizwan; Ashfaq Ahmad, M.; Ajmal Khan, M.; Abbas, Ghazanfar; Waseem Boota, M.; Khalid Imran, S.; Arshad, Sarfraz; Ikram, Muhammad

2018-03-01

Solid Oxide Fuel Cells is received a significant attention in recent years due to higher efficiency and fuel flexibility. The one of the main challenge for SOFC is to lower the operating temperature of SOFCs. Therefore, different strategies are used in order to enhance the ionic conduction of electrolyte, which can lower the overall SOFC operating temperature. The present work is focused on this strategy to enhance the electrolytic conductivity. Therefore, the ceria based composite electrolytes Ce0.80Sm0.20B0.80Y0.20O3-δ (YBSDC) are synthesized using three different approaches i.e. co-precipitation (YBSDC-1), sol-gel (YBSDC-2) and ball milling (YBSDC-3). Their crystal structures and surface morphologies are characterized through X-ray Diffraction (XRD) and Scanning Electron Microscopy (SEM) techniques, respectively. The four-probe technique is employed to measure their dc conductivities in the temperature range (300-700) °C under air atmosphere. The open circuit voltage (OCV) and current are recorded with natural gas as fuel {flow rate kept at 100 ml min-1 at 1 atm pressure} over the temperature range (300-600) °C. The electrolyte (YBSDC-1) prepared by co-precipitation technique is shown better results as compare to other two electrolytes (YBSDC-2 and YBSDC-3). The electrolyte (YBSDC-1) having maximum dc conductivity (0.096 S/cm), peak power density 224 mW cm-2 and OCV 0.94 V at 600 °C. These results show that YBSDC-1electrolyte is potential candidate for low temperature SOFCs.

Asymmetric battery having a semi-solid cathode and high energy density anode

DOEpatents

Tan, Taison; Chiang, Yet-Ming; Ota, Naoki; Wilder, Throop; Duduta, Mihai

2017-11-28

Embodiments described herein relate generally to devices, systems and methods of producing high energy density batteries having a semi-solid cathode that is thicker than the anode. An electrochemical cell can include a positive electrode current collector, a negative electrode current collector and an ion-permeable membrane disposed between the positive electrode current collector and the negative electrode current collector. The ion-permeable membrane is spaced a first distance from the positive electrode current collector and at least partially defines a positive electroactive zone. The ion-permeable membrane is spaced a second distance from the negative electrode current collector and at least partially defines a negative electroactive zone. The second distance is less than the first distance. A semi-solid cathode that includes a suspension of an active material and a conductive material in a non-aqueous liquid electrolyte is disposed in the positive electroactive zone, and an anode is disposed in the negative electroactive zone.

Asymmetric battery having a semi-solid cathode and high energy density anode

DOEpatents

Tan, Taison; Chiang, Yet-Ming; Ota, Naoki; Wilder, Throop; Duduta, Mihai

2016-09-06

Embodiments described herein relate generally to devices, systems and methods of producing high energy density batteries having a semi-solid cathode that is thicker than the anode. An electrochemical cell can include a positive electrode current collector, a negative electrode current collector and an ion-permeable membrane disposed between the positive electrode current collector and the negative electrode current collector. The ion-permeable membrane is spaced a first distance from the positive electrode current collector and at least partially defines a positive electroactive zone. The ion-permeable membrane is spaced a second distance from the negative electrode current collector and at least partially defines a negative electroactive zone. The second distance is less than the first distance. A semi-solid cathode that includes a suspension of an active material and a conductive material in a non-aqueous liquid electrolyte is disposed in the positive electroactive zone, and an anode is disposed in the negative electroactive zone.

The effect of crystal orientation on the aluminum anodes of the aluminum-air batteries in alkaline electrolytes

NASA Astrophysics Data System (ADS)

Fan, Liang; Lu, Huimin; Leng, Jing; Sun, Zegao; Chen, Chunbo

2015-12-01

Recently, aluminum-air (Al-air) batteries have received attention from researchers as an exciting option for safe and efficient batteries. The electrochemical performance of Aluminum anode remains an active area of investigation. In this paper, the electrochemical properties of polycrystalline Al, Al (001), (110) and (111) single crystals are investigated using potentiodynamic polarization and electrochemical impedance spectroscopy (EIS) in 4 M NaOH and KOH. Hydrogen corrosion rates of the Al anodes are determined by hydrogen collection. Battery performance using the anodes is tested by constant current discharge at 10 mA cm-2. This is the first report showing that the electrochemical properties of Al are closely related to the crystallographic orientation in alkaline electrolytes. The (001) crystallographic plane has good corrosion resistance but (110) is more sensitive. Al (001) single crystals display higher anode efficiency and capacity density. Controlling the crystallographic orientation of the Al anode is another way to improve the performance of Al-air batteries in alkaline electrolytes.

Electrochemical device for converting carbon dioxide to a reaction product

DOE Office of Scientific and Technical Information (OSTI.GOV)

Masel, Richard I.; Chen, Qingmei; Liu, Zengcai

An electrochemical device converts carbon dioxide to a reaction product. The device includes an anode and a cathode, each comprising a quantity of catalyst. The anode and cathode each has reactant introduced thereto. A polymer electrolyte membrane is interposed between the anode and the cathode. At least a portion of the cathode catalyst is directly exposed to gaseous carbon dioxide during electrolysis. The average current density at the membrane is at least 20 mA/cm.sup.2, measured as the area of the cathode gas diffusion layer that is covered by catalyst, and CO selectivity is at least 50% at a cell potentialmore » of 3.0 V. In some embodiments, the polymer electrolyte membrane comprises a polymer in which a constituent monomer is (p-vinylbenzyl)-R, where R is selected from the group consisting of imidazoliums, pyridiniums and phosphoniums. In some embodiments, the polymer electrolyte membrane is a Helper Membrane comprising a polymer containing an imidazolium ligand, a pyridinium ligand, or a phosphonium ligand.« less

Hierarchical mesoporous perovskite La0.5Sr0.5CoO2.91 nanowires with ultrahigh capacity for Li-air batteries

PubMed Central

Zhao, Yunlong; Xu, Lin; Mai, Liqiang; Han, Chunhua; An, Qinyou; Xu, Xu; Liu, Xue; Zhang, Qingjie

2012-01-01

Lithium-air batteries have captured worldwide attention due to their highest energy density among the chemical batteries. To provide continuous oxygen channels, here, we synthesized hierarchical mesoporous perovskite La0.5Sr0.5CoO2.91 (LSCO) nanowires. We tested the intrinsic oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) activity in both aqueous electrolytes and nonaqueous electrolytes via rotating disk electrode (RDE) measurements and demonstrated that the hierarchical mesoporous LSCO nanowires are high-performance catalysts for the ORR with low peak-up potential and high limiting diffusion current. Furthermore, we fabricated Li-air batteries on the basis of hierarchical mesoporous LSCO nanowires and nonaqueous electrolytes, which exhibited ultrahigh capacity, ca. over 11,000 mAh⋅g –1, one order of magnitude higher than that of LSCO nanoparticles. Besides, the possible reaction mechanism is proposed to explain the catalytic activity of the LSCO mesoporous nanowire. PMID:23150570

Developing New Electrolytes for Advanced Li-ion Batteries

NASA Astrophysics Data System (ADS)

McOwen, Dennis Wayne

The use of renewable energy sources is on the rise, as new energy generating technologies continue to become more efficient and economical. Furthermore, the advantages of an energy infrastructure which relies more on sustainable and renewable energy sources are becoming increasingly apparent. The most readily available of these renewable energy sources, wind and solar energy in particular, are naturally intermittent. Thus, to enable the continued expansion and widespread adoption of renewable energy generating technology, a cost-effective energy storage system is essential. Additionally, the market for electric/hybrid electric vehicles, which both require efficient energy storage, continues to grow as more consumers seek to reduce their consumption of gasoline. These vehicles, however, remain quite expensive, due primarily to costs associated with storing the electrical energy. High-voltage and thermally stable Li-ion battery technology is a promising solution for both grid-level and electric vehicle energy storage. Current limitations in materials, however, limit the energy density and safe operating temperature window of the battery. Specifically, the state-of-the-art electrolyte used in Li-ion batteries is not compatible with recently developed high-voltage positive electrodes, which are one of the most effectual ways of increasing the energy density. The electrolyte is also thermally unstable above 50 °C, and prone to thermal runaway reaction if exposed to prolonged heating. The lithium salt used in such electrolytes, LiPF6, is a primary contributor to both of these issues. Unfortunately, an improved lithium salt which meets the myriad property requirements for Li-ion battery electrolytes has eluded researchers for decades. In this study, a renewed effort to find such a lithium salt was begun, using a recently developed methodology to rapidly screen for desirable properties. Four new lithium salts and one relatively new but uncharacterized lithium salt were synthesized for this investigation: dilithium 1,2,5-thiadiazolidine-3,4-dione-1,1-dioxide (Li2TDD), lithium ethyl N-trifluoroacetylcarbamate (LiETAC), lithium hexafluoroisopropoxide (LiHFI), lithium pentafluorophenolate (LiPFPO), and lithium 2-trifluoromethyl-4,5-dicyanoimidazolide (LiTDI). Using crystalline solvate structure analysis and electrolyte solvation numbers, each of these lithium salts were compared to more well-characterized lithium salts, such as LiPF6 and LiBF4. From this study, links between anion structural characteristics and the anion...Li+ cation interactions (i.e., ionic association strength) were made. From the screening of the five lithium salts that were synthesized, LiTDI was determined to be a promising candidate for Li-ion battery electrolytes. Further characterization of carbonate- and mixed carbonate-LiTDI electrolytes (e.g., ionic conductivity) confirmed this to be the case. Coin cells containing LiTDI or LiPF6 electrolytes showed that cells with either electrolyte could deliver nearly identical power density at 25 °C. Additionally, thermogravimetric analysis (TGA) and NMR suggested that the LiTDI salt and carbonate-LiTDI electrolytes are thermally stable up to at least 60 °C. Further supporting this finding, coin cells cycled at 60 °C with LiPF6 lost significantly more capacity than those with LiTDI. Therefore, LiTDI is a prime candidate for the complete replacement of LiPF6 to significantly increase Li-ion battery tolerance to heat, improving the safety characteristics. In addition to searching for new lithium salts, the effect of lithium salt concentration on electrolyte physicochemical properties was investigated. This radically different approach to modifying electrolyte properties determined that amorphous, highly concentrated carbonate-lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) electrolytes have drastically different behavior than more dilute electrolytes. For example, the thermal stability and anodic stability vs. a Pt electrode of the concentrated electrolytes are significantly higher. Most striking, however, was the suppression of Al corrosion by the concentrated carbonate-LiTFSI electrolytes, despite the fact that Al corrosion of more dilute carbonate-LiTFSI electrolytes has consistently been attributed to the TFSI- anion in the literature. These results, explained by crystalline solvate analysis, Raman spectroscopy, and molecular dynamics simulations, could change the way Li-ion battery electrolytes are designed.

Functional Carbon Materials for Electrochemical Energy Storage

NASA Astrophysics Data System (ADS)

Zhou, Huihui

The ability to harvest and convert solar energy has been associated with the evolution of human civilization. The increasing consumption of fossil fuels since the industrial revolution, however, has brought to concerns in ecological deterioration and depletion of the fossil fuels. Facing these challenges, humankind is forced to seek for clean, sustainable and renewable energy resources, such as biofuels, hydraulic power, wind power, geothermal energy and other kinds of alternative energies. However, most alternative energy sources, generally in the form of electrical energy, could not be made available on a continuous basis. It is, therefore, essential to store such energy into chemical energy, which are portable and various applications. In this context, electrochemical energy-storage devices hold great promises towards this goal. The most common electrochemical energy-storage devices are electrochemical capacitors (ECs, also called supercapacitors) and batteries. In comparison to batteries, ECs posses high power density, high efficiency, long cycling life and low cost. ECs commonly utilize carbon as both (symmetric) or one of the electrodes (asymmetric), of which their performance is generally limited by the capacitance of the carbon electrodes. Therefore, developing better carbon materials with high energy density has been emerging as one the most essential challenges in the field. The primary objective of this dissertation is to design and synthesize functional carbon materials with high energy density at both aqueous and organic electrolyte systems. The energy density (E) of ECs are governed by E = CV 2/2, where C is the total capacitance and V is the voltage of the devices. Carbon electrodes with high capacitance and high working voltage should lead to high energy density. In the first part of this thesis, a new class of nanoporous carbons were synthesized for symmetric supercapacitors using aqueous Li2SO4 as the electrolyte. A unique precursor was adopted to create uniformly distributed nanopores with large surface area, leading to high-performance electrodes with high capacitance, excellent rate performance and stable cycling, even under a high working voltage of 1.6V. The second part of this dissertation work further improved the capacitance of the carbon electrodes by fluorine doping. This doping process enhances the affinity of the carbon surface with organic electrolytes, leading to further improved capacitance and energy density. In the third part, carbon materials were synthesized with high surface area, capacitance and working voltage of 4V in organic electrolyte, leading to the construction of prototyped devices with energy density comparable to those of the current lead-acid batteries. Besides the abovementioned research, hierarchical graphitic carbons were also explored for lithium ion batteries and supercapacitors. Overall, through rational design of carbons with optimized pore configuration and surface chemistry, carbon electrodes with improved energy density and rate performance were improved significantly. Collectively, this thesis work systematically unveils simple yet effective strategies to achieve high performance carbon-based supercapacitors with high power density and high energy density, including the following aspects: 1) Constructed electrodes with high capacitance through building favorable ion/electron transportation pathways, tuning pore structure and pore size. 2) Improved the capacitance through enhancing the affinity between the carbon electrodes and electrolytes by doping the carbons with heteroatoms. 3) Explored and understand the roles of heteroatom doping in the capacitive behavior by both experimental measurement and computational modeling. 4) Improved energy density of carbon electrodes by enlarging their working voltage in aqueous and organic electrolyte. 5) Scalable and effective production of hierarchically porous graphite particles through aerosol process for use as the anode materials of lithium ion batteries. These strategies can be extended as a general design platform for other high-performance energy storage materials such as fuel cells and lithium-ion batteries.

Dense garnet-like Li5La3Nb2O12 solid electrolyte prepared by self-consolidation method

NASA Astrophysics Data System (ADS)

Zhao, Pengcheng; Xiang, Yu; Xu, Yan; Wen, Yuehua; Zhang, Wenfeng; Zhu, Xiayu; Li, Meng; Zhang, Sontong; Ming, Hai; Jin, Zhaoqing; Cao, Gaoping

2018-06-01

Li5La3Nb2O12 (LLNO) is a typical garnet-like solid electrolyte with solitary cubic structure. However, its ionic conductivity is relatively low due to the low relative density when prepared by cold isostatic pressing method, which usually involves high-pressure machines, poor productivity, tedious pressing operations, and low density. In this paper, self-consolidation method is developed to sinter dense LLNO electrolyte. Although not any pressing operations are employed in the entire process, the relative density of LLNO is promoted up to 95%, which is much higher than the reported values of 45-80%. SEM images reveal that the sample is built by huge particles in size of 80 μm indicating that there are few boundaries in the sample. Moreover, a rich content of Li-Al-O compounds is detected out in the boundary areas, which may act as sintering aids for the sample to consolidate automatically. According to the highest density, the bulk ionic conductivity of LLNO sample reaches up to 1.61 × 10-4 S cm-1 at 30 °C, which is in the same order of magnitude as the value of cubic Li7La3Zr2O12 electrolyte. This work verifies the self-consolidation mechanism for the sintering of ceramic electrolytes and could significantly facilitate the development of LLNO membrane technology.

Scalable preparation of porous micron-SnO2/C composites as high performance anode material for lithium ion battery

NASA Astrophysics Data System (ADS)

Wang, Ming-Shan; Lei, Ming; Wang, Zhi-Qiang; Zhao, Xing; Xu, Jun; Yang, Wei; Huang, Yun; Li, Xing

2016-03-01

Nano tin dioxide-carbon (SnO2/C) composites prepared by various carbon materials, such as carbon nanotubes, porous carbon, and graphene, have attracted extensive attention in wide fields. However, undesirable concerns of nanoparticles, including in higher surface area, low tap density, and self-agglomeration, greatly restricted their large-scale practical applications. In this study, novel porous micron-SnO2/C (p-SnO2/C) composites are scalable prepared by a simple hydrothermal approach using glucose as a carbon source and Pluronic F127 as a pore forming agent/soft template. The SnO2 nanoparticles were homogeneously dispersed in micron carbon spheres by assembly with F127/glucose. The continuous three-dimensional porous carbon networks have effectively provided strain relaxation for SnO2 volume expansion/shrinkage during lithium insertion/extraction. In addition, the carbon matrix could largely minimize the direct exposure of SnO2 to the electrolyte, thus ensure formation of stable solid electrolyte interface films. Moreover, the porous structure could also create efficient channels for the fast transport of lithium ions. As a consequence, the p-SnO2/C composites exhibit stable cycle performance, such as a high capacity retention of over 96% for 100 cycles at a current density of 200 mA g-1 and a long cycle life up to 800 times at a higher current density of 1000 mA g-1.

Synthesis, characterization and electrochemical performance of graphene decorated with 1D NiMoO4.nH2O nanorods

NASA Astrophysics Data System (ADS)

Ghosh, Debasis; Giri, Soumen; Das, Chapal Kumar

2013-10-01

One-dimensional NiMoO4.nH2O nanorods and their graphene based hybrid composite with good electrochemical properties have been synthesized by a cost effective hydrothermal procedure. The formation of the mixed metal oxide and the composite was confirmed by XRD, XPS and Raman analyses. The morphological characterizations were carried out using FESEM and TEM analyses. The materials were subjected to electrochemical characterization through cyclic voltammetry (CV), galvanostatic charge-discharge (GCD) and electrochemical impedance spectroscopy (EIS) studies with 6 M KOH as the supporting electrolyte. For NiMoO4.nH2O, a maximum specific capacitance of 161 F g-1 was obtained at 5 A g-1 current density, accompanied with an energy density of 4.53 W h kg-1 at a steady power delivery rate of 1125 W kg-1. The high utility of the pseudocapacitive NiMoO4.nH2O was achieved in its graphene based composite, which exhibited a high specific capacitance of 367 F g-1 at 5 A g-1 current density and a high energy density of 10.32 W h kg-1 at a power density of 1125 W kg-1 accompanied with long term cyclic stability.One-dimensional NiMoO4.nH2O nanorods and their graphene based hybrid composite with good electrochemical properties have been synthesized by a cost effective hydrothermal procedure. The formation of the mixed metal oxide and the composite was confirmed by XRD, XPS and Raman analyses. The morphological characterizations were carried out using FESEM and TEM analyses. The materials were subjected to electrochemical characterization through cyclic voltammetry (CV), galvanostatic charge-discharge (GCD) and electrochemical impedance spectroscopy (EIS) studies with 6 M KOH as the supporting electrolyte. For NiMoO4.nH2O, a maximum specific capacitance of 161 F g-1 was obtained at 5 A g-1 current density, accompanied with an energy density of 4.53 W h kg-1 at a steady power delivery rate of 1125 W kg-1. The high utility of the pseudocapacitive NiMoO4.nH2O was achieved in its graphene based composite, which exhibited a high specific capacitance of 367 F g-1 at 5 A g-1 current density and a high energy density of 10.32 W h kg-1 at a power density of 1125 W kg-1 accompanied with long term cyclic stability. Electronic supplementary information (ESI) available: Materials used, characterization techniques and preparation of electrode, tables containing specific capacitance, coulombic efficiency, energy density and power density values at different current densities of NiMoO4.nH2O and Gr-NiMoO4.nH2O. See DOI: 10.1039/c3nr02444j

High power density proton exchange membrane fuel cells

NASA Technical Reports Server (NTRS)

Murphy, Oliver J.; Hitchens, G. Duncan; Manko, David J.

