Structure-Property Relationships of Organic Electrolytes and Their Effects on Li/S Battery Performance.

PubMed

Kaiser, Mohammad Rejaul; Chou, Shulei; Liu, Hua-Kun; Dou, Shi-Xue; Wang, Chunsheng; Wang, Jiazhao

2017-12-01

Electrolytes, which are a key component in electrochemical devices, transport ions between the sulfur/carbon composite cathode and the lithium anode in lithium-sulfur batteries (LSBs). The performance of a LSB mostly depends on the electrolyte due to the dissolution of polysulfides into the electrolyte, along with the formation of a solid-electrolyte interphase. The selection of the electrolyte and its functionality during charging and discharging is intricate and involves multiple reactions and processes. The selection of the proper electrolyte, including solvents and salts, for LSBs strongly depends on its physical and chemical properties, which is heavily controlled by its molecular structure. In this review, the fundamental properties of organic electrolytes for LSBs are presented, and an attempt is made to determine the relationship between the molecular structure and the properties of common organic electrolytes, along with their effects on the LSB performance. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Electrochemical performance evaluations and safety investigations of pentafluoro(phenoxy)cyclotriphosphazene as a flame retardant electrolyte additive for application in lithium ion battery systems using a newly designed apparatus for improved self-extinguishing time measurements

NASA Astrophysics Data System (ADS)

Dagger, Tim; Lürenbaum, Constantin; Schappacher, Falko M.; Winter, Martin

2017-02-01

A modified self-extinguishing time (SET) device which enhances the reproducibility of the results is presented. Pentafluoro(phenoxy)cyclotriphosphazene (FPPN) is investigated as flame retardant electrolyte additive for lithium ion batteries (LIBs) in terms of thermal stability and electrochemical performance. SET measurements and adiabatic reaction calorimetry are applied to determine the flammability and the reactivity of a standard LIB electrolyte containing 5% FPPN. The results reveal that the additive-containing electrolyte is nonflammable for 10 s whereas the commercially available reference electrolyte inflames instantaneously after 1 s of ignition. The onset temperature of the safety enhanced electrolyte is delayed by ≈ 21 °C. Compatibility tests in half cells show that the electrolyte is reductively stable while the cyclic voltammogram indicates oxidative decomposition during the first cycle. Cycling experiments in full cells show improved cycling performance and rate capability, which can be attributed to cathode passivation during the first cycle. Post-mortem analysis of the electrolyte by gas chromatography-mass spectrometry confirms the presence of the additive in high amounts after 501 cycles which ensures enhanced safety of the electrolyte. The investigations present FPPN as stable electrolyte additive that improves the intrinsic safety of the electrolyte and its cycling performance at the same time.

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.

Performance Demonstration of Mcmb-LiNiCoO2 Cells Containing Electrolytes Designed for Wide Operating Temperature Range

NASA Technical Reports Server (NTRS)

Smart, M. C.; Ratnakumar, B. V.; Whicanack, L. D.; Smith, K. A.; Santee, S.; Puglia, F. J.; Gitzendanner, R.

2009-01-01

With the intent of improving the performance of Li-ion cells over a wide operating temperature range, we have investigated the use of co-solvents to improve the properties of electrolyte formulations. In the current study, we have focused upon evaluating promising electrolytes which have been incorporated into large capacity (7 Ah) prototype Li-ion cells, fabricated by Yardney Technical Products, Inc. The electrolytes selected for performance evaluation include the use of a number of esters as co-solvents, including methyl propionate (MP), ethyl propionate (EP), ethyl butyrate (EB), propyl butyrate (PB), and 2,2,2-trifluoroethyl butyrate (TFEB). The performance of the prototype cells containing the ester-based electrolytes was compared with an extensive data base generated on cells containing previously developed all carbonate-based electrolytes. A number of performance tests were performed, including determining (i) the discharge rate capacity over a wide range of temperatures, (ii) the charge characteristics, (iii) the cycle life characteristics under various conditions, and (iv) the impedance characteristics.

Ionic Liquid Hybrid Electrolytes for Lithium-Ion Batteries: A Key Role of the Separator-Electrolyte Interface in Battery Electrochemistry.

PubMed

Huie, Matthew M; DiLeo, Roberta A; Marschilok, Amy C; Takeuchi, Kenneth J; Takeuchi, Esther S

2015-06-10

Batteries are multicomponent systems where the theoretical voltage and stoichiometric electron transfer are defined by the electrochemically active anode and cathode materials. While the electrolyte may not be considered in stoichiometric electron-transfer calculations, it can be a critical factor determining the deliverable energy content of a battery, depending also on the use conditions. The development of ionic liquid (IL)-based electrolytes has been a research area of recent reports by other researchers, due, in part, to opportunities for an expanded high-voltage operating window and improved safety through the reduction of flammable solvent content. The study reported here encompasses a systematic investigation of the physical properties of IL-based hybrid electrolytes including quantitative characterization of the electrolyte-separator interface via contact-angle measurements. An inverse trend in the conductivity and wetting properties was observed for a series of IL-based electrolyte candidates. Test-cell measurements were undertaken to evaluate the electrolyte performance in the presence of functioning anode and cathode materials, where several promising IL-based hybrid electrolytes with performance comparable to that of conventional carbonate electrolytes were identified. The study revealed that the contact angle influenced the performance more significantly than the conductivity because the cells containing IL-tetrafluoroborate-based electrolytes with higher conductivity but poorer wetting showed significantly decreased performance relative to the cells containing IL-bis(trifluoromethanesulfonyl)imide electrolytes with lower conductivity but improved wetting properties. This work contributes to the development of new IL battery-based electrolyte systems with the potential to improve the deliverable energy content as well as safety of lithium-ion battery systems.

Performance comparison: Aluminum electrolytic and solid tantalum capacitor

NASA Technical Reports Server (NTRS)

Hawthornthwaite, B. G.; Piper, J.; Holland, H. W.

1981-01-01

Several key electrical and environmental parameters of latest technology aluminum electrolytic and solid tantalum capacitors were evaluated in terms of price fluctuations of tantalum metal. Performance differences between solid tantalums and aluminum electrolytics are examined.

Preparation and electrochemical characterization of polymer electrolytes based on electrospun poly(vinylidene fluoride- co-hexafluoropropylene)/polyacrylonitrile blend/composite membranes for lithium batteries

NASA Astrophysics Data System (ADS)

Raghavan, Prasanth; Zhao, Xiaohui; Shin, Chorong; Baek, Dong-Ho; Choi, Jae-Won; Manuel, James; Heo, Min-Yeong; Ahn, Jou-Hyeon; Nah, Changwoon

Apart from PEO based solid polymer electrolytes, tailor-made gel polymer electrolytes based on blend/composite membranes of poly(vinylidene fluoride- co-hexafluoropropylene) and polyacrylonitrile are prepared by electrospinning using 14 wt% polymer solution in dimethylformamide. The membranes show uniform morphology with an average fiber diameter of 320-490 nm, high porosity and electrolyte uptake. Polymer electrolytes are prepared by soaking the electrospun membranes in 1 M lithium hexafluorophosphate in ethylene carbonate/dimethyl carbonate. Temperature dependent ionic conductivity and their electrochemical performance are studied. The blend/composite polymer electrolytes show good ionic conductivity in the range of 10 -3 S cm -1 at ambient temperature and good electrochemical performance. All the Polymer electrolytes show an anodic stability >4.6 V with stable interfacial resistance with storage time. The prototype cell shows good charge-discharge properties and stable cycle performance with comparable capacity fade compared to liquid electrolyte under the test conditions.

Nonflammable Perfluoropolyether Electrolytes for Safer Lithiumbased Batteries

NASA Astrophysics Data System (ADS)

Olson, Kevin Raymond

The importance of batteries to sustainable energy is widely recognized. Lithium-ion batteries (LIBs) not only power handheld electronics but also are increasingly being implemented in electric vehicles and "smart-grid" applications to store energy from intermittent solar and wind sources, making sustainable energy a reality. Unfortunately, LIBs contain a highly flammable solvent and can exhibit catastrophic failure, as was brought to the public's attention by the Boeing 787, Samsung Galaxy Note 7, hoverboard, and Tesla battery fires. Thus, realizing the full potential of LIBs in large-scale systems requires the development of nonflammable electrolytes. Perfluoropolyether (PFPE)-based electrolytes address many of the shortcomings of conventional carbonate-based electrolytes or polymer electrolytes such as poly(ethylene oxide). PFPE-based electrolytes transport lithium more efficiently than conventional electrolytes, which has important implications on long-term battery performance. PFPEs make interesting electrolyte solvents because they are nonflammable, nonvolatile, liquid across a broad temperature range, chemically stable, and interact favorably with the anion of fluorinated salts. In this work, the molecular underpinnings for ion transport in PFPE electrolytes will be established by systematically probing how PFPE structure affects electrolyte performance including ionic conductivity, diffusivity, and transference number. End group polarity, end group concentration, and PFPE molecular weight all have important implications on electrolyte performance.

Crown Ethers in Nonaqueous Electrolytes for Lithium/Air Batteries

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

Xu, Wu; Xiao, Jie; Wang, Deyu

2010-02-04

The effects of three crown ethers, 12-crown-4, 15-crown-5, and 18-crown-6, as additives and co-solvents in non-aqueous electrolytes on the cell performance of primary Li/air batteries operated in a dry air environment were investigated. Crown ethers have large effects on the discharge performance of non-aqueous electrolytes in Li/air batteries. A small amount (normally less than 10% by weight or volume in electrolytes) of 12-Crown-4 and 15-crown-5 reduces the battery performance and a minimum discharge capacity appears at the crown ether content of ca. 5% in the electrolytes. However, when the content increases to about 15%, both crown ethers improve the capacitymore » of Li/air cells by about 28% and 16%, respectively. 15-Crown-5 based electrolytes even show a maximum discharge capacity in the crown ether content range from 10% to 15%. On the other hand, the increase of 18-crown-6 amount in the electrolytes continuously lowers of the cell performance. The different battery performances of these three crown ethers in electrolytes are explained by the combined effects from the electrolytes’ contact angle, oxygen solubility, viscosity, ionic conductivity, and the stability of complexes formed between crown ether molecules and lithium ions.« less

A concentrated electrolyte for zinc hexacyanoferrate electrodes in aqueous rechargeable zinc-ion batteries

NASA Astrophysics Data System (ADS)

Kim, D.; Lee, C.; Jeong, S.

2018-01-01

In this study, a concentrated electrolyte was applied in an aqueous rechargeable zinc-ion battery system with a zinc hexacyanoferrate (ZnHCF) electrode to improve the electrochemical performance by changing the hydration number of the zinc ions. To optimize the active material, ZnHCF was synthesized using aqueous solutions of zinc nitrate with three different concentrations. The synthesized materials exhibited some differences in structure, crystallinity, and particle size, as observed by X-ray diffraction and scanning electron microscopy. Subsequently, these well-structured materials were applied in electrochemical tests. A more than two-fold improvement in the charge/discharge capacities was observed when the concentrated electrolyte was used instead of the dilute electrolyte. Additionally, the cycling performance observed in the concentrated electrolyte was superior to that in the dilute electrolyte. This improvement in the electrochemical performance may result from a decrease in the hydration number of the zinc ions in the concentrated electrolyte.

Electrolyte volume effects on electrochemical performance and solid electrolyte interphase in Si-graphite/NMC lithium-ion pouch cells

DOE PAGES

An, Seong Jin; Li, Jianlin; Daniel, Claus; ...

2017-05-15

This study aims to explore the correlations between electrolyte volume, electrochemical performance, and properties of the solid electrolyte interphase in pouch cells with Si-graphite composite anodes. The electrolyte is 1.2 M LiPF 6 in ethylene carbonate:ethylmethyl carbonate with 10 wt.% fluoroethylene carbonate. Single layer pouch cells (100 mAh) were constructed with 15 wt.% Si-graphite/LiNi 0.5Mn 0.3CO 0.2O 2 electrodes. It is found that a minimum electrolyte volume factor of 3.1 times the total pore volume of cell components (cathode, anode, and separator) is needed for better cycling stability. Less electrolyte causes increases in ohmic and charge transfer resistances. Lithium dendritesmore » are observed when the electrolyte volume factor is low. The resistances from the anodes become significant as the cells are discharged. As a result, solid electrolyte interphase thickness grows as the electrolyte volume factor increases and is non-uniform after cycling.« less

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.

Charge-discharge characteristics of nickel/zinc battery with polymer hydrogel electrolyte

NASA Astrophysics Data System (ADS)

Iwakura, Chiaki; Murakami, Hiroki; Nohara, Shinji; Furukawa, Naoji; Inoue, Hiroshi

A new nickel/zinc (Ni/Zn) battery was assembled by using polymer hydrogel electrolyte prepared from cross-linked potassium poly(acrylate) and KOH aqueous solution, and its charge-discharge characteristics were investigated. The experimental Ni/Zn cell with the polymer hydrogel electrolyte exhibited well-defined charge-discharge curves and remarkably improved charge-discharge cycle performance, compared to that with a KOH aqueous solution. Moreover, it was found that dendritic growth hardly occurred on the zinc electrode surface during charge-discharge cycles in the polymer hydrogel electrolyte. These results indicate that the polymer hydrogel electrolyte can successfully be used in Ni/Zn batteries as an electrolyte with excellent performance.

Non-flammable polyphosphonate electrolytes

NASA Astrophysics Data System (ADS)

Dixon, Brian G.; Morris, R. Scott; Dallek, Steven

This research is directed towards the development of safe, and thermally stable polymeric electrolytes. Advanced electrolytes are described, including thermal test data, which are ionically highly conductive, and non-flammable. These novel multi-heteropolymer electrolytes represent a significant advance in the design of high-performance rechargeable lithium systems that possess superior safety and handling characteristics. Representative results are shown by the figures contained in this text. These DSC/TGA results compare a typical liquid carbonate-based electrolyte system, ethylene carbonate and ethyl methyl carbonate, with novel polyphosphonates as synthesized in this program. These tests were performed with the electrolytes in combination with lithium metal, and the impressive relative thermal stability of the phosphonates is apparent.

Ternary mixtures of nitrile-functionalized glyme, non-flammable hydrofluoroether and fluoroethylene carbonate as safe electrolytes for lithium-ion batteries

NASA Astrophysics Data System (ADS)

Liu, Yi; Fang, Shaohua; Shi, Pei; Luo, Dong; Yang, Li; Hirano, Shin-ichi

2016-11-01

New mixtures of 3-(2-methoxyethoxy)propanenitrile, fluoroethylene carbonate and 1,1,2,2-tetrafluoroethyl-2,2,3,3-tetrafluoropropyl ether are introduced as safe electrolytes for lithium-ion batteries. The electrolytes with 30 wt% 1,1,2,2-tetrafluoroethyl-2,2,3,3-tetrafluoropropyl ether can own high safety and better wettability to separator and electrodes than the conventional electrolyte. The oxidation potentials of these electrolytes are about 4.8 V versus Li/Li+, and their conductivity can reach 5.42 mS cm-1 at 25 °C. Graphite/LiMn2O4 coin cells are used to evaluate the electrochemical performances, and this kind of safe electrolytes can exhibit better rate and cycle performances than the conventional electrolyte. These results indicate that such ternary electrolytes have a great potential for practical application.

Towards Versatile and Sustainable Hydrogen Production through Electrocatalytic Water Splitting: Electrolyte Engineering

PubMed Central

Shinagawa, Tatsuya

2017-01-01

Abstract Recent advances in power generation from renewable resources necessitate conversion of electricity to chemicals and fuels in an efficient manner. Electrocatalytic water splitting is one of the most powerful and widespread technologies. The development of highly efficient, inexpensive, flexible, and versatile water electrolysis devices is desired. This review discusses the significance and impact of the electrolyte on electrocatalytic performance. Depending on the circumstances under which the water splitting reaction is conducted, the required solution conditions, such as the identity and molarity of ions, may significantly differ. Quantitative understanding of such electrolyte properties on electrolysis performance is effective to facilitate the development of efficient electrocatalytic systems. The electrolyte can directly participate in reaction schemes (kinetics), affect electrode stability, and/or indirectly impact the performance by influencing the concentration overpotential (mass transport). This review aims to guide fine‐tuning of the electrolyte properties, or electrolyte engineering, for (photo)electrochemical water splitting reactions. PMID:27984671

High performance solid-state electric double layer capacitor from redox mediated gel polymer electrolyte and renewable tamarind fruit shell derived porous carbon.

PubMed

Senthilkumar, S T; Selvan, R Kalai; Melo, J S; Sanjeeviraja, C

2013-11-13

The activated carbon was derived from tamarind fruit shell and utilized as electrodes in a solid state electrochemical double layer capacitor (SSEDLC). The fabricated SSEDLC with PVA (polyvinyl alcohol)/H2SO4 gel electrolyte delivered high specific capacitance and energy density of 412 F g(-1) and 9.166 W h kg(-1), respectively, at 1.56 A g(-1). Subsequently, Na2MoO4 (sodium molybdate) added PVA/H2SO4 gel electrolyte was also prepared and applied for SSEDLC, to improve the performance. Surprisingly, 57.2% of specific capacitance (648 F g(-1)) and of energy density (14.4 Wh kg(-1)) was increased while introducing Na2MoO4 as the redox mediator in PVA/H2SO4 gel electrolyte. This improved performance is owed to the redox reaction between Mo(VI)/Mo(V) and Mo(VI)/Mo(IV) redox couples in Na2MoO4/PVA/H2SO4 gel electrolyte. Similarly, the fabricated device shows the excellent capacitance retention of 93% for over 3000 cycles. The present work suggests that the Na2MoO4 added PVA/H2SO4 gel is a potential electrolyte to improve the performance instead of pristine PVA/H2SO4 gel electrolyte. Based on the overall performance, it is strongly believed that the combination of tamarind fruit shell derived activated carbon and Na2MoO4/PVA/H2SO4 gel electrolyte is more attractive in the near future for high performance SSEDLCs.

Development of wide temperature electrolyte for graphite/ LiNiMnCoO2 Li-ion cells: High throughput screening

NASA Astrophysics Data System (ADS)

Kafle, Janak; Harris, Joshua; Chang, Jeremy; Koshina, Joe; Boone, David; Qu, Deyang

2018-07-01

In this report, we demonstrate that the low temperature power capability of a Li-ion battery can be substantially improved not by adding commercially unavailable additives into the electrolyte, but by rational design of the composition of the most commonly used solvents. Through the detail analysis with electrochemical impedance spectroscopy, the formation of a homogenous solid electrolyte interface (SEI) layer on the carbon anode surface is found to be critical to ensure the performance of a Li-ion battery in a wide temperature range. The post mortem analysis of the negative electrode by XPS revealed that all the electrolyte compositions form similar compounds in the solid electrolyte interphase. However, the electrolytes which give higher capacities at low temperature showed higher percentage of LiF and lower percentage of carbon containing species such as lithium carbonate and lithium ethylene di-carbonate. The electrolyte compositions where cyclic carbonates make up less than 25% of the total solvent showed increased low temperature performance. The solvent composition with higher percentage of linear short chain carbonates showed an improved low temperature performance. The high temperature performances were similar in almost all the combinations.

Solid-state supercapacitors with ionic liquid based gel polymer electrolyte: Effect of lithium salt addition

NASA Astrophysics Data System (ADS)

Pandey, G. P.; Hashmi, S. A.

2013-12-01

Performance characteristics of the solid-state supercapacitors fabricated with ionic liquid (IL) incorporated gel polymer electrolyte and acid treated multiwalled carbon nanotube (MWCNT) electrodes have been studied. The effect of Li-salt (LiPF6) addition in the IL (1-ethyl-3-methylimidazolium tris(pentafluoroethyl) trifluorophosphate, EMImFAP) based gel electrolyte on the performance of supercapacitors has been specifically investigated. The LiPF6/IL/poly(vinylidine fluoride-co-hexafluoropropylene) (PVdF-HFP) gel electrolyte film possesses excellent electrochemical window of 4 V (from -2.0 to 2.0 V), high ionic conductivity ∼2.6 × 10-3 S cm-1 at 20 °C and high enough thermal stability. The comparative performance of supercapacitors employing electrolytes with and without lithium salt has been evaluated by impedance spectroscopy and cyclic voltammetric studies. The acid-treated MWCNT electrodes show specific capacitance of ∼127 F g-1 with IL/LiPF6 containing gel polymer electrolyte as compared to that with the gel polymer electrolyte without Li-salt, showing the value of ∼76 F g-1. The long cycling stability of the solid state supercapacitor based on the Li-salt containing gel polymer electrolyte confirms the electrochemical stability of the electrolyte.

Electrochemical performance of solid oxide fuel cells having electrolytes made by suspension and solution precursor plasma spraying

NASA Astrophysics Data System (ADS)

Marr, M.; Kuhn, J.; Metcalfe, C.; Harris, J.; Kesler, O.

2014-01-01

Yttria-stabilized zirconia (YSZ) electrolytes were deposited by suspension plasma spraying (SPS) and solution precursor plasma spraying (SPPS). The electrolytes were evaluated for permeability, microstructure, and electrochemical performance. With SPS, three different suspensions were tested to explore the influence of powder size distribution and liquid properties. Electrolytes made from suspensions of a powder with d50 = 2.6 μm were more gas-tight than those made from suspensions of a powder with d50 = 0.6 μm. A peak open circuit voltage of 1.00 V was measured at 750 °C with a cell with an electrolyte made from a suspension of d50 = 2.6 μm powder. The use of a flammable suspension liquid was beneficial for improving electrolyte conductivity when using lower energy plasmas, but the choice of liquid was less important when using higher energy plasmas. With SPPS, peak electrolyte conductivities were comparable to the peak conductivities of the SPS electrolytes. However, leak rates through the SPPS electrolytes were higher than those through the electrolytes made from suspensions of d50 = 2.6 μm powder. The electrochemical test data on SPPS electrolytes are the first reported in the literature.

Electrolytes for Use in High Energy Lithium-Ion Batteries with Wide Operating Temperature Range

NASA Technical Reports Server (NTRS)

Smart, Marshall C.; Ratnakumar, B. V.; West, W. C.; Whitcanack, L. D.; Huang, C.; Soler, J.; Krause, F. C.

2011-01-01

Objectives of this work are: (1) Develop advanced Li -ion electrolytes that enable cell operation over a wide temperature range (i.e., -30 to +60C). (2) Improve the high temperature stability and lifetime characteristics of wide operating temperature electrolytes. (3) Improve the high voltage stability of these candidate electrolytes systems to enable operation up to 5V with high specific energy cathode materials. (4) Define the performance limitations at low and high temperature extremes, as well as, life limiting processes. (5) Demonstrate the performance of advanced electrolytes in large capacity prototype cells.

Electrochemical Stability of Li 10GeP 2S 12 and Li 7La 3Zr 2O 12 Solid Electrolytes

DOE PAGES

Han, Fudong; Zhu, Yizhou; He, Xingfeng; ...

2016-01-21

The electrochemical stability window of solid electrolyte is overestimated by the conventional experimental method using a Li/electrolyte/inert metal semiblocking electrode because of the limited contact area between solid electrolyte and inert metal. Since the battery is cycled in the overestimated stability window, the decomposition of the solid electrolyte at the interfaces occurs but has been ignored as a cause for high interfacial resistances in previous studies, limiting the performance improvement of the bulk-type solid-state battery despite the decades of research efforts. Thus, there is an urgent need to identify the intrinsic stability window of the solid electrolyte. The thermodynamic electrochemicalmore » stability window of solid electrolytes is calculated using first principles computation methods, and an experimental method is developed to measure the intrinsic electrochemical stability window of solid electrolytes using a Li/electrolyte/electrolyte-carbon cell. The most promising solid electrolytes, Li10GeP2S12 and cubic Li-garnet Li7La3Zr2O12, are chosen as the model materials for sulfide and oxide solid electrolytes, respectively. The results provide valuable insights to address the most challenging problems of the interfacial stability and resistance in high-performance solid-state batteries.« less

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.

Evaluating electrolyte additives for lithium-ion cells: A new Figure of Merit approach

NASA Astrophysics Data System (ADS)

Tornheim, Adam; Peebles, Cameron; Gilbert, James A.; Sahore, Ritu; Garcia, Juan C.; Bareño, Javier; Iddir, Hakim; Liao, Chen; Abraham, Daniel P.

2017-10-01

Electrolyte additives are known to improve the performance of lithium-ion cells. In this work we examine the performance of Li1.03Ni0.5Mn0.3Co0.3O2-graphite (NMC532/Gr) cells containing combinations of lithium bis(oxalate)borate (LiBOB), vinylene carbonate (VC), trivinylcyclotriboroxane (tVCBO), prop-1-ene-1,3-sultone (PES), phenyl boronic acid ethylene glycol ester (PBE), tris(trimethylsilyl) phosphite (TMSPi), triethyl phosphite (TEPi), and lithium difluoro(oxalate)borate (LiDFOB) added to our baseline (1.2 M LiPF6 in EC:EMC, 3:7 w/w) electrolyte. In order to rank performance of the various electrolytes, we developed two separate figures of merit (FOM), which are based on the energy retention and power retention of the cells. Using these two metrics in conjunction, we show that only one of the fifteen electrolyte formulations tested significantly outperforms the baseline electrolyte: this electrolyte contains the 0.25 wt% tVCBO + 1 wt% TMSPi additive mix. Little correlation was observed between the FOMs for energy retention and power retention, which indicates that the mechanisms that govern these performance parameters are likely independent of each other. Our FOM approach has general applicability and can be used to develop electrolyte and electrode formulations that prolong the life of lithium-ion batteries.

Evaluating electrolyte additives for lithium-ion cells: A new Figure of Merit approach

DOE PAGES

Tornheim, Adam; Peebles, Cameron; Gilbert, James A.; ...

2017-09-01

Electrolyte additives are known to improve the performance of lithium-ion cells. In this work we examine the performance of Li 1.03Ni 0.5Mn 0.3Co 0.3O 2-graphite (NMC532/Gr) cells containing combinations of lithium bis(oxalate)borate (LiBOB), vinylene carbonate (VC), trivinylcyclotriboroxane (tVCBO), prop-1-ene-1,3-sultone (PES), phenyl boronic acid ethylene glycol ester (PBE), tris(trimethylsilyl) phosphite (TMSPi), triethylphosphite (TEPi), and lithium difluoro(oxalate)borate (LiDFOB) added to our baseline (1.2M LiPF 6 in EC:EMC, 3:7 w/w) electrolyte. In order to rank performance of the various electrolytes, we developed two separate figures of merit (FOM), which are based on the energy retention and power retention of the cells. Using thesemore » two metrics in conjunction, we show that only one of the fifteen electrolyte formulations tested significantly outperforms the baseline electrolyte: this electrolyte contains the 0.25 wt% tVCBO + 1 wt% TMSPi additive mix. Little correlation was observed between the FOMs for energy retention and power retention, which indicates that the mechanisms that govern these performance parameters are likely independent of each other. In conclusion, our FOM approach has general applicability and can be used to develop electrolyte and electrode formulations that prolong the life of lithium-ion batteries.« less

Evaluating electrolyte additives for lithium-ion cells: A new Figure of Merit approach

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

Tornheim, Adam; Peebles, Cameron; Gilbert, James A.

Electrolyte additives are known to improve the performance of lithium-ion cells. In this work we examine the performance of Li 1.03Ni 0.5Mn 0.3Co 0.3O 2-graphite (NMC532/Gr) cells containing combinations of lithium bis(oxalate)borate (LiBOB), vinylene carbonate (VC), trivinylcyclotriboroxane (tVCBO), prop-1-ene-1,3-sultone (PES), phenyl boronic acid ethylene glycol ester (PBE), tris(trimethylsilyl) phosphite (TMSPi), triethylphosphite (TEPi), and lithium difluoro(oxalate)borate (LiDFOB) added to our baseline (1.2M LiPF 6 in EC:EMC, 3:7 w/w) electrolyte. In order to rank performance of the various electrolytes, we developed two separate figures of merit (FOM), which are based on the energy retention and power retention of the cells. Using thesemore » two metrics in conjunction, we show that only one of the fifteen electrolyte formulations tested significantly outperforms the baseline electrolyte: this electrolyte contains the 0.25 wt% tVCBO + 1 wt% TMSPi additive mix. Little correlation was observed between the FOMs for energy retention and power retention, which indicates that the mechanisms that govern these performance parameters are likely independent of each other. In conclusion, our FOM approach has general applicability and can be used to develop electrolyte and electrode formulations that prolong the life of lithium-ion batteries.« less

Towards High-Performance Aqueous Sodium-Ion Batteries: Stabilizing the Solid/Liquid Interface for NASICON-Type Na2 VTi(PO4 )3 using Concentrated Electrolytes.

PubMed

Zhang, Huang; Jeong, Sangsik; Qin, Bingsheng; Vieira Carvalho, Diogo; Buchholz, Daniel; Passerini, Stefano

2018-04-25

Aqueous Na-ion batteries may offer a solution to the cost and safety issues of high-energy batteries. However, substantial challenges remain in the development of electrode materials and electrolytes enabling high performance and long cycle life. Herein, we report the characterization of a symmetric Na-ion battery with a NASICON-type Na 2 VTi(PO 4 ) 3 electrode material in conventional aqueous and "water-in-salt" electrolytes. Extremely stable cycling performance for 1000 cycles at a high rate (20 C) is found with the highly concentrated aqueous electrolytes owing to the formation of a resistive but protective interphase between the electrode and electrolyte. These results provide important insight for the development of aqueous Na-ion batteries with stable long-term cycling performance for large-scale energy storage. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Alkyl Pyrocarbonate Electrolyte Additives for Performance Enhancement of Li Ion Cells

NASA Technical Reports Server (NTRS)

Smart, M. C.; Ratnakumar, B. V.; Surampudi, S.

2000-01-01

Lithium ion rechargeable batteries are being developed for various aerospace applications under a NASA-DoD Interagency program. These applications require further improvements in several areas, specifically in the cycle life for LEO and GEO satellites and in the low temperature performance for the Mars Lander and Rover missions. Accordingly, we have been pursuing research studies to achieve improvement in the low temperature performance, long cycle life and active life of Li ion cells. The studies are mainly focused on electrolytes, to identify newer formulations of new electrolyte additives to enhance Li permeability (at low temperatures) and stability towards the electrode. The latter approach is particularly aimed at the formation suitable SEI (solid electrolyte interphase) on carbon electrodes. In this paper, we report the beneficial effect of using alkyl pyrocarbonates as electrolyte additives to improve the low temperature performance of Li ion cells.

Electrochemical performance of tris(2-chloroethyl) phosphate as a flame-retarding additive for lithium-ion batteries

NASA Astrophysics Data System (ADS)

Shim, Eun-Gi; Park, In-Jun; Nam, Tae-Heum; Kim, Jung-Gu; Kim, Hyun-Soo; Moon, Seong-In

2010-08-01

We studied tris(2-chloroethyl) phosphate (TCEP) as a potential flame-retarding additive and its effect on the electrochemical cell performance of lithium-ion battery electrolytes. The electrochemical cell performance of additive-containing electrolytes in combination with a cell comprised of a LiCoO2 cathode and a mesocarbon microbeads anode was tested in coin cells. The cyclic voltammetry results show that the oxidation potential of TCEP-containing electrolyte is about 5.1 V (vs. Li/Li+). A cell with TCEP has a better electrochemical cell performance than a cell without TCEP in an initial charge and discharge test. In a cycling test, a cell containing a TCEP-containing electrolyte has a greater discharge capacity and better capacity retention than a TCEP-free electrolyte after cycling. The results confirm the promising potential of TCEP as a flame-retarding additive and as a means of improving the electrochemical cell performance of lithium-ion batteries.

High-Performance Protonic Ceramic Fuel Cells with Thin-Film Yttrium-Doped Barium Cerate-Zirconate Electrolytes on Compositionally Gradient Anodes.

PubMed

Bae, Kiho; Lee, Sewook; Jang, Dong Young; Kim, Hyun Joong; Lee, Hunhyeong; Shin, Dongwook; Son, Ji-Won; Shim, Joon Hyung

2016-04-13

In this study, we used a compositionally gradient anode functional layer (AFL) consisting of Ni-BaCe(0.5)Zr(0.35)Y(0.15)O(3-δ) (BCZY) with increasing BCZY contents toward the electrolyte-anode interface for high-performance protonic ceramic fuel cells. It is identified that conventional homogeneous AFLs fail to stably accommodate a thin film of BCZY electrolyte. In contrast, a dense 2 μm thick BCZY electrolyte was successfully deposited onto the proposed gradient AFL with improved adhesion. A fuel cell containing this thin electrolyte showed a promising maximum peak power density of 635 mW cm(-2) at 600 °C, with an open-circuit voltage of over 1 V. Impedance analysis confirmed that minimizing the electrolyte thickness is essential for achieving a high power output, suggesting that the anode structure is important in stably accommodating thin electrolytes.

A Synopsis of Interfacial Phenomena in Lithium-Based Polymer Electrolyte Electrochemical Cells

NASA Technical Reports Server (NTRS)

Baldwin, Richard S.; Bennett, William R.

2007-01-01

The interfacial regions between electrode materials, electrolytes and other cell components play key roles in the overall performance of lithium-based batteries. For cell chemistries employing lithium metal, lithium alloy or carbonaceous materials (i.e., lithium-ion cells) as anode materials, a "solid electrolyte interphase" (SEI) layer forms at the anode/electrolyte interface, and the properties of this "passivating" layer significantly affect the practical cell/battery quality and performance. A thin, ionically-conducting SEI on the electrode surface can beneficially reduce or eliminate undesirable side reactions between the electrode and the electrolyte, which can result in a degradation in cell performance. The properties and phenomena attributable to the interfacial regions existing at both anode and cathode surfaces can be characterized to a large extent by electrochemical impedance spectroscopy (EIS) and related techniques. The intention of the review herewith is to support the future development of lithium-based polymer electrolytes by providing a synopsis of interfacial phenomena that is associated with cell chemistries employing either lithium metal or carbonaceous "composite" electrode structures which are interfaced with polymer electrolytes (i.e., "solvent-free" as well as "plasticized" polymer-binary salt complexes and single ion-conducting polyelectrolytes). Potential approaches to overcoming poor cell performance attributable to interfacial effects are discussed.

Optimized Li-Ion Electrolytes Containing Fluorinated Ester Co-Solvents

NASA Technical Reports Server (NTRS)

Prakash, G. K. Surya; Smart, Marshall; Smith, Kiah; Bugga, Ratnakumar

2010-01-01

A number of experimental lithium-ion cells, consisting of MCMB (meso-carbon microbeads) carbon anodes and LiNi(0.8)Co(0.2)O2 cathodes, have been fabricated with increased safety and expanded capability. These cells serve to verify and demonstrate the reversibility, low-temperature performance, and electrochemical aspects of each electrode as determined from a number of electrochemical characterization techniques. A number of Li-ion electrolytes possessing fluorinated ester co-solvents, namely trifluoroethyl butyrate (TFEB) and trifluoroethyl propionate (TFEP), were demonstrated to deliver good performance over a wide temperature range in experimental lithium-ion cells. The general approach taken in the development of these electrolyte formulations is to optimize the type and composition of the co-solvents in ternary and quaternary solutions, focusing upon adequate stability [i.e., EC (ethylene carbonate) content needed for anode passivation, and EMC (ethyl methyl carbonate) content needed for lowering the viscosity and widening the temperature range, while still providing good stability], enhancing the inherent safety characteristics (incorporation of fluorinated esters), and widening the temperature range of operation (the use of both fluorinated and non-fluorinated esters). Further - more, the use of electrolyte additives, such as VC (vinylene carbonate) [solid electrolyte interface (SEI) promoter] and DMAc (thermal stabilizing additive), provide enhanced high-temperature life characteristics. Multi-component electrolyte formulations enhance performance over a temperature range of -60 to +60 C. With the need for more safety with the use of these batteries, flammability was a consideration. One of the solvents investigated, TFEB, had the best performance with improved low-temperature capability and high-temperature resilience. This work optimized the use of TFEB as a co-solvent by developing the multi-component electrolytes, which also contain non-halogenated esters, film forming additives, thermal stabilizing additives, and flame retardant additives. Further optimization of these electrolyte formulations is anticipated to yield improved performance. It is also anticipated that much improved performance will be demonstrated once these electrolyte solutions are incorporated into hermetically sealed, large capacity prototype cells, especially if effort is devoted to ensure that all electrolyte components are highly pure.

Study of ceria-carbonate nanocomposite electrolytes for low-temperature solid oxide fuel cells.

PubMed

Fan, L; Wang, C; Di, J; Chen, M; Zheng, J; Zhu, B

2012-06-01

Composite and nanocomposite samarium doped ceria-carbonates powders were prepared by solid-state reaction, citric acid-nitrate combustion and modified nanocomposite approaches and used as electrolytes for low temperature solid oxide fuel cells. X-ray Diffraction, Scanning Electron Microscope, low-temperature Nitrogen Adsorption/desorption Experiments, Electrochemical Impedance Spectroscopy and fuel cell performance test were employed in characterization of these materials. All powders are nano-size particles with slight aggregation and carbonates are amorphous in composites. Nanocomposite electrolyte exhibits much lower impedance resistance and higher ionic conductivity than those of the other electrolytes at lower temperature. Fuel cell using the electrolyte prepared by modified nanocomposite approach exhibits the best performance in the whole operation temperature range and achieves a maximum power density of 839 mW cm(-2) at 600 degrees C with H2 as fuel. The excellent physical and electrochemical performances of nanocomposite electrolyte make it a promising candidate for low-temperature solid oxide fuel cells.

Towards Versatile and Sustainable Hydrogen Production through Electrocatalytic Water Splitting: Electrolyte Engineering.

PubMed

Shinagawa, Tatsuya; Takanabe, Kazuhiro

2017-04-10

Recent advances in power generation from renewable resources necessitate conversion of electricity to chemicals and fuels in an efficient manner. Electrocatalytic water splitting is one of the most powerful and widespread technologies. The development of highly efficient, inexpensive, flexible, and versatile water electrolysis devices is desired. This review discusses the significance and impact of the electrolyte on electrocatalytic performance. Depending on the circumstances under which the water splitting reaction is conducted, the required solution conditions, such as the identity and molarity of ions, may significantly differ. Quantitative understanding of such electrolyte properties on electrolysis performance is effective to facilitate the development of efficient electrocatalytic systems. The electrolyte can directly participate in reaction schemes (kinetics), affect electrode stability, and/or indirectly impact the performance by influencing the concentration overpotential (mass transport). This review aims to guide fine-tuning of the electrolyte properties, or electrolyte engineering, for (photo)electrochemical water splitting reactions. © 2017 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA.

Nanostructure enhanced ionic transport in fullerene reinforced solid polymer electrolytes.

PubMed

Sun, Che-Nan; Zawodzinski, Thomas A; Tenhaeff, Wyatt E; Ren, Fei; Keum, Jong Kahk; Bi, Sheng; Li, Dawen; Ahn, Suk-Kyun; Hong, Kunlun; Rondinone, Adam J; Carrillo, Jan-Michael Y; Do, Changwoo; Sumpter, Bobby G; Chen, Jihua

2015-03-28

Solid polymer electrolytes, such as polyethylene oxide (PEO) based systems, have the potential to replace liquid electrolytes in secondary lithium batteries with flexible, safe, and mechanically robust designs. Previously reported PEO nanocomposite electrolytes routinely use metal oxide nanoparticles that are often 5-10 nm in diameter or larger. The mechanism of those oxide particle-based polymer nanocomposite electrolytes is under debate and the ion transport performance of these systems is still to be improved. Herein we report a 6-fold ion conductivity enhancement in PEO/lithium bis(trifluoromethanesulfonyl) imide (LiTFSI)-based solid electrolytes upon the addition of fullerene derivatives. The observed conductivity improvement correlates with nanometer-scale fullerene crystallite formation, reduced crystallinities of both the (PEO)6:LiTFSI phase and pure PEO, as well as a significantly larger PEO free volume. This improved performance is further interpreted by enhanced decoupling between ion transport and polymer segmental motion, as well as optimized permittivity and conductivity in bulk and grain boundaries. This study suggests that nanoparticle induced morphological changes, in a system with fullerene nanoparticles and no Lewis acidic sites, play critical roles in their ion conductivity enhancement. The marriage of fullerene derivatives and solid polymer electrolytes opens up significant opportunities in designing next-generation solid polymer electrolytes with improved performance.