1993-01-01

Proton exchange membrane (PEM) fuel cells use a perfluorosulfonic acid solid polymer film as an electrolyte which simplifies water and electrolyte management. Their thin electrolyte layers give efficient systems of low weight, and their materials of construction show extremely long laboratory lifetimes. Their high reliability and their suitability for use in a microgravity environment makes them particularly attractive as a substitute for batteries in satellites utilizing high-power, high energy-density electrochemical energy storage systems. In this investigation, the Dow experimental PEM (XUS-13204.10) and unsupported high platinum loading electrodes yielded very high power densities, of the order of 2.5 W cm(exp -2). A platinum black loading of 5 mg per cm(exp 2) was found to be optimum. On extending the three-dimensional reaction zone of fuel cell electrodes by impregnating solid polymer electrolyte into the electrode structures, Nafion was found to give better performance than the Dow experimental PEM. The depth of penetration of the solid polymer electrolyte into electrode structures was 50-70 percent of the thickness of the platinum-catalyzed active layer. However, the degree of platinum utilization was only 16.6 percent and the roughness factor of a typical electrode was 274.

Improved Performance of Ionic Liquid Supercapacitors by using Tetracyanoborate Anions.

PubMed

Martins, Vitor L; Rennie, Anthony J R; Sanchez-Ramirez, Nedher; Torresi, Roberto M; Hall, Peter J

2018-02-01

Supercapacitors are energy storage devices designed to operate at higher power densities than conventional batteries, but their energy density is still too low for many applications. Efforts are made to design new electrolytes with wider electrochemical windows than aqueous or conventional organic electrolytes in order to increase energy density. Ionic liquids (ILs) with wide electrochemical stability windows are excellent candidates to be employed as supercapacitor electrolytes. ILs containing tetracyanoborate anions [B(CN) 4 ] offer wider electrochemical stability than conventional electrolytes and maintain a high ionic conductivity (6.9 mS cm -1 ). Herein, we report the use of ILs containing the [B(CN) 4 ] anion for such an application. They presented a high maximum operating voltage of 3.7 V, and two-electrode devices demonstrate high specific capacitances even when operating at relatively high rates (ca. 20 F g -1 @ 15 A g -1 ). This supercapacitor stored more energy and operated at a higher power at all rates studied when compared with cells using a commonly studied ILs.

Investigation of low temperature solid oxide fuel cells for air-independent UUV applications

NASA Astrophysics Data System (ADS)

Moton, Jennie Mariko

Unmanned underwater vehicles (UUVs) will benefit greatly from high energy density (> 500 Wh/L) power systems utilizing high-energy-density fuels and air-independent oxidizers. Current battery-based systems have limited energy densities (< 400 Wh/L), which motivate development of alternative power systems such as solid oxide fuel cells (SOFCs). SOFC-based power systems have the potential to achieve the required UUV energy densities, and the current study explores how SOFCs based on gadolinia-doped ceria (GDC) electrolytes with operating temperatures of 650°C and lower may operate in the unique environments of a promising UUV power plant. The plant would contain a H 2O2 decomposition reactor to supply humidified O2 to the SOFC cathode and exothermic aluminum/H2O combustor to provide heated humidified H2 fuel to the anode. To characterize low-temperature SOFC performance with these unique O2 and H2 source, SOFC button cells based on nickel/GDC (Gd0.1Ce0.9O 1.95) anodes, GDC electrolytes, and lanthanum strontium cobalt ferrite (La0.6Sr0.4Co0.2Fe0.8O3-δ or LSCF)/GDC cathodes were fabricated and tested for performance and stability with humidity on both the anode and the cathode. Cells were also tested with various reactant concentrations of H2 and O2 to simulate gas depletion down the channel of an SOFC stack. Results showed that anode performance depended primarily on fuel concentration and less on the concentration of the associated increase in product H2O. O 2 depletion with humidified cathode flows also caused significant loss in cell current density at a given voltage. With the humidified flows in either the anode or cathode, stability tests of the button cells at 650 °C showed stable voltage is maintained at low operating current (0.17 A/cm2) at up to 50 % by mole H2O, but at higher current densities (0.34 A/cm2), irreversible voltage degradation occurred at rates of 0.8-3.7 mV/hour depending on exposure time. From these button cell results, estimated average current densities over the length of a low-temperature SOFC stack were estimated and used to size a UUV power system based on Al/H 2O oxidation for fuel and H2O2 decomposition for O2. The resulting system design suggested that energy densities above 300 Wh/L may be achieved at neutral buoyancy with seawater if the cell is operated at high reactant utilizations in the SOFC stack for missions longer than 20 hours.

[4,4‧-bi(1,3,2-dioxathiolane)] 2,2‧-dioxide: A novel cathode additive for high-voltage performance in lithium ion batteries

NASA Astrophysics Data System (ADS)

Lee, Sang Hyun; Yoon, Sukeun; Hwang, Eui-Hyung; Kwon, Young-Gil; Lee, Young-Gi; Cho, Kuk Young

2018-02-01

High-voltage operation of lithium-ion batteries (LIBs) is a facile approach to obtaining high specific energy density, especially for LiNi0·5Mn0·3Co0·2O2 (NMC532) cathodes currently used in mid- and large-sized energy storage devices. However, high-voltage charging (>4.3 V) is accompanied by a rapid capacity fade over long cycles due to severe continuous electrolyte decomposition and instability at the cathode surface. In this study, the sulfite-based compound, [4,4‧-bi(1,3,2-dioxathiolane)] 2,2‧-dioxide (BDTD) is introduced as a novel electrolyte additive to enhance electrochemical performances of alumina-coated NMC532 cathodes cycled in the voltage range of 3.0-4.6 V. X-ray photoelectron spectroscopy (XPS) and AC impedance of cells reveal that BDTD preferentially oxidizes prior to the electrolyte solvents and forms stable film layers on to the cathode surface, preventing increased impedance caused by repeated electrolyte solvent decomposition in high-voltage operation. The cycling performance of the Li/NMC532 half-cell using an electrolyte of 1.0 M LiPF6 in ethylene carbonate/ethyl methyl carbonate (3/7, in volume) can be improved by adding a small amount of BDTD into the electrolyte. BDTD enables the usage of sulfite-type additives for cathodes in high-voltage operation.

The photocapacitance of the HgI2/electrolyte system

NASA Astrophysics Data System (ADS)

Burger, A.; Shi, W.; Silberman, E.; Franks, L.; Schnepple, W. F.

1989-11-01

Electrochemical photocapacitance spectroscopy (EPS) measurements in the range 1.5-2.3 eV are reported for mercuric iodide crystals. Two peaks in the photocapacitance were identified at 1.75 and 1.64 eV. The determination of densities of states and kinetic parameters is presented and the results are compared with the results obtained by the method of thermally stimulated currents (TSC), as reported in the literature.

Formation of protective composite coatings with the use of solution of TFE telomers

NASA Astrophysics Data System (ADS)

Mashtalyar, D. V.; Gnedenkov, S. V.; Sinebryukhov, S. L.; Nadaraia, K. V.; Kiryukhin, D. P.; Kushch, P. P.; Kichigina, G. A.; Buznik, V. M.

2017-09-01

This paper presents the method of fabricate and the results of investigation of electrochemical properties and wettability of the composite coatings obtained on the magnesium alloy by plasma electrolytic oxidation (PEO) and the use of the solution of tetrafluoroethylene (TFE) telomers. The fluoropolymer-containing coatings decrease corrosion current density, increase contact angle in comparison with the base PEO-coating and the bare alloy.

Treatment of high salinity organic wastewater by membrane electrolysis

NASA Astrophysics Data System (ADS)

Dongfang, Shen; Jinghuan, Ma; Ying, Liu; Chenguang, Zhao

2018-03-01

The effects of different operating conditions on the treatment of electrolytic wastewater were investigated by analyzing the removal rate of ammonia and COD before and after wastewater treatment by cation exchange membrane. Experiment shows that as the running time increases the electrolysis effect first increases after the smooth. The removal rate of ammonia will increase with the increase of current density, and the removal rate of COD will increase first and then decrease with the increase of current density. The increase of the temperature of the electrolytic solution will slowly increase the COD removal rate to saturation, but does not affect the removal of ammonia nitrogen. When the flow rate is less than 60L / h, the change of influent flow rate will not affect the removal of ammonia nitrogen, but the effect on COD is small, which will increase and decrease slightly. After the experiment, the surface of the cation exchange membrane was analyzed by cold field scanning electron microscopy and X-ray energy dispersive spectrometer. The surface contamination and the pollutant were determined. The experimental results showed that the aggregates were mainly chlorinated Sodium, calcium and magnesium inorganic salts, which will change the morphology of the film to reduce porosity, reduce the mass transfer efficiency, affecting the electrolysis effect.

A review of recent developments in rechargeable lithium-sulfur batteries.

PubMed

Kang, Weimin; Deng, Nanping; Ju, Jingge; Li, Quanxiang; Wu, Dayong; Ma, Xiaomin; Li, Lei; Naebe, Minoo; Cheng, Bowen

2016-09-22

The research and development of advanced energy-storage systems must meet a large number of requirements, including high energy density, natural abundance of the raw material, low cost and environmental friendliness, and particularly reasonable safety. As the demands of high-performance batteries are continuously increasing, with large-scale energy storage systems and electric mobility equipment, lithium-sulfur batteries have become an attractive candidate for the new generation of high-performance batteries due to their high theoretical capacity (1675 mA h g -1 ) and energy density (2600 Wh kg -1 ). However, rapid capacity attenuation with poor cycle and rate performances make the batteries far from ideal with respect to real commercial applications. Outstanding breakthroughs and achievements have been made to alleviate these problems in the past ten years. This paper presents an overview of recent advances in lithium-sulfur battery research. We cover the research and development to date on various components of lithium-sulfur batteries, including cathodes, binders, separators, electrolytes, anodes, collectors, and some novel cell configurations. The current trends in materials selection for batteries are reviewed and various choices of cathode, binder, electrolyte, separator, anode, and collector materials are discussed. The current challenges associated with the use of batteries and their materials selection are listed and future perspectives for this class of battery are also discussed.

Degradation of caffeine by conductive diamond electrochemical oxidation.

PubMed

Indermuhle, Chloe; Martín de Vidales, Maria J; Sáez, Cristina; Robles, José; Cañizares, Pablo; García-Reyes, Juan F; Molina-Díaz, Antonio; Comninellis, Christos; Rodrigo, Manuel A

2013-11-01

The use of Conductive-Diamond Electrochemical Oxidation (CDEO) and Sonoelectrochemical Oxidation (CDSEO) has been evaluated for the removal of caffeine of wastewater. Effects of initial concentration, current density and supporting electrolyte on the process efficiency are assessed. Results show that caffeine is very efficiently removed with CDEO and that depletion of caffeine has two stages depending on its concentration. At low concentrations, opposite to what it is expected in a mass-transfer controlled process, the efficiency increases with current density very significantly, suggesting a very important role of mediated oxidation processes on the removal of caffeine. In addition, the removal of caffeine is faster than TOC, indicating the formation of reaction intermediates. The number and relative abundance of them depend on the operating conditions and supporting electrolyte used. In chloride media, removal of caffeine is faster and more efficiently, although the occurrence of more intermediates takes place. CDSEO does not increase the efficiency of caffeine removal, but it affects to the formation of intermediates. A detailed characterization of intermediates by liquid chromatography time-of-flight mass spectrometry seems to indicate that the degradation of caffeine by CDEO follows an oxidation pathway similar to mechanism proposed by other advanced oxidation processes. Copyright © 2013 Elsevier Ltd. All rights reserved.

The morphological study of porous silicon formed by electrochemical anodization method

NASA Astrophysics Data System (ADS)

Suryana, R.; Sandi, D. K.; Nakatsuka, O.

2018-03-01

Due to its good physical and chemical properties, porous silicon (PSi) is very attractive to study. In this research, PSi has been fabricated on n-type Si (100) by the electrochemical anodization method. The electrolyte solution used was a mixture of HF (40%), ethanol (99%) and aquadest with volume ratio of 1:1:2, respectively. It was anodized on Si(100) surface at different current densities of 10 mA/cm2 and 20 mA/cm2 with the anodization time at each current density for 10 min, 20 min, and 30 min. The Scanning Electron Microscope (SEM) images showed that the PSi surfaces have inhomogeneous sized pores in the range of 95.00 nm–1.46 μm. The PSi layers with current density and anodization time of 10 mA/cm2 (10 min), 10mA/cm2 (20 min), and 20mA/cm2 (10 min) have spherical shaped pores while the others have some uncommon (cross sectional) shaped pores on surfaces. It is considered that the cross sectional shaped maybe caused by unstable the current during the electrochemical anodization process.

Exactly solvable model of the two-dimensional electrical double layer.

PubMed

Samaj, L; Bajnok, Z

2005-12-01

We consider equilibrium statistical mechanics of a simplified model for the ideal conductor electrode in an interface contact with a classical semi-infinite electrolyte, modeled by the two-dimensional Coulomb gas of pointlike unit charges in the stability-against-collapse regime of reduced inverse temperatures 0< or = beta < 2. If there is a potential difference between the bulk interior of the electrolyte and the grounded electrode, the electrolyte region close to the electrode (known as the electrical double layer) carries some nonzero surface charge density. The model is mappable onto an integrable semi-infinite sine-Gordon theory with Dirichlet boundary conditions. The exact form-factor and boundary state information gained from the mapping provide asymptotic forms of the charge and number density profiles of electrolyte particles at large distances from the interface. The result for the asymptotic behavior of the induced electric potential, related to the charge density via the Poisson equation, confirms the validity of the concept of renormalized charge and the corresponding saturation hypothesis. It is documented on the nonperturbative result for the asymptotic density profile at a strictly nonzero beta that the Debye-Hückel beta-->0 limit is a delicate issue.

Lithium Polymer Electrolytes and Solid State NMR

NASA Technical Reports Server (NTRS)

Berkeley, Emily R.

2004-01-01

Research is being done at the Glenn Research Center (GRC) developing new kinds of batteries that do not depend on a solution. Currently, batteries use liquid electrolytes containing lithium. Problems with the liquid electrolyte are (1) solvents used can leak out of the battery, so larger, more restrictive, packages have to be made, inhibiting the diversity of application and decreasing the power density; (2) the liquid is incompatible with the lithium metal anode, so alternative, less efficient, anodes are required. The Materials Department at GRC has been working to synthesize polymer electrolytes that can replace the liquid electrolytes. The advantages are that polymer electrolytes do not have the potential to leak so they can be used for a variety of tasks, small or large, including in the space rover or in space suits. The polymers generated by Dr. Mary Ann Meador's group are in the form of rod -coil structures. The rod aspect gives the polymer structural integrity, while the coil makes it flexible. Lithium ions are used in these polymers because of their high mobility. The coils have repeating units of oxygen which stabilize the positive lithium by donating electron density. This aids in the movement of the lithium within the polymer, which contributes to higher conductivity. In addition to conductivity testing, these polymers are characterized using DSC, TGA, FTIR, and solid state NMR. Solid state NMR is used in classifying materials that are not soluble in solvents, such as polymers. The NMR spins the sample at a magic angle (54.7') allowing the significant peaks to emerge. Although solid state NMR is a helpful technique in determining bonding, the process of preparing the sample and tuning it properly are intricate jobs that require patience; especially since each run takes about six hours. The NMR allows for the advancement of polymer synthesis by showing if the expected results were achieved. Using the NMR, in addition to looking at polymers, allows for participation on a variety of other projects, including aero-gels and carbon graphite mat en als. The goals of the polymer electrolyte research are to improve the physical properties of the polymers. This includes improving conductivity, durability, and expanding the temperature range over which it is effective. Currently, good conductivity is only present at high temperatures. My goals are to experiment with different arrangements of rods and coils to achieve these desirable properties. Some of my experiments include changing the number of repeat units in the polymer, the size of the diamines, and the types of coil. Analysis of these new polymers indicates improvement in some properties, such as lower glass transition temperature; however, they are not as flexible as desired. With further research we hope to produce polymers that encompass all of these properties to a high degree.

Evaluation and optimization of mass transport of redox species in silicon microwire-array photoelectrodes

PubMed Central

Xiang, Chengxiang; Meng, Andrew C.; Lewis, Nathan S.

2012-01-01

Physical integration of a Ag electrical contact internally into a metal/substrate/microstructured Si wire array/oxide/Ag/electrolyte photoelectrochemical solar cell has produced structures that display relatively low ohmic resistance losses, as well as highly efficient mass transport of redox species in the absence of forced convection. Even with front-side illumination, such wire-array based photoelectrochemical solar cells do not require a transparent conducting oxide top contact. In contact with a test electrolyte that contained 50 mM/5.0 mM of the cobaltocenium+/0 redox species in CH3CN–1.0 M LiClO4, when the counterelectrode was placed in the solution and separated from the photoelectrode, mass transport restrictions of redox species in the internal volume of the Si wire array photoelectrode produced low fill factors and limited the obtainable current densities to 17.6 mA cm-2 even under high illumination. In contrast, when the physically integrated internal Ag film served as the counter electrode, the redox couple species were regenerated inside the internal volume of the photoelectrode, especially in regions where depletion of the redox species due to mass transport limitations would have otherwise occurred. This behavior allowed the integrated assembly to operate as a two-terminal, stand-alone, photoelectrochemical solar cell. The current density vs. voltage behavior of the integrated photoelectrochemical solar cell produced short-circuit current densities in excess of 80 mA cm-2 at high light intensities, and resulted in relatively low losses due to concentration overpotentials at 1 Sun illumination. The integrated wire array-based device architecture also provides design guidance for tandem photoelectrochemical cells for solar-driven water splitting. PMID:22904185

Enhanced photoresponse in dye-sensitized solar cells via localized surface plasmon resonance through highly stable nickel nanoparticles

NASA Astrophysics Data System (ADS)

Rahman, Md. Mahbubur; Im, Sang Hyuk; Lee, Jae-Joon

2016-03-01

We demonstrated the localized surface plasmon resonance (LSPR) effect of Ni nanoparticles (NiNPs) on the performance of dye-sensitized solar cells (DSSCs). Our study revealed that NiNPs in a conventional I-/I3- electrolyte (NiNPs@I-/I3-) increased the net optical absorption of a N719 dye over a broad wavelength range by LSPR, and concurrently improved the power conversion efficiency (PCE) in DSSCs. At an optimized concentration of the NiNPs@I-/I3- electrolyte (1 mg mL-1), N719-sensitized DSSCs with a photoanode thickness of ca. 2, 5, and 10 μm, exhibited net PCEs of 2.32, 6.02, and 9.83%, respectively. These efficiencies were consistent with a net improvement of 43.2, 20.4, and 12.7%, respectively and were mainly attributed to a significant enhancement of the short circuit current density (Jsc) by the LSPR from the NiNPs. Similar effects were observed for cells sensitized by the N3, Ru505, and Z907 dyes. Furthermore, the NiNPs exhibited excellent resistance to corrosion from a conventional I-/I3- electrolyte over a period of 60 days.We demonstrated the localized surface plasmon resonance (LSPR) effect of Ni nanoparticles (NiNPs) on the performance of dye-sensitized solar cells (DSSCs). Our study revealed that NiNPs in a conventional I-/I3- electrolyte (NiNPs@I-/I3-) increased the net optical absorption of a N719 dye over a broad wavelength range by LSPR, and concurrently improved the power conversion efficiency (PCE) in DSSCs. At an optimized concentration of the NiNPs@I-/I3- electrolyte (1 mg mL-1), N719-sensitized DSSCs with a photoanode thickness of ca. 2, 5, and 10 μm, exhibited net PCEs of 2.32, 6.02, and 9.83%, respectively. These efficiencies were consistent with a net improvement of 43.2, 20.4, and 12.7%, respectively and were mainly attributed to a significant enhancement of the short circuit current density (Jsc) by the LSPR from the NiNPs. Similar effects were observed for cells sensitized by the N3, Ru505, and Z907 dyes. Furthermore, the NiNPs exhibited excellent resistance to corrosion from a conventional I-/I3- electrolyte over a period of 60 days. Electronic supplementary information (ESI) available: Details of the materials, optimization of the amount of NiNPs, and the stability of the devices. See DOI: 10.1039/c5nr08155f

Fabrication of Self-Ordered Nanoporous Alumina with 69-115 nm Interpore Distances in Sulfuric/Oxalic Acid Mixtures by Hard Anodization

NASA Astrophysics Data System (ADS)

Almasi Kashi, Mohammad; Ramazani, Abdolali; Mayamai, Yashar; Noormohammadi, Mohammad

2010-01-01

Well-ordered nanoporous arrays have been obtained using hard anodization of aluminium in oxalic/sulfuric mixture. Various ordered nanoporous alumina films with pore intervals from 69 to 115 nm were fabricated on aluminum by high current anodization approach with various sulfuric concentrations in the oxalic/sulfuric mixture electrolyte under 36-60 V. The sulfuric acid concentration was changed from 0.06 to 0.2 M. Different configurations of the current-time curve are seen to influence the self-ordering of the nanohole arrays. A current density-time curve with exponential oscillating decay configuration is seen to damage the self-ordered array of the nanopores while those with exponential decay under certain conditions cause ordered nanopore arrays. For each electrolyte mixture, the interpore distance was dependent upon the anodization voltages with proportionality constants of almost 2 nm V-1. The porosity of the samples (about 3.5%) follows the porosity rule of HA. Final anodization and increasing voltage rate (rin) as a function of sulfuric acid concentration are the main sources to influence the self-ordering of the samples.