Highly Conductive Solid-State Hybrid Electrolytes Operating at Subzero Temperatures.

PubMed

Kwon, Taeyoung; Choi, Ilyoung; Park, Moon Jeong

2017-07-19

We report a unique, highly conductive, dendrite-inhibited, solid-state polymer electrolyte platform that demonstrates excellent battery performance at subzero temperatures. A design based on functionalized inorganic nanoparticles with interconnected mesopores that contain surface nitrile groups is the key to this development. Solid-state hybrid polymer electrolytes based on succinonitrile (SN) electrolytes and porous nanoparticles were fabricated via a simple UV-curing process. SN electrolytes were effectively confined within the mesopores. This stimulated favorable interactions with lithium ions, reduced leakage of SN electrolytes over time, and improved mechanical strength of membranes. Inhibition of lithium dendrite growth and improved electrochemical stability up to 5.2 V were also demonstrated. The hybrid electrolytes exhibited high ionic conductivities of 2 × 10 -3 S cm -1 at room temperature and >10 -4 S cm -1 at subzero temperatures, leading to stable and improved battery performance at subzero temperatures. Li cells made with lithium titanate anodes exhibited stable discharge capacities of 151 mAh g -1 at temperatures below -10 °C. This corresponds to 92% of the capacity achieved at room temperature (164 mAh g -1 ). Our work represents a significant advance in solid-state polymer electrolyte technology and far exceeds the performance available with conventional polymeric battery separators.

The limits of low-temperature performance of Li-ion cells

NASA Technical Reports Server (NTRS)

Huang, C.; Sakamoto, J.; Wolfenstine, J.; Surampudi, S.

2000-01-01

The results of electrode and electrolyte studies reveal that the poor low-temperature (<-30 degrees C) performance of Li-ion cells is mainly caused by the carbon electrodes and not the organic electrolytes and solid electrolyte interphase, as previously suggested. It is suggested that the main causes for the poor performance in the carbon electrodes are (i) the low value and concentration depedence of the Li diffusivity and (ii) limited Li capacity.

Electrochemical insertion of magnesium ions into V2O5 from aprotic electrolytes with varied water content.

PubMed

Yu, Long; Zhang, Xiaogang

2004-10-01

The electrochemical performance of V2O5 has been studied in propylene carbonate (PC)-containing magnesium perchlorate [Mg(ClO4)2] electrolytes in view of their application as positive electrode in the rechargeable magnesium batteries. V2O5 exhibited good properties in hosting magnesium ions and its electrochemical performance depended on the amount of H2O in the electrolytes. The highest first discharge specific capacities of V2O5 electrode was up to 158.6 mAh/g in 1 mol dm(-3) Mg(ClO4)2 + 1.79 mol dm(-3) H2O/PC electrolytes. Electrochemical impedance spectroscopy (EIS) and charging-discharging tests showed that a reasonable amount of H2O in the electrolyte solution facilitated the electrochemical performance of V2O5 electrodes.

Li-Ion Electrolytes with Improved Safety and Tolerance to High-Voltage Systems

NASA Technical Reports Server (NTRS)

Smart, Marshall C.; Bugga, Ratnakumar V.; Prakash, Surya; Krause, Frederick C.

2013-01-01

Given that lithium-ion (Li-ion) technology is the most viable rechargeable energy storage device for near-term applications, effort has been devoted to improving the safety characteristics of this system. Therefore, extensive effort has been devoted to developing nonflammable electrolytes to reduce the flammability of the cells/battery. A number of promising electrolytes have been developed incorporating flame-retardant additives, and have been shown to have good performance in a number of systems. However, these electrolyte formulations did not perform well when utilizing carbonaceous anodes with the high-voltage materials. Thus, further development was required to improve the compatibility. A number of Li-ion battery electrolyte formulations containing a flame-retardant additive [i.e., triphenyl phosphate (TPP)] were developed and demonstrated in high-voltage systems. These electrolytes include: (1) formulations that incorporate varying concentrations of the flame-retardant additive (from 5 to 15%), (2) the use of mono-fluoroethylene carbonate (FEC) as a co-solvent, and (3) the use of LiBOB as an electrolyte additive intended to improve the compatibility with high-voltage systems. Thus, improved safety has been provided without loss of performance in the high-voltage, high-energy system.

Synthesis of Ionic Liquid Based Electrolytes, Assembly of Li-ion Batteries, and Measurements of Performance at High Temperature.

PubMed

Lin, Xinrong; Chapman Varela, Jennifer; Grinstaff, Mark W

2016-12-20

The chemical instability of the traditional electrolyte remains a safety issue in widely used energy storage devices such as Li-ion batteries. Li-ion batteries for use in devices operating at elevated temperatures require thermally stable and non-flammable electrolytes. Ionic liquids (ILs), which are non-flammable, non-volatile, thermally stable molten salts, are an ideal replacement for flammable and low boiling point organic solvent electrolytes currently used today. We herein describe the procedures to: 1) synthesize mono- and di-phosphonium ionic liquids paired with chloride or bis(trifluoromethane)sulfonimide (TFSI) anions; 2) measure the thermal properties and stability of these ionic liquids by differential scanning calorimetry (DSC) and thermal gravimetric analysis (TGA); 3) measure the electrochemical properties of the ionic liquids by cyclic voltammetry (CV); 4) prepare electrolytes containing lithium bis(trifluoromethane)sulfonamide; 5) measure the conductivity of the electrolytes as a function of temperature; 6) assemble a coin cell battery with two of the electrolytes along with a Li metal anode and LiCoO2 cathode; and 7) evaluate battery performance at 100 °C. We additionally describe the challenges in execution as well as the insights gained from performing these experiments.

Designed synergetic effect of electrolyte additives to improve interfacial chemistry of MCMB electrode in propylene carbonate-based electrolyte for enhanced low and room temperature performance.

PubMed

Wotango, Aselefech Sorsa; Su, Wei-Nien; Haregewoin, Atetegeb Meazah; Chen, Hung-Ming; Cheng, Ju-Hsiang; Lin, Ming-Hsien; Wang, Chia-Hsin; Hwang, Bing-Joe

2018-05-09

The performance of lithium ion batteries rapidly falls at lower temperatures due to decreasing conductivity of electrolytes and Solid Electrolyte Interphase (SEI) on graphite anode. Hence, it limits the practical use of lithium ion batteries at sub-zero temperatures and also affects the development of lithium ion batteries for widespread applications. The SEI formed on the graphite surface is very influential in determining the performance of the battery. Herein, a new electrolyte additive, 4-Chloromethyl-1,3,2-dioxathiolane-2-oxide (CMDO), is prepared to improve the properties of commonly used electrolyte constituents - ethylene carbonate (EC), and fluoroethylene carbonate (FEC). The formation of an efficient passivation layer in propylene carbonate (PC) -based electrolyte for MCMB electrode was investigated. The addition of CMDO resulted in a much less irreversible capacity loss and induces thin SEI formation. However, the combination of the three additives played a key role to enhance reversible capacity of MCMB electrode at lower or ambient temperature. The electrochemical measurement analysis showed that the SEI formed from a mixture of the three additives gave better intercalation-deintercalation of lithium ions.

Assessment of Lithium-based Battery Electrolytes Developed under the NASA PERS Program

NASA Technical Reports Server (NTRS)

Bennett, William R.; Baldwin, Richard S.

2006-01-01

Recently, NASA formally completed the Polymer Energy Rechargeable System (PERS) Program, which was established in 2000 in collaboration with the Air Force Research Laboratory (AFRL) to support the development of polymer-based, lithium-based cell chemistries and battery technologies to address the next generation of aerospace applications and mission needs. The goal of this program was to ultimately develop an advanced, space-qualified battery technology, which embodied a solid polymer electrolyte (SPE) and complementary components, with improved performance characteristics that would address future aerospace battery requirements. Programmatically, the PERS initiative exploited both interagency collaborations to address common technology and engineering issues and the active participation of academia and private industry. The initial program phases focused on R&D activities to address the critical technical issues and challenges at the cell level. A variety of cell and polymeric electrolyte concepts were pursued as part of the development efforts undertaken at numerous governmental, industrial and academic laboratories. Numerous candidate electrolyte materials were developed, synthesized and optimized for evaluation. Utilizing the component screening facility and the "standardized" test procedures developed at the NASA Glenn Research Center, electrochemical screening and performance evaluations of promising candidate materials were completed. This overview summarizes test results for a variety of candidate electrolyte materials that were developed under the PERS Program. Electrolyte properties are contrasted and compared to the original project goals, and the strengths and weaknesses of the electrolyte chemistries are discussed. Limited cycling data for full-cells using lithium metal and vanadium oxide electrodes are also presented. Based on measured electrolyte properties, the projected performance characteristics and temperature limitations of batteries utilizing the advanced electrolytes and components have been estimated. Limitations for the achievement of practical performance levels are also discussed, as well as needs for future research and development.

Electrolytes for Use in High Energy Lithium-ion Batteries with Wide Operating Temperature Range

NASA Technical Reports Server (NTRS)

Smart, Marshall C.; Ratnakumar, B. V.; West, W. C.; Whitcanack, L. D.; Huang, C.; Soler, J.; Krause, F. C.

2012-01-01

Met programmatic milestones for program. Demonstrated improved performance with wide operating temperature electrolytes containing ester co-solvents (i.e., methyl butyrate) containing electrolyte additives in A123 prototype cells: Previously demonstrated excellent low temperature performance, including 11C rates at -30 C and the ability to perform well down to -60 C. Excellent cycle life at room temperature has been displayed, with over 5,000 cycles being demonstrated. Good high temperature cycle life performance has also been achieved. Demonstrated improved performance with methyl propionate-containing electrolytes in large capacity prototype cells: Demonstrated the wide operating temperature range capability in large cells (12 Ah), successfully scaling up technology from 0.25 Ah size cells. Demonstrated improved performance at low temperature and good cycle life at 40 C with methyl propionate-based electrolyte containing increasing FEC content and the use of LiBOB as an additive. Utilized three-electrode cells to investigate the electrochemical characteristics of high voltage systems coupled with wide operating temperature range electrolytes: From Tafel polarization measurements on each electrode, it is evident the NMC-based cathode displays poor lithium kinetics (being the limiting electrode). The MB-based formulations containing LiBOB delivered the best rate capability at low temperature, which is attributed to improved cathode kinetics. Whereas, the use of lithium oxalate as an additive lead to the highest reversible capacity and lower irreversible losses.

Electrochemical Performance of LiNi0.5Mn1.5O4 by Sol-gel Self-combustion Reaction Method in Different Kinds of Electrolyte for High-voltage Rechargeable Lithium Cells

NASA Astrophysics Data System (ADS)

Liang, Xinghua; Shi, Lin; Liu, Yusi; Zeng, Shuaibo; Ye, Chaochao

2015-07-01

LiNi0.5Mn1.5O4 cathode material was synthesized through sol-gel self-combustion reaction method. LiNi0.5Mn1.5O4 powders were subsequently characterized as cathode materials in a Li-ion coin cell comprising a Li anode with electrolyte A or electrolyte B. 1.0 mol/L Lithium Hexafluorophosphate (LiPF6) dissolved in volume ration of ethylene carbonate (EC) to ethyl methyl carbonate (EMC) to diethyl carbonate (DEC) corresponded to 4:3:3as electrolyte A, 1.0 mol/L LiPF6 dissolved in volume ration of EC to EMC to DEC corresponded to 4:2:4 as electrolyte B. Electrochemical performance of lithium cells was evaluated. These tests showed that no matter the cells with electrolyte A or electrolyte B has good discharge platform in 4.7V range (3.5V-4.75V) at the rate of 0.1C, the initial discharge capacity of cell with electrolyte B was higher than that with electrolyte A.

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.

Computer model for characterizing, screening, and optimizing electrolyte systems

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

Gering, Kevin L.

2015-06-15

Electrolyte systems in contemporary batteries are tasked with operating under increasing performance requirements. All battery operation is in some way tied to the electrolyte and how it interacts with various regions within the cell environment. Seeing the electrolyte plays a crucial role in battery performance and longevity, it is imperative that accurate, physics-based models be developed that will characterize key electrolyte properties while keeping pace with the increasing complexity of these liquid systems. Advanced models are needed since laboratory measurements require significant resources to carry out for even a modest experimental matrix. The Advanced Electrolyte Model (AEM) developed at themore » INL is a proven capability designed to explore molecular-to-macroscale level aspects of electrolyte behavior, and can be used to drastically reduce the time required to characterize and optimize electrolytes. Although it is applied most frequently to lithium-ion battery systems, it is general in its theory and can be used toward numerous other targets and intended applications. This capability is unique, powerful, relevant to present and future electrolyte development, and without peer. It redefines electrolyte modeling for highly-complex contemporary systems, wherein significant steps have been taken to capture the reality of electrolyte behavior in the electrochemical cell environment. This capability can have a very positive impact on accelerating domestic battery development to support aggressive vehicle and energy goals in the 21st century.« less

Electrolyte and composition effects on the performances of asymmetric supercapacitors constructed with Mn3O4 nanoparticles-graphene nanocomposites

NASA Astrophysics Data System (ADS)

Xiao, Yuanhua; Cao, Yongbo; Gong, Yuyin; Zhang, Aiqin; Zhao, Jihong; Fang, Shaoming; Jia, Dianzeng; Li, Feng

2014-01-01

Nanocomposites of Mn3O4 nanoparticles and graphene (GR) nanosheets - Mn3O4@GR can be made by growing Mn3O4 nanoparticles directly on the surfaces of GR in solvothermal reactions. The asymmetric supercapacitors constructed with Mn3O4@GR as positive and activated carbon (AC) as negative electrodes, respectively, show highly enhanced performances in energy storage. It was found that the electrolytes employed in constructing electrodes of the devices can influence the performances of Mn3O4@GR supercapacitors dramatically. Compared to their energy density in KOH electrolyte, the devices exhibit improved charge storage performances in Na2SO4 electrolyte. Furthermore, the charge storage abilities of the devices are closely related to the amount of Mn3O4 nanoparticles loaded onto the surface of GR nanosheets. The performances of Mn3O4@GR//AC asymmetric supercapacitors can be optimized by carefully tailoring the composition of electrode materials and adjusting the electrolytes for making the devices.

Study of the H2O/Al2O3 Interface and the Acting Mechanism of Water in the Working Electrolyte

NASA Astrophysics Data System (ADS)

Jia, Ming; Li, Qiang; Li, Lixiang; Cao, Liang; Yang, Juan; Zhou, Xiangyang; Ai, Liang

2018-04-01

Using a working electrolyte containing mixed solvents of ethylene glycol and N,N-dimethylformamide, this paper presents a study of the reactions on the H2O/Al2O3 interface with sum frequency vibrational spectroscopy and the effects of different water content on the performance of the working electrolyte and an aluminum electrolytic capacitor and summarizes the rules of the variations in the performance parameters of the working electrolyte and aluminum electrolytic capacitor with respect to the water content. The results demonstrate that, when the water content is increased from 2.5 to 15%, the conductivity of the working electrolyte increased by 930 μS/cm, and the sparking voltage decreased by 27 V. Also, the increased water content causes lower oxidation efficiency and lower thermal stability. The leakage current of the aluminum electrolytic capacitor after high-temperature storage increases with an increase in the water content, and the attenuation rate of capacitor's the low-temperature capacitance decreases with an increase in the water content.

A Newly Designed Composite Gel Polymer Electrolyte Based on Poly(Vinylidene Fluoride-Hexafluoropropylene) (PVDF-HFP) for Enhanced Solid-State Lithium-Sulfur Batteries.

PubMed

Xia, Yan; Wang, Xiuli; Xia, Xinhui; Xu, Ruochen; Zhang, Shengzhao; Wu, Jianbo; Liang, Yanfei; Gu, Changdong; Tu, Jiangping

2017-10-26

Developing high-performance solid-state electrolytes is crucial for the innovation of next-generation lithium-sulfur batteries. Herein, a facile method for preparation of a novel gel polymer electrolyte (GPE) based on poly(vinylidene fluoride-hexafluoropropylene) (PVDF-HFP) is reported. Furthermore, Li 1.5 Al 0.5 Ti 1.5 (PO 4 ) 3 (LATP) nanoparticles as the active fillers are uniformly embedded into the GPE to form the final PVDF-HFP/LATP composite gel polymer electrolyte (CPE). Impressively, the obtained CPE demonstrates a high lithium ion transference number of 0.51 and improved electrochemical stability as compared to commercial liquid electrolyte. In addition, the assembled solid-sate Li-S battery with the composite gel polymer electrolyte membrane presents a high initial capacity of 918 mAh g -1 at 0.05 C, and better cycle performance than the counterparts with liquid electrolyte. Our designed PVDF-HFP/LATP composite can be a promising electrolyte for next-generation solid-state batteries with high cycling stability. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Optimization of Pore Structure of Cathodic Carbon Supports for Solvate Ionic Liquid Electrolytes Based Lithium-Sulfur Batteries.

PubMed

Zhang, Shiguo; Ikoma, Ai; Li, Zhe; Ueno, Kazuhide; Ma, Xiaofeng; Dokko, Kaoru; Watanabe, Masayoshi

2016-10-04

Lithium-sulfur (Li-S) batteries are a promising energy-storage technology owing to their high theoretical capacity and energy density. However, their practical application remains a challenge because of the serve shuttle effect caused by the dissolution of polysulfides in common organic electrolytes. Polysulfide-insoluble electrolytes, such as solvate ionic liquids (ILs), have recently emerged as alternative candidates and shown great potential in suppressing the shuttle effect and improving the cycle stability of Li-S batteries. Redox electrochemical reactions in polysulfide-insoluble electrolytes occur via a solid-state process at the interphase between the electrolyte and the composite cathode; therefore, creating an appropriate interface between sulfur and a carbon support is of great importance. Nevertheless, the porous carbon supports established for conventional organic electrolytes may not be suitable for polysulfide-insoluble electrolytes. In this work, we investigated the effect of the porous structure of carbon materials on the Li-S battery performance in polysulfide-insoluble electrolytes using solvate ILs as a model electrolyte. We determined that the pore volume (rather than the surface area) exerts a major influence on the discharge capacity of S composite cathodes. In particular, inverse opal carbons with three-dimensionally ordered interconnected macropores and a large pore volume deliver the highest discharge capacity. The battery performance in both polysulfide-soluble electrolytes and solvate ILs was used to study the effect of electrolytes. We propose a plausible mechanism to explain the different porous structure requirements in polysulfide-soluble and polysulfide-insoluble electrolytes.

High Performance Solid Polymer Electrolytes for Rechargeable Batteries: A Self-Catalyzed Strategy toward Facile Synthesis.

PubMed

Cui, Yanyan; Liang, Xinmiao; Chai, Jingchao; Cui, Zili; Wang, Qinglei; He, Weisheng; Liu, Xiaochen; Liu, Zhihong; Cui, Guanglei; Feng, Jiwen

2017-11-01

It is urgent to seek high performance solid polymer electrolytes (SPEs) via a facile chemistry and simple process. The lithium salts are composed of complex anions that are stabilized by a Lewis acid agent. This Lewis acid can initiate the ring opening polymerization. Herein, a self-catalyzed strategy toward facile synthesis of crosslinked poly(ethylene glycol) diglycidyl ether-based solid polymer electrolyte (C-PEGDE) is presented. It is manifested that the poly(ethylene glycol) diglycidyl ether-based solid polymer electrolyte possesses a superior electrochemical stability window up to 4.5 V versus Li/Li + and considerable ionic conductivity of 8.9 × 10 -5 S cm -1 at ambient temperature. Moreover, the LiFePO 4 /C-PEGDE/Li batteries deliver stable charge/discharge profiles and considerable rate capability. It is demonstrated that this self-catalyzed strategy can be a very effective approach for high performance solid polymer electrolytes.

Coordination chemistry in magnesium battery electrolytes: how ligands affect their performance.