High-performance supercapacitors based on poly(ionic liquid)-modified graphene electrodes.

PubMed

Kim, Tae Young; Lee, Hyun Wook; Stoller, Meryl; Dreyer, Daniel R; Bielawski, Christopher W; Ruoff, Rodney S; Suh, Kwang S

2011-01-25

We report a high-performance supercapacitor incorporating a poly(ionic liquid)-modified reduced graphene oxide (PIL:RG-O) electrode and an ionic liquid (IL) electrolyte (specifically, 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)amide or EMIM-NTf(2)). PIL:RG-O provides enhanced compatibility with the IL electrolyte, thereby increasing the effective electrode surface area accessible to electrolyte ions. The supercapacitor assembled with PIL:RG-O electrode and EMIM-NTf(2) electrolyte showed a stable electrochemical response up to 3.5 V operating voltage and was capable of yielding a maximum energy density of 6.5 W·h/kg with a power density of 2.4 kW/kg. These results demonstrate the potential of the PIL:RG-O material as an electrode in high-performance supercapacitors.

One step shift towards flexible supercapacitors based on carbon nanotubes - A review

DOE Office of Scientific and Technical Information (OSTI.GOV)

Yar, A., E-mail: asfandyarhargan@gmail.com, E-mail: johndennis@petronas.com.my, E-mail: noranimuti-mohamed@petronas.com.my, E-mail: asad-032@yahoo.com, E-mail: imrancssp@gmail.com; Dennis, J. O., E-mail: asfandyarhargan@gmail.com, E-mail: johndennis@petronas.com.my, E-mail: noranimuti-mohamed@petronas.com.my, E-mail: asad-032@yahoo.com, E-mail: imrancssp@gmail.com; Mohamed, N. M., E-mail: asfandyarhargan@gmail.com, E-mail: johndennis@petronas.com.my, E-mail: noranimuti-mohamed@petronas.com.my, E-mail: asad-032@yahoo.com, E-mail: imrancssp@gmail.com

2014-10-24

Supercapacitors have emerged as prominent energy storage devices that offer high energy density compared to conventional capacitors and high power density which is not found in batteries. Carbon nanotubes (CNTs) because of their high surface area and tremendous electrical properties are used as electrode material for supercapacitors. In this review we focused on the factors like surface area, role of the electrolyte and techniques adopted to improve performance of CNTs based supercapacitors. The supercapacitors are widely tested in liquid electrolytes which are normally hazardous in nature, toxic, flammable and their leakage has safety concerns. This review also focuses on researchmore » which is replacing these unsafe electrolytes by solid electrolytes with the combination of low cost CNTs deposited flexible supports for supercapacitors.« less

Morphological Study on Porous Silicon Carbide Membrane Fabricated by Double-Step Electrochemical Etching

NASA Astrophysics Data System (ADS)

Omiya, Takuma; Tanaka, Akira; Shimomura, Masaru

2012-07-01

The structure of porous silicon carbide membranes that peeled off spontaneously during electrochemical etching was studied. They were fabricated from n-type 6H SiC(0001) wafers by a double-step electrochemical etching process in a hydrofluoric electrolyte. Nanoporous membranes were obtained after double-step etching with current densities of 10-20 and 60-100 mA/cm2 in the first and second steps, respectively. Microporous membranes were also fabricated after double-step etching with current densities of 100 and 200 mA/cm2. It was found that the pore diameter is influenced by the etching current in step 1, and that a higher current is required in step 2 when the current in step 1 is increased. During the etching processes in steps 1 and 2, vertical nanopore and lateral crack formations proceed, respectively. The influx pathway of hydrofluoric solution, expansion of generated gases, and transfer limitation of positive holes to the pore surface are the key factors in the peeling-off mechanism of the membrane.

Hierarchically porous carbon nanosheets derived from Moringa oleifera stems as electrode material for high-performance electric double-layer capacitors

NASA Astrophysics Data System (ADS)

Cai, Yijin; Luo, Ying; Dong, Hanwu; Zhao, Xiao; Xiao, Yong; Liang, Yeru; Hu, Hang; Liu, Yingliang; Zheng, Mingtao

2017-06-01

A facile one-step pyrolysis route for the synthesis of hierarchically porous carbon nanosheets (PCNSs) derived from Moringa oleifera stems (MOSs) is reported, in which no post-activation-process in needed. The as-prepared PCNSs possesses unique porous nanosheet morphology with high specific surface area of ca. 2250 m2 g-1, large pore volume of ca. 2.3 cm3 g-1, appropriate porosity as well as heteroatom doping (N and O), endowing outstanding electrochemical properties as electrode material for high-performance supercapacitors. The PCNS-based electrodes are investigated in various aqueous electrolytes including 1.0 M Na2SO4, 1.0 M H2SO4, and 6.0 M KOH. The PCNSs exhibit a maximum specific capacitance of ca. 283 F g-1 (0.5 A g-1), excellent rate capability (ca. 72% of capacitance retention even at an ultrahigh current density of 50 A g-1), and a tremendous long-term cycling stability in the three-electrode system. Moreover, the as-assembled PCNS-based symmetric supercapacitor shows a high energy density of ca. 25.8 Wh kg-1 (in 1.0 M Na2SO4 electrolyte) and remarkable long-term cycling stability (almost no capacitance fade in aqueous electrolytes), indicating the promising of the as-prepared PCNSs for electrochemical energy storage and conversion.

La0.8Sr0.2Fe0.8Cu0.2O3-δ as “cobalt-free” cathode for La0.8Sr0.2Ga0.8Mg0.2O3-δ electrolyte

NASA Astrophysics Data System (ADS)

Zurlo, Francesca; Di Bartolomeo, Elisabetta; D'Epifanio, Alessandra; Felice, Valeria; Natali Sora, Isabella; Tortora, Luca; Licoccia, Silvia

2014-12-01

A "cobalt-free" cathode material with stoichiometric composition La0.8Sr0.2Fe0.8Cu0.2O3-δ (LSFCu) was specifically developed for use with La0.8Sr0.2Ga0.8Mg0.2O3-δ (LSGM) electrolyte in intermediate temperature solid oxide fuel cell (IT-SOFC) systems. The chemical stability of LSFCu in contact with LSGM electrolyte was investigated by structural and morphological analysis. The electrochemical properties of LSFCu dense pellets were investigated in the temperature range 600-750 °C by electrochemical impedance spectroscopy (EIS). LSFCu|LSGM|LSFCu symmetrical cells were prepared and area specific resistance (ASR) values, directly depending on the rate limiting step of the oxygen reduction reaction, were evaluated. Fuel cells were prepared using LSFCu as cathode material on a LSGM pellet and electrochemical tests were performed in the 700-800 °C temperature range and compared to similar fuel cells prepared by using commercial La0.6Sr0.4Fe0.8Co0.2O3-δ (LSFCo) as a cathode. The maximum current density and power density recorded for LSFCu and LSFCo were similar. This fact demonstrates that Cu can be used as Co substitute in perovskite cathode materials.

A high performance ceramic-polymer separator for lithium batteries

NASA Astrophysics Data System (ADS)

Kumar, Jitendra; Kichambare, Padmakar; Rai, Amarendra K.; Bhattacharya, Rabi; Rodrigues, Stanley; Subramanyam, Guru

2016-01-01

A three-layered (ceramic-polymer-ceramic) hybrid separator was prepared by coating ceramic electrolyte [lithium aluminum germanium phosphate (LAGP)] over both sides of polyethylene (PE) polymer membrane using electron beam physical vapor deposition (EB-PVD) technique. Ionic conductivities of membranes were evaluated after soaking PE and LAGP/PE/LAGP membranes in a 1 Molar (1M) lithium hexafluroarsenate (LiAsF6) electrolyte in ethylene carbonate (EC), dimethyl carbonate (DMC) and ethylmethyl carbonate (EMC) in volume ratio (1:1:1). Scanning electron microscopy (SEM) and X-ray diffraction (XRD) techniques were employed to evaluate morphology and structure of the separators before and after cycling performance tests to better understand structure-property correlation. As compared to regular PE separator, LAGP/PE/LAGP hybrid separator showed: (i) higher liquid electrolyte uptake, (ii) higher ionic conductivity, (iii) lower interfacial resistance with lithium and (iv) lower cell voltage polarization during lithium cycling at high current density of 1.3 mA cm-2 at room temperature. The enhanced performance is attributed to higher liquid uptake, LAGP-assisted faster ion conduction and dendrite prevention. Optimization of density and thickness of LAGP layer on PE or other membranes through manipulation of PVD deposition parameters will enable practical applications of this novel hybrid separator in rechargeable lithium batteries with high energy, high power, longer cycle life, and higher safety level.

High energy density asymmetric supercapacitors with a nickel oxide nanoflake cathode and a 3D reduced graphene oxide anode

NASA Astrophysics Data System (ADS)

Luan, Feng; Wang, Gongming; Ling, Yichuan; Lu, Xihong; Wang, Hanyu; Tong, Yexiang; Liu, Xiao-Xia; Li, Yat

2013-08-01

Here we demonstrate a high energy density asymmetric supercapacitor with nickel oxide nanoflake arrays as the cathode and reduced graphene oxide as the anode. Nickel oxide nanoflake arrays were synthesized on a flexible carbon cloth substrate using a seed-mediated hydrothermal method. The reduced graphene oxide sheets were deposited on three-dimensional (3D) nickel foam by hydrothermal treatment of nickel foam in graphene oxide solution. The nanostructured electrodes provide a large effective surface area. The asymmetric supercapacitor device operates with a voltage of 1.7 V and achieved a remarkable areal capacitance of 248 mF cm-2 (specific capacitance of 50 F g-1) at a charge/discharge current density of 1 mA cm-2 and a maximum energy density of 39.9 W h kg-1 (based on the total mass of active materials of 5.0 mg). Furthermore, the device showed an excellent charge/discharge cycling performance in 1.0 M KOH electrolyte at a current density of 5 mA cm-2, with a capacitance retention of 95% after 3000 cycles.

High energy density asymmetric supercapacitors with a nickel oxide nanoflake cathode and a 3D reduced graphene oxide anode.

PubMed

Luan, Feng; Wang, Gongming; Ling, Yichuan; Lu, Xihong; Wang, Hanyu; Tong, Yexiang; Liu, Xiao-Xia; Li, Yat

2013-09-07

Here we demonstrate a high energy density asymmetric supercapacitor with nickel oxide nanoflake arrays as the cathode and reduced graphene oxide as the anode. Nickel oxide nanoflake arrays were synthesized on a flexible carbon cloth substrate using a seed-mediated hydrothermal method. The reduced graphene oxide sheets were deposited on three-dimensional (3D) nickel foam by hydrothermal treatment of nickel foam in graphene oxide solution. The nanostructured electrodes provide a large effective surface area. The asymmetric supercapacitor device operates with a voltage of 1.7 V and achieved a remarkable areal capacitance of 248 mF cm(-2) (specific capacitance of 50 F g(-1)) at a charge/discharge current density of 1 mA cm(-2) and a maximum energy density of 39.9 W h kg(-1) (based on the total mass of active materials of 5.0 mg). Furthermore, the device showed an excellent charge/discharge cycling performance in 1.0 M KOH electrolyte at a current density of 5 mA cm(-2), with a capacitance retention of 95% after 3000 cycles.

High rate and stable cycling of lithium metal anode

DOE PAGES

Qian, Jiangfeng; Henderson, Wesley A.; Xu, Wu; ...

2015-02-20

Lithium (Li) metal is an ideal anode material for rechargeable batteries. However, dendritic Li growth and limited Coulombic efficiency (CE) during repeated Li deposition/stripping processes have prevented the application of this anode in rechargeable Li metal batteries, especially for use at high current densities. Here, we report that the use of highly concentrated electrolytes composed of ether solvents and the lithium bis(fluorosulfonyl)imide (LiFSI) salt enables the high rate cycling of a Li metal anode at high CE (up to 99.1 %) without dendrite growth. With 4 M LiFSI in 1,2-dimethoxyethane (DME) as the electrolyte, a Li|Li cell can be cycledmore » at high rates (10 mA cm -2) for more than 6000 cycles with no increase in the cell impedance, and a Cu|Li cell can be cycled at 4 mA cm-2 for more than 1000 cycles with an average CE of 98.4%. These excellent high rate performances can be attributed to the increased solvent coordination and increased availability of Li+ concentration in the electrolyte. Lastly, further development of this electrolyte may lead to practical applications for Li metal anode in rechargeable batteries. The fundamental mechanisms behind the high rate ion exchange and stability of the electrolytes also shine light on the stability of other electrochemical systems.« less

Solid electrolytes for fluoride ion batteries: ionic conductivity in polycrystalline tysonite-type fluorides.

PubMed

Rongeat, Carine; Reddy, M Anji; Witter, Raiker; Fichtner, Maximilian

2014-02-12

Batteries based on a fluoride shuttle (fluoride ion battery, FIB) can theoretically provide high energy densities and can thus be considered as an interesting alternative to Li-ion batteries. Large improvements are still needed regarding their actual performance, in particular for the ionic conductivity of the solid electrolyte. At the current state of the art, two types of fluoride families can be considered for electrolyte applications: alkaline-earth fluorides having a fluorite-type structure and rare-earth fluorides having a tysonite-type structure. As regard to the latter, high ionic conductivities have been reported for doped LaF3 single crystals. However, polycrystalline materials would be easier to implement in a FIB due to practical reasons in the cell manufacturing. Hence, we have analyzed in detail the ionic conductivity of La(1-y)Ba(y)F(3-y) (0 ≤ y ≤ 0.15) solid solutions prepared by ball milling. The combination of DC and AC conductivity analyses provides a better understanding of the conduction mechanism in tysonite-type fluorides with a blocking effect of the grain boundaries. Heat treatment of the electrolyte material was performed and leads to an improvement of the ionic conductivity. This confirms the detrimental effect of grain boundaries and opens new route for the development of solid electrolytes for FIB with high ionic conductivities.

Fabrication of vertically aligned Pd nanowire array in AAO template by electrodeposition using neutral electrolyte.

PubMed

Taşaltın, Nevin; Oztürk, Sadullah; Kılınç, Necmettin; Yüzer, Hayrettin; Oztürk, Zaferziya

2010-05-01

A vertically aligned Pd nanowire array was successfully fabricated on an Au/Ti substrate using an anodic aluminum oxide (AAO) template by a direct voltage electrodeposition method at room temperature using diluted neutral electrolyte. The fabrication of Pd nanowires was controlled by analyzing the current-time transient during electrodeposition using potentiostat. The AAO template and the Pd nanowires were characterized by scanning electron microscopy (SEM), energy-dispersive X-ray (EDX) methods and X-Ray diffraction (XRD). It was observed that the Pd nanowire array was standing freely on an Au-coated Ti substrate after removing the AAO template in a relatively large area of about 5 cm2, approximately 50 nm in diameter and 2.5 μm in length with a high aspect ratio. The nucleation rate and the number of atoms in the critical nucleus were determined from the analysis of current transients. Pd nuclei density was calculated as 3.55 × 108 cm-2. Usage of diluted neutral electrolyte enables slower growing of Pd nanowires owing to increase in the electrodeposition potential and thus obtained Pd nanowires have higher crystallinity with lower dislocations. In fact, this high crystallinity of Pd nanowires provides them positive effect for sensor performances especially.

Advancing Polymer-Supported Ionogel Electrolytes Formed via Radical Polymerization

NASA Astrophysics Data System (ADS)

Visentin, Adam F.

Applications ranging from consumer electronics to the electric grid have placed demands on current energy storage technologies. There is a drive for devices that store more energy for rapid consumption in the case of electric cars and the power grid, and safer, versatile design options for consumer electronics. Electrochemical double-layer capacitors (EDLCs) are an option that has garnered attention as a means to address these varied energy storage demands. EDLCs utilize charge separation in electrolytes to store energy. This energy storage mechanism allows for greater power density (W kg -1) than batteries and higher energy density (Wh kg-1) than conventional capacitors - along with a robust lifetime in the range of thousands to millions of charge-discharge cycles. Safety and working voltage windows of EDLCs currently on the market are limited by the organic solvents utilized in the electrolyte. A potential solution lies in the replacement of the organic solvents with ionic liquids, or room-temperature molten salts. Ionic liquids possess many superior properties in comparison to conventional solvents: wide electrochemical window, low volatility, nonflammability, and favorable ionic conductivity. It has been an endeavor of this work to exploit these advantages while altering the liquid form factor into a gel. An ionic liquid/solid support scaffold composite electrolyte, or ionogel, adds additional benefits: flexible device design, lower encapsulation weight, and elimination of electrolyte leakage. This work has focused on investigations of a UV-polymerizable monomer, poly(ethylene glycol) diacrylate, as a precursor for forming ionogels in situ. The trade-off between gaining mechanical stability at the cost of ionic conductivity has been investigated for numerous ionogel systems. While gaining a greater understanding of the interactions between the gel scaffold and ionic liquid, an ionogel with the highest known ionic conductivity to date (13.1 mS cm-1) was fabricated. In addition to developing an understanding of UV-polymerized systems, a rapid 10 to 20 second, microwave-assisted polymerization method was developed as a novel means to create ionogels. These ionogels exhibited comparable mechanical response and ionic conductivity levels to those gels fabricated by the UV method. Lastly, an EDLC prototype was fabricated using a UV-polymerized ionogel formed in situ between two high-surface area carbon electrodes. The device performance metrics were comparable to commercial EDLCs, and functioned for several thousand cycles with limited loss in capacitance.

Synthesis of ultrathin mesoporous NiCo2O4 nanosheets on carbon fiber paper as integrated high-performance electrodes for supercapacitors

NASA Astrophysics Data System (ADS)

Deng, Fangze; Yu, Lin; Cheng, Gao; Lin, Ting; Sun, Ming; Ye, Fei; Li, Yongfeng

2014-04-01

Two-dimensional ultrathin mesoporous NiCo2O4 nanosheets on carbon fiber paper (CFP) are synthesized through a facile solvothermal method combined with a post thermal treatment. The well interconnected ultrathin NiCo2O4 nanosheets directly grown on the carbon nanofibers could allow for easy diffusion of the electrolyte, shorten the transport path of ion and electron and accommodate the strain during cycling. As a result, superior pseudocapacitive performance is achieved with large specific capacitance of 999 F g-1 at a high current density of 20 A g-1. The capacitance loss is 15.6% after 3000 cycles at a current density of 10 A g-1, displaying good cycle ability and high rate capability.

Dendritic Ag-Fe nanocrystalline alloy synthesized by pulsed electrodeposition and its characterization

NASA Astrophysics Data System (ADS)

Santhi, Kalavathy; Revathy, T. A.; Narayanan, V.; Stephen, A.

2014-10-01

Synthesis of dendrite shaped Ag-Fe alloy nanomaterial by pulsed electrodeposition route was investigated. The alloy samples were deposited at different current densities from electrolytes of different compositions to study the influence of current density and bath composition on metal contents in the alloy, which was determined by ICP-OES analysis. The XRD studies were carried out to determine the structure of these samples. Magnetic characterization at room temperature and during heating was carried out to understand their magnetic behaviour and to confirm the inferences drawn from the XRD results. The XPS spectra proved the presence of Fe and Ag in the metallic form in the alloy samples. The FESEM and TEM micrographs were taken to view the surface morphology of the nanosized particles.

Poly(ethylene terephthalate)-based carbons as electrode material in supercapacitors

NASA Astrophysics Data System (ADS)

Domingo-García, M.; Fernández, J. A.; Almazán-Almazán, M. C.; López-Garzón, F. J.; Stoeckli, F.; Centeno, T. A.

A systematic study by complementary techniques shows that PET-waste from plastic vessels is a competitive precursor of carbon electrodes for supercapacitors. PET derived-activated carbons follow the general trends observed for highly porous carbons and display specific capacitances at low current density as high as 197 F g -1 in 2 M H 2SO 4 aqueous electrolyte and 98 F g -1 in the aprotic medium 1 M (C 2H 5) 4NBF 4/acetonitrile. Additionally, high performance has also been achieved at high current densities, which confirms the potential of this type of materials for electrical energy storage. A new method based on the basic solvolysis of PET-waste and the subsequent carbonization seems to be an interesting alternative to obtain porous carbons with enhanced properties for supercapacitors.

An Outlook on Lithium Ion Battery Technology

DOE Office of Scientific and Technical Information (OSTI.GOV)

Manthiram, Arumugam

Lithium ion batteries as a power source are dominating in portable electronics, penetrating the electric vehicle market, and on the verge of entering the utility market for grid-energy storage. Depending on the application, trade-offs among the various performance parameters—energy, power, cycle life, cost, safety, and environmental impact—are often needed, which are linked to severe materials chemistry challenges. The current lithium ion battery technology is based on insertion-reaction electrodes and organic liquid electrolytes. With an aim to increase the energy density or optimize the other performance parameters, new electrode materials based on both insertion reaction and dominantly conversion reaction along withmore » solid electrolytes and lithium metal anode are being intensively pursued. In conclusion, this article presents an outlook on lithium ion technology by providing first the current status and then the progress and challenges with the ongoing approaches. In light of the formidable challenges with some of the approaches, the article finally points out practically viable near-term strategies.« less

Resistance characterization of nickel sulfide electrodes in LiCl-containing molten salt electrolytes

NASA Astrophysics Data System (ADS)

Redey, L.; Vissers, D. R.

The electrode kinetics of a high area loading: (545.6 mAh/cm(2) for the Ni reversible NiS transition), porous nickel sulfide electrode were studied under one-dimensional current distribution in a half-cell-type test arrangement. Area-specific resistance values (ASR/sub t/) were measured under wide variety of conditions: temperature, 450 to 490(0)C; current density, 0.01 to 3A/cm(2); and mechanical stress, 0.11 to 1.68 kg/cm(2). The ASR/sub t/ values were used for quantitative characterization of the ohmic-related and electrochemical-related resistances of the electrode bed. When cycled in the Ni reversible NiS transition range, the electrode showed good utilization and excellent power characteristics in an all-lithium-cation (LiF-LiCl-LiBr) electrolyte. Capability of continuous cycling at high rates (up to 800 mA/cm(12) was demonstrated. The performance of the electrode was also found to be dependent on the mechanical stress developed in the electrode.

An Outlook on Lithium Ion Battery Technology

DOE PAGES

Manthiram, Arumugam

2017-09-07

Lithium ion batteries as a power source are dominating in portable electronics, penetrating the electric vehicle market, and on the verge of entering the utility market for grid-energy storage. Depending on the application, trade-offs among the various performance parameters—energy, power, cycle life, cost, safety, and environmental impact—are often needed, which are linked to severe materials chemistry challenges. The current lithium ion battery technology is based on insertion-reaction electrodes and organic liquid electrolytes. With an aim to increase the energy density or optimize the other performance parameters, new electrode materials based on both insertion reaction and dominantly conversion reaction along withmore » solid electrolytes and lithium metal anode are being intensively pursued. In conclusion, this article presents an outlook on lithium ion technology by providing first the current status and then the progress and challenges with the ongoing approaches. In light of the formidable challenges with some of the approaches, the article finally points out practically viable near-term strategies.« less

An Outlook on Lithium Ion Battery Technology

PubMed Central

2017-01-01

Lithium ion batteries as a power source are dominating in portable electronics, penetrating the electric vehicle market, and on the verge of entering the utility market for grid-energy storage. Depending on the application, trade-offs among the various performance parameters—energy, power, cycle life, cost, safety, and environmental impact—are often needed, which are linked to severe materials chemistry challenges. The current lithium ion battery technology is based on insertion-reaction electrodes and organic liquid electrolytes. With an aim to increase the energy density or optimize the other performance parameters, new electrode materials based on both insertion reaction and dominantly conversion reaction along with solid electrolytes and lithium metal anode are being intensively pursued. This article presents an outlook on lithium ion technology by providing first the current status and then the progress and challenges with the ongoing approaches. In light of the formidable challenges with some of the approaches, the article finally points out practically viable near-term strategies. PMID:29104922

MEMS-based thin-film fuel cells

DOEpatents

Jankowksi, Alan F.; Morse, Jeffrey D.

2003-10-28

A micro-electro-mechanical systems (MEMS) based thin-film fuel cells for electrical power applications. The MEMS-based fuel cell may be of a solid oxide type (SOFC), a solid polymer type (SPFC), or a proton exchange membrane type (PEMFC), and each fuel cell basically consists of an anode and a cathode separated by an electrolyte layer. Additionally catalyst layers can also separate the electrodes (cathode and anode) from the electrolyte. Gas manifolds are utilized to transport the fuel and oxidant to each cell and provide a path for exhaust gases. The electrical current generated from each cell is drawn away with an interconnect and support structure integrated with the gas manifold. The fuel cells utilize integrated resistive heaters for efficient heating of the materials. By combining MEMS technology with thin-film deposition technology, thin-film fuel cells having microflow channels and full-integrated circuitry can be produced that will lower the operating temperature an will yield an order of magnitude greater power density than the currently known fuel cells.

Flexible superior electrode architectures based on three-dimensional porous spinous α-Fe2O3 with a high performance as a supercapacitor.

PubMed

Nan, Honghong; Yu, Liutao; Ma, Wenqin; Geng, Baoyou; Zhang, Xiaojun

2015-05-28

Flexible supercapacitors have recently attracted increasing attention as they show unique promising advantages, such as flexibility and shape diversity, and they are light-weight and so on. Herein, we designed a series of 3D porous spinous iron oxide materials synthesized on a thin iron plate through a facile method under mild conditions. The unique nanostructural features endow them with excellent electrochemical performance. The electrochemical properties of the integrated electrodes as active electrode materials for supercapacitors have been investigated using different electrochemical techniques including cyclic voltammetry, and galvanostatic charge-discharge in Na2SO4 and LiPF6/EC : DEC electrolyte solutions. These integrated electrodes showed high specific capacitance (as high as 524.6 F g(-1) at the current density of 1 A g(-1)) in 1.0 M Na2SO4 (see Table S1). Moreover, the integrated electrodes also show high power densities and high energy densities in a LiPF6/EC : DEC electrolyte solution; for example, the energy densities were 319.3, 252.5, 152.1, 74.13 and 38.6 W h kg(-1) at different power densities of 8.81, 21.59, 56.65, 92.09 and 152.64 kW kg(-1), respectively. Additionally, the flexible superior electrode exhibited excellent stability with capacitance retention of 92.9% after 5000 cycles. Therefore, such flexible integrated devices might be used in smart and portable electronics.

Improvement of electricity generating performance and life expectancy of MCFC stack by applying Li/Na carbonate electrolyte. Test results and analysis of 0.44 m 2/10 kW- and 1.03 m 2/10 kW-class stack

NASA Astrophysics Data System (ADS)

Yoshiba, Fumihiko; Morita, Hiroshi; Yoshikawa, Masahiro; Mugikura, Yoshihiro; Izaki, Yoshiyuki; Watanabe, Takao; Komoda, Mineo; Masuda, Yuji; Zaima, Nobuyuki

Following the development of a 10 kW-class MCFC stack with a reactive area of 0.44 and 1.03 m 2, which applies a Li/Na carbonate electrolyte and a press stamping separator, many tests have now been carried out. In the installation tests, the observed cell voltages of the 0.44 m 2/10 kW-class stack agreed with the voltage predicted from the test results of the 100 cm 2 bench scale cell. This agreement proves that the installing procedure of the bench scale cell can be applied to the 0.44 m 2/10 kW-class stacks. The temperature distribution analysis model applied to the 100 kW-class stack was modified to calculate the temperature distribution of the 0.44 m 2/10 kW-class stack. Taking the heat loss and the heat transfer effect of the stack holder into account, the calculated temperature was close to the measured temperature; this result proves that the modification was adequate for the temperature analysis model. In the high current density operating tests on the 0.44 m 2/10 kW-class stack, an electrical power density of 2.46 kW/m 2 was recorded at an operating current density of 3000 A/m 2. In the endurance test on the 0.44 m 2/10 kW-class stack, however, unexpected Ni shortening occurred during the operating period 2500-4500 h, which had been caused by a defective formation of the electrolyte matrix. The shortening seems to have been caused by the crack, which appeared in the electrolyte matrix. The voltage degradation rate of the 0.44 m 2/10 kW-class stack was 0.52% over 1000 h, which proves that the matrix was inadequate for a long life expectancy of the MCFC stack. A final endurance test was carried out on the 1.03 m 2/10 kW-class stack, of which the matrix had been revised. The fuel utilisation and the leakage of anode gas never changed during the 10,000 h operating test. This result suggests that no shortening occurred during the 10,000 h endurance test. The cell voltage degradation rate was around 0.2-0.3% over 1000 h in the 1.03 m 2/10 kW-class stack. According to a comparison of the stack electricity generating performance of the 0.44 m 2 and the 1.03 m 2/10 kW-class stack under the same operating conditions, the performance of the 1.03 m 2 stack was lower at the beginning of the endurance test, however, its performance exceeded the performance of the 0.44 m 2/10 kW-class stack during the 10,000 h operating test. By carrying out the high current density operating test and the 10,000-hour endurance test using commercial sized 10 kW-class stacks, the stability of the MCFC stack with a Li/Na carbonate electrolyte and a press stamping separator has been proven.

New materials for polymer electrolyte membrane fuel cell current collectors

NASA Astrophysics Data System (ADS)

Hentall, Philip L.; Lakeman, J. Barry; Mepsted, Gary O.; Adcock, Paul L.; Moore, Jon M.

Polymer Electrolyte Membrane Fuel cells for automotive applications need to have high power density, and be inexpensive and robust to compete effectively with the internal combustion engine. Development of membranes and new electrodes and catalysts have increased power significantly, but further improvements may be achieved by the use of new materials and construction techniques in the manufacture of the bipolar plates. To show this, a variety of materials have been fabricated into flow field plates, both metallic and graphitic, and single fuel cell tests were conducted to determine the performance of each material. Maximum power was obtained with materials which had lowest contact resistance and good electrical conductivity. The performance of the best material was characterised as a function of cell compression and flow field geometry.

Toward garnet electrolyte–based Li metal batteries: An ultrathin, highly effective, artificial solid-state electrolyte/metallic Li interface

PubMed Central

Fu, Kun (Kelvin); Gong, Yunhui; Liu, Boyang; Zhu, Yizhou; Xu, Shaomao; Yao, Yonggang; Luo, Wei; Wang, Chengwei; Lacey, Steven D.; Dai, Jiaqi; Chen, Yanan; Mo, Yifei; Wachsman, Eric; Hu, Liangbing

2017-01-01

Solid-state batteries are a promising option toward high energy and power densities due to the use of lithium (Li) metal as an anode. Among all solid electrolyte materials ranging from sulfides to oxides and oxynitrides, cubic garnet–type Li7La3Zr2O12 (LLZO) ceramic electrolytes are superior candidates because of their high ionic conductivity (10−3 to 10−4 S/cm) and good stability against Li metal. However, garnet solid electrolytes generally have poor contact with Li metal, which causes high resistance and uneven current distribution at the interface. To address this challenge, we demonstrate a strategy to engineer the garnet solid electrolyte and the Li metal interface by forming an intermediary Li-metal alloy, which changes the wettability of the garnet surface (lithiophobic to lithiophilic) and reduces the interface resistance by more than an order of magnitude: 950 ohm·cm2 for the pristine garnet/Li and 75 ohm·cm2 for the surface-engineered garnet/Li. Li7La2.75Ca0.25Zr1.75Nb0.25O12 (LLCZN) was selected as the solid-state electrolyte (SSE) in this work because of its low sintering temperature, stabilized cubic garnet phase, and high ionic conductivity. This low area-specific resistance enables a solid-state garnet SSE/Li metal configuration and promotes the development of a hybrid electrolyte system. The hybrid system uses the improved solid-state garnet SSE Li metal anode and a thin liquid electrolyte cathode interfacial layer. This work provides new ways to address the garnet SSE wetting issue against Li and get more stable cell performances based on the hybrid electrolyte system for Li-ion, Li-sulfur, and Li-oxygen batteries toward the next generation of Li metal batteries. PMID:28435874

Toward garnet electrolyte–based Li metal batteries: An ultrathin, highly effective, artificial solid-state electrolyte/metallic Li interface

DOE Office of Scientific and Technical Information (OSTI.GOV)

Fu, Kun; Gong, Yunhui; Liu, Boyang

Solid-state batteries are a promising option toward high energy and power densities due to the use of lithium (Li) metal as an anode. Among all solid electrolyte materials ranging from sulfides to oxides and oxynitrides, cubic garnet–type Li 7La 3Zr 2O 12 (LLZO) ceramic electrolytes are superior candidates because of their high ionic conductivity (10 -3 to 10 -4 S/cm) and good stability against Li metal. However, garnet solid electrolytes generally have poor contact with Li metal, which causes high resistance and uneven current distribution at the interface. To address this challenge, we demonstrate a strategy to engineer the garnetmore » solid electrolyte and the Li metal interface by forming an intermediary Li-metal alloy, which changes the wettability of the garnet surface (lithiophobic to lithiophilic) and reduces the interface resistance by more than an order of magnitude: 950 ohm·cm2 for the pristine garnet/Li and 75 ohm·cm 2 for the surface-engineered garnet/Li. Li 7La 2.75Ca 0.25Zr 1.75Nb 0.25O 12 (LLCZN) was selected as the solid-state electrolyte (SSE) in this work because of its low sintering temperature, stabilized cubic garnet phase, and high ionic conductivity. This low area-specific resistance enables a solid-state garnet SSE/Li metal configuration and promotes the development of a hybrid electrolyte system. The hybrid system uses the improved solid-state garnet SSE Li metal anode and a thin liquid electrolyte cathode interfacial layer. This work provides new ways to address the garnet SSE wetting issue against Li and get more stable cell performances based on the hybrid electrolyte system for Li-ion, Li-sulfur, and Li-oxygen batteries toward the next generation of Li metal batteries.« less

Toward garnet electrolyte–based Li metal batteries: An ultrathin, highly effective, artificial solid-state electrolyte/metallic Li interface

DOE PAGES

Fu, Kun; Gong, Yunhui; Liu, Boyang; ...

2017-04-07

Solid-state batteries are a promising option toward high energy and power densities due to the use of lithium (Li) metal as an anode. Among all solid electrolyte materials ranging from sulfides to oxides and oxynitrides, cubic garnet–type Li 7La 3Zr 2O 12 (LLZO) ceramic electrolytes are superior candidates because of their high ionic conductivity (10 -3 to 10 -4 S/cm) and good stability against Li metal. However, garnet solid electrolytes generally have poor contact with Li metal, which causes high resistance and uneven current distribution at the interface. To address this challenge, we demonstrate a strategy to engineer the garnetmore » solid electrolyte and the Li metal interface by forming an intermediary Li-metal alloy, which changes the wettability of the garnet surface (lithiophobic to lithiophilic) and reduces the interface resistance by more than an order of magnitude: 950 ohm·cm2 for the pristine garnet/Li and 75 ohm·cm 2 for the surface-engineered garnet/Li. Li 7La 2.75Ca 0.25Zr 1.75Nb 0.25O 12 (LLCZN) was selected as the solid-state electrolyte (SSE) in this work because of its low sintering temperature, stabilized cubic garnet phase, and high ionic conductivity. This low area-specific resistance enables a solid-state garnet SSE/Li metal configuration and promotes the development of a hybrid electrolyte system. The hybrid system uses the improved solid-state garnet SSE Li metal anode and a thin liquid electrolyte cathode interfacial layer. This work provides new ways to address the garnet SSE wetting issue against Li and get more stable cell performances based on the hybrid electrolyte system for Li-ion, Li-sulfur, and Li-oxygen batteries toward the next generation of Li metal batteries.« less

High performance all-solid-state symmetric supercapacitor based on porous carbon made from a metal-organic framework compound

NASA Astrophysics Data System (ADS)

Yu, Feng; Wang, Teng; Wen, Zubiao; Wang, Hongxia

2017-10-01

In this work, we demonstrate the synthesis of porous carbon material with high specific surface area by using metal-organic framework (MOF) as precursor. Scanning electron microscopy (SEM) and transmission electron microscopy (TEM) have confirmed that the material was amorphous and consisted of nanoparticles (5-6 nm) and hierarchical distribution of pores. The characterization of the material by N2 adsorption/desorption isotherm measurement have shown that the material had a high specific surface area reaching to 2618.7 m2 g-1 and abundant porosity with pore size less than 10 nm. The investigation of the electrochemical properties of the material has shown the porous carbon electrode possessed excellent rate performance with high specific capacitances of 150.8 F g-1 at a current density of 5 A g-1, and 133.6 F g-1 at a current density of 50 A g-1, respectively. An all-solid-state symmetric supercapacitor assembled using the as-prepared porous carbon as electrodes and Na2SO4/PVA gel as an electrolyte delivered a high power density of 13 516.4 W kg-1 with an energy density of 8.26 Wh kg-1. A high energy density of 17.37 Wh kg-1 was obtained at discharge current density of 1 A g-1. In addition, the device exhibited superior cycling performance with 94.8% retention rate after 10 000 cycles at a current density of 10 A g-1.