PubMed

Shao, Yuyan; Liu, Tianbiao; Li, Guosheng; Gu, Meng; Nie, Zimin; Engelhard, Mark; Xiao, Jie; Lv, Dongping; Wang, Chongmin; Zhang, Ji-Guang; Liu, Jun

2013-11-04

Magnesium battery is potentially a safe, cost-effective, and high energy density technology for large scale energy storage. However, the development of magnesium battery has been hindered by the limited performance and the lack of fundamental understandings of electrolytes. Here, we present a study in understanding coordination chemistry of Mg(BH₄)₂ in ethereal solvents. The O donor denticity, i.e. ligand strength of the ethereal solvents which act as ligands to form solvated Mg complexes, plays a significant role in enhancing coulombic efficiency of the corresponding solvated Mg complex electrolytes. A new electrolyte is developed based on Mg(BH₄)₂, diglyme and LiBH₄. The preliminary electrochemical test results show that the new electrolyte demonstrates a close to 100% coulombic efficiency, no dendrite formation, and stable cycling performance for Mg plating/stripping and Mg insertion/de-insertion in a model cathode material Mo₆S₈ Chevrel phase.

Optimized Carbonate and Ester-Based Li-Ion Electrolytes

NASA Technical Reports Server (NTRS)

Smart, Marshall; Bugga, Ratnakumar

2008-01-01

To maintain high conductivity in low temperatures, electrolyte co-solvents have been designed to have a high dielectric constant, low viscosity, adequate coordination behavior, and appropriate liquid ranges and salt solubilities. Electrolytes that contain ester-based co-solvents in large proportion (greater than 50 percent) and ethylene carbonate (EC) in small proportion (less than 20 percent) improve low-temperature performance in MCMB carbon-LiNiCoO2 lithium-ion cells. These co-solvents have been demonstrated to enhance performance, especially at temperatures down to 70 C. Low-viscosity, ester-based co-solvents were incorporated into multi-component electrolytes of the following composition: 1.0 M LiPF6 in ethylene carbonate (EC) + ethyl methyl carbonate (EMC) + X (1:1:8 volume percent) [where X = methyl butyrate (MB), ethyl butyrate EB, methyl propionate (MP), or ethyl valerate (EV)]. These electrolyte formulations result in improved low-temperature performance of lithium-ion cells, with dramatic results at temperatures below 40 C.

Coordination Chemistry in magnesium battery electrolytes: how ligands affect their performance

DOE PAGES

Shao, Yuyan; Liu, Tianbiao L.; Li, Guosheng; ...

2013-11-04

Magnesium battery is potentially a safe, cost-effective, and high energy density technology for large scale energy storage. However, the development of magnesium battery has been hindered by the limited performance and the lack of fundamental understandings of electrolytes. Here, we present a coordination chemistry study of Mg(BH 4) 2 in ethereal solvents. The O donor denticity, i.e. ligand strength of the ethereal solvents which act as ligands to form solvated Mg complexes, plays a significant role in enhancing coulombic efficiency of the corresponding solvated Mg complex electrolytes. A new and safer electrolyte is developed based on Mg(BH4)2, diglyme and optimizedmore » LiBH4 additive. The new electrolyte demonstrates 100% coulombic efficiency, no dendrite formation, and stable cycling performance with the cathode capacity retention of ~90% for 300 cycles in a prototype magnesium battery.« less

Fire-extinguishing organic electrolytes for safe batteries

NASA Astrophysics Data System (ADS)

Wang, Jianhui; Yamada, Yuki; Sodeyama, Keitaro; Watanabe, Eriko; Takada, Koji; Tateyama, Yoshitaka; Yamada, Atsuo

2018-01-01

Severe safety concerns are impeding the large-scale employment of lithium/sodium batteries. Conventional electrolytes are highly flammable and volatile, which may cause catastrophic fires or explosions. Efforts to introduce flame-retardant solvents into the electrolytes have generally resulted in compromised battery performance because those solvents do not suitably passivate carbonaceous anodes. Here we report a salt-concentrated electrolyte design to resolve this dilemma via the spontaneous formation of a robust inorganic passivation film on the anode. We demonstrate that a concentrated electrolyte using a salt and a popular flame-retardant solvent (trimethyl phosphate), without any additives or soft binders, allows stable charge-discharge cycling of both hard-carbon and graphite anodes for more than 1,000 cycles (over one year) with negligible degradation; this performance is comparable or superior to that of conventional flammable carbonate electrolytes. The unusual passivation character of the concentrated electrolyte coupled with its fire-extinguishing property contributes to developing safe and long-lasting batteries, unlocking the limit toward development of much higher energy-density batteries.

Capacitance enhancement of polyaniline coated curved-graphene supercapacitors in a redox-active electrolyte

NASA Astrophysics Data System (ADS)

Chen, Wei; Rakhi, R. B.; Alshareef, H. N.

2013-05-01

We show, for the first time, a redox-active electrolyte in combination with a polyaniline-coated curved graphene active material to achieve significant enhancement in the capacitance (36-92% increase) compared to supercapacitors that lack the redox-active contribution from the electrolyte. The supercapacitors based on the redox-active electrolyte also exhibit excellent rate capability and very long cycling performance (>50 000 cycles).We show, for the first time, a redox-active electrolyte in combination with a polyaniline-coated curved graphene active material to achieve significant enhancement in the capacitance (36-92% increase) compared to supercapacitors that lack the redox-active contribution from the electrolyte. The supercapacitors based on the redox-active electrolyte also exhibit excellent rate capability and very long cycling performance (>50 000 cycles). Electronic supplementary information (ESI) available: Experimental section, supporting figures including SEM, TEM, XPS, BET, CV and CD curves and a summary table of capacitance. See DOI: 10.1039/c3nr00773a

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.

Molten salt electrolyte separator

DOEpatents

Kaun, Thomas D.

1996-01-01

A molten salt electrolyte/separator for battery and related electrochemical systems including a molten electrolyte composition and an electrically insulating solid salt dispersed therein, to provide improved performance at higher current densities and alternate designs through ease of fabrication.

Electrolyte formulations

DOEpatents

Zhu, Ye; Strand, Deidre; Cheng, Gang

2018-05-29

An electrochemical cell including a silicon-based anode and an electrolyte, where the electrolyte is formulated to contain solvents having cyclic sulfone or cyclic sulfite chemical structure. Specific additional solvent and salt combinations yield superior performance in these electrochemical cells.

Effects of a Carbohydrate-Electrolyte Drink on Specific Soccer Tests and Performance

PubMed Central

Ostojic, Sergej M.; Mazic, Sanja

2002-01-01

The aim of this study was to examine the effects of a carbohydrate-electrolyte drink on specific soccer tests and performance. Twenty-two professional male soccer players volunteered to participate in the study. The players were allocated to two assigned trials ingesting carbohydrate-electrolyte drink (7% carbohydrates, sodium 24 mmol.l-1, chloride 12 mmol.l-1, potassium 3 mmol.l-1) or placebo during a 90 min on-field soccer match. The trials were matched for subjects’ age, weight, height and maximal oxygen uptake. Immediately after the match, players completed four soccer-specific skill tests. Blood glucose concentration [mean (SD)] was higher at the end of the match-play in the carbohydrate-electrolyte trial than in the placebo trial (4.4 (0.3) vs. 4.0 (0.3) mmol.l-1, P < 0.05). Subjects in the carbohydrate-electrolyte trial finished the specific dribble test faster in comparison with subjects in the placebo trial (12.9 (0.4) vs. 13.6 (0.5) s, P < 0.05). Ratings of the precision test were higher in the carbohydrate-electrolyte trial as compared to the placebo trial (17.2 (4.8) vs. 15.1 (5.2), P < 0.05) but there were no differences in coordination test and power test results between trials. The main finding of the present study indicates that supplementation with carbohydrate-electrolyte solution improved soccer-specific skill performance and recovery after an on-field soccer match compared with ingestion of placebo. This suggests that soccer players should consume carbohydrate-electrolyte fluid throughout a game to help prevent deterioration in specific skill performance. PMID:24688270

Influence of Silicate Concentration in Electrolyte on the Growth and Performance of Plasma Electrolytic Oxidation Coatings Prepared on Low Carbon Steel

NASA Astrophysics Data System (ADS)

Yang, Wenbin; Peng, Zhenjun; Liu, Baixing; Liu, Weimin; Liang, Jun

2018-04-01

Plasma electrolytic oxidation (PEO) coatings were prepared on low carbon steel from electrolytes with different silicate concentrations. The microstructure, elemental and phase compositions of the PEO coatings were analyzed by scanning electron microscope, energy-dispersive spectrometer, and x-ray diffraction, respectively. The adhesion of PEO coatings with low carbon steel substrate was qualitatively examined by thermal shock tests. The tribological properties were evaluated by a reciprocating tribometer sliding against a Si3N4 ceramic ball. The corrosion behaviors of PEO coatings were investigated in 3.5 wt.% NaCl solution by electrochemical impedance spectra and potentiodynamic polarization. Results indicated that all the PEO coatings were comprised of amorphous SiO2 and Fe-containing oxides; however, the silicate concentration in electrolyte showed significant influence on the growth and the performance of PEO coatings. The PEO coating prepared from the electrolyte with silicate concentration of 30 g/L had the highest Fe content because the substrate was more readily oxidized and showed a dense structure, resulting in the best comprehensive performance of adhesion, wear resistance, and corrosion resistance.

Influence of Silicate Concentration in Electrolyte on the Growth and Performance of Plasma Electrolytic Oxidation Coatings Prepared on Low Carbon Steel

NASA Astrophysics Data System (ADS)

Yang, Wenbin; Peng, Zhenjun; Liu, Baixing; Liu, Weimin; Liang, Jun

2018-05-01

Plasma electrolytic oxidation (PEO) coatings were prepared on low carbon steel from electrolytes with different silicate concentrations. The microstructure, elemental and phase compositions of the PEO coatings were analyzed by scanning electron microscope, energy-dispersive spectrometer, and x-ray diffraction, respectively. The adhesion of PEO coatings with low carbon steel substrate was qualitatively examined by thermal shock tests. The tribological properties were evaluated by a reciprocating tribometer sliding against a Si3N4 ceramic ball. The corrosion behaviors of PEO coatings were investigated in 3.5 wt.% NaCl solution by electrochemical impedance spectra and potentiodynamic polarization. Results indicated that all the PEO coatings were comprised of amorphous SiO2 and Fe-containing oxides; however, the silicate concentration in electrolyte showed significant influence on the growth and the performance of PEO coatings. The PEO coating prepared from the electrolyte with silicate concentration of 30 g/L had the highest Fe content because the substrate was more readily oxidized and showed a dense structure, resulting in the best comprehensive performance of adhesion, wear resistance, and corrosion resistance.

Improved Wide Operating Temperature Range of LiNiCoAiO2-based Li-ion Cells with Methyl Propionate-based Electrolytes

NASA Technical Reports Server (NTRS)

Smart, Marshall C.; Tomcsi, Michael R.; Hwang, C.; Whitcanack, L. D.; Bugga, Ratnakumar V.; Nagata, Mikito; Visco, Vince; Tsukamoto, Hisashi

2012-01-01

Demonstration of wide operating temperature range Li-ion electrolytes Methyl propionate-based wide operating temperature range electrolytes were demonstrated to provide dramatic improvement of the low temperature capability of Quallion prototype Li-ion cells (MCMB-LiNiCoAlO2). Some formulations were observed to deliver over 60% of the room temperature capacity using a 5C rate at - 40oC !! Represents over a 4-fold improvement over the baseline electrolyte system. Demonstrated operational capability of a number of systems over a wide temperature range (-40 to +70 C) Demonstrated reasonably good long term cycle life performance at high temperature (i.e., at +40deg and +50 C) A number of formulations containing electrolytes additives (i.e., FEC, VC, LiBOB, and lithium oxalate) have been shown to have enhanced lithium kinetics at low temperature and promising high temperature resilience. Demonstrated good performance in larger capacity (12 Ah) Quallion Li-ion cells with methyl propionate-based electrolytes. Current efforts focused upon performing life studies and the impact upon low temperature capability.

Applications of laser-induced breakdown spectroscopy in the aluminum electrolysis industry

NASA Astrophysics Data System (ADS)

Sun, Lanxiang; Yu, Haibin; Cong, Zhibo; Lu, Hui; Cao, Bin; Zeng, Peng; Dong, Wei; Li, Yang

2018-04-01

The industrial aluminum reduction cell is an electrochemistry reactor that operates under high temperatures and corrosive conditions. Monitoring the molten aluminum and electrolyte components is very important for controlling the chemical reaction process. Due to the lack of fast methods to monitor the components, controlling aluminum reduction cells is difficult. In this work, laser-induced breakdown spectroscopy (LIBS) was applied to aluminum electrolysis. A new method for calculating the molecular ratio, which is an important control parameter that represents the acidity of the electrolyte, was proposed. Experiments were first performed on solid electrolyte samples to test the performance of the proposed method. Using this method, the average relative standard deviation (RSD) of the molecular ratio measurement was 0.39%, and the average root mean square error (RMSE) was 0.0236. These results prove that LIBS can accurately measure the molecular ratio. Then, in situ measurements of the molten aluminum and electrolyte were performed in industrial aluminum induction cells using the developed LIBS equipment. The spectra of the molten electrolyte were successfully obtained and were consistent with the spectra of the solid electrolyte.

The Evaluation of Triphenyl Phosphate as a Flame Retardant Additive to Improve the Safety of Lithium-Ion Battery Electrolytes

NASA Technical Reports Server (NTRS)

Smart, M. C.; Krause, F. C.; Hwang, C.; West, W. C.; Soler, J.; Prakash, G. K. S.; Ratnakumar, B. V.

2011-01-01

With the intent of improving the safety characteristics of lithium ion cells, electrolytes containing flame retardant additives have been investigated. A number of triphenyl phosphate-containing electrolytes were evaluated in both coin cells and experimental three electrode lithium-ion cells (containing reference electrodes). A number of chemistries were investigated, including MCMB carbon/LiNi(0.8)Co(0.2)O2 (NCO), graphite/LiNi(0.8)Co(0.15)Al(0.05)O2 (NCA), Li/Li(Li(0.17)Ni(0.25)Mn(0.58))O2, Li/LiNiMnCoO2 (NMC) and graphite/LiNiMnCoO2 (NMC), to study the effect that different electrolyte compositions have upon performance. A wide range of TPP-containing electrolytes were demonstrated to have good compatibility with the C/NCO, C/NCA, and Li/NMC systems, however, poor performance was initially observed with the high voltage C/NMC system. This necessitated the development of improved electrolytes with stabilizing additives, leading to formulations containing lithium bis(oxalato)borate (LiBOB) that displayed substantially improved performance.

Performance Characteristics of Lithium Ion Polymeric Electrolyte Cells

NASA Technical Reports Server (NTRS)

Shen, D.; Nagasubramanian, G.; Huang, C-K.; Surampudi, S.; Halpert, G.

1994-01-01

A series of polyacrylonitrile-based (PAN) electrolytes containing LiAsF6 and a number of solvent mixtures including ethylene carbonate (EC) + propylene carbonate (PC) were prepared, electrochemically evaluated and used as electrolyte in the polymer cells.

Low temperature electrolytes for lithium/silver vanadium oxide cells

NASA Technical Reports Server (NTRS)

Tuhovak, Denise R.; Takeuchi, Esther S.

1991-01-01

Combinations of methyl formate (MF) and propylene carbonate (PC) using salt concentrations of 0.6 to 2.4 M, with lithium hexafluoroarsenate and lithium tetrafluoroborate in a five to one molar ratio, were investigated as electrolytes in lithium/silver vanadium oxide batteries. The composition of the electrolyte affected cell performance at low temperature, self-discharge and abuse resistance as characterized by short circuit and crush testing. The electrolyte that provided the best combination of good low temperature performance, low cell self-discharge and abuse resistance was 0.6 M salt in 10:90 PC/MF.

High-performance solid polymer electrolytes for lithium batteries operational at ambient temperature

NASA Astrophysics Data System (ADS)

Mindemark, Jonas; Sun, Bing; Törmä, Erik; Brandell, Daniel

2015-12-01

Incorporation of carbonate repeating units in a poly(ε-caprolactone) (PCL) backbone used as a host material in solid polymer electrolytes is found to not only suppress crystallinity in the polyester material, but also give higher ionic conductivity in a wide temperature range exceeding the melting point of PCL crystallites. Combined with high cation transference numbers, this electrolyte material has sufficient lithium transport properties to be used in battery cells that are operational at temperatures down to below 23 °C, thus clearly demonstrating the potential of using non-polyether electrolytes in high-performance all-solid lithium polymer batteries.

Maximum a posteriori Bayesian estimation of mycophenolic Acid area under the concentration-time curve: is this clinically useful for dosage prediction yet?

PubMed

Staatz, Christine E; Tett, Susan E

2011-12-01

This review seeks to summarize the available data about Bayesian estimation of area under the plasma concentration-time curve (AUC) and dosage prediction for mycophenolic acid (MPA) and evaluate whether sufficient evidence is available for routine use of Bayesian dosage prediction in clinical practice. A literature search identified 14 studies that assessed the predictive performance of maximum a posteriori Bayesian estimation of MPA AUC and one report that retrospectively evaluated how closely dosage recommendations based on Bayesian forecasting achieved targeted MPA exposure. Studies to date have mostly been undertaken in renal transplant recipients, with limited investigation in patients treated with MPA for autoimmune disease or haematopoietic stem cell transplantation. All of these studies have involved use of the mycophenolate mofetil (MMF) formulation of MPA, rather than the enteric-coated mycophenolate sodium (EC-MPS) formulation. Bias associated with estimation of MPA AUC using Bayesian forecasting was generally less than 10%. However some difficulties with imprecision was evident, with values ranging from 4% to 34% (based on estimation involving two or more concentration measurements). Evaluation of whether MPA dosing decisions based on Bayesian forecasting (by the free website service https://pharmaco.chu-limoges.fr) achieved target drug exposure has only been undertaken once. When MMF dosage recommendations were applied by clinicians, a higher proportion (72-80%) of subsequent estimated MPA AUC values were within the 30-60 mg · h/L target range, compared with when dosage recommendations were not followed (only 39-57% within target range). Such findings provide evidence that Bayesian dosage prediction is clinically useful for achieving target MPA AUC. This study, however, was retrospective and focussed only on adult renal transplant recipients. Furthermore, in this study, Bayesian-generated AUC estimations and dosage predictions were not compared with a later full measured AUC but rather with a further AUC estimate based on a second Bayesian analysis. This study also provided some evidence that a useful monitoring schedule for MPA AUC following adult renal transplant would be every 2 weeks during the first month post-transplant, every 1-3 months between months 1 and 12, and each year thereafter. It will be interesting to see further validations in different patient groups using the free website service. In summary, the predictive performance of Bayesian estimation of MPA, comparing estimated with measured AUC values, has been reported in several studies. However, the next step of predicting dosages based on these Bayesian-estimated AUCs, and prospectively determining how closely these predicted dosages give drug exposure matching targeted AUCs, remains largely unaddressed. Further prospective studies are required, particularly in non-renal transplant patients and with the EC-MPS formulation. Other important questions remain to be answered, such as: do Bayesian forecasting methods devised to date use the best population pharmacokinetic models or most accurate algorithms; are the methods simple to use for routine clinical practice; do the algorithms actually improve dosage estimations beyond empirical recommendations in all groups that receive MPA therapy; and, importantly, do the dosage predictions, when followed, improve patient health outcomes?

Effect of The Addition of PEG and PVA Polymer for Gel Electrolytes in Dye-Sensitized Solar Cell (DSSC) with Chlorophyll as Dye Sensitizer

NASA Astrophysics Data System (ADS)

Seni, Ramadhanti S.; Puspitasari, Nurrisma; Endarko

2017-07-01

Dye-sensitized Solar Cell (DSSC) is a third-generation solar cell that consists of a working electrode, electrolyte and counter electrode. One of the most important parts of DSSC is an electrolyte that roles as a medium and regenerates the electron transport of electrons in the dye. However, the liquid electrolyte has a lack of stability in long-term use and easily evaporate or leak in DSSC. Therefore, this study aims to investigate an effect of the addition of polymer material such as PEG 1000, 4000 and PVA 60000 for fabricating a gel electrolyte to solve the problems of liquid electrolyte. The synthesized TiO2 nanoparticles used in this study was prepared using co-precipitation (CPT) method which produces TiO2 anatase phase with a crystal size of 11.1 nm. DSSC has been successfully conducted and analyzed to evaluate its performance. The results showed that the efficiency of DSSC cells using gel electrolyte prepared with PVA 60000 was better than a liquid electrolyte, PEG 1000, 4000, with the efficiency could be obtained at 0.083, 0.018, 0.033, and 0.054%, respectively. The results demonstrated that the addition PEG and/or PVA could be enhanced the performance of DSSC due to gel electrolyte produced current and voltage more stable compared to the liquid electrolyte.