Flexible and Self-Healing Aqueous Supercapacitors for Low Temperature Applications: Polyampholyte Gel Electrolytes with Biochar Electrodes.

PubMed

Li, Xinda; Liu, Li; Wang, Xianzong; Ok, Yong Sik; Elliott, Janet A W; Chang, Scott X; Chung, Hyun-Joong

2017-05-10

A flexible and self-healing supercapacitor with high energy density in low temperature operation was fabricated using a combination of biochar-based composite electrodes and a polyampholyte hydrogel electrolyte. Polyampholytes, a novel class of tough hydrogel, provide self-healing ability and mechanical flexibility, as well as low temperature operation for the aqueous electrolyte. Biochar is a carbon material produced from the low-temperature pyrolysis of biological wastes; the incorporation of reduced graphene oxide conferred mechanical integrity and electrical conductivity and hence the electrodes are called biochar-reduced-graphene-oxide (BC-RGO) electrodes. The fabricated supercapacitor showed high energy density of 30 Wh/kg with ~90% capacitance retention after 5000 charge-discharge cycles at room temperature at a power density of 50 W/kg. At -30 °C, the supercapacitor exhibited an energy density of 10.5 Wh/kg at a power density of 500 W/kg. The mechanism of the low-temperature performance excellence is likely to be associated with the concept of non-freezable water near the hydrophilic polymer chains, which can motivate future researches on the phase behaviour of water near polyampholyte chains. We conclude that the combination of the BC-RGO electrode and the polyampholyte hydrogel electrolyte is promising for supercapacitors for flexible electronics and for low temperature environments.

Crosslinked Polymer Ionic Liquid/Ionic Liquid Blends Prepared by Photopolymerization as Solid-State Electrolytes in Supercapacitors.

PubMed

Wang, Po-Hsin; Wang, Tzong-Liu; Lin, Wen-Churng; Lin, Hung-Yin; Lee, Mei-Hwa; Yang, Chien-Hsin

2018-04-07

A photopolymerization method is used to prepare a mixture of polymer ionic liquid (PIL) and ionic liquid (IL). This mixture is used as a solid-state electrolyte in carbon nanoparticle (CNP)-based symmetric supercapacitors. The solid electrolyte is a binary mixture of a PIL and its corresponding IL. The PIL matrix is a cross-linked polyelectrolyte with an imidazole salt cation coupled with two anions of Br - in PIL-M-(Br) and TFSI - in PIL-M-(TFSI), respectively. The corresponding ionic liquids have imidazolium salt cation coupled with two anions of Br - and TFSI - , respectively. This study investigates the electrochemical characteristics of PILs and their corresponding IL mixtures used as a solid electrolyte in supercapacitors. Results show that a specific capacitance, maximum power density and energy density of 87 and 58 F·g - ¹, 40 and 48 kW·kg - ¹, and 107 and 59.9 Wh·kg - ¹ were achieved in supercapacitors based on (PIL-M-(Br)) and (PIL-M-(TFSI)) solid electrolytes, respectively.

An innovative concept of use of redox-active electrolyte in asymmetric capacitor based on MWCNTs/MnO2 and Fe2O3 thin films

PubMed Central

Chodankar, Nilesh R.; Dubal, Deepak P.; Lokhande, Abhishek C.; Patil, Amar M.; Kim, Jin H.; Lokhande, Chandrakant D.

2016-01-01

In present investigation, we have prepared a nanocomposites of highly porous MnO2 spongy balls and multi-walled carbon nanotubes (MWCNTs) in thin film form and tested in novel redox-active electrolyte (K3[Fe(CN)6] doped aqueous Na2SO4) for supercapacitor application. Briefly, MWCNTs were deposited on stainless steel substrate by “dip and dry” method followed by electrodeposition of MnO2 spongy balls. Further, the supercapacitive properties of these hybrid thin films were evaluated in hybrid electrolyte ((K3[Fe(CN)6 doped aqueous Na2SO4). Thus, this is the first proof-of-design where redox-active electrolyte is applied to MWCNTs/MnO2 hybrid thin films. Impressively, the MWCNTs/MnO2 hybrid film showed a significant improvement in electrochemical performance with maximum specific capacitance of 1012 Fg−1 at 2 mA cm−2 current density in redox-active electrolyte, which is 1.5-fold higher than that of conventional electrolyte (Na2SO4). Further, asymmetric capacitor based on MWCNTs/MnO2 hybrid film as positive and Fe2O3 thin film as negative electrode was fabricated and tested in redox-active electrolytes. Strikingly, MWCNTs/MnO2//Fe2O3 asymmetric cell showed an excellent supercapacitive performance with maximum specific capacitance of 226 Fg−1 and specific energy of 54.39 Wh kg−1 at specific power of 667 Wkg−1. Strikingly, actual practical demonstration shows lightning of 567 red LEDs suggesting “ready-to sell” product for industries. PMID:27982087

Influence of anodizing conditions on generation of internal cracks in anodic porous tin oxide films grown in NaOH electrolyte

NASA Astrophysics Data System (ADS)

Zaraska, Leszek; Gawlak, Karolina; Gurgul, Magdalena; Dziurka, Magdalena; Nowak, Marlena; Gilek, Dominika; Sulka, Grzegorz D.

2018-05-01

Nanoporous tin oxide layers were synthesized via simple one-step anodic oxidation of a low-purity Sn foil (98.8%) in sodium hydroxide electrolyte. The process of pore formation at the early stage of anodization was discussed on the basis of concepts of oxygen bubble mould effect and viscous flow of oxide. The effect of anodizing conditions on the generation of internal cracks and fractures within the anodic film was investigated in detail. It was confirmed that crack-free tin oxide films can be obtained if the anodization is carried out at the potential of 4 V independently of the electrolyte concentration. On the other hand, the porous anodic film with a totally stacked internal morphology is obtained at the potential of 5 V in 0.1 M NaOH electrolyte. The generation of internal cracks and voids can be attributed to a much lower surface porosity and local trapping of O2 inside the pores of the oxide layer. However, increasing electrolyte concentration allows for obtaining less cracked porous films due to effective and uniform liberation of oxygen bubbles from the channels through completely open pore mouths. Furthermore, it was confirmed that uniformity of the anodic tin oxide layers can be significantly improved by vigorous electrolyte stirring. Finally, we observed that the addition of ethanol to the electrolyte can reduce anodic current density and the oxide growth rate. In consequence, less cracked anodic film can be formed even at the potential of 6 V. The generation of oxygen at the pore bottoms, together with the open pore mouths were found to be critical factors responsible for the anodic formation of crack-free porous tin oxide films.

An innovative concept of use of redox-active electrolyte in asymmetric capacitor based on MWCNTs/MnO2 and Fe2O3 thin films.

PubMed

Chodankar, Nilesh R; Dubal, Deepak P; Lokhande, Abhishek C; Patil, Amar M; Kim, Jin H; Lokhande, Chandrakant D

2016-12-16

In present investigation, we have prepared a nanocomposites of highly porous MnO 2 spongy balls and multi-walled carbon nanotubes (MWCNTs) in thin film form and tested in novel redox-active electrolyte (K 3 [Fe(CN) 6 ] doped aqueous Na 2 SO 4 ) for supercapacitor application. Briefly, MWCNTs were deposited on stainless steel substrate by "dip and dry" method followed by electrodeposition of MnO 2 spongy balls. Further, the supercapacitive properties of these hybrid thin films were evaluated in hybrid electrolyte ((K 3 [Fe(CN) 6 doped aqueous Na 2 SO 4 ). Thus, this is the first proof-of-design where redox-active electrolyte is applied to MWCNTs/MnO 2 hybrid thin films. Impressively, the MWCNTs/MnO 2 hybrid film showed a significant improvement in electrochemical performance with maximum specific capacitance of 1012 Fg -1 at 2 mA cm -2 current density in redox-active electrolyte, which is 1.5-fold higher than that of conventional electrolyte (Na 2 SO 4 ). Further, asymmetric capacitor based on MWCNTs/MnO 2 hybrid film as positive and Fe 2 O 3 thin film as negative electrode was fabricated and tested in redox-active electrolytes. Strikingly, MWCNTs/MnO 2 //Fe 2 O 3 asymmetric cell showed an excellent supercapacitive performance with maximum specific capacitance of 226 Fg -1 and specific energy of 54.39 Wh kg -1 at specific power of 667 Wkg -1 . Strikingly, actual practical demonstration shows lightning of 567 red LEDs suggesting "ready-to sell" product for industries.

Robust Pinhole-free Li3N Solid Electrolyte Grown from Molten Lithium

PubMed Central

2017-01-01

Lithium metal is the ultimate anode choice for high energy density rechargeable lithium batteries. However, it suffers from inferior electrochemical performance and safety issues due to its high reactivity and the growth of lithium dendrites. It has long been desired to develop a materials coating on Li metal, which is pinhole-free, mechanically robust without fracture during Li metal deposition and stripping, and chemically stable against Li metal and liquid electrolytes, all while maintaining adequate ionic conductivity. However, such an ideal material coating has yet to be found. Here we report a novel synthesis method by reacting clean molten lithium foil directly with pure nitrogen gas to generate instantaneously a pinhole-free and ionically conductive α-Li3N film directly bonded onto Li metal foil. The film consists of highly textured large Li3N grains (tens of μm) with (001) crystalline planes parallel to the Li metal surface. The bonding between textured grains is strong, resulting in a mechanically robust film which does not crack even when bent to a 0.8 cm curvature radius and is found to maintain pinhole-free coverage during Li metal deposition and stripping. The measured ionic conductivity is up to 5.2 × 10–4 S cm–1, sufficient for maintaining regular current densities for controllable film thicknesses ranging from 2 to 30 μm. This Li3N coating is chemically stable, isolating the reactive metallic lithium from liquid electrolyte, prevents continuous electrolyte consumption during battery cycling, and promotes dendrite-free uniform lithium plating/stripping underneath. We demonstrated Li|Li4Ti5O12 cells with stable and flat potential profiles for 500 cycles without capacity decay or an increase in potential hysteresis. PMID:29392181

A Lithium/Polysulfide Battery with Dual-Working Mode Enabled by Liquid Fuel and Acrylate-Based Gel Polymer Electrolyte.

PubMed

Liu, Ming; Ren, Yuxun; Zhou, Dong; Jiang, Haoran; Kang, Feiyu; Zhao, Tianshou

2017-01-25

The low density associated with low sulfur areal loading in the solid-state sulfur cathode of current Li-S batteries is an issue hindering the development of this type of battery. Polysulfide catholyte as a recyclable liquid fuel was proven to enhance both the energy density and power density of the battery. However, a critical barrier with this lithium (Li)/polysulfide battery is that the shuttle effect, which is the crossover of polysulfides and side deposition on the Li anode, becomes much more severe than that in conventional Li-S batteries with a solid-state sulfur cathode. In this work, we successfully applied an acrylate-based gel polymer electrolyte (GPE) to the Li/polysulfide system. The GPE layer can effectively block the detrimental diffusion of polysulfides and protect the Li metal from the side passivation reaction. Cathode-static batteries utilizing 2 M catholyte (areal sulfur loading of 6.4 mg cm -2 ) present superior cycling stability (727.4 mAh g -1 after 500 cycles at 0.2 C) and high rate capability (814 mAh g -1 at 2 C) and power density (∼10 mW cm -2 ), which also possess replaceable and encapsulated merits for mobile devices. In the cathode-flow mode, the Li/polysulfide system with catholyte supplied from an external tank demonstrates further improved power density (∼69 mW cm -2 ) and stable cycling performance. This novel and simple Li/polysulfide system represents a significant advancement of high energy density sulfur-based batteries for future power sources.

Daikin Advanced Lithium Ion Battery Technology – High Voltage Electrolyte - REVISED

DOE Office of Scientific and Technical Information (OSTI.GOV)

Sunstrom, Joseph; Hendershot, Ron E.

An evaluation of high voltage electrolytes which contain fluorochemicals as solvents/additive has been completed with the objective of formulating a safe, stable electrolyte capable of operation to 4.6 V. Stable cycle performance has been demonstrated in LiNi1/3Mn1/3Co1/3O2 (NMC111)/graphite cells to 4.5 V. The ability to operate at high voltage results in significant energy density gain (>30%) which would manifest as longer battery life resulting in higher range for electric vehicles. Alternatively, a higher energy density battery can be made smaller without sacrificing existing energy. In addition, the fluorinated electrolytes examined showed better safety performance when tested in abuse conditions. Themore » results are promising for future advanced battery development for vehicles as well as other applications.« less

Cycle life improvement of alkaline batteries via optimization of pulse current deposition of manganese dioxide under low bath temperatures

NASA Astrophysics Data System (ADS)

Adelkhani, H.; Ghaemi, M.; Jafari, S. M.

Pulse current electrodeposition (PCD) method has been applied to the preparation of novel electrolytic manganese dioxide (EMD) in order to enhance the cycle life of rechargeable alkaline MnO 2-Zn batteries (RAM). The investigation was carried out under atmospheric pressure through a systematic variation of pulse current parameters using additive free sulfuric acid-MnSO 4 electrolyte solutions. On time (t on) was varied from 0.1 to 98.5 ms, off time (t off) from 0.25 to 19.5 ms, pulse frequencies (f) from 10 to 1000 Hz and duty cycles (θ) from 0.02 to 0.985. A constant pulse current density (I p) of 0.8 A dm -2 and average current densities (I a) in the range of 0.08-0.8 A dm -2 were applied in all experiments. Resultant materials were characterized by analyzing their chemical compositions, X-ray diffractions (XRD) and scanning electron microscopy (SEM). Electrochemical characterizations carried out by charge/discharge cycling of samples in laboratory designed RAM batteries and cyclic voltammetric experiments (CV). It has been proved that specific selection of duty cycle, in the order of 0.25, and a pulse frequency of 500 Hz, results in the production of pulse deposited samples (pcMDs) with more uniform distribution of particles and more compact structure than those obtained by direct current techniques (dcMDs). Results of the test batteries demonstrated that, in spite of reduction of bath temperature in the order of 40 °C, the cycle life of batteries made of pcMDs (bath temperature: 60 °C) was rather higher than those made of conventional dcMDs (boiling electrolyte solution). Under the same conditions of EMD synthesis temperature of 80 °C and battery testing, the maximum obtainable cycle life of optimized pcMD was nearly 230 cycles with approximately 30 mAh g -1 MnO 2, compared to that of dcMD, which did not exceed 20 cycles. In accordance to these results, CV has confirmed that the pulse duty cycle is the most influential parameter on the cycle life than the pulse frequency. Because of operating at lower bath temperatures, the presented synthetic mode could improve its competitiveness in economical aspects.

Improved Performance of Ionic Liquid Supercapacitors by using Tetracyanoborate Anions

PubMed Central

Martins, Vitor L.; Rennie, Anthony J. R.; Sanchez‐Ramirez, Nedher; Torresi, Roberto M.; Hall, Peter J.

2018-01-01

Abstract Supercapacitors are energy storage devices designed to operate at higher power densities than conventional batteries, but their energy density is still too low for many applications. Efforts are made to design new electrolytes with wider electrochemical windows than aqueous or conventional organic electrolytes in order to increase energy density. Ionic liquids (ILs) with wide electrochemical stability windows are excellent candidates to be employed as supercapacitor electrolytes. ILs containing tetracyanoborate anions [B(CN)4] offer wider electrochemical stability than conventional electrolytes and maintain a high ionic conductivity (6.9 mS cm−1). Herein, we report the use of ILs containing the [B(CN)4] anion for such an application. They presented a high maximum operating voltage of 3.7 V, and two‐electrode devices demonstrate high specific capacitances even when operating at relatively high rates (ca. 20 F g−1 @ 15 A g−1). This supercapacitor stored more energy and operated at a higher power at all rates studied when compared with cells using a commonly studied ILs. PMID:29577008

NH3 assisted photoreduction and N-doping of graphene oxide for high performance electrode materials in supercapacitors

NASA Astrophysics Data System (ADS)

Huang, Haifu; Luo, Guangsheng; Xu, Lianqiang; Lei, Chenglong; Tang, Yanmei; Tang, Shaolong; Du, Youwei

2015-01-01

Nitrogen-doped graphene was synthesized by simple photoreduction of graphene oxide (GO) deposited on nickel foam under NH3 atmosphere. The combination of photoreduction and NH3 not only reduces the GO in a shorter time but also induces nitrogen doping easily. The nitrogen doped content of N-rGO@NF reaches a high of 5.99 at% with 15 min of irradiation. The nitrogen-doped graphene deposited on Ni foam (N-rGO@NF) can be directly used as an electrode for supercapacitors, without any conductive agents and polymer binders. In the electrochemical measurement, N-rGO@NF displays remarkable electrochemical performance. In particular, the N-rGO@NF irradiated for 45 min at a high current density of 92.3 A g-1 retained about 77% (190.4 F g-1) of its initial specific capacitance (247.1 F g-1 at 0.31 A g-1). Furthermore, the stable voltage window could be extended to 2.0 and 1.5 V by using Li2SO4 and a mixed Li2SO4/KOH electrolyte, and the maximum energy density was high up to 32.6 and 21.2 Wh kg-1, respectively. The results show that compared to Li2SO4, a mixed electrolyte (Li2SO4/KOH) more efficiently balances the relationship between the high energy densities and high power densities.Nitrogen-doped graphene was synthesized by simple photoreduction of graphene oxide (GO) deposited on nickel foam under NH3 atmosphere. The combination of photoreduction and NH3 not only reduces the GO in a shorter time but also induces nitrogen doping easily. The nitrogen doped content of N-rGO@NF reaches a high of 5.99 at% with 15 min of irradiation. The nitrogen-doped graphene deposited on Ni foam (N-rGO@NF) can be directly used as an electrode for supercapacitors, without any conductive agents and polymer binders. In the electrochemical measurement, N-rGO@NF displays remarkable electrochemical performance. In particular, the N-rGO@NF irradiated for 45 min at a high current density of 92.3 A g-1 retained about 77% (190.4 F g-1) of its initial specific capacitance (247.1 F g-1 at 0.31 A g-1). Furthermore, the stable voltage window could be extended to 2.0 and 1.5 V by using Li2SO4 and a mixed Li2SO4/KOH electrolyte, and the maximum energy density was high up to 32.6 and 21.2 Wh kg-1, respectively. The results show that compared to Li2SO4, a mixed electrolyte (Li2SO4/KOH) more efficiently balances the relationship between the high energy densities and high power densities. Electronic supplementary information (ESI) available: Digital images of nickel foam, GO deposited in nickel foam, N-rGO@NF, and N-rGO@NF electrodes (1.0 × 1.0 cm); Digital images: (1) N-rGO@NF sheet was put into 1 M FeCl3 at room temperature dissolve the Ni metal and (2) a whole N-rGO sheet without Ni foam support after nickel etching; image of film with fragile features after being irradiated by a high-pressure Hg lamp (500 W) in Ar and NH3 atmosphere. See DOI: 10.1039/c4nr05776g

Aluminum reference electrode

DOEpatents

Sadoway, Donald R.

1988-01-01

A stable reference electrode for use in monitoring and controlling the process of electrolytic reduction of a metal. In the case of Hall cell reduction of aluminum, the reference electrode comprises a pool of molten aluminum and a solution of molten cryolite, Na.sub.3 AlF.sub.6, wherein the electrical connection to the molten aluminum does not contact the highly corrosive molten salt solution. This is accomplished by altering the density of either the aluminum (decreasing the density) or the electrolyte (increasing the density) so that the aluminum floats on top of the molten salt solution.