High Voltage LiNi0.5Mn1.5O4/Li4Ti5O12 Lithium Ion Cells at Elevated Temperatures: Carbonate- versus Ionic Liquid-Based Electrolytes.

PubMed

Cao, Xia; He, Xin; Wang, Jun; Liu, Haidong; Röser, Stephan; Rad, Babak Rezaei; Evertz, Marco; Streipert, Benjamin; Li, Jie; Wagner, Ralf; Winter, Martin; Cekic-Laskovic, Isidora

2016-10-05

Thanks to its high operating voltage, the LiNi 0.5 Mn 1.5 O 4 (LNMO) spinel represents a promising next-generation cathode material candidate for Lithium ion batteries. However, LNMO-based full-cells with organic carbonate solvent electrolytes suffer from severe capacity fading issues, associated with electrolyte decomposition and concurrent degradative reactions at the electrode/electrolyte interface, especially at elevated temperatures. As promising alternatives, two selected LiTFSI/pyrrolidinium bis(trifluoromethane-sulfonyl)imide room temperature ionic liquid (RTIL) based electrolytes with inherent thermal stability were investigated in this work. Linear sweep voltammetry (LSV) profiles of the investigated LiTFSI/RTIL electrolytes display much higher oxidative stability compared to the state-of-the-art LiPF 6 /organic carbonate based electrolyte at elevated temperatures. Cycling performance of the LNMO/Li 4 Ti 5 O 12 (LTO) full-cells with LiTFSI/RTIL electrolytes reveals remarkable improvements with respect to capacity retention and Coulombic efficiency. Scanning electron microscopy (SEM) images and X-ray diffraction (XRD) patterns indicate maintained pristine morphology and structure of LNMO particles after 50 cycles at 0.5C. The investigated LiTFSI/RTIL based electrolytes outperform the LiPF 6 /organic carbonate-based electrolyte in terms of cycling performance in LNMO/LTO full-cells at elevated temperatures.

Low temperature solid oxide electrolytes (LT-SOE): A review

NASA Astrophysics Data System (ADS)

Singh, B.; Ghosh, S.; Aich, S.; Roy, B.

2017-01-01

Low temperature solid oxide fuel cell (LT-SOFC) can be a source of power for vehicles, online grid, and at the same time reduce system cost, offer high reliability, and fast start-up. A huge amount of research work, as evident from the literature has been conducted for the enhancement of the ionic conductivity of LT electrolytes in the last few years. The basic conduction mechanisms, advantages and disadvantages of different LT oxide ion conducting electrolytes {BIMEVOX systems, bilayer systems including doped cerium oxide/stabilised bismuth oxide and YSZ/DCO}, mixed ion conducting electrolytes {doped cerium oxides/alkali metal carbonate composites}, and proton conducting electrolytes {doped and undoped BaCeO3, BaZrO3, etc.} are discussed here based on the recent research articles. Effect of various material aspects (composition, doping, layer thickness, etc.), fabrication methods (to achieve different microstructures and particle size), design related strategies (interlayer, sintering aid etc.), characterization temperature & environment on the conductivity of the electrolytes and performance of the fuel cells made from these electrolytes are shown in tabular form and discussed. The conductivity of the electrolytes and performance of the corresponding fuel cells are compared. Other applications of the electrolytes are mentioned. A few considerations regarding the future prospects are pointed.

Multifunctional Sandwich‐Structured Electrolyte for High‐Performance Lithium–Sulfur Batteries

PubMed Central

Qu, Hongtao; Zhang, Jianjun; Du, Aobing; Chen, Bingbing; Chai, Jingchao; Xue, Nan; Wang, Longlong; Qiao, Lixin; Wang, Chen; Zang, Xiao; Yang, Jinfeng; Wang, Xiaogang

2018-01-01

Abstract Due to its high theoretical energy density (2600 Wh kg−1), low cost, and environmental benignity, the lithium–sulfur (Li‐S) battery is attracting strong interest among the various electrochemical energy storage systems. However, its practical application is seriously hampered by the so‐called shuttle effect of the highly soluble polysulfides. Herein, a novel design of multifunctional sandwich‐structured polymer electrolyte (polymer/cellulose nonwoven/nanocarbon) for high‐performance Li‐S batteries is demonstrated. It is verified that Li‐S battery with this sandwich‐structured polymer electrolyte delivers excellent cycling stability (only 0.039% capacity decay cycle−1 on average exceeding 1500 cycles at 0.5 C) and rate capability (with a reversible capacity of 594 mA h g−1 at 4 C). These electrochemical performances are attributed to the synergistic effect of each layer in this unique sandwich‐structured polymer electrolyte including steady lithium stripping/plating, strong polysulfide absorption ability, and increased redox reaction sites. More importantly, even with high sulfur loading of 4.9 mg cm−2, Li‐S battery with this sandwich‐structured polymer electrolyte can deliver high initial areal capacity of 5.1 mA h cm−2. This demonstrated strategy here may open up a new era of designing hierarchical structured polymer electrolytes for high‐performance Li‐S batteries. PMID:29593953

Electrode-Electrolyte Interfaces in Lithium-Sulfur Batteries with Liquid or Inorganic Solid Electrolytes.

PubMed

Yu, Xingwen; Manthiram, Arumugam

2017-11-21

Electrode-electrolyte interfacial properties play a vital role in the cycling performance of lithium-sulfur (Li-S) batteries. The issues at an electrode-electrolyte interface include electrochemical and chemical reactions occurring at the interface, formation mechanism of interfacial layers, compositional/structural characteristics of the interfacial layers, ionic transport across the interface, and thermodynamic and kinetic behaviors at the interface. Understanding the above critical issues is paramount for the development of strategies to enhance the overall performance of Li-S batteries. Liquid electrolytes commonly used in Li-S batteries bear resemblance to those employed in traditional lithium-ion batteries, which are generally composed of a lithium salt dissolved in a solvent matrix. However, due to a series of unique features associated with sulfur or polysulfides, ether-based solvents are generally employed in Li-S batteries rather than simply adopting the carbonate-type solvents that are generally used in the traditional Li + -ion batteries. In addition, the electrolytes of Li-S batteries usually comprise an important additive, LiNO 3 . The unique electrolyte components of Li-S batteries do not allow us to directly take the interfacial theories of the traditional Li + -ion batteries and apply them to Li-S batteries. On the other hand, during charging/discharging a Li-S battery, the dissolved polysulfide species migrate through the battery separator and react with the Li anode, which magnifies the complexity of the interfacial problems of Li-S batteries. However, current Li-S battery development paths have primarily been energized by advances in sulfur cathodes. Insight into the electrode-electrolyte interfacial behaviors has relatively been overshadowed. In this Account, we first examine the state-of-the-art contributions in understanding the solid-electrolyte interphase (SEI) formed on the Li-metal anode and sulfur cathode in conventional liquid-electrolyte Li-S batteries and how the resulting chemical and physical properties of the SEI affect the overall battery performance. A few strategies recently proposed for improving the stability of SEI are briefly summarized. Solid Li + -ion conductive electrolytes have been attempted for the development of Li-S batteries to eliminate the polysulfide shuttle issues. One approach is based on a concept of "all-solid-state Li-S battery," in which all the cell components are in the solid state. Another approach is based on a "hybrid-electrolyte Li-S battery" concept, in which the solid electrolyte plays roles both as a Li + -ion conductor for the electrochemical reaction and as a separator to prevent polysulfide shuttle. However, these endeavors with the solid electrolyte are not able to provide an overall satisfactory cell performance. In addition to the low ionic conductivity of solid-state electrolytes, a critical issue lies in the poor interfacial properties between the electrode and the solid electrolyte. This Account provides a survey of the relevant research progress in understanding and manipulating the interfaces of electrode and solid electrolytes in both the "all-solid-state Li-S batteries" and the "hybrid-electrolyte Li-S batteries". A recently proposed "semi-solid-state Li-S battery" concept is also briefly discussed. Finally, future research and development directions in all the above areas are suggested.

Molten salt electrolyte separator

DOEpatents

Kaun, T.D.

1996-07-09

The patent describes a molten salt electrolyte/separator for battery and related electrochemical systems including a molten electrolyte composition and an electrically insulating solid salt dispersed therein, to provide improved performance at higher current densities and alternate designs through ease of fabrication. 5 figs.

Investigation of a novel ternary electrolyte based on dimethyl sulfite and lithium difluoromono(oxalato)borate for lithium ion batteries

NASA Astrophysics Data System (ADS)

Chen, Renjie; Zhu, Lu; Wu, Feng; Li, Li; Zhang, Rong; Chen, Shi

2014-01-01

Lithium difluoromono(oxalato)borate (LiODFB) has been used as a novel lithium salt for battery in recent studies. In this study, a series of novel electrolytes has been prepared by adding 30 vol% dimethyl sulfite (DMS) or dimethyl carbonate (DMC) as co-solvent into an ethylene carbonate (EC)/ethyl methyl carbonate (EMC) + LiX mixture, in which the LiX could be LiClO4, LiODFB, LiBOB, LiTFSI, or LiCF3SO3. These ternary electrolytes have been investigated for use in lithium ion batteries. FT-IR spectroscopy analysis shows that characteristic functional groups (-CO3, -SO3) undergo red-shift or blue-shift with the addition of different lithium salts. The LiODFB-EC/EMC/DMS electrolyte exhibits high ionic conductivity, which is mainly because of the low melting point of DMS, and LiODFB possessing high solubility. The Li/MCMB cells containing this novel electrolyte exhibit high capacities, good cycling performance, and excellent rate performance. These performances are probably because both LiODFB and DMS can assist in the formation of SEI films by reductive decomposition. Additionally, the discharge capacity of Li/LiCoO2 half cell containing LiODFB-EC/EMC/DMS electrolyte is 130.9 mAh g-1 after 50 cycles, and it is very comparable with the standard-commercial electrolyte. The results show that this study produces a promising electrolyte candidate for lithium ion batteries.

Organic solvents, electrolytes, and lithium ion cells with good low temperature performance

NASA Technical Reports Server (NTRS)

Huang, Chen-Kuo (Inventor); Smart, Marshall C. (Inventor); Surampudi, Subbarao (Inventor); Bugga, Ratnakumar V. (Inventor)

2002-01-01

Multi-component organic solvent systems, electrolytes and electrochemical cells characterized by good low temperature performance are provided. In one embodiment, an improved organic solvent system contains a ternary mixture of ethylene carbonate, dimethyl carbonate and diethyl carbonate. In other embodiments, quaternary systems include a fourth component, i.e, an aliphatic ester, an asymmetric alkyl carbonate or a compound of the formula LiOX, where X is R, COOR, or COR, where R is alkyl or fluoroalkyl. Electrolytes based on such organic solvent systems are also provided and contain therein a lithium salt of high ionic mobility, such as LiPF.sub.6. Reversible electrochemical cells, particularly lithium ion cells, are constructed with the improved electrolytes, and preferably include a carbonaceous anode, an insertion type cathode, and an electrolyte interspersed therebetween.

Symposium on Rechargeable Lithium Batteries, Hollywood, FL, Oct. 19-24, 1989, Proceedings

NASA Technical Reports Server (NTRS)

Subbarao, S. (Editor); Koch, V. R. (Editor); Owens, B. B. (Editor); Smyrl, W. H. (Editor)

1990-01-01

Recent advances in the technology and applications of rechargeable Li cells are discussed in reviews and reports. A general overview of the field is provided, and sections are devoted to organic electrolyte systems, polymeric electrolyte systems, inorganic electrolytes systems, and molten-salt electrolytes. Particular attention is given to electrolyte stabilization, the effects of organic additives on electrolyte performance, a cycle-life sensor, consumer-product applications, in situ measurements of gas evolution in Li secondary cells, ultrathin polymer cathodes, electrochemical growth of conducting polymers, and sealing Li/FeS(x) cells for a bipolar battery.

Stability of the Solid Electrolyte Interface on the Li Electrode in Li–S Batteries

DOE PAGES

Zheng, Dong; Yang, Xiao-Qing; Qu, Deyang

2016-04-05

In this study, by means of high performance liquid chromatography–mass spectroscopy, the concentration of sulfur and polysulfides was determined in nonaqueous electrolytes. The stability of sulfur and Li in eight electrolytes was studied quantitatively. It was found that sulfur reacted with Li in most of the commonly used electrolytes for lithium–sulfur batteries. The reaction products between sulfur and Li were qualitatively identified. In some cases, the solid electrolyte interface on the Li can successfully prevent the interaction between S and Li; however, it was found that the solid electrolyte interface was damaged by polysulfide ions.

New Solid Polymer Electrolytes for Improved Lithium Batteries

NASA Technical Reports Server (NTRS)

Hehemann, David G.

2002-01-01

The objective of this work was to identify, synthesize and incorporate into a working prototype, next-generation solid polymer electrolytes, that allow our pre-existing solid-state lithium battery to function better under extreme conditions. We have synthesized polymer electrolytes in which emphasis was placed on the temperature-dependent performance of these candidate electrolytes. This project was designed to produce and integrate novel polymer electrolytes into a lightweight thin-film battery that could easily be scaled up for mass production and adapted to different applications.

High Performance Solid Polymer Electrolytes for Rechargeable Batteries: A Self‐Catalyzed Strategy toward Facile Synthesis

PubMed Central

Cui, Yanyan; Liang, Xinmiao; Chai, Jingchao; Cui, Zili; Wang, Qinglei; He, Weisheng; Liu, Xiaochen; Feng, Jiwen

2017-01-01

Abstract It is urgent to seek high performance solid polymer electrolytes (SPEs) via a facile chemistry and simple process. The lithium salts are composed of complex anions that are stabilized by a Lewis acid agent. This Lewis acid can initiate the ring opening polymerization. Herein, a self‐catalyzed strategy toward facile synthesis of crosslinked poly(ethylene glycol) diglycidyl ether‐based solid polymer electrolyte (C‐PEGDE) is presented. It is manifested that the poly(ethylene glycol) diglycidyl ether‐based solid polymer electrolyte possesses a superior electrochemical stability window up to 4.5 V versus Li/Li+ and considerable ionic conductivity of 8.9 × 10−5 S cm−1 at ambient temperature. Moreover, the LiFePO4/C‐PEGDE/Li batteries deliver stable charge/discharge profiles and considerable rate capability. It is demonstrated that this self‐catalyzed strategy can be a very effective approach for high performance solid polymer electrolytes. PMID:29201612

Primary and Secondary Lithium Batteries Capable of Operating at Low Temperatures for Planetary Exploration

NASA Technical Reports Server (NTRS)

Smart, M. C.; Ratnakumar, B. V.; West, W. C.; Brandon, E. J.

2011-01-01

Objectives and Approach: (1) Develop advanced Li ]ion electrolytes that enable cell operation over a wide temperature range (i.e., -60 to +60 C). Improve the high temperature stability and lifetime characteristics of wide operating temperature electrolytes. (2) Define the performance limitations at low and high temperature extremes, as well as, life limiting processes. (3) Demonstrate the performance of advanced electrolytes in large capacity prototype cells.

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.

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

Electrodeposition of polymer electrolyte in nanostructured electrodes for enhanced electrochemical performance of thin-film Li-ion microbatteries

NASA Astrophysics Data System (ADS)

Salian, Girish D.; Lebouin, Chrystelle; Demoulin, A.; Lepihin, M. S.; Maria, S.; Galeyeva, A. K.; Kurbatov, A. P.; Djenizian, Thierry

2017-02-01

We report that electrodeposition of polymer electrolyte in nanostructured electrodes has a strong influence on the electrochemical properties of thin-film Li-ion microbatteries. Electropolymerization of PMMA-PEG (polymethyl methacrylate-polyethylene glycol) was carried out on both the anode (self-supported titania nanotubes) and the cathode (porous LiNi0.5Mn1.5O4) by cyclic voltammetry and the resulting electrode-electrolyte interface was examined by scanning electron microscopy. The electrochemical characterizations performed by galvanostatic experiments reveal that the capacity values obtained at different C-rates are doubled when the electrodes are completely filled by the polymer electrolyte.

Taichi-inspired rigid-flexible coupling cellulose-supported solid polymer electrolyte for high-performance lithium batteries

PubMed Central

Zhang, Jianjun; Yue, Liping; Hu, Pu; Liu, Zhihong; Qin, Bingsheng; Zhang, Bo; Wang, Qingfu; Ding, Guoliang; Zhang, Chuanjian; Zhou, Xinhong; Yao, Jianhua; Cui, Guanglei; Chen, Liquan

2014-01-01

Inspired by Taichi, we proposed rigid-flexible coupling concept and herein developed a highly promising solid polymer electrolyte comprised of poly (ethylene oxide), poly (cyano acrylate), lithium bis(oxalate)borate and robust cellulose nonwoven. Our investigation revealed that this new class solid polymer electrolyte possessed comprehensive properties in high mechanical integrity strength, sufficient ionic conductivity (3 × 10−4 S cm−1) at 60°C and improved dimensional thermostability (up to 160°C). In addition, the lithium iron phosphate (LiFePO4)/lithium (Li) cell using such solid polymer electrolyte displayed superior rate capacity (up to 6 C) and stable cycle performance at 80°C. Furthermore, the LiFePO4/Li battery could also operate very well even at an elevated temperature of 160°C, thus improving enhanced safety performance of lithium batteries. The use of this solid polymer electrolyte mitigates the safety risk and widens the operation temperature range of lithium batteries. Thus, this fascinating study demonstrates a proof of concept of the use of rigid-flexible coupling solid polymer electrolyte toward practical lithium battery applications with improved reliability and safety. PMID:25183416

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.

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.

Chemical Passivation of Li(exp +)-Conducting Solid Electrolytes

NASA Technical Reports Server (NTRS)

West, William; Whitacre, Jay; Lim, James

2008-01-01

Plates of a solid electrolyte that exhibits high conductivity for positive lithium ions can now be passivated to prevent them from reacting with metallic lithium. Such passivation could enable the construction and operation of high-performance, long-life lithium-based rechargeable electrochemical cells containing metallic lithium anodes. The advantage of this approach, in comparison with a possible alternative approach utilizing lithium-ion graphitic anodes, is that metallic lithium anodes could afford significantly greater energy-storage densities. A major impediment to the development of such cells has been the fact that the available solid electrolytes having the requisite high Li(exp +)-ion conductivity are too highly chemically reactive with metallic lithium to be useful, while those solid electrolytes that do not react excessively with metallic lithium have conductivities too low to be useful. The present passivation method exploits the best features of both extremes of the solid-electrolyte spectrum. The basic idea is to coat a higher-conductivity, higher-reactivity solid electrolyte with a lower-conductivity, lower-reactivity solid electrolyte. One can then safely deposit metallic lithium in contact with the lower-reactivity solid electrolyte without incurring the undesired chemical reactions. The thickness of the lower-reactivity electrolyte must be great enough to afford the desired passivation but not so great as to contribute excessively to the electrical resistance of the cell. The feasibility of this method was demonstrated in experiments on plates of a commercial high-performance solid Li(exp +)- conducting electrolyte. Lithium phosphorous oxynitride (LiPON) was the solid electrolyte used for passivation. LiPON-coated solid-electrolyte plates were found to support electrochemical plating and stripping of Li metal. The electrical resistance contributed by the LiPON layers were found to be small relative to overall cell impedances.

Enhancing Capacity Performance by Utilizing the Redox Chemistry of the Electrolyte in a Dual-Electrolyte Sodium-Ion Battery.