A copper-based layered coordination polymer: synthesis, magnetic properties and electrochemical performance in supercapacitors.

PubMed

Liu, Qi; Liu, Xiuxiu; Shi, Changdong; Zhang, Yanpeng; Feng, Xuejun; Cheng, Mei-Ling; Su, Seng; Gu, Jiande

2015-11-28

A copper-based layered coordination polymer ([Cu(hmt)(tfbdc)(H2O)]; hmt = hexamethylenetetramine, tfbdc = 2,3,5,6-tetrafluoroterephthalate; Cu-LCP) has been synthesized, and it has been structurally and magnetically characterized. The Cu-LCP shows ferromagnetic interactions between the adjacent copper(II) ions. Density functional theory calculations on the special model of Cu-LCP support the occurrence of ferromagnetic interactions. As an electrode material for supercapacitors, Cu-LCP exhibits a high specific capacitance of 1274 F g(-1) at a current density of 1 A g(-1) in 1 M LiOH electrolyte, and the capacitance retention is about 88% after 2000 cycles.

Direct conversion of CO 2 to meso/macro-porous frameworks of surface-microporous graphene for efficient asymmetrical supercapacitors

DOE PAGES

Chang, Liang; Stacchiola, Dario J.; Hu, Yun Hang

2017-10-11

CO 2 conversion to useful materials is the most attractive approach to control its content in the atmosphere. An ideal electrode material for supercapacitors should possess suitable meso/macro-pores as electrolyte reservoirs and rich micro-pores as places for the adsorption of electrolyte ions. In this paper, we designed and synthesized such an ideal material, meso/macro-porous frameworks of surface-microporous graphene (MFSMG), from CO 2via its one-step exothermic reaction with potassium. Furthermore, the MFSMG electrode exhibited a high gravimetric capacitance of 178 F g -1 at 0.2 A g -1 in 2 M KOH and retained 85% capacitance after increasing current density bymore » 50 times. The combination of the MFSMG electrode and the activated carbon (AC) electrode constructed an asymmetrical AC//MFSMG capacitor, leading to a high capacitance of 242.4 F g -1 for MFSMG and 97.4 F g -1 for AC. With the extended potential, the asymmetrical capacitor achieved an improved energy density of 9.43 W h kg -1 and a power density of 3504 W kg -1. Finally, this work provides a novel solution to solve the CO 2 issue and creates an efficient electrode material for supercapacitors.« less

DOE Office of Scientific and Technical Information (OSTI.GOV)

Sitler, Steven J.; Raja, Krishnan S.; Charit, Indrajit

Spark plasma sintered transition metal diborides such as HfB 2, ZrB 2 and their solid solutions were investigated as electrode materials for electrochemical hydrogen evolutions reactions (HER) in 1 M H 2SO 4 and 1 M NaOH electrolytes. HfB 2 and ZrB 2 formed complete solid solutions when mixed in 1:1, 1:4, and 4:1 ratios and they were stable in both electrolytes. The HER kinetics of the diborides were slower in the basic solution than in the acidic solutions. The Tafel slopes in 1 M H 2SO 4 were in the range of 0.15 - 0.18 V/decade except for puremore » HfB 2 which showed a Tafel slope of 0.38 V/decade. In 1 M NaOH the Tafel slopes were in the range of 0.12 - 0.27 V/decade. The composition of Hf xZr 1-xB 2 solid solutions with x = 0.2 - 0.8, influenced the exchange current densities, overpotentials and Tafel slopes of the HER. As a result, the EIS data were fitted with a porous film equivalent circuit model in order to better understand the HER behavior. In addition, modeling calculations, using density functional theory approach, were carried out to estimate the density of states and band structure of the boride solid solutions.« less

Enhanced tortuosity for electrolytes in microwave irradiated self-organized carbon-doped Ni/Co hydroxide nanocomposite electrodes with higher Ni/Co atomic ratio and rate capability for an asymmetric supercapacitor

NASA Astrophysics Data System (ADS)

Kumar, Niraj; Kumar, Viresh; Panda, H. S.

2017-11-01

We demonstrate a green, facile and rapid microwave-mediated process for fabricating carbon black (CB) incorporated Ni/Co hydroxide porous nanocomposites and study the effect of various mass loading of CB on supercapacitor performance. The structure and interactions between CB and Ni/Co hydroxide are characterized by using x-ray diffraction, Fourier-transform infrared spectroscopy and x-ray photoelectron spectroscopy, which suggest the miniaturization of the single-phase Ni/Co hydroxide formation time. A morphology study reveals that the addition of CB into Ni/Co hydroxide develops a loose network structure with well-defined architectural pores. In addition, the nanocomposites demonstrate noticeable improvements in porosity and atomic ratio of Ni/Co with an increasing percentage of carbon, which results in a higher diffusion of electrolytes, and hence electrical conduction. The developed electrode materials exhibit a maximum specific capacitance value of 1526 Fg-1 at current density 1 Ag-1 with excellent cyclic stability (92% retention at 5000 cycles), energy density (76 Wh Kg-1), power density (250 W Kg-1) and rate capability. A solid state asymmetric supercapacitor device is fabricated and utilized to brighten a commercial LED effectively for validating real usage.

Energy density and rate limitations in structural composite supercapacitors

NASA Astrophysics Data System (ADS)

Snyder, J. F.; Gienger, E.; Wetzel, E. D.; Xu, K.

2012-06-01

The weight and volume of conventional energy storage technologies greatly limits their performance in mobile platforms. Traditional research efforts target improvements in energy density to reduce device size and mass. Enabling a device to perform additional functions, such as bearing mechanical load, is an alternative approach as long as the total mass efficiency exceeds that of the individual materials it replaces. Our research focuses on structural composites that function as batteries and supercapacitors. These multifunctional devices could be used to replace conventional structural components, such as vehicle frame elements, to provide significant system-level weight reductions and extend mission times. Our approach is to design structural properties directly into the electrolyte and electrode materials. Solid polymer electrolyte materials bind the system and transfer load to the fibers while conducting ions between the electrodes. Carbon fiber electrodes provide a route towards optimizing both energy storage and load-bearing capabilities, and may also obviate the need for a separate current collector. The components are being integrated using scalable, cost-effective composite processing techniques that are amenable to complex part shapes. Practical considerations of energy density and rate behavior are described here as they relate to materials used. Our results highlight the viability as well as the challenges of this multifunctional approach towards energy storage.

Enhanced tortuosity for electrolytes in microwave irradiated self-organized carbon-doped Ni/Co hydroxide nanocomposite electrodes with higher Ni/Co atomic ratio and rate capability for an asymmetric supercapacitor.

PubMed

Kumar, Niraj; Kumar, Viresh; Panda, H S

2017-11-03

We demonstrate a green, facile and rapid microwave-mediated process for fabricating carbon black (CB) incorporated Ni/Co hydroxide porous nanocomposites and study the effect of various mass loading of CB on supercapacitor performance. The structure and interactions between CB and Ni/Co hydroxide are characterized by using x-ray diffraction, Fourier-transform infrared spectroscopy and x-ray photoelectron spectroscopy, which suggest the miniaturization of the single-phase Ni/Co hydroxide formation time. A morphology study reveals that the addition of CB into Ni/Co hydroxide develops a loose network structure with well-defined architectural pores. In addition, the nanocomposites demonstrate noticeable improvements in porosity and atomic ratio of Ni/Co with an increasing percentage of carbon, which results in a higher diffusion of electrolytes, and hence electrical conduction. The developed electrode materials exhibit a maximum specific capacitance value of 1526 Fg -1 at current density 1 Ag -1 with excellent cyclic stability (92% retention at 5000 cycles), energy density (76 Wh Kg -1 ), power density (250 W Kg -1 ) and rate capability. A solid state asymmetric supercapacitor device is fabricated and utilized to brighten a commercial LED effectively for validating real usage.

Metal coordination polymer derived mesoporous Co3O4 nanorods with uniform TiO2 coating as advanced anodes for lithium ion batteries

NASA Astrophysics Data System (ADS)

Geng, Hongbo; Ang, Huixiang; Ding, Xianguang; Tan, Huiteng; Guo, Guile; Qu, Genlong; Yang, Yonggang; Zheng, Junwei; Yan, Qingyu; Gu, Hongwei

2016-01-01

In this work, a one-dimensional Co3O4@TiO2 core-shell electrode material with superior electrochemical performance is fabricated by a convenient and controllable route. The approach involves two main steps: the homogeneous deposition of polydopamine and TiO2 layers in sequence on the cobalt coordination polymer and the thermal decomposition of the polymer matrix. The as-prepared electrode material can achieve excellent electrochemical properties and stability as an anode material for lithium ion batteries, such as a high specific capacity of 1279 mA h g-1, good cycling stability (around 803 mA h g-1 at a current density of 200 mA g-1 after 100 cycles), and stable rate performance (around 520 mA h g-1 at a current density of 1000 mA g-1). This dramatic electrochemical performance is mainly attributed to the excellent structural characteristics, which could improve the electrical conductivity and lithium ion mobility, as well as electrolyte permeability and architectural stability during cycling.In this work, a one-dimensional Co3O4@TiO2 core-shell electrode material with superior electrochemical performance is fabricated by a convenient and controllable route. The approach involves two main steps: the homogeneous deposition of polydopamine and TiO2 layers in sequence on the cobalt coordination polymer and the thermal decomposition of the polymer matrix. The as-prepared electrode material can achieve excellent electrochemical properties and stability as an anode material for lithium ion batteries, such as a high specific capacity of 1279 mA h g-1, good cycling stability (around 803 mA h g-1 at a current density of 200 mA g-1 after 100 cycles), and stable rate performance (around 520 mA h g-1 at a current density of 1000 mA g-1). This dramatic electrochemical performance is mainly attributed to the excellent structural characteristics, which could improve the electrical conductivity and lithium ion mobility, as well as electrolyte permeability and architectural stability during cycling. Electronic supplementary information (ESI) available. See DOI: 10.1039/c5nr08570e

High performance, flexible, poly(3,4-ethylenedioxythiophene) supercapacitors achieved by doping redox mediators in organogel electrolytes

NASA Astrophysics Data System (ADS)

Zhang, Huanhuan; Li, Jinyu; Gu, Cheng; Yao, Mingming; Yang, Bing; Lu, Ping; Ma, Yuguang

2016-11-01

The relatively low energy density is now a central issue hindering the development of supercapacitors as energy storage devices. Various approaches are thus developed to enhance the energy density, mainly centering on the fabrication of electrode materials or optimization of cell configurations. Compared with these approaches, modifications in electrolytes are much simple and versatile. Herein, we integrate the wide voltages endowed by organic electrolytes and the additional capacitances brought by redox mediators, to fabricate high energy density supercapacitors. On the basis of this idea, supercapacitors with poly(3,4-ethylenedioxythiophene) (PEDOT) as electrode material exhibit extended operating voltage of 1.5 V, extraordinary capacitance of 363 F g-1 and high energy density of 27.4 Wh kg-1. The redox mediators reported here, ferrocene and 4-oxo-2,2,6,6-tetramethylpiperidinooxy, are the first time being applied in supercapacitors, especially in the gel state. While providing additional faradaic capacitances, they also exhibit synergistic interaction with PEDOT and improve the cycling stability of supercapacitors.

Flowable Conducting Particle Networks in Redox-Active Electrolytes for Grid Energy Storage

DOE Office of Scientific and Technical Information (OSTI.GOV)

Hatzell, K. B.; Boota, M.; Kumbur, E. C.

2015-01-01

This study reports a new hybrid approach toward achieving high volumetric energy and power densities in an electrochemical flow capacitor for grid energy storage. The electrochemical flow capacitor suffers from high self-discharge and low energy density because charge storage is limited to the available surface area (electric double layer charge storage). Here, we examine two carbon materials as conducting particles in a flow battery electrolyte containing the VO2+/VO2+ redox couple. Highly porous activated carbon spheres (CSs) and multi-walled carbon nanotubes (MWCNTs) are investigated as conducting particle networks that facilitate both faradaic and electric double layer charge storage. Charge storage contributionsmore » (electric double layer and faradaic) are distinguished for flow-electrodes composed of MWCNTs and activated CSs. A MWCNT flow-electrode based in a redox-active electrolyte containing the VO2+/VO2+ redox couple demonstrates 18% less self-discharge, 10 X more energy density, and 20 X greater power densities (at 20 mV s-1) than one based on a non-redox active electrolyte. Furthermore, a MWCNT redox-active flow electrode demonstrates 80% capacitance retention, and >95% coulombic efficiency over 100 cycles, indicating the feasibility of utilizing conducting networks with redox chemistries for grid energy storage.« less

Flowable conducting particle networks in redox-active electrolytes for grid energy storage

DOE PAGES

Hatzell, K. B.; Boota, M.; Kumbur, E. C.; ...

2015-01-09

This paper reports a new hybrid approach toward achieving high volumetric energy and power densities in an electrochemical flow capacitor for grid energy storage. The electrochemical flow capacitor suffers from high self-discharge and low energy density because charge storage is limited to the available surface area (electric double layer charge storage). Here, we examine two carbon materials as conducting particles in a flow battery electrolyte containing the VO 2+/VO 2 + redox couple. Highly porous activated carbon spheres (CSs) and multi-walled carbon nanotubes (MWCNTs) are investigated as conducting particle networks that facilitate both faradaic and electric double layer charge storage.more » Charge storage contributions (electric double layer and faradaic) are distinguished for flow-electrodes composed of MWCNTs and activated CSs. A MWCNT flow-electrode based in a redox-active electrolyte containing the VO 2+/VO 2 + redox couple demonstrates 18% less self-discharge, 10 X more energy density, and 20 X greater power densities (at 20 mV s -1) than one based on a non-redox active electrolyte. Additionally, a MWCNT redox-active flow electrode demonstrates 80% capacitance retention, and >95% coulombic efficiency over 100 cycles, indicating the feasibility of utilizing conducting networks with redox chemistries for grid energy storage.« less

Trace water sensor

NASA Technical Reports Server (NTRS)

Stephens, James B. (Inventor); Yang, Mary M. (Inventor); Laue, Eric G. (Inventor)

1985-01-01

A solid electrolytic type hygrometer is described, which operates with high reliability while providing rapid and sensitive response. A gold foil electrode (16) is wrapped about a hollow glass cylinder (18), a sheet (12) of hygroscopic-electrolytic material is wrapped about the foil, and a wire (14) is wound around the outside of the electrolytic sheet. Moisture passing between wire turns can be absorbed by the electrolytic material (12), and then dissociated by current passed by the electrodes (14, 16) through the electrolytic material. The cylinder has a slit (20) extending along its length, to allow resilient expansion to press the sheet of electrolytic material firmly against the electrodes. The wire turns lie against one another to cause rapid dissociation of moisture throughout the electrolytic material. Additional guard wires (42,44, FIG. 2) lie at opposite ends of the electrolytic sheet, and currents pass through them to avoid moisture buildup at the ends of the main wire coil. The electrical current through the sheet or membrane is proportional to the partial pressure of the water-vapor.

Solid oxide reversible cells (SORCs) using LaGaO3-based oxide electrolyte and oxide fuel electrode

NASA Astrophysics Data System (ADS)

Ishihara, Tatsumi

2017-09-01

Activity of La0.8Sr0.2FeO3 (LSF) to the fuel electrode reaction in Solid Oxide Reversible Cells (SORCs) was investigated by using La0.9Sr0.1Ga0.8Mg0.2O3 (LSGM) and Ba0.6La0.4CoO3 (BLC) as electrolyte and air electrode, respectively. In electrolysis mode (SOEC), LSF electrode exhibited small overpotential under the atmosphere without H2 co-feeding; the current densities reached -1.42, -0.92, -0.36 A/cm2 at 1.4 V at 900, 800, 700 °C, respectively and H2 formation rate is well agreed with that estimated by Faraday's law. On the other hand, in the SOEC-SOFC reversible mode with the gas composition of 20% steam /20%H2/60%Ar, the maximum power densities of 0.42, 0.28, 0.11 W/cm2 were achieved at 900, 800 and 700 °C, respectively. In addition, the cyclic reversible operation was also investigated at 800 °C, and it was found that the cell showed high stability over 30 cycles. DC polarization measurement suggests that the exchange current density of LSF is 14 mA/cm2 at 700 °C, which is almost the same with that of Ni-YSZ reported. XRD measurement and SEM observation after the reversible measurement suggest that LSF is highly stable under SOEC-SOFC cyclic operation condition. Therefore, LSF is promising as the fuel electrode for SORCs, although the conductivity is not sufficiently high as electrode.

Formulation of Ionic-Liquid Electrolyte To Expand the Voltage Window of Supercapacitors

DOE Office of Scientific and Technical Information (OSTI.GOV)

Van Aken, Katherine L.; Beidaghi, Majid; Gogotsi, Yury

An effective method to expand the operating potential window (OPW) of electrochemical capacitors based on formulating the ionic-liquid (IL) electrolytes is reported. Using model electrochemical cells based on two identical onion-like carbon (OLC) electrodes and two different IL electrolytes and their mixtures, it was shown that the asymmetric behavior of the electrolyte cation and anion toward the two electrodes limits the OPW of the cell and therefore its energy density. Also, a general solution to this problem is proposed by formulating the IL electrolyte mixtures to balance the capacitance of electrodes in a symmetric supercapacitor.

Noncovalent Pi-Pi Stacking at the Carbon-Electrolyte Interface: Controlling the Voltage Window of Electrochemical Supercapacitors.

PubMed

Li, Mengya; Westover, Andrew S; Carter, Rachel; Oakes, Landon; Muralidharan, Nitin; Boire, Timothy C; Sung, Hak-Joon; Pint, Cary L

2016-08-03

A key parameter in the operation of an electrochemical double-layer capacitor is the voltage window, which dictates the device energy density and power density. Here we demonstrate experimental evidence that π-π stacking at a carbon-ionic liquid interface can modify the operation voltage of a supercapacitor device by up to 30%, and this can be recovered by steric hindrance at the electrode-electrolyte interface introduced by poly(ethylene oxide) polymer electrolyte additives. This observation is supported by Raman spectroscopy, electrochemical impedance spectroscopy, and differential scanning calorimetry that each independently elucidates the signature of π-π stacking between imidazole groups in the ionic liquid and the carbon surface and the role this plays to lower the energy barrier for charge transfer at the electrode-electrolyte interface. This effect is further observed universally across two separate ionic liquid electrolyte systems and is validated by control experiments showing an invariant electrochemical window in the absence of a carbon-ionic liquid electrode-electrolyte interface. As interfacial or noncovalent interactions are usually neglected in the mechanistic picture of double-layer capacitors, this work highlights the importance of understanding chemical properties at supercapacitor interfaces to engineer voltage and energy capability.

Three-dimensional interconnected porous graphitic carbon derived from rice straw for high performance supercapacitors

NASA Astrophysics Data System (ADS)

Jin, Hong; Hu, Jingpeng; Wu, Shichao; Wang, Xiaolan; Zhang, Hui; Xu, Hui; Lian, Kun

2018-04-01

Three-dimensional interconnected porous graphitic carbon materials are synthesized via a combination of graphitization and activation process with rice straw as the carbon source. The physicochemical properties of the three-dimensional interconnected porous graphitic carbon materials are characterized by Nitrogen adsorption/desorption, Fourier-transform infrared spectroscopy, X-ray diffraction, Raman spectroscopy, Scanning electron microscopy and Transmission electron microscopy. The results demonstrate that the as-prepared carbon is a high surface area carbon material (a specific surface area of 3333 m2 g-1 with abundant mesoporous and microporous structures). And it exhibits superb performance in symmetric double layer capacitors with a high specific capacitance of 400 F g-1 at a current density of 0.1 A g-1, good rate performance with 312 F g-1 under a current density of 5 A g-1 and favorable cycle stability with 6.4% loss after 10000 cycles at a current density of 5 A g-1 in the aqueous electrolyte of 6M KOH. Thus, rice straw is a promising carbon source for fabricating inexpensive, sustainable and high performance supercapacitors' electrode materials.