PubMed

Senthilkumar, Sirugaloor Thangavel; Bae, Hyuntae; Han, Jinhyup; Kim, Youngsik

2018-05-04

A strategy is described to increase charge storage in a dual electrolyte Na-ion battery (DESIB) by combining the redox chemistry of the electrolyte with a Na + ion de-insertion/insertion cathode. Conventional electrolytes do not contribute to charge storage in battery systems, but redox-active electrolytes augment this property via charge transfer reactions at the electrode-electrolyte interface. The capacity of the cathode combined with that provided by the electrolyte redox reaction thus increases overall charge storage. An aqueous sodium hexacyanoferrate (Na 4 Fe(CN) 6 ) solution is employed as the redox-active electrolyte (Na-FC) and sodium nickel Prussian blue (Na x -NiBP) as the Na + ion insertion/de-insertion cathode. The capacity of DESIB with Na-FC electrolyte is twice that of a battery using a conventional (Na 2 SO 4 ) electrolyte. The use of redox-active electrolytes in batteries of any kind is an efficient and scalable approach to develop advanced high-energy-density storage systems. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Novel ternary molten salt electrolytes for intermediate-temperature sodium/nickel chloride batteries

NASA Astrophysics Data System (ADS)

Li, Guosheng; Lu, Xiaochuan; Coyle, Christopher A.; Kim, Jin Y.; Lemmon, John P.; Sprenkle, Vincent L.; Yang, Zhenguo

2012-12-01

The sodium-nickel chloride (ZEBRA) battery is operated at relatively high temperature (250-350 °C) to achieve adequate electrochemical performance. Reducing the operating temperature in the range of 150200 °C can not only lead to enhanced cycle life by suppressing temperature-related degradations, but also allow the use of lower cost materials for construction. To achieve adequate electrochemical performance at lower operating temperatures, reduction in ohmic losses is required, including the reduced ohmic resistance of β″-alumina solid electrolyte (BASE) and the incorporation of low melting point secondary electrolytes. In present work, planar-type Na/NiCl2 cells with a thin BASE (600 μm) and low melting point secondary electrolyte were evaluated at reduced temperatures. Molten salts used as secondary electrolytes were fabricated by the partial replacement of NaCl in the standard secondary electrolyte (NaAlCl4) with other lower melting point alkali metal salts such as NaBr, LiCl, and LiBr. Electrochemical characterization of these ternary molten salts demonstrated improved ionic conductivity and sufficient electrochemical window at reduced temperatures. Furthermore, Na/NiCl2 cells with 50 mol% NaBr-containing secondary electrolyte exhibited reduced polarizations at 175 °C compared to the cell with the standard NaAlCl4 catholyte. The cells also exhibited stable cycling performance even at 150 °C.

Quasi-solid state electrolytes for low-grade thermal energy harvesting using a cobalt redox couple.

PubMed

Taheri, Abuzar; MacFarlane, Douglas; Pozo-Gonzalo, Cristina; Pringle, Jennifer M

2018-06-06

Thermoelectrochemical cells, also known as thermocells, are electrochemical devices for the conversion of thermal energy directly to electricity. They are a promising method for harvesting low-grade waste heat from a variety of different natural and man-made sources. The development of solid or quasi-solid state electrolytes for thermocells could address the possible leakage problems of liquid electrolytes and make this technology more applicable for wearable devices. Here we report the gelation of an organic solvent-based electrolyte system containing a redox couple, for application in thermocell technologies. The effect of gelation of the liquid electrolyte, comprising a cobalt bipyridyl redox couple dissolved in 3-methoxypropionitrile (MPN), on the performance of thermocells was investigated. Polyvinylidene difluoride (PVDF) and poly(vinylidene fluoride-co-hexafluoropropene) (PVDF-HFP) were used for gelation of the electrolyte, and the influence of the different polymers on the mechanical properties was studied. The Seebeck coefficient and diffusivity of the cobalt redox couple were measured in both liquid and gelled electrolytes and the effect of gelation on the thermocell performance is reported. Finally, the cell performance was further improved by optimising the redox couple concentration and the separation between the hot and cold electrode, and the stability of the device over 25 hours of operation is demonstrated. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Electrical, structural, thermal and electrochemical properties of corn starch-based biopolymer electrolytes.

PubMed

Liew, Chiam-Wen; Ramesh, S

2015-06-25

Biopolymer electrolytes containing corn starch, lithium hexafluorophosphate (LiPF6) and ionic liquid, 1-butyl-3-methylimidazolium hexafluorophosphate (BmImPF6) are prepared by solution casting technique. Temperature dependence-ionic conductivity studies reveal Vogel-Tamman-Fulcher (VTF) relationship which is associated with free volume theory. Ionic liquid-based biopolymer electrolytes show lower glass transition temperature (Tg) than ionic liquid-free biopolymer electrolyte. X-ray diffraction (XRD) studies demonstrate higher amorphous region of ionic liquid-added biopolymer electrolytes. In addition, the potential stability window of the biopolymer electrolyte becomes wider and stable up to 2.9V. Conclusively, the fabricated electric double layer capacitor (EDLC) shows improved electrochemical performance upon addition of ionic liquid into the biopolymer electrolyte. The specific capacitance of EDLC based on ionic liquid-added polymer electrolyte is relatively higher than that of ionic liquid-free polymer electrolyte as depicted in cyclic voltammogram. Copyright © 2015 Elsevier Ltd. All rights reserved.

Improving halide-containing magnesium-ion electrolyte performance via sterically hindered alkoxide ligands

NASA Astrophysics Data System (ADS)

Nist-Lund, Carl A.; Herb, Jake T.; Arnold, Craig B.

2017-09-01

While homoleptic magnesium dialkoxides (MgR2, R = alkoxide) have shown promise as precursors for magnesium-ion electrolytes, the effect of ligand steric bulk on the performance of electrolytes based on these compounds is not fully understood. Increasing steric hindrance, studied via R groups with additional phenyl moieties, produces electrolytes with sequentially lower deposition overpotentials (less than -90 mV), higher purity Mg deposits (ca. 100% Mg), and lower overall cell impedances. The two largest alkoxide ligands show consistent cycling behavior and low stripping and plating overpotentials over 200 constant-current plating/stripping cycles. A deep-red visual change and the presence of large solubilized magnesium particulates above 450 nm in size is observed in an electrolyte containing magnesium bis(triphenylmethoxide) and aluminum chloride in contact with an abraded magnesium anode. Further morphological and impedance characterization show that this electrolyte system rapidly activates the magnesium metal anode surface to produce low overpotentials and, as such, is a candidate for further investigation.

Vanadium Electrolyte Studies for the Vanadium Redox Battery-A Review.

PubMed

Skyllas-Kazacos, Maria; Cao, Liuyue; Kazacos, Michael; Kausar, Nadeem; Mousa, Asem

2016-07-07

The electrolyte is one of the most important components of the vanadium redox flow battery and its properties will affect cell performance and behavior in addition to the overall battery cost. Vanadium exists in several oxidation states with significantly different half-cell potentials that can produce practical cell voltages. It is thus possible to use the same element in both half-cells and thereby eliminate problems of cross-contamination inherent in all other flow battery chemistries. Electrolyte properties vary with supporting electrolyte composition, state-of-charge, and temperature and this will impact on the characteristics, behavior, and performance of the vanadium battery in practical applications. This Review provides a broad overview of the physical properties and characteristics of the vanadium battery electrolyte under different conditions, together with a description of some of the processing methods that have been developed to produce vanadium electrolytes for vanadium redox flow battery applications. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Ionic liquids and ionic liquid acids with high temperature stability for fuel cell and other high temperature applications, method of making and cell employing same

DOEpatents

Angell, C Austen [Mesa, AZ; Xu, Wu [Broadview Heights, OH; Belieres, Jean-Philippe [Chandler, AZ; Yoshizawa, Masahiro [Tokyo, JP

2011-01-11

Disclosed are developments in high temperature fuel cells including ionic liquids with high temperature stability and the storage of inorganic acids as di-anion salts of low volatility. The formation of ionically conducting liquids of this type having conductivities of unprecedented magnitude for non-aqueous systems is described. The stability of the di-anion configuration is shown to play a role in the high performance of the non-corrosive proton-transfer ionic liquids as high temperature fuel cell electrolytes. Performance of simple H.sub.2(g) electrolyte/O.sub.2(g) fuel cells with the new electrolytes is described. Superior performance both at ambient temperature and temperatures up to and above 200.degree. C. are achieved. Both neutral proton transfer salts and the acid salts with HSO.sup.-.sub.4 anions, give good results, the bisulphate case being particularly good at low temperatures and very high temperatures. The performance of all electrolytes is improved by the addition of a small amount of involatile base of pK.sub.a value intermediate between those of the acid and base that make the bulk electrolyte. The preferred case is the imidazole-doped ethylammonium hydrogensulfate which yields behavior superior in all respects to that of the industry standard phosphoric acid electrolyte.

Bulk Bismuth as a High-Capacity and Ultralong Cycle-Life Anode for Sodium-Ion Batteries by Coupling with Glyme-Based Electrolytes.

PubMed

Wang, Chenchen; Wang, Liubin; Li, Fujun; Cheng, Fangyi; Chen, Jun

2017-09-01

Sodium-ion batteries (SIBs) have attracted great interest for large-scale electric energy storage in recent years. However, anodes with long cycle life and large reversible capacities are still lacking and therefore limiting the development of SIBs. Here, a bulk Bi anode with surprisingly high Na storage performance in combination with glyme-based electrolytes is reported. This study shows that the bulk Bi electrode is gradually developed into a porous integrity during initial cycling, which is totally different from that in carbonate-based electrolytes and ensures facile Na + transport and structural stability. The achievable capacity of bulk Bi in the NaPF 6 -diglyme electrolyte is high up to 400 mAh g -1 , and the capacity retention is 94.4% after 2000 cycles, corresponding to a capacity loss of 0.0028% per cycle. It exhibits two flat discharge/charge plateaus at 0.67/0.77 and 0.46/0.64 V, ascribed to the typical two-phase reactions of Bi ↔ NaBi and NaBi ↔ Na 3 Bi, respectively. The excellent performance is attributed to the unique porous integrity, stable solid electrolyte interface, and good electrode wettability of glymes. This interplay between electrolyte and electrode to boost Na storage performance will pave a new pathway for high-performance SIBs. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Ceramic and polymeric solid electrolytes for lithium-ion batteries

NASA Astrophysics Data System (ADS)

Fergus, Jeffrey W.

Lithium-ion batteries are important for energy storage in a wide variety of applications including consumer electronics, transportation and large-scale energy production. The performance of lithium-ion batteries depends on the materials used. One critical component is the electrolyte, which is the focus of this paper. In particular, inorganic ceramic and organic polymer solid-electrolyte materials are reviewed. Solid electrolytes provide advantages in terms of simplicity of design and operational safety, but typically have conductivities that are lower than those of organic liquid electrolytes. This paper provides a comparison of the conductivities of solid-electrolyte materials being used or developed for use in lithium-ion batteries.

Nonflammable perfluoropolyether-based electrolytes for lithium batteries.

PubMed

Wong, Dominica H C; Thelen, Jacob L; Fu, Yanbao; Devaux, Didier; Pandya, Ashish A; Battaglia, Vincent S; Balsara, Nitash P; DeSimone, Joseph M

2014-03-04

The flammability of conventional alkyl carbonate electrolytes hinders the integration of large-scale lithium-ion batteries in transportation and grid storage applications. In this study, we have prepared a unique nonflammable electrolyte composed of low molecular weight perfluoropolyethers and bis(trifluoromethane)sulfonimide lithium salt. These electrolytes exhibit thermal stability beyond 200 °C and a remarkably high transference number of at least 0.91 (more than double that of conventional electrolytes). Li/LiNi1/3Co1/3Mn1/3O2 cells made with this electrolyte show good performance in galvanostatic cycling, confirming their potential as rechargeable lithium batteries with enhanced safety and longevity.

Nonflammable perfluoropolyether-based electrolytes for lithium batteries

PubMed Central

Wong, Dominica H. C.; Thelen, Jacob L.; Fu, Yanbao; Devaux, Didier; Pandya, Ashish A.; Battaglia, Vincent S.; Balsara, Nitash P.; DeSimone, Joseph M.

2014-01-01

The flammability of conventional alkyl carbonate electrolytes hinders the integration of large-scale lithium-ion batteries in transportation and grid storage applications. In this study, we have prepared a unique nonflammable electrolyte composed of low molecular weight perfluoropolyethers and bis(trifluoromethane)sulfonimide lithium salt. These electrolytes exhibit thermal stability beyond 200 °C and a remarkably high transference number of at least 0.91 (more than double that of conventional electrolytes). Li/LiNi1/3Co1/3Mn1/3O2 cells made with this electrolyte show good performance in galvanostatic cycling, confirming their potential as rechargeable lithium batteries with enhanced safety and longevity. PMID:24516123

Capacitance enhancement of polyaniline coated curved-graphene supercapacitors in a redox-active electrolyte.

PubMed

Chen, Wei; Rakhi, R B; Alshareef, H N

2013-05-21

We show, for the first time, a redox-active electrolyte in combination with a polyaniline-coated curved graphene active material to achieve significant enhancement in the capacitance (36-92% increase) compared to supercapacitors that lack the redox-active contribution from the electrolyte. The supercapacitors based on the redox-active electrolyte also exhibit excellent rate capability and very long cycling performance (>50,000 cycles).

Graphite Recycling from Spent Lithium-Ion Batteries.

PubMed

Rothermel, Sergej; Evertz, Marco; Kasnatscheew, Johannes; Qi, Xin; Grützke, Martin; Winter, Martin; Nowak, Sascha

2016-12-20

The present work reports on challenges in utilization of spent lithium-ion batteries (LIBs)-an increasingly important aspect associated with a significantly rising demand for electric vehicles (EVs). In this context, the feasibility of anode recycling in combination with three different electrolyte extraction concepts is investigated. The first method is based on a thermal treatment of graphite without electrolyte recovery. The second method additionally utilizes a subcritical carbon-dioxide (subcritical CO 2 )-assisted electrolyte extraction prior to thermal treatment. And the final investigated approach uses supercritical carbon dioxide (scCO 2 ) as extractant, subsequently followed by the thermal treatment. It is demonstrated that the best performance of recycled graphite anodes can be achieved when electrolyte extraction is performed using subcritical CO 2 . Comparative studies reveal that, in the best case, the electrochemical performance of recycled graphite exceeds the benchmark consisting of a newly synthesized graphite anode. As essential efforts towards electrolyte extraction and cathode recycling have been made in the past, the electrochemical behavior of recycled graphite, demonstrating the best performance, is investigated in combination with a recycled LiNi 1/3 Co 1/3 Mn 1/3 O 2 cathode. © 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Surface and interface sciences of Li-ion batteries. -Research progress in electrode-electrolyte interface-

NASA Astrophysics Data System (ADS)

Minato, Taketoshi; Abe, Takeshi

2017-12-01

The application potential of Li-ion batteries is growing as demand increases in different fields at various stages in energy systems, in addition to their conventional role as power sources for portable devices. In particular, applications in electric vehicles and renewable energy storage are increasing for Li-ion batteries. For these applications, improvements in battery performance are necessary. The Li-ion battery produces and stores electric power from the electrochemical redox reactions between the electrode materials. The interface between the electrodes and electrolyte strongly affects the battery performance because the charge transfer causing the electrode redox reaction begins at this interface. Understanding of the surface structure, electronic structure, and chemical reactions at the electrode-electrolyte interface is necessary to improve battery performance. However, the interface is located between the electrode and electrolyte materials, hindering the experimental analysis of the interface; thus, the physical properties and chemical processes have remained poorly understood until recently. Investigations of the physical properties and chemical processes at the interface have been performed using advanced surface science techniques. In this review, current knowledge and future research prospects regarding the electrode-electrolyte interface are described for the further development of Li-ion batteries.

Electrolytes for Li-Ion Cells in Low Temperature Applications

NASA Technical Reports Server (NTRS)

Smart, M. C.; Ratnakumar, B. V.; Surampudi, S.

2000-01-01

Prototype AA-size lithium-ion cells have been demonstrated to operate effectively at temperatures as low as -30 to -40 C. These improvements in low temperature cell performance have been realized by the incorporation of ethylene carbonate-based electrolytes which possess low melting, low viscosity cosolvents, such as methyl acetate, ethyl acetate, gamma-butyrolactone, and ethyl methyl carbonate. The cells containing a 0.75M LiPF6 EC+DEC+DMC+EMC (1:1:1:1) electrolyte displayed the best performance at -30 C (> 90% of the room temperature capacity at approximately C/15 rate), whereas, at -40 C the cells with the 0.75M LiPF6 EC+DEC+DMC+MA (1:1:1:1) and 0.75M LiPF6 EC+DEC+DMC+EA (1:1:1:1) electrolytes showed superior performance.

(abstract) Effect of Electrolyte Composition on Carbon Electrode Performance

NASA Technical Reports Server (NTRS)

Huang, C-K.; Surampudi, S.; Shen, D. H.; Halpert, G.

1993-01-01

Rechargeable lithium cells containing lithium foil anodes are reported to have limited cycle life (at 100% DOD) performance and safety problems. These limitations are understood to be due to the high reactivity of elemental Li with the electrolyte and the formation of high surface area Li during cycling. To mitigate these problems, several lithium alloys and lithium intercalation compounds are being investigated as alternate lithium anode materials. Li(sub x)C has been identified as a promising lithium anode material due to its low equivalent weight, low voltage vs. Li, and improved stability towards various electrolytes. In this paper, we report the results of our studies on the electrolyte evaluation for the Li(sub x)C anode.

A high performance lithium–sulfur battery enabled by a fish-scale porous carbon/sulfur composite and symmetric fluorinated diethoxyethane electrolyte

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

Gao, Mengyao; Su, ChiCheung; He, Meinan

A high performance lithium–sulfur (Li–S) battery comprising a symmetric fluorinated diethoxyethane electrolyte coupled with a fish-scale porous carbon/S composite electrode was demonstrated. 1,2-Bis(1,1,2,2-tetrafluoroethoxy)ethane (TFEE) was first studied as a new electrolyte solvent for Li–S chemistry. When co-mixed with 1,3-dioxolane (DOL), the DOL/TFEE electrolyte suppressed the polysulfide dissolution and shuttling reaction. Lastly, when coupled with a fish-scale porous carbon/S composite electrode, the Li–S cell exhibited a significantly high capacity retention of 99.5% per cycle for 100 cycles, which is far superior to the reported numerous systems.

Role of solvents on the oxygen reduction and evolution of rechargeable Li-O2 battery

NASA Astrophysics Data System (ADS)

Christy, Maria; Arul, Anupriya; Zahoor, Awan; Moon, Kwang Uk; Oh, Mi Young; Stephan, A. Manuel; Nahm, Kee Suk

2017-02-01

The choice of electrolyte solvent is expected to play a key role in influencing the lithium-oxygen battery performance. The electrochemical performances of three electrolytes composed of lithium bis (trifluoromethane sulfonyl) imide (LiTFSI) salt and different solvents namely, ethylene carbonate/propylene carbonate (EC/PC), tetra ethylene glycol dimethyl ether (TEGDME) and dimethyl sulfoxide (DMSO) are investigated by assembling lithium oxygen cells. The electrolyte composition significantly varied the specific capacity of the battery. The choice of electrolyte also influences the overpotential, cycle life, and rechargeability of the battery. Electrochemical impedance spectra, cyclic voltammetry, and chronoamperometry were utilized to determine the reversible reactions associated with the air cathode.

A high performance lithium–sulfur battery enabled by a fish-scale porous carbon/sulfur composite and symmetric fluorinated diethoxyethane electrolyte

DOE PAGES

Gao, Mengyao; Su, ChiCheung; He, Meinan; ...