Surface properties of AZ91 magnesium alloy after PEO treatment using molybdate salts and low current densities

NASA Astrophysics Data System (ADS)

Pezzato, Luca; Brunelli, Katya; Napolitani, Enrico; Magrini, Maurizio; Dabalà, Manuele

2015-12-01

Plasma electrolytic oxidation (PEO) process is a recently developed electrochemical method used to produce on the surface of various metals oxide ceramic coatings that improve corrosion and wear properties of the substrate. In this work, PEO process was applied on AZ91 magnesium alloy using low current densities (0.05 A/cm2) and an alkaline solution of silicates with different concentrations of sodium molybdate (0.3-3 g/l). The effect of the low current densities of process and of molybdate salts on the corrosion resistance of the coatings was studied with potentiodynamic polarization tests and electrochemical impedance spectroscopy (EIS) in chloride and sulfate environment. The morphology, the phases and the chemical composition of the coatings were examined using a scanning electron microscope equipped with EDS, X-ray diffraction, secondary ion mass spectrometry and X-ray photoelectron spectroscopy. The corrosion properties of the PEO coated samples were remarkably improved if compared with the uncoated samples. The addition of sodium molybdate, in determinate conditions, had a positive effect on the characteristics of the coatings in terms of corrosion resistance.

MoS2/Ni3S4 composite nanosheets on interconnected carbon shells as an excellent supercapacitor electrode architecture for long term cycling at high current densities

NASA Astrophysics Data System (ADS)

Qin, Shengchun; Yao, Tinghui; Guo, Xin; Chen, Qiang; Liu, Dequan; Liu, Qiming; Li, Yali; Li, Junshuai; He, Deyan

2018-05-01

In this paper, we report an electrode architecture of molybdenum disulfide (MoS2)/nickel sulfide (Ni3S4) composite nanosheets anchored on interconnected carbon (C) shells (C@MoS2/Ni3S4). Electrochemical measurements indicate that the C@MoS2/Ni3S4 structure possesses excellent supercapacitive properties especially for long term cycling at high current densities. A specific capacitance as high as ∼640.7 F g-1 can still be delivered even after 10,000 cycles at a high current density of 20 A g-1. From comparison of microstructures and electrochemical properties of the related materials/structures, the improved performance of C@MoS2/Ni3S4 can be attributed to the relatively dispersedly distributed nanosheet-shaped MoS2/Ni3S4 that provides efficient contact with electrolyte and effectively buffers the volume change during charge/discharge processes, enhanced cycling stability by MoS2, and reduced equivalent series resistance by the interconnected C shells.

Novel ultrathin Bi2O3 nanowires for supercapacitor electrode materials with high performance

NASA Astrophysics Data System (ADS)

Qiu, Yongfu; Fan, Hongbo; Chang, Xueyi; Dang, Haifeng; Luo, Qun; Cheng, Zhiyu

2018-03-01

In this paper, the ultrathin Bi2O3 nanowires are synthesized by an oxidative metal vapor transport deposition technique. Their diameters and length are about 10 nm and several tens of micrometers, the growth direction is along [101] and the specific surface area is about 7.34 m2 g-1. The galvanostatic charge-discharge measurement results show that the specific capacitances of the Bi2O3 nanowires-based electrodes increase with the decrease of the current densities. The maximum capacitance is 691.3 F g-1 at the current density of 2.0 A g-1. The Ragone plot shows that the Bi2O3 nanowires has excellent supercapacitive performance. Moreover, the cyclic stability is measured by the galvanostatic charge/discharge technique at a constant current density of 10.0 A g-1 in 6.0 M KOH electrolyte. The results show the excellent capacitance retention of 75.5% over 3000 cycles. In a word, the Bi2O3 nanowires should be the ideal potential electrode materials for low-costing and effective electrochemical supercapacitors.

A Physical Interpretation of the Phenomenological Coefficients of Membrane Permeability

PubMed Central

Kedem, O.; Katchalsky, A.

1961-01-01

A "translation" of the phenomenological permeability coefficients into friction and distribution coefficients amenable to physical interpretation is presented. Expressions are obtained for the solute permeability coefficient ω and the reflection coefficient σ for both non-electrolytic and electrolytic permeants. An analysis of the coefficients is given for loose membranes as well as for dense natural membranes where transport may go through capillaries or by solution in the lipoid parts of the membrane. Water diffusion and filtration and the relation between these and capillary pore radius of the membrane are discussed. For the permeation of ions through the charged membranes equations are developed for the case of zero electrical current in the membrane. The correlation of σ with ω and Lp for electrolytes resembles that for non-electrolytes. In this case ω and σ depend markedly on ion concentration and on the charge density of the membrane. The reflection coefficient may assume negative values indicating anomalous osmosis. An analysis of the phenomena of anomalous osmosis was carried out for the model of Teorell and Meyer and Sievers and the results agree with the experimental data of Loeb and of Grim and Sollner. A set of equations and reference curves are presented for the evaluation of ω and σ in the transport of polyvalent ions through charged membranes. PMID:13752127

Influence of process parameters on plasma electrolytic surface treatment of tantalum for biomedical applications

NASA Astrophysics Data System (ADS)

Sowa, Maciej; Woszczak, Maja; Kazek-Kęsik, Alicja; Dercz, Grzegorz; Korotin, Danila M.; Zhidkov, Ivan S.; Kurmaev, Ernst Z.; Cholakh, Seif O.; Basiaga, Marcin; Simka, Wojciech

2017-06-01

This work aims to quantify the effect of anodization voltage and electrolyte composition used during DC plasma electrolytic oxidation (PEO), operated as a 2-step process, on the surface properties of the resulting oxide coatings on tantalum. The first step consisted of galvanostatic anodization (150 mA cm-2) of the tantalum workpiece up to several limiting voltages (200, 300, 400 and 500 V). After attaining the limiting voltage, the process was switched to voltage control, which resulted in a gradual decrease of the anodic current density. The anodic treatment was realized in a 0.5 M Ca(H2PO2)2 solution, which was then modified by the addition of 1.15 M Ca(HCOO)2 as well as 1.15 M and 1.5 M Mg(CH3COO)2. The increasing voltage of anodization led to the formation of thicker coatings, with larger pores and enriched with electrolytes species to a higher extent. The solutions containing HCOO- and CH3COO- ions caused the formation of coatings which were slightly hydrophobic (high contact angle). In the case of the samples anodized up to 500 V, scattered crystalline deposits were observed. Bioactive phases, such as hydroxyapatite, were detected in the treated oxide coatings by XRD and XPS.

Kinetics Tuning the Electrochemistry of Lithium Dendrites Formation in Lithium Batteries through Electrolytes

DOE PAGES

Tao, Ran; Bi, Xuanxuan; Li, Shu; ...

2017-02-13

Lithium batteries are one of the most advance energy storage devices in the world and have attracted extensive research interests. However, lithium dendrite growth was a safety issue which handicapped the application of pure lithium metal in the negative electrode. In this paper, two solvents, propylene carbonate (PC) and 2-methyl-tetrahydrofuran (2MeTHF), and four Li + salts, LiPF 6, LiAsF 6, LiBF 4 and LiClO 4 were investigated in terms of their effects on the kinetics of lithium dendrite formation in eight electrolyte solutions. The kinetic parameters of charge transfer step (exchange current density, j 0, transfer coefficient, α) of Limore » +/Li redox system, the mass transfer parameters of Li + (transfer number of Li +, t Li+, diffusion coefficient of Li +, D Li+), and the conductivity (κ) of each electrolyte were studied separately. The results demonstrate that the solvents play a critical role in the measured j 0, t Li+, D Li+, and κ of the electrolyte, while the choice of Li + salts only slightly affect the measured parameters. Finally, the understanding of the kinetics will gain insight into the mechanism of lithium dendrite formation and provide guidelines to the future application of lithium metal.« less

Kinetics Tuning the Electrochemistry of Lithium Dendrites Formation in Lithium Batteries through Electrolytes

DOE Office of Scientific and Technical Information (OSTI.GOV)

Tao, Ran; Bi, Xuanxuan; Li, Shu

Lithium batteries are one of the most advance energy storage devices in the world and have attracted extensive research interests. However, lithium dendrite growth was a safety issue which handicapped the application of pure lithium metal in the negative electrode. In this paper, two solvents, propylene carbonate (PC) and 2-methyl-tetrahydrofuran (2MeTHF), and four Li + salts, LiPF 6, LiAsF 6, LiBF 4 and LiClO 4 were investigated in terms of their effects on the kinetics of lithium dendrite formation in eight electrolyte solutions. The kinetic parameters of charge transfer step (exchange current density, j 0, transfer coefficient, α) of Limore » +/Li redox system, the mass transfer parameters of Li + (transfer number of Li +, t Li+, diffusion coefficient of Li +, D Li+), and the conductivity (κ) of each electrolyte were studied separately. The results demonstrate that the solvents play a critical role in the measured j 0, t Li+, D Li+, and κ of the electrolyte, while the choice of Li + salts only slightly affect the measured parameters. Finally, the understanding of the kinetics will gain insight into the mechanism of lithium dendrite formation and provide guidelines to the future application of lithium metal.« less

Computational Examination of Orientation-Dependent Morphological Evolution during the Electrodeposition and Electrodissolution of Magnesium

DOE PAGES

DeWitt, S.; Hahn, N.; Zavadil, K.; ...

2015-12-30

Here a new model of electrodeposition and electrodissolution is developed and applied to the evolution of Mg deposits during anode cycling. The model captures Butler-Volmer kinetics, facet evolution, the spatially varying potential in the electrolyte, and the time-dependent electrolyte concentration. The model utilizes a diffuse interface approach, employing the phase field and smoothed boundary methods. Scanning electron microscope (SEM) images of magnesium deposited on a gold substrate show the formation of faceted deposits, often in the form of hexagonal prisms. Orientation-dependent reaction rate coefficients were parameterized using the experimental SEM images. Three-dimensional simulations of the growth of magnesium deposits yieldmore » deposit morphologies consistent with the experimental results. The simulations predict that the deposits become narrower and taller as the current density increases due to the depletion of the electrolyte concentration near the sides of the deposits. Increasing the distance between the deposits leads to increased depletion of the electrolyte surrounding the deposit. Two models relating the orientation-dependence of the deposition and dissolution reactions are presented. Finally, the morphology of the Mg deposit after one deposition-dissolution cycle is significantly different between the two orientation-dependence models, providing testable predictions that suggest the underlying physical mechanisms governing morphology evolution during deposition and dissolution.« less

Characterization of ceria electrolyte in solid oxide fuel cell applications

NASA Astrophysics Data System (ADS)

Milliken, Christopher Edward

The goal of this research effort is to characterize cation doped cerium dioxide for use as an electrolyte material in solid oxide fuel cell applications. A variety of analytical techniques including thermogravimetric analysis, controlled atmosphere dilatometry, and AC/DC electronic measurements on single cells and stacks have been coupled with thermodynamic calculations to evaluate the suitability of several doping schemes. The results of this analysis indicate that doping CeOsb2 with 20% SmOsb{1.5} or codoping with 19% GdOsb{1.5} + 1% PrOsb{1.83} provides the best combination of stability and performance. Under dual atmosphere fuel cell conditions, these dopants do not provide sufficient stabilization energy to prevent the reduction of ceria. A significant oxygen leakage current can be expected, particularly near open circuit conditions. Incorporation of 10% SrO provides similar short-term advantages to the lanthanide doped system but this electrolyte material undergoes an irreversible degradation mechanism that results in cell failure within 1500 hours of test. Under fuel cell conditions, the maximum efficiency of such systems in stacks will be below 40% at 200 mW/cmsp2 when operated on humidified hydrogen fuels. This compares to an expected efficiency of 45-50% at a similar power density for nonmixed conducting electrolyte (e.g., YSZ).

A temperature-controlled photoelectrochemical cell for quantitative product analysis.

PubMed

Corson, Elizabeth R; Creel, Erin B; Kim, Youngsang; Urban, Jeffrey J; Kostecki, Robert; McCloskey, Bryan D

2018-05-01

In this study, we describe the design and operation of a temperature-controlled photoelectrochemical cell for analysis of gaseous and liquid products formed at an illuminated working electrode. This cell is specifically designed to quantitatively analyze photoelectrochemical processes that yield multiple gas and liquid products at low current densities and exhibit limiting reactant concentrations that prevent these processes from being studied in traditional single chamber electrolytic cells. The geometry of the cell presented in this paper enables front-illumination of the photoelectrode and maximizes the electrode surface area to electrolyte volume ratio to increase liquid product concentration and hence enhances ex situ spectroscopic sensitivity toward them. Gas is bubbled through the electrolyte in the working electrode chamber during operation to maintain a saturated reactant concentration and to continuously mix the electrolyte. Gaseous products are detected by an in-line gas chromatograph, and liquid products are analyzed ex situ by nuclear magnetic resonance. Cell performance was validated by examining carbon dioxide reduction on a silver foil electrode, showing comparable results both to those reported in the literature and identical experiments performed in a standard parallel-electrode electrochemical cell. To demonstrate a photoelectrochemical application of the cell, CO 2 reduction experiments were carried out on a plasmonic nanostructured silver photocathode and showed different product distributions under dark and illuminated conditions.

A temperature-controlled photoelectrochemical cell for quantitative product analysis

NASA Astrophysics Data System (ADS)

Corson, Elizabeth R.; Creel, Erin B.; Kim, Youngsang; Urban, Jeffrey J.; Kostecki, Robert; McCloskey, Bryan D.

2018-05-01

In this study, we describe the design and operation of a temperature-controlled photoelectrochemical cell for analysis of gaseous and liquid products formed at an illuminated working electrode. This cell is specifically designed to quantitatively analyze photoelectrochemical processes that yield multiple gas and liquid products at low current densities and exhibit limiting reactant concentrations that prevent these processes from being studied in traditional single chamber electrolytic cells. The geometry of the cell presented in this paper enables front-illumination of the photoelectrode and maximizes the electrode surface area to electrolyte volume ratio to increase liquid product concentration and hence enhances ex situ spectroscopic sensitivity toward them. Gas is bubbled through the electrolyte in the working electrode chamber during operation to maintain a saturated reactant concentration and to continuously mix the electrolyte. Gaseous products are detected by an in-line gas chromatograph, and liquid products are analyzed ex situ by nuclear magnetic resonance. Cell performance was validated by examining carbon dioxide reduction on a silver foil electrode, showing comparable results both to those reported in the literature and identical experiments performed in a standard parallel-electrode electrochemical cell. To demonstrate a photoelectrochemical application of the cell, CO2 reduction experiments were carried out on a plasmonic nanostructured silver photocathode and showed different product distributions under dark and illuminated conditions.

Current density distributions, field distributions and impedance analysis of segmented deep brain stimulation electrodes

NASA Astrophysics Data System (ADS)

Wei, Xuefeng F.; Grill, Warren M.

2005-12-01

Deep brain stimulation (DBS) electrodes are designed to stimulate specific areas of the brain. The most widely used DBS electrode has a linear array of 4 cylindrical contacts that can be selectively turned on depending on the placement of the electrode and the specific area of the brain to be stimulated. The efficacy of DBS therapy can be improved by localizing the current delivery into specific populations of neurons and by increasing the power efficiency through a suitable choice of electrode geometrical characteristics. We investigated segmented electrode designs created by sectioning each cylindrical contact into multiple rings. Prototypes of these designs, made with different materials and larger dimensions than those of clinical DBS electrodes, were evaluated in vitro and in simulation. A finite element model was developed to study the effects of varying the electrode characteristics on the current density and field distributions in an idealized electrolytic medium and in vitro experiments were conducted to measure the electrode impedance. The current density over the electrode surface increased towards the edges of the electrode, and multiple edges increased the non-uniformity of the current density profile. The edge effects were more pronounced over the end segments than over the central segments. Segmented electrodes generated larger magnitudes of the second spatial difference of the extracellular potentials, and thus required lower stimulation intensities to achieve the same level of neuronal activation as solid electrodes. For a fixed electrode conductive area, increasing the number of segments (edges) decreased the impedance compared to a single solid electrode, because the average current density over the segments increased. Edge effects played a critical role in determining the current density distributions, neuronal excitation patterns, and impedance of cylindrical electrodes, and segmented electrodes provide a means to increase the efficiency of DBS.

A hybrid electrochemical device based on a synergetic inner combination of Li ion battery and Li ion capacitor for energy storage.

PubMed

Zheng, Jun-Sheng; Zhang, Lei; Shellikeri, Annadanesh; Cao, Wanjun; Wu, Qiang; Zheng, Jim P

2017-02-07

Li ion battery (LIB) and electrochemical capacitor (EC) are considered as the most widely used energy storage systems (ESSs) because they can produce a high energy density or a high power density, but it is a huge challenge to achieve both the demands of a high energy density as well as a high power density on their own. A new hybrid Li ion capacitor (HyLIC), which combines the advantages of LIB and Li ion capacitor (LIC), is proposed. This device can successfully realize a potential match between LIB and LIC and can avoid the excessive depletion of electrolyte during the charge process. The galvanostatic charge-discharge cycling tests reveal that at low current, the HyLIC exhibits a high energy density, while at high current, it demonstrates a high power density. Ragone plot confirms that this device can make a synergetic balance between energy and power and achieve a highest energy density in the power density range of 80 to 300 W kg -1 . The cycle life test proves that HyLIC exhibits a good cycle life and an excellent coulombic efficiency. The present study shows that HyLIC, which is capable of achieving a high energy density, a long cycle life and an excellent power density, has the potential to achieve the winning combination of a high energy and power density.

A hybrid electrochemical device based on a synergetic inner combination of Li ion battery and Li ion capacitor for energy storage

PubMed Central

Zheng, Jun-Sheng; Zhang, Lei; Shellikeri, Annadanesh; Cao, Wanjun; Wu, Qiang; Zheng, Jim P.

2017-01-01

Li ion battery (LIB) and electrochemical capacitor (EC) are considered as the most widely used energy storage systems (ESSs) because they can produce a high energy density or a high power density, but it is a huge challenge to achieve both the demands of a high energy density as well as a high power density on their own. A new hybrid Li ion capacitor (HyLIC), which combines the advantages of LIB and Li ion capacitor (LIC), is proposed. This device can successfully realize a potential match between LIB and LIC and can avoid the excessive depletion of electrolyte during the charge process. The galvanostatic charge-discharge cycling tests reveal that at low current, the HyLIC exhibits a high energy density, while at high current, it demonstrates a high power density. Ragone plot confirms that this device can make a synergetic balance between energy and power and achieve a highest energy density in the power density range of 80 to 300 W kg−1. The cycle life test proves that HyLIC exhibits a good cycle life and an excellent coulombic efficiency. The present study shows that HyLIC, which is capable of achieving a high energy density, a long cycle life and an excellent power density, has the potential to achieve the winning combination of a high energy and power density. PMID:28169329

Reaction of Cl- ions in electrolyte solution induced electrical discharge plasma in the presence of argon fine bubbles

NASA Astrophysics Data System (ADS)

Hayashi, Yui; Takada, Noriharu; Wahyudiono, Kanda, Hideki; Goto, Motonobu

2017-05-01

Active chlorine species such as chlorine molecules and hypochlorous acid have been known as high performance sanitizers. They would act more reactive on chemical and biological substances when an electrical discharge was introduced in water containing an electrolyte substance. Here, the reaction of chloride (Cl-) ions were examined by introducing of a pulsed discharge plasma in sodium chloride (NaCl) solution as an electrolyte solution at room temperature. The results show that a large electrical current generated by the pulsed discharge plasma affected the reaction of Cl- ions to result available chlorine. The reaction pathway for available chlorine production was assumed similar with the reaction pathway as electrolysis. A pulsed discharge plasma in NaCl solution in the presence of argon (Ar) fine bubbles exhibited intense emissions and high electron density compared to when no Ar fine bubbles were introduced. At these conditions, the dissociation reaction rate of water increased drastically leads to the formation of 0 atoms. As a result, the reaction of Cl- ions and the available chlorine generation were also increased.