2017-03-07

A high performance lithium–sulfur (Li–S) battery comprising a symmetric fluorinated diethoxyethane electrolyte coupled with a fish-scale porous carbon/S composite electrode was demonstrated. 1,2-Bis(1,1,2,2-tetrafluoroethoxy)ethane (TFEE) was first studied as a new electrolyte solvent for Li–S chemistry. When co-mixed with 1,3-dioxolane (DOL), the DOL/TFEE electrolyte suppressed the polysulfide dissolution and shuttling reaction. Lastly, when coupled with a fish-scale porous carbon/S composite electrode, the Li–S cell exhibited a significantly high capacity retention of 99.5% per cycle for 100 cycles, which is far superior to the reported numerous 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

A novel quasi-solid state electrolyte with highly effective polysulfide diffusion inhibition for lithium-sulfur batteries

PubMed Central

Zhong, Hai; Wang, Chunhua; Xu, Zhibin; Ding, Fei; Liu, Xinjiang

2016-01-01

Polymer solid state electrolytes are actively sought for their potential application in energy storage devices, particularly lithium metal rechargeable batteries. Herein, we report a polymer with high concentration salts as a quasi-solid state electrolyte used for lithium-sulfur cells, which shows an ionic conductivity of 1.6 mS cm−1 at room temperature. The cycling performance of Li-S battery with this electrolyte shows a long cycle life (300 cycles) and high coulombic efficiency (>98%), without any consuming additives in the electrolyte. Moreover, it also shows a remarkably decreased self-discharge (only 0.2%) after storage for two weeks at room temperature. The reason can be attributed to that the electrolyte can suppress polysulfide anions diffusion, due to the high ratio oxygen atoms with negative charges which induce an electrical repulsion to the polysulfide anions, and their relatively long chains which can provide additional steric hindrance. Thus, the polysulfide anions can be located around carbon particles, which result in remarkably improved overall electrochemical performance, and also the electrolyte have a function of suppress the formation of lithium dendrites on the lithium anode surface. PMID:27146645

Small quaternary alkyl phosphonium bis(fluorosulfonyl)imide ionic liquid electrolytes for sodium-ion batteries with P2- and O3-Na2/3[Fe2/3Mn1/3]O2 cathode material

NASA Astrophysics Data System (ADS)

Hilder, Matthias; Howlett, Patrick C.; Saurel, Damien; Gonzalo, Elena; Armand, Michel; Rojo, Teófilo; Macfarlane, Douglas R.; Forsyth, Maria

2017-05-01

A saturated solution of 2.3 M sodium bis(fluorosulfonyl)imide in trimethyl iso-butyl phosphonium bis(fluorosulfonyl)imide ionic liquid shows a high conductivity (0.94 mScm-1 at 50 °C), low ion association, and a wide operational temperature window (-71 °C-305 °C) making it a promising electrolyte for sodium battery applications. Cycling with P2- and O3-Na2/3[Fe2/3Mn1/3]O2 cathode display excellent performance at 50 °C outperforming conventional organic solvent based electrolytes in terms of capacities (at C/10) and long term cycle stability (at C/2). Post analysis of the electrolyte shows no measurable changes while the sodium metal anode and the cathode surface shows the presence of electrolyte specific elements after cycling, suggesting the formation of a stabilizing solid electrolyte interface. Additionally, cycling changes the topography and particle morphology of the cathode. Thus, the electrolyte properties and cell performance match or outperform previously reported results with the additional benefit of replacing the hazardous and flammable organic solvent solutions commonly employed.

Ionic liquid electrolytes for Li-air batteries: lithium metal cycling.

PubMed

Grande, Lorenzo; Paillard, Elie; Kim, Guk-Tae; Monaco, Simone; Passerini, Stefano

2014-05-08

In this work, the electrochemical stability and lithium plating/stripping performance of N-butyl-N-methylpyrrolidinium bis(trifluoromethanesulfonyl)imide (Pyr14TFSI) are reported, by investigating the behavior of Li metal electrodes in symmetrical Li/electrolyte/Li cells. Electrochemical impedance spectroscopy measurements and galvanostatic cycling at different temperatures are performed to analyze the influence of temperature on the stabilization of the solid electrolyte interphase (SEI), showing that TFSI-based ionic liquids (ILs) rank among the best candidates for long-lasting Li-air cells.

Ionic Liquid Electrolytes for Li–Air Batteries: Lithium Metal Cycling

PubMed Central

Grande, Lorenzo; Paillard, Elie; Kim, Guk-Tae; Monaco, Simone; Passerini, Stefano

2014-01-01

In this work, the electrochemical stability and lithium plating/stripping performance of N-butyl-N-methylpyrrolidinium bis(trifluoromethanesulfonyl)imide (Pyr14TFSI) are reported, by investigating the behavior of Li metal electrodes in symmetrical Li/electrolyte/Li cells. Electrochemical impedance spectroscopy measurements and galvanostatic cycling at different temperatures are performed to analyze the influence of temperature on the stabilization of the solid electrolyte interphase (SEI), showing that TFSI-based ionic liquids (ILs) rank among the best candidates for long-lasting Li–air cells. PMID:24815072

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.

Electrochemical Preparation of Polyaniline Nanowires with the Used Electrolyte Solution Treated with the Extraction Process and Their Electrochemical Performance.

PubMed

Wu, Ying; Wang, Jixiao; Ou, Bin; Zhao, Song; Wang, Zhi; Wang, Shichang

2018-02-12

Electrochemical polymerization of aniline is one of the most promising methods to prepare polyaniline (PANI) materials. However, during this process, the electrolyte solution must be replaced after electropolymerization of a certain time because of the generation and the accumulation of the by-products, which have significant effects on the morphology, purity and properties of PANI products. Treatment and recycling of the used electrolyte solution are worthwhile to study to reduce the high treatment cost of the used electrolyte solution containing aniline and its polymerization by-products. Here, the composition of the used electrolyte solution was separated and determined by high performance liquid chromatography coupled with diode array detection (HPLC-DAD) in the range of ultraviolet and visible (UV-Vis) light. The analysis results revealed that the used electrolyte solution consisted of aniline, p-hydroquinone (HQ), p-benzoquinone (BQ), co-oligomers of aniline and p-benzoquinone (CAB) and acid. Then, n-octanol and 2-octanone were selected as extracts to remove HQ, BQ and CAB from the used electrolyte solution. Following that, the recycled electrolyte solution was prepared by adjusting the concentration of aniline and acid of the aqueous phase, and the electrochemical polymerization process was conducted. Finally, the obtained PANI was characterized by scanning electron microscope (SEM) and electrochemical methods. The experimental results clearly demonstrate that the morphology and specific capacitance of PANI produced from the recycled electrolyte solution can be recovered completely. This research paves the way for reusing the used electrolyte solution for aniline electrochemical polymerization.

Electrochemical Preparation of Polyaniline Nanowires with the Used Electrolyte Solution Treated with the Extraction Process and Their Electrochemical Performance

PubMed Central

Wu, Ying; Wang, Jixiao; Ou, Bin; Zhao, Song; Wang, Zhi; Wang, Shichang

2018-01-01

Electrochemical polymerization of aniline is one of the most promising methods to prepare polyaniline (PANI) materials. However, during this process, the electrolyte solution must be replaced after electropolymerization of a certain time because of the generation and the accumulation of the by-products, which have significant effects on the morphology, purity and properties of PANI products. Treatment and recycling of the used electrolyte solution are worthwhile to study to reduce the high treatment cost of the used electrolyte solution containing aniline and its polymerization by-products. Here, the composition of the used electrolyte solution was separated and determined by high performance liquid chromatography coupled with diode array detection (HPLC-DAD) in the range of ultraviolet and visible (UV-Vis) light. The analysis results revealed that the used electrolyte solution consisted of aniline, p-hydroquinone (HQ), p-benzoquinone (BQ), co-oligomers of aniline and p-benzoquinone (CAB) and acid. Then, n-octanol and 2-octanone were selected as extracts to remove HQ, BQ and CAB from the used electrolyte solution. Following that, the recycled electrolyte solution was prepared by adjusting the concentration of aniline and acid of the aqueous phase, and the electrochemical polymerization process was conducted. Finally, the obtained PANI was characterized by scanning electron microscope (SEM) and electrochemical methods. The experimental results clearly demonstrate that the morphology and specific capacitance of PANI produced from the recycled electrolyte solution can be recovered completely. This research paves the way for reusing the used electrolyte solution for aniline electrochemical polymerization. PMID:29439514

Flexible thin-film battery based on solid-like ionic liquid-polymer electrolyte

NASA Astrophysics Data System (ADS)

Li, Qin; Ardebili, Haleh

2016-01-01

The development of high-performance flexible batteries is imperative for several contemporary applications including flexible electronics, wearable sensors and implantable medical devices. However, traditional organic liquid-based electrolytes are not ideal for flexible batteries due to their inherent safety and stability issues. In this study, a non-volatile, non-flammable and safe ionic liquid (IL)-based polymer electrolyte film with solid-like feature is fabricated and incorporated in a flexible lithium ion battery. The ionic liquid is 1-Ethyl-3-methylimidazolium dicyanamide (EMIMDCA) and the polymer is composed of poly(vinylidene fluoride-co-hexafluoropropene) (PVDF-HFP). The electrolyte exhibits good thermal stability (i.e. no weight loss up to 300 °C) and relatively high ionic conductivity (6 × 10-4 S cm-1). The flexible thin-film lithium ion battery based on solid-like electrolyte film is encapsulated using a thermal-lamination process and demonstrates excellent electrochemical performance, in both flat and bent configurations.

Basic investigation into the electrical performance of solid electrolyte membranes

NASA Technical Reports Server (NTRS)

Richter, R.

1982-01-01

The electrical performance of solid electrolyte membranes was investigated analytically and the results were compared with experimental data. It is concluded that in devices that are used for pumping oxygen the major power losses have to be attributed to the thin film electrodes. Relations were developed by which the effectiveness of tubular solid electrolyte membranes can be determined and the optimum length evaluated. The observed failure of solid electrolyte tube membranes in very localized areas is explained by the highly non-uniform current distribution in the membranes. The analysis points to a possible contact resistance between the electrodes and the solid electrolyte material. This possible contact resistance remains to be investigated experimentally. It is concluded that film electrodes are not appropriate for devices which operate with current flow, i.e., pumps though they can be employed without reservation in devices that measure oxygen pressures if a limited increase in the response time can be tolerated.

Electrolyte Structure near Electrode Interfaces in Lithium-Ion Batteries

NASA Astrophysics Data System (ADS)

Lordi, Vincenzo; Ong, Mitchell; Verners, Osvalds; van Duin, Adri; Draeger, Erik; Pask, John

2014-03-01

The performance of lithium-ion secondary batteries (LIBs) is strongly tied to electrochemistry and ionic transport near the electrode-electrolyte interface. Changes in ion solvation near the interface affect ion conductivity and also are associated with the formation and evolution of solid-electrolyte interphase (SEI) layers, which impede transport but also passivate the interface. Thus, understanding these effects is critical to optimizing battery performance. Here we present molecular dynamics (MD) simulations of typical organic liquid LIB electrolytes in contact with graphite electrodes to understand differences in molecular structure and solvation near the interface compared to the bulk electrolyte. Results for different graphite terminations are presented. We compare the results of density-functional based MD to the empirical reactive forcefield ReaxFF and the non-reactive, non-polarizable COMPASS forcefield. Notable differences in the predictive power of each of these techniques are discussed. Prepared by LLNL under Contract DE-AC52-07NA27344.

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

Xu, Wu; Xiao, Jie; Zhang, Jian

The selection and optimization of non-aqueous electrolytes for ambient operations of lithium/air batteries has been studied. Organic solvents with low volatility and low moisture absorption are necessary to minimize the change of electrolyte compositions and the reaction between lithium anode and water during discharge process. It is critical to make the electrolytes with high polarity so that it can reduce wetting and flooding of carbon based air electrode and lead to improved battery performance. For ambient operations, the viscosity, ionic conductivity, and oxygen solubility of the electrolyte are less important than the polarity of organic solvents once the electrolyte hasmore » reasonable viscosity, conductivity, and oxygen solubility. It has been found that PC/EC mixture is the best solvent system and LiTFSI is the most feasible salt for ambient operations of Li/air batteries. Battery performance is not very sensitive to PC/EC ratio or salt concentration.« less

Improved Low-Temperature Performance of Li-Ion Cells Using New Electrolytes

NASA Technical Reports Server (NTRS)

Smart, Marshall C.; Buga, Ratnakumar V.; Gozdz, Antoni S.; Mani, Suresh

2010-01-01

As part of the continuing efforts to develop advanced electrolytes to improve the performance of lithium-ion cells, especially at low temperatures, a number of electrolyte formulations have been developed that result in improved low-temperature performance (down to 60 C) of 26650 A123Systems commercial lithium-ion cells. The cell type/design, in which the new technology has been demonstrated, has found wide application in the commercial sector (i.e., these cells are currently being used in commercial portable power tools). In addition, the technology is actively being considered for hybrid electric vehicle (HEV) and electric vehicle (EV) applications. In current work, a number of low-temperature electrolytes have been developed based on advances involving lithium hexafluorophosphate-based solutions in carbonate and carbonate + ester solvent blends, which have been further optimized in the context of the technology and targeted applications. The approaches employed, which include the use of ternary mixtures of carbonates, the use of ester co-solvents [e.g., methyl butyrate (MB)], and optimized lithium salt concentrations (e.g., LiPF6), were compared with the commercial baseline electrolyte, as well as an electrolyte being actively considered for DoE HEV applications and previously developed by a commercial enterprise, namely LiPF6 in ethylene carbonate (EC) + ethyl methyl carbonate (EMC)(30:70%).

Fluorinated phosphazene co-solvents for improved thermal and safety performance in lithium-ion battery electrolytes

NASA Astrophysics Data System (ADS)

Rollins, Harry W.; Harrup, Mason K.; Dufek, Eric J.; Jamison, David K.; Sazhin, Sergiy V.; Gering, Kevin L.; Daubaras, Dayna L.

2014-10-01

The safety of lithium-ion batteries is coming under increased scrutiny as they are being adopted for large format applications especially in the vehicle transportation industry and for grid-scale energy storage. The primary short-comings of lithium-ion batteries are the flammability of the liquid electrolyte and sensitivity to high voltage and elevated temperatures. We have synthesized a series of non-flammable fluorinated phosphazene liquids and blended them with conventional carbonate solvents. While the use of these phosphazenes as standalone electrolytes is highly desirable, they simply do not satisfy all of the many requirements that must be met such as high LiPF6 solubility and low viscosity, thus we have used them as additives and co-solvents in blends with typical carbonates. The physical and electrochemical properties of the electrolyte blends were characterized, and then the blends were used to build 2032-type coin cells. We have evaluated the performance of the electrolytes by determining the physical properties, thermal stability, electrochemical window, cell cycling data, and the ability to form solid electrolyte interphase (SEI) films. This paper presents our most recent results on a new series of fluorinated cyclic phosphazene trimers, the FM series, which has exhibited numerous beneficial effects on battery performance, lifetimes, and safety aspects.

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.

1,3,6-Hexanetricarbonitrile as electrolyte additive for enhancing electrochemical performance of high voltage Li-rich layered oxide cathode

NASA Astrophysics Data System (ADS)

Wang, Long; Ma, Yulin; Li, Qin; Zhou, Zhenxin; Cheng, Xinqun; Zuo, Pengjian; Du, Chunyu; Gao, Yunzhi; Yin, Geping

2017-09-01

1,3,6-Hexanetricarbonitrile (HTN) has been investigated as an electrolyte additive to improve the electrochemical performance of the Li1.2Ni0.13Co0.13Mn0.54O2 cathode at high operating voltage (4.8 V). Linear sweep voltammetry (LSV) results indicate that HTN can improve the oxidation potential of the electrolyte. The influences of HTN on the electrochemical behaviors and surface properties of the cathode at high voltage have been investigated by galvanostatic charge/discharge test, electrochemical impedance spectroscopy (EIS), and ex-situ physical characterizations. Charge-discharge results demonstrate that the capacity retention of the Li1.2Ni0.13Co0.13Mn0.54O2 cathode in 1% HTN-containing electrolyte after 150 cycles at 0.5 C is improved to 92.3%, which is much higher than that in the standard electrolyte (ED). Combined with the theoretical calculation, ICP tests, XRD and XPS analysis, more stable and homogeneous interface film is confirmed to form on the cathode surface with incorporation of HTN, meanwhile, the electrolyte decomposition and the cathode structural destruction are restrained effectively upon cycling at high voltage, leading to improved electrochemical performance of Li1.2Ni0.13Co0.13Mn0.54O2 cathode.

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.

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.

Lithium-Ion Electrolytes Containing Flame Retardant Additives for Increased Safety Characteristics

NASA Technical Reports Server (NTRS)

Bugga, Ratnakumar V. (Inventor); Krause, Frederick Charles (Inventor); Smart, Marshall C. (Inventor); Prakash, Surya G. (Inventor); Smith, Kiah A. (Inventor)

2014-01-01

The invention discloses various embodiments of Li-ion electrolytes containing flame retardant additives that have delivered good performance over a wide temperature range, good cycle life characteristics, and improved safety characteristics, namely, reduced flammability. In one embodiment of the invention there is provided an electrolyte for use in a lithium-ion electrochemical cell, the electrolyte comprising a mixture of an ethylene carbonate (EC), an ethyl methyl carbonate (EMC), a fluorinated co-solvent, a flame retardant additive, and a lithium salt. In another embodiment of the invention there is provided an electrolyte for use in a lithium-ion electrochemical cell, the electrolyte comprising a mixture of an ethylene carbonate (EC), an ethyl methyl carbonate (EMC), a flame retardant additive, a solid electrolyte interface (SEI) film forming agent, and a lithium salt.

Wide Operating Temperature Range Electrolytes for High Voltage and High Specific Energy Li-Ion Cells

NASA Technical Reports Server (NTRS)

Smart, M. C.; Hwang, C.; Krause, F. C.; Soler, J.; West, W. C.; Ratnakumar, B. V.; Amine, K.

2012-01-01

A number of electrolyte formulations that have been designed to operate over a wide temperature range have been investigated in conjunction with layered-layered metal oxide cathode materials developed at Argonne. In this study, we have evaluated a number of electrolytes in Li-ion cells consisting of Conoco Phillips A12 graphite anodes and Toda HE5050 Li(1.2)Ni(0.15)Co(0.10)Mn(0.55)O2 cathodes. The electrolytes studied consisted of LiPF6 in carbonate-based electrolytes that contain ester co-solvents with various solid electrolyte interphase (SEI) promoting additives, many of which have been demonstrated to perform well in 4V systems. More specifically, we have investigated the performance of a number of methyl butyrate (MB) containing electrolytes (i.e., LiPF6 in ethylene carbonate (EC) + ethyl methyl carbonate (EMC) + MB (20:20:60 v/v %) that contain various additives, including vinylene carbonate, lithium oxalate, and lithium bis(oxalato)borate (LiBOB). When these systems were evaluated at various rates at low temperatures, the methyl butyrate-based electrolytes resulted in improved rate capability compared to cells with all carbonate-based formulations. It was also ascertained that the slow cathode kinetics govern the generally poor rate capability at low temperature in contrast to traditionally used LiNi(0.80)Co(0.15)Al(0.05)O2-based systems, rather than being influenced strongly by the electrolyte type.

Promoting Effect of Layered Titanium Phosphate on the Electrochemical and Photovoltaic Performance of Dye-Sensitized Solar Cells

PubMed Central

2010-01-01

We reported a composite electrolyte prepared by incorporating layered α-titanium phosphate (α-TiP) into an iodide-based electrolyte using 1-ethyl-3-methylimidazolium tetrafluoroborate(EmimBF4) ionic liquid as solvent. The obtained composite electrolyte exhibited excellent electrochemical and photovoltaic properties compared to pure ionic liquid electrolyte. Both the diffusion coefficient of triiodide (I3−) in the electrolyte and the charge-transfer reaction at the electrode/electrolyte interface were improved markedly. The mechanism for the enhanced electrochemical properties of the composite electrolyte was discussed. The highest conversion efficiency of dye-sensitized solar cell (DSSC) was obtained for the composite electrolyte containing 1wt% α-TiP, with an improvement of 58% in the conversion efficiency than the blank one, which offered a broad prospect for the fabrication of stable DSSCs with a high conversion efficiency. PMID:20676195

Improved performance and safety of lithium ion cells with the use of fluorinated carbonate-based electrolytes

NASA Technical Reports Server (NTRS)

Smart, M. C.; Ratnakumar, B. V.; Ryan, V. S.; Surampudi, S.; Prakashi, G. K. S.; Hu, J.; Cheung, I.