Synthesis and Compatibility of Ionic Liquid Containing Rod-Coil Polyimide Gel Electrolytes with Lithium Metal Electrodes

NASA Technical Reports Server (NTRS)

Tigelaar, Dean M.; Palker, Allyson E.; Meador, Mary Ann B.; Bennett, William R.

2008-01-01

A highly cross-linked polyimide-polyethylene oxide copolymer has been synthesized that is capable of holding large volumes of liquid component, simultaneously maintaining good dimensional stability. An amine end capped oligomer was made that was imidized in solution, followed by reaction with a triisocyanate in the presence of desired additives at ambient temperature. Polymer films are able to hold over 4 times their weight in room temperature ionic liquid RTIL or carbonate solvent. Electrolytes were studied that contained varying amounts of RTIL, lithium trifluoromethanesulfonimide LiTFSi, and alumina nanoparticles. Electrochemical stability of these electrolytes with lithium metal electrodes was studied by galvanic cycling and impedance spectroscopy. Improved cycling stability and decreased interfacial resistance were observed when increasing amounts of RTIL and LiTFSi were added. The addition of small amounts of alumina further decreased interfacial resistance by nearly an order of magnitude. During the course of the study, cycling stability increased from less than 3 to greater than 1000 h at 60 C and 0.25 mA/cm2 current density.

A preliminary systems-engineering study of an advanced nuclear-electrolytic hydrogen-production facility

NASA Technical Reports Server (NTRS)

Escher, W. J. D.; Donakowski, T. D.; Tison, R. R.

1975-01-01

An advanced nuclear-electrolytic hydrogen-production facility concept was synthesized at a conceptual level with the objective of minimizing estimated hydrogen-production costs. The concept is a closely-integrated, fully-dedicated (only hydrogen energy is produced) system whose components and subsystems are predicted on ''1985 technology.'' The principal components are: (1) a high-temperature gas-cooled reactor (HTGR) operating a helium-Brayton/ammonia-Rankine binary cycle with a helium reactor-core exit temperature of 980 C, (2) acyclic d-c generators, (3) high-pressure, high-current-density electrolyzers based on solid-polymer electrolyte technology. Based on an assumed 3,000 MWt HTGR the facility is capable of producing 8.7 million std cu m/day of hydrogen at pipeline conditions, 6,900 kPa. Coproduct oxygen is also available at pipeline conditions at one-half this volume. It has further been shown that the incorporation of advanced technology provides an overall efficiency of about 43 percent, as compared with 25 percent for a contemporary nuclear-electric plant powering close-coupled contemporary industrial electrolyzers.

Solid-State Lithium Conductors for Lithium Metal Batteries Based on Electrospun Nanofiber/Plastic Crystal Composites.

PubMed

Zhou, Yundong; Wang, Xiaoen; Zhu, Haijin; Yoshizawa-Fujita, Masahiro; Miyachi, Yukari; Armand, Michel; Forsyth, Maria; Greene, George W; Pringle, Jennifer M; Howlett, Patrick C

2017-08-10

Organic ionic plastic crystals (OIPCs) are a class of solid-state electrolytes with good thermal stability, non-flammability, non-volatility, and good electrochemical stability. When prepared in a composite with electrospun polyvinylidene fluoride (PVdF) nanofibers, a 1:1 mixture of the OIPC N-ethyl-N-methylpyrrolidinium bis(fluorosulfonyl)imide ([C 2 mpyr][FSI]) and lithium bis(fluorosulfonyl)imide (LiFSI) produced a free-standing, robust solid-state electrolyte. These high-concentration Li-containing electrolyte membranes had a transference number of 0.37(±0.02) and supported stable lithium symmetric-cell cycling at a current density of 0.13 mA cm -2 . The effect of incorporating PVdF in the Li-containing plastic crystal was investigated for different ratios of PVdF and [Li][FSI]/[C 2 mpyr][FSI]. In addition, Li|LiNi 1/3 Co 1/3 Mn 1/3 O 2 cells were prepared and cycled at ambient temperature and displayed a good rate performance and stability. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Capacitive behaviour of MnF2 and CoF2 submicro/nanoparticles synthesized via a mild ionic liquid-assisted route

NASA Astrophysics Data System (ADS)

Ma, Ruguang; Zhou, Yao; Yao, Lin; Liu, Guanghui; Zhou, Zhenzhen; Lee, Jong-Min; Wang, Jiacheng; Liu, Qian

2016-01-01

Submicro-/nano-sized MnF2 rods and hierarchical CoF2 cuboids are respectively synthesized via a facile precipitation method assisted by ionic liquid under a mild condition. The as-prepared MF2 (M = Mn, Co) submicro/nanoparticles exhibit impressive specific capacitance in 1.0 M KOH aqueous solution, especially at relatively high current densities, e.g. 91.2, 68.7 and 56.4 F g-1 for MnF2, and 81.7, 70.6 and 63.0 F g-1 for CoF2 at 5, 8 and 10 A g-1, respectively. The mechanism of striking capacitance of MF2 is clarified on the basis of analysing the cycled electrodes by different characterization techniques. Such remarkable capacitance is ascribed to the redox reactions between MF2 and MOOH in aqueous alkaline electrolytes, which can not be obtained in aqueous neutral electrolytes. This study for the first time provides direct evidences on the pseudocapacitance mechanism of MF2 in alkaline electrolytes and paves the way of application of transition metal fluorides as electrodes in supercapacitors.

Electro Decomposition of Ammonia into Hydrogen for Fuel Cell Use

DTIC Science & Technology

2012-01-01

electrolyte for the experiments reflects the average amount of urea observed in human urine , 20 g/L/day. Figure 5 shows the flow dia- gram of a single cell...to improve the current density of the urea electrolysis process and to reduce the onset potential of the urea oxidation. The synthesis of layered...the new developments in the synthesis of nickel nanosheets can be coupled with the ammonia and urea electrolysis technology. This work concludes

Flexible, solid-state, ion-conducting membrane with 3D garnet nanofiber networks for lithium batteries

PubMed Central

Fu, Kun (Kelvin); Gong, Yunhui; Dai, Jiaqi; Gong, Amy; Han, Xiaogang; Yao, Yonggang; Wang, Chengwei; Wang, Yibo; Chen, Yanan; Yan, Chaoyi; Li, Yiju; Wachsman, Eric D.; Hu, Liangbing

2016-01-01

Beyond state-of-the-art lithium-ion battery (LIB) technology with metallic lithium anodes to replace conventional ion intercalation anode materials is highly desirable because of lithium’s highest specific capacity (3,860 mA/g) and lowest negative electrochemical potential (∼3.040 V vs. the standard hydrogen electrode). In this work, we report for the first time, to our knowledge, a 3D lithium-ion–conducting ceramic network based on garnet-type Li6.4La3Zr2Al0.2O12 (LLZO) lithium-ion conductor to provide continuous Li+ transfer channels in a polyethylene oxide (PEO)-based composite. This composite structure further provides structural reinforcement to enhance the mechanical properties of the polymer matrix. The flexible solid-state electrolyte composite membrane exhibited an ionic conductivity of 2.5 × 10−4 S/cm at room temperature. The membrane can effectively block dendrites in a symmetric Li | electrolyte | Li cell during repeated lithium stripping/plating at room temperature, with a current density of 0.2 mA/cm2 for around 500 h and a current density of 0.5 mA/cm2 for over 300 h. These results provide an all solid ion-conducting membrane that can be applied to flexible LIBs and other electrochemical energy storage systems, such as lithium–sulfur batteries. PMID:27307440

Lithium-sulfur batteries based on nitrogen-doped carbon and an ionic-liquid electrolyte.

PubMed

Sun, Xiao-Guang; Wang, Xiqing; Mayes, Richard T; Dai, Sheng

2012-10-01

Nitrogen-doped mesoporous carbon (NC) and sulfur were used to prepare an NC/S composite cathode, which was evaluated in an ionic-liquid electrolyte of 0.5 M lithium bis(trifluoromethane sulfonyl)imide (LiTFSI) in methylpropylpyrrolidinium bis(trifluoromethane sulfonyl)imide ([MPPY][TFSI]) by cyclic voltammetry (CV), electrochemical impedance spectroscopy (EIS), and cycle testing. To facilitate the comparison, a C/S composite based on activated carbon (AC) without nitrogen doping was also fabricated under the same conditions. Compared with the AC/S composite, the NC/S composite showed enhanced activity toward sulfur reduction, as evidenced by the lower onset sulfur reduction potential, higher redox current density in the CV test, and faster charge-transfer kinetics, as indicated by EIS measurements. At room temperature under a current density of 84 mA g(-1) (C/20), the battery based on the NC/S composite exhibited a higher discharge potential and an initial capacity of 1420 mAh g(-1), whereas the battery based on the AC/S composite showed a lower discharge potential and an initial capacity of 1120 mAh g(-1). Both batteries showed similar capacity fading with cycling due to the intrinsic polysulfide solubility and the polysulfide shuttle mechanism; capacity fading can be improved by further cathode modification. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Photo-assisted electrochemical degradation of polychlorinated biphenyls with boron-doped diamond electrodes.

PubMed

Gutiérrez-Hernández, Rubén F; Bello-Mendoza, Ricardo; Hernández-Ramírez, Aracely; Malo, Edi A; Nájera-Aguilar, Hugo A

2017-09-19

The capacity of the photo electro-Fenton (PEF) process to degrade a mixture of seven polychlorinated biphenyl (PCB) congeners was studied. Boron-doped diamond (BDD) sheets were used as anode and cathode in the experimental electrolytic cell that contained Na 2 SO 4 0.05 M at pH 3 as supporting electrolyte for the electro generation of H 2 O 2 at the cathode. The effects of UV light intensity (254 and 365 nm), current density (8, 16 and 24 mA cm -2 ) and ferrous ion dosage (0.1, 0.2 and 0.3 mM) on PCB (C 0 = 50 μg L -1 ) degradation were evaluated. The highest level of PCB degradation (97%) was achieved with 16 mA cm -2 of current density, 0.1 mM of ferrous ion and UV light at 365 nm as irradiation source after 6 h of reaction. PCB28, PCB52 and PCB101 were not detected after 0.5, 1.5 and 3 h of reaction, respectively. The degradation of PCB138, PCB153, PCB180 and PCB209 was also high (>95%). The PEF system outperformed other oxidation processes (electro-Fenton, anodic oxidation, Fenton, photo-Fenton and UV photolysis) in terms of reaction rate and degradation efficiency. These results demonstrate for the first time the degradation of PCB209, the most highly chlorinated PCB congener, by an advanced electrochemical oxidation process.

Unique Urchin-like Ca2Ge7O16 Hierarchical Hollow Microspheres as Anode Material for the Lithium Ion Battery.

PubMed

Li, Dan; Feng, Chuanqi; Liu, Hua Kun; Guo, Zaiping

2015-06-10

Germanium is an outstanding anode material in terms of electrochemical performance, especially rate capability, but its developments are hindered by its high price because it is rare in the crust of earth, and its huge volume variation during the lithium insertion and extraction. Introducing other cheaper elements into the germanium-based material is an efficient way to dilute the high price, but normally sacrifice its electrochemical performance. By the combination of nanostructure design and cheap element (calcium) introduction, urchin-like Ca2Ge7O16 hierarchical hollow microspheres have been successfully developed in order to reduce the price and maintain the good electrochemical properties of germanium-based material. The electrochemical test results in different electrolytes show that ethylene carbonate/dimethyl carbonate/diethyl carbonate (3/4/3 by volume) with 5 wt% fluoroethylene carbonate additive is the most suitable solvent for the electrolyte. From the electrochemical evaluation, the as-synthesized Ca2Ge7O16 hollow microspheres exhibit high reversible specific capacity of up to 804.6 mA h g(-1) at a current density of 100 mA g(-1) after 100 cycles and remarkable rate capability of 341.3 mA h g(-1) at a current density of 4 A g(-1). The growth mechanism is proposed based on our experimental results on the growth process.

Experimental design approach applied to the elimination of crystal violet in water by electrocoagulation with Fe or Al electrodes.

PubMed

Durango-Usuga, Paula; Guzmán-Duque, Fernando; Mosteo, Rosa; Vazquez, Mario V; Peñuela, Gustavo; Torres-Palma, Ricardo A

2010-07-15

An experimental design methodology was applied to evaluate the decolourization of crystal violet (CV) dye by electrocoagulation using iron or aluminium electrodes. The effects and interactions of four parameters, initial pH (3-9), current density (6-28 A m(-2)), substrate concentration (50-200 mg L(-1)) and supporting electrolyte concentration (284-1420 mg L(-1) of Na(2)SO(4)), were optimized and evaluated. Although the results using iron anodes were better than for aluminium, the effects and interactions of the studied parameters were quite similar. With a confidence level of 95%, initial pH and supporting electrolyte concentration showed limited effects on the removal rate of CV, whereas current density, pollutant concentration and the interaction of both were significant. Reduced models taking into account significant variables and interactions between variables have shown good correlations with the experimental results. Under optimal conditions, almost complete removal of CV and chemical oxygen demand were obtained after electrocoagulation for 5 and 30 min, using iron and aluminium electrodes, respectively. These results indicate that electrocoagulation with iron anodes is a rapid, economical and effective alternative to the complete removal of CV in waters. Evolutions of pH and residual iron or aluminium concentrations in solution are also discussed. 2010 Elsevier B.V. All rights reserved.

Carbon dioxide as a green carbon source for the synthesis of carbon cages encapsulating porous silicon as high performance lithium-ion battery anodes.

PubMed

Zhang, Yaguang; Du, Ning; Chen, Yifan; Lin, Yangfan; Jiang, Jinwei; He, Yuanhong; Lei, Yu; Yang, Deren

2018-03-28

Si/C composite is one of the most promising candidate materials for next-generation lithium-ion battery anodes. Herein, we demonstrate the novel structure of carbon cages encapsulating porous Si synthesized by the reaction between magnesium silicide (Mg 2 Si) and carbon dioxide (CO 2 ) and subsequent acid washing. Benefitting from the in situ deposition through magnesiothermic reduction of CO 2 , the carbon cage seals the inner Si completely and shows higher graphitization than that obtained from the decomposition of acetylene. After removing MgO, pores are created, which can accommodate the volume change of the Si anode during the charge/discharge process. As the anode material for lithium-ion batteries, the porous Si/C electrode shows a charge capacity of ∼1124 mA h g -1 after 100 cycles with 86.4% capacity retention at the current density of 0.4 A g -1 . When the current density increases to 1.6 and 3.2 A g -1 , the capacity can still be maintained at ∼860 and ∼460 mA h g -1 , respectively. The prominent cycling and rate performance is contributed by the built-in space for Si expansion, static carbon cages that prevent penetration of electrolyte and stabilize the solid electrolyte interface (SEI) outside, and fast charge transport by the novel structure.

Flexible, solid-state, ion-conducting membrane with 3D garnet nanofiber networks for lithium batteries

NASA Astrophysics Data System (ADS)

Kun, Kelvin; Gong, Yunhui; Dai, Jiaqi; Gong, Amy; Han, Xiaogang; Yao, Yonggang; Wang, Chengwei; Wang, Yibo; Chen, Yanan; Yan, Chaoyi; Li, Yiju; Wachsman, Eric D.; Hu, Liangbing

2016-06-01

Beyond state-of-the-art lithium-ion battery (LIB) technology with metallic lithium anodes to replace conventional ion intercalation anode materials is highly desirable because of lithium's highest specific capacity (3,860 mA/g) and lowest negative electrochemical potential (˜3.040 V vs. the standard hydrogen electrode). In this work, we report for the first time, to our knowledge, a 3D lithium-ion-conducting ceramic network based on garnet-type Li6.4La3Zr2Al0.2O12 (LLZO) lithium-ion conductor to provide continuous Li+ transfer channels in a polyethylene oxide (PEO)-based composite. This composite structure further provides structural reinforcement to enhance the mechanical properties of the polymer matrix. The flexible solid-state electrolyte composite membrane exhibited an ionic conductivity of 2.5 × 10-4 S/cm at room temperature. The membrane can effectively block dendrites in a symmetric Li | electrolyte | Li cell during repeated lithium stripping/plating at room temperature, with a current density of 0.2 mA/cm2 for around 500 h and a current density of 0.5 mA/cm2 for over 300 h. These results provide an all solid ion-conducting membrane that can be applied to flexible LIBs and other electrochemical energy storage systems, such as lithium-sulfur batteries.

Sono assisted electrocoagulation process for the removal of pollutant from pulp and paper industry effluent.

PubMed

Asaithambi, P; Aziz, Abdul Raman Abdul; Sajjadi, Baharak; Daud, Wan Mohd Ashri Bin Wan

2017-02-01

In the present work, the efficiency of the sonication, electrocoagulation, and sono-electrocoagulation process for removal of pollutants from the industrial effluent of the pulp and paper industry was compared. The experimental results showed that the sono-electrocoagulation process yielded higher pollutant removal percentage compared to the sonication and electrocoagulation process alone. The effect of the operating parameters in the sono-electrocoagulation process such as electrolyte concentration (1-5 g/L), current density (1-5 A/dm 2 ), effluent pH (3-11), COD concentration (1500-6000 mg/L), inter-electrode distance (1-3 cm), and electrode combination (Fe and Al) on the color removal, COD removal, and power consumption were studied. The maximum color and COD removal percentages of 100 and 95 %, respectively, were obtained at the current density of 4 A/dm 2 , electrolyte concentration of 4 g/L, effluent pH of 7, COD concentration of 3000 mg/L, electrode combination of Fe/Fe, inter-electrode distance of 1 cm, and reaction time of 4 h, respectively. The color and COD removal percentages were analyzed by using an UV/Vis spectrophotometer and closed reflux method. The results showed that the sono-electrocoagulation process could be used as an efficient and environmental friendly technique for complete pollutant removal.

Structure of an electric double layer containing a 2:2 valency dimer electrolyte

DOE PAGES

Silvestre-Alcantara, Whasington; Henderson, Douglas; Wu, Jianzhong; ...

2014-12-05

In this study, the structure of a planar electric double layer formed by a 2:2 valency dimer electrolyte in the vicinity of a uniformly charged planar hard electrode is investigated using density functional theory and Monte Carlo simulations. The dimer electrolyte consists of a mixture of charged divalent dimers and charged divalent monomers in a dielectric continuum. A dimer is constructed by two tangentially tethered rigid spheres, one of which is divalent and positively charged and the other neutral, whereas the monomer is a divalent and negatively charged rigid sphere. The density functional theory reproduces well the simulation results formore » (i) the singlet distributions of the various ion species with respect to the electrode, and (ii) the mean electrostatic potential. Lastly, comparison with earlier results for a 2:1/1:2 dimer electrolyte shows that the double layer structure is similar when the counterion has the same valency.« less