2002-01-01

There has been increasing interest in developing lithium-ion electrolytes that possess enhanced safety characteristics, while still able to provide the desired stability and performance. Toward this end, our efforts have been focused on the development of lithium-ion electrolytes which contain partially and fully fluorinated carbonate solvents. The advantage of using such solvents is that they possess the requisite stability demonstrated by the hydrocarbon-based carbonates, while also possessing more desirable physical properties imparted by the presence of the fluorine substituents, such as lower melting points, increased stability toward oxidation, and favorable SEI film forming Characteristics on carbon. Specifically, we have demonstrated the beneficial effect of electrolytes which contain the following fluorinated carbonate-based solvents: methyl 2,2,2-trifluoroethyl carbonate (MTFEC), ethyl-2,2,2 trifluoroethyl carbonate (ETFEC), propyl 2,2,2-trifluoroethyl carbonate (PTFEC), methyl-2,2,2,2',2',2' -hexafluoro-i-propyl carbonate (MHFPC), ethyl- 2,2,2,2',2',2' -hexafluoro-i-propyl carbonate (EHFPC), and di-2,2,2-trifluoroethyl carbonate (DTFEC). These solvents have been incorporated into multi-component ternary and quaternary carbonate-based electrolytes and evaluated in lithium-carbon and carbon-LiNio.8Coo.202 cells (equipped with lithium reference electrodes). In addition to determining the charge/discharge behavior of these cells, a number of electrochemical techniques were employed (i.e., Tafel polarization measurements, linear polarization measurements, and electrochemical impedance spectroscopy (EIS)) to further characterize the performance of these electrolytes, including the SEI formation characteristics and lithium intercalatiodde-intercalation kinetics. In addition to their evaluation in experimental cells, cyclic voltammetry (CV) and conductivity measurements were performed on select electrolyte formulations to further our understanding of the trends in stability and ionic mobility imparted by different alkyl substituents in linear carbonates.

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.

Electrolyte bi-layering strategy to improve the performance of an intermediate temperature solid oxide fuel cell: A review

NASA Astrophysics Data System (ADS)

Shri Prakash, B.; Pavitra, R.; Senthil Kumar, S.; Aruna, S. T.

2018-03-01

Lowering of operation temperature has become one of the primary goals of solid oxide fuel (SOFC) research as reduced temperature improves the prospects for widespread commercialization of this energy system. Reduced operational temperature also mitigates the issues associated with high temperature SOFCs and paves way not only for the large scale stationary power generation but also makes SOFCs viable for portable and transport applications. However, there are issues with electrolyte and cathode materials at low temperatures, individually as well as in association with other components, which makes the performance of the SOFCs less satisfactory than expected at lowered temperatures. Bi-layering of electrolytes and impregnation of cathodes have emerged as two important strategies to overcome these issues and achieve higher performance at low temperatures. This review article provides the perspective on the strategy of bi-layering of electrolyte to achieve the desired high performance from SOFC at low to intermediate temperatures.

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.

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.

Electrochemical testing of industrially produced PEO-based polymer electrolytes

NASA Astrophysics Data System (ADS)

Appetecchi, G. B.; Alessandrini, F.; Duan, R. G.; Arzu, A.; Passerini, S.

The present report describes the results of the electrochemical tests performed on polyethyleneoxide-based polymer electrolyte thin films industrially manufactured by blown-extrusion. The polymer electrolyte composition was PEO 20 LiCF 3SO 3: 16.7% γLiAlO 2. The polymer electrolyte film was tested to evaluate the ionic conductivity as well as the interfacial properties with lithium metal anodes. The work was developed within the advanced lithium polymer electrolyte (ALPE) project, an Italian project devoted to the realization of lithium polymer batteries for electric vehicle applications, in collaboration with Union Carbide.

Evaluation of mixed solvent electrolytes for ambient temperature secondary lithium cells

NASA Technical Reports Server (NTRS)

Shen, D. H.; Subbarao, S.; Deligiannis, F.; Dawson, S.; Halpert, G.

1988-01-01

The ethylene carbonate/2-methyltetrahydrofuran (EC/2-MeTHF) mixed-solvent electrolyte has been experimentally found to possess many desirable electrolyte characteristics for ambient-temperature secondary Li-TiS2 cell applications. As many as 300 cycles have been demonstrated, and a cycling efficiency figure-of-merit of 38.5 percent, for 10-percent EC/90-percent MeTHF mixed-solvent electrolyte in experimental Li-TiS2 cells. The improved performance of this electrolyte is attributable to the formation of a beneficial passivating film on the Li electrode by interaction with the EC.

High performance of SDC and GDC core shell type composite electrolytes using methane as a fuel for low temperature SOFC

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

Irshad, Muneeb; Siraj, Khurram, E-mail: razahussaini786@gmail.com, E-mail: khurram.uet@gmail.com; Javed, Fayyaz

Nanocomposites Samarium doped Ceria (SDC), Gadolinium doped Ceria (GDC), core shell SDC amorphous Na{sub 2}CO{sub 3} (SDCC) and GDC amorphous Na{sub 2}CO{sub 3} (GDCC) were synthesized using co-precipitation method and then compared to obtain better solid oxide electrolytes materials for low temperature Solid Oxide Fuel Cell (SOFCs). The comparison is done in terms of structure, crystallanity, thermal stability, conductivity and cell performance. In present work, XRD analysis confirmed proper doping of Sm and Gd in both single phase (SDC, GDC) and dual phase core shell (SDCC, GDCC) electrolyte materials. EDX analysis validated the presence of Sm and Gd in bothmore » single and dual phase electrolyte materials; also confirming the presence of amorphous Na{sub 2}CO{sub 3} in SDCC and GDCC. From TGA analysis a steep weight loss is observed in case of SDCC and GDCC when temperature rises above 725 °C while SDC and GDC do not show any loss. The ionic conductivity and cell performance of single phase SDC and GDC nanocomposite were compared with core shell GDC/amorphous Na{sub 2}CO{sub 3} and SDC/ amorphous Na{sub 2}CO{sub 3} nanocomposites using methane fuel. It is observed that dual phase core shell electrolytes materials (SDCC, GDCC) show better performance in low temperature range than their corresponding single phase electrolyte materials (SDC, GDC) with methane fuel.« less

Improved Wide Operating Temperature Range of Li-Ion Cells

NASA Technical Reports Server (NTRS)

Smart, Marshall C.; Bugga, Ratnakumar V.

2013-01-01

Future NASA missions aimed at exploring the Moon, Mars, and the outer planets require rechargeable batteries that can operate over a wide temperature range (-60 to +60 C) to satisfy the requirements of various applications including landers, rovers, penetrators, CEV, CLV, etc. This work addresses the need for robust rechargeable batteries that can operate well over a wide temperature range. The Department of Energy (DoE) has identified a number of technical barriers associated with the development of Liion rechargeable batteries for PHEVs. For this reason, DoE has interest in the development of advanced electrolytes that will improve performance over a wide range of temperatures, and lead to long life characteristics (5,000 cycles over a 10-year life span). There is also interest in improving the high-voltage stability of these candidate electrolyte systems to enable the operation of up to 5 V with high specific energy cathode materials. Currently, the state-of-the-art lithium-ion system has been demonstrated to operate over a wide range of temperatures (-40 to +40 C); however, the rate capability at the lower temperatures is very poor. In addition, the low-temperature performance typically deteriorates rapidly upon being exposed to high temperatures. A number of electrolyte formulations were developed that incorporate the use of electrolyte additives to improve the high-temperature resilience, low-temperature power capability, and life characteristics of methyl propionate (MP)-based electrolyte solutions. These electrolyte additives include mono-fluoroethylene carbonate (FEC), lithium oxalate, vinylene carbonate (VC), and lithium bis(oxalate borate) (LiBOB), which have previously been shown to result in improved high-temperature resilience of all carbonate-based electrolytes. These MP-based electrolytes with additives have been shown to have improved performance in experiments with MCMB-LiNiCoAlO2 cells.

Effects of carbohydrate-hydration strategies on glucose metabolism, sprint performance and hydration during a soccer match simulation in recreational players.

PubMed

Kingsley, Michael; Penas-Ruiz, Carlos; Terry, Chris; Russell, Mark

2014-03-01

This study compared the effects of three carbohydrate-hydration strategies on blood glucose concentration, exercise performance and hydration status throughout simulated soccer match-play. A randomized, double-blind and cross-over study design was employed. After familiarization, 14 recreational soccer players completed the soccer match simulation on three separate occasions. Participants consumed equal volumes of 9.6% carbohydrate-caffeine-electrolyte (∼ 6 mg/kg BW caffeine) solution with carbohydrate-electrolyte gels (H-CHO), 5.6% carbohydrate-electrolyte solution with electrolyte gels (CHO) or electrolyte solution and electrolyte gels (PL). Blood samples were taken at rest, immediately before exercise and every 15 min during exercise (first half: 15, 30, 45 min; second half: 60, 75, 90 min). Supplementation influenced blood glucose concentration (time × treatment interaction: p<0.001); however, none of the supplementation regimes were effective in preventing a drop in blood glucose at 60 min. Mean sprint speed was 3 ± 1% faster in H-CHO when compared with PL (treatment: p=0.047). Supplementation caused a 2.3 ± 0.5% increase in plasma osmolality in H-CHO (p<0.001) without change in CHO or PL. Similarly, mean sodium concentrations were 2.1 ± 0.4% higher in H-CHO when compared with PL (p=0.006). Combining high carbohydrate availability with caffeine resulted in improved sprint performance and elevated blood glucose concentrations throughout the first half and at 90 min of exercise; however, this supplementation strategy negatively influenced hydration status when compared with 5.6% carbohydrate-electrolyte and electrolyte solutions. Copyright © 2013 Sports Medicine Australia. Published by Elsevier Ltd. All rights reserved.

Li Anode Technology for Improved Performance

NASA Technical Reports Server (NTRS)

Chen, Tuqiang

2011-01-01

A novel, low-cost approach to stabilization of Li metal anodes for high-performance rechargeable batteries was developed. Electrolyte additives are selected and used in Li cell electrolyte systems, promoting formation of a protective coating on Li metal anodes for improved cycle and safety performance. Li batteries developed from the new system will show significantly improved battery performance characteristics, including energy/power density, cycle/ calendar life, cost, and safety.

Ionically conducting PVA-LiClO4 gel electrolyte for high performance flexible solid state supercapacitors.

PubMed

Chodankar, Nilesh R; Dubal, Deepak P; Lokhande, Abhishek C; Lokhande, Chandrakant D

2015-12-15

The synthesis of polymer gel electrolyte having high ionic conductivity, excellent compatibility with active electrode material, mechanical tractability and long life is crucial to obtain majestic electrochemical performance for flexible solid state supercapacitors (FSS-SCs). Our present work describes effect of different polymers gel electrolytes on electrochemical properties of MnO2 based FSS-SCs device. It is revealed that, MnO2-FSS-SCs with polyvinyl alcohol (PVA)-Lithium perchlorate (LiClO4) gel electrolyte demonstrate excellent electrochemical features such as maximum operating potential window (1.2V), specific capacitance of 112Fg(-1) and energy density of 15Whkg(-1) with extended cycling stability up to 2500CV cycles. Moreover, the calendar life suggests negligible decrease in the electrochemical performance of MnO2-FSS-SCs after 20days. Copyright © 2015 Elsevier Inc. All rights reserved.

The Role of Electrolyte Upon the SEI Formation Characteristics and Low Temperature Performance of Lithium-Ion Cells With Graphite Anodes

NASA Technical Reports Server (NTRS)

Smart, M. C.; Ratnakumar, B. V.; Greenbaum, S.; Surampudi, S.

2000-01-01

Quarternary lithium-ion battery electrolyte solutions containing ester co-solvents in mixtures of carbonates have been demonstrated to have high conductivity at low temperatures (< -20C). However, in some cases the presence of such co-solvents does not directly translate into improved low temperature cell performance, presumably due to the formation of ionically resistive surface films on carbonaceous anodes. In order to understand this behavior, a number of lithium-graphite cells have been studied containing electrolytes with various ester co-solvents, including methyl acetate (MA), ethyl acetate (EA), ethyl propionate (EP), and ethyl butyrate (EB). The charge/discharge characterization of these cells indicates that the higher molecular weight esters result in electrolytes which possess superior low temperature performance in contrast to the lower molecular weight ester-containing solutions, even though these solutions display lower conductivity values.

Electrolytic Polishing and Etching Techniques for Preparing Specimens of Bismuth and Antimony and Their Alloys: Materials and Structures.

DTIC Science & Technology

Electrolytic polishing was performed in a solution of methyl alcohol, sulphuric acid , hydrocloric acid and ethylene glycol. Etching was done...electrolytically in a 5 percent chromic acid solution. Use of these techniques has permitted detailed studies of the microstructures of bismuth-antimony single

Preliminary study of application of Moringa oleifera resin as polymer electrolyte in DSSC solar cells

NASA Astrophysics Data System (ADS)

Saehana, Sahrul; Darsikin, Muslimin

2016-04-01

This study reports the preliminary study of application of Moringa oleifera resin as polymer electrolyte in dye-sensitized solar cell (DSSC). We found that polymer electrolyte membrane was formed by using solution casting methods. It is observed that polymer electrolyte was in elastic form and it is very potential to application as DSSC component. Performance of DSSC which employing Moringa oleifera resin was also observed and photovoltaic effect was found.

Electrochemical testing of suspension plasma sprayed solid oxide fuel cell electrolytes

NASA Astrophysics Data System (ADS)

Waldbillig, D.; Kesler, O.

Electrochemical performance of metal-supported plasma sprayed (PS) solid oxide fuel cells (SOFCs) was tested for three nominal electrolyte thicknesses and three electrolyte fabrication conditions to determine the effects of electrolyte thickness and microstructure on open circuit voltage (OCV) and series resistance (R s). The measured OCV values were approximately 90% of the Nernst voltages, and electrolyte area specific resistances below 0.1 Ω cm 2 were obtained at 750 °C for electrolyte thicknesses below 20 μm. Least-squares fitting was used to estimate the contributions to R s of the YSZ bulk material, its microstructure, and the contact resistance between the current collectors and the cells. It was found that the 96% dense electrolyte layers produced from high plasma gas flow rate conditions had the lowest permeation rates, the highest OCV values, and the smallest electrolyte-related voltage losses. Optimal electrolyte thicknesses were determined for each electrolyte microstructure that would result in the lowest combination of OCV loss and voltage loss due to series resistance for operating voltages of 0.8 V and 0.7 V.

Molecular Engineering toward Stabilized Interface: An Electrolyte Additive for High-Performance Li-Ion Battery

DOE PAGES

Zhang, Lu; Huang, Jinhua; Youssef, Kyrrilos; ...

2014-10-31

A novel electrolyte additive, 3-oxabicyclo[3.1.0]hexane-2,4-dione (OHD), has been discovered and evaluated in Li- 1.1(Mn 1/3Ni 1/3Co 1/3) 0.9O 2/graphite cells under elevated temperature. When an appropriate amount of OHD is used, the cell capacity retention is improved from 60% (Gen 2 electrolyte alone) to 82% (Gen 2 electrolyte plus OHD) after 200 cycles with no obvious impedance increase. The amount of OHD added is the key to achieving the superior cell performance. In conclusion, the effect of OHD additive was investigated by means of electrochemical analysis, fourier transform infrared spectroscopy, scanning electron microscopy, and density functional theory computation.

Solid electrolyte fuel cells

NASA Astrophysics Data System (ADS)

Isaacs, H. S.

Progress in the development of functioning solid electrolyte fuel cells is summarized. The solid electrolyte cells perform at 1000 C, a temperature elevated enough to indicate high efficiencies are available, especially if the cell is combined with a steam generator/turbine system. The system is noted to be sulfur tolerant, so coal containing significant amounts of sulfur is expected to yield satisfactory performances with low parasitic losses for gasification and purification. Solid oxide systems are electrically reversible, and are usable in both fuel cell and electrolysis modes. Employing zirconium and yttrium in the electrolyte provides component stability with time, a feature not present with other fuel cells. The chemical reactions producing the cell current are reviewed, along with materials choices for the cathodes, anodes, and interconnections.

Enhancing the High-Voltage Cycling Performance of LiNi1/3Co1/3Mn1/3O2/Graphite Batteries Using Alkyl 3,3,3-Trifluoropropanoate as an Electrolyte Additive.

PubMed

Zheng, Xiangzhen; Huang, Tao; Pan, Ying; Wang, Wenguo; Fang, Guihuang; Ding, Kaining; Wu, Maoxiang

2017-06-07

The present study demonstrates that the use of alkyl 3,3,3-trifluoropropanoate, including methyl 3,3,3-trifluoropropanoate (TFPM) and ethyl 3,3,3-trifluoropropanoate (TFPE), as new electrolyte additive can dramatically enhance the high-voltage performance of LiNi 1/3 Co 1/3 Mn 1/3 O 2 /graphite lithium-ion batteries (3.0-4.6 V, vs Li/Li + ). The capacity retention was significantly increased from 45.6% to 75.4% after 100 charge-discharge cycles due to the addition of 0.2 wt % TFPM in the electrolyte, and significantly increased from 45.6% to 76.1% after 100 charge-discharge cycles due to the addition of 0.5 wt % TFPE in the electrolyte, verifying their suitability in this application. Electrochemical impedance spectroscopy, X-ray diffraction, Fourier transform infrared spectroscopy, scanning electron microscopy, and X-ray photoelectron spectroscopy were employed to study the effect of TFPM and TFPE on cell performance. The data indicates that the improved cycling activity can be ascribed to the participation of TFPM or TFPE in the formation of a thinner cathode/electrolyte interfacial film, thereby enhancing the cell cycling performance owing to a reduced interfacial resistance at high voltage.

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.

Effect of cation on diffusion coefficient of ionic liquids at onion-like carbon electrodes.

PubMed

Van Aken, Katherine L; McDonough, John K; Li, Song; Feng, Guang; Chathoth, Suresh M; Mamontov, Eugene; Fulvio, Pasquale F; Cummings, Peter T; Dai, Sheng; Gogotsi, Yury

2014-07-16

While most supercapacitors are limited in their performance by the stability of the electrolyte, using neat ionic liquids (ILs) as the electrolyte can expand the voltage window and temperature range of operation. In this study, ILs with bis(trifluoromethylsulfonyl)imide (Tf2N) as the anion were investigated as the electrolyte in onion-like carbon-based electrochemical capacitors. To probe the influence of cations on the electrochemical performance of supercapacitors, three different cations were used: 1-ethyl-3-methylimidazolium, 1-hexyl-3-methylimidazolium and 1,6-bis(3-methylimidazolium-1-yl). A series of electrochemical characterization tests was performed using cyclic voltammetry (CV), galvanostatic cycling and electrochemical impedance spectroscopy (EIS). Diffusion coefficients were measured using EIS and correlated with quasielastic neutron scattering and molecular dynamics simulation. These three techniques were used in parallel to confirm a consistent trend between the three ILs. It was found that the IL with the smaller sized cation had a larger diffusion coefficient, leading to a higher capacitance at faster charge-discharge rates. Furthermore, the IL electrolyte performance was correlated with increasing temperature, which limited the voltage stability window and led to the formation of a solid electrolyte interphase on the carbon electrode surface, evident in both the CV and EIS experiments.

Magnesium-based energy storage systems and methods having improved electrolytes

DOEpatents

Liu, Tianbiao; Li, Guosheng; Liu, Jun; Shao, Yuyan

2016-12-20

Electrolytes for Mg-based energy storage devices can be formed from non-nucleophilic Mg.sup.2+ sources to provide outstanding electrochemical performance and improved electrophilic susceptibility compared to electrolytes employing nucleophilic sources. The instant electrolytes are characterized by high oxidation stability (up to 3.4 V vs Mg), improved electrophile compatibility and electrochemical reversibility (up to 100% coulombic efficiency). Synthesis of the Mg.sup.2+ electrolytes utilizes inexpensive and safe magnesium dihalides as non-nucleophilic Mg.sup.2+ sources in combination with Lewis acids, MR.sub.aX.sub.3-a (for 3.gtoreq.a.gtoreq.1). Furthermore, addition of free-halide-anion donors can improve the coulombic efficiency of Mg electrolytes from nucleophilic or non-nucleophilic Mg.sup.2+ sources.

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.

A new anion receptor for improving the interface between lithium- and manganese-rich layered oxide cathode and the electrolyte

DOE PAGES

Ma, Yulin; Zhou, Yan; Du, Chunyu; ...

2017-02-15

Surface degradation on cycled lithium-ion battery cathode particles is governed not only by intrinsic thermodynamic properties of the material but also, oftentimes more predominantly, by the side reactions with the electrolytic solution. A superior electrolyte inhibits these undesired side reactions on the cathode and at the electrolyte interface, which consequently minimizes the deterioration of the cathode surface. The present study investigates a new boron-based anion receptor, tris(2,2,2-trifluoroethyl)borate (TTFEB), as an electrolyte additive in cells containing a lithium- and manganese-rich layered oxide cathode, Li 1.16Ni 0.2Co 0.1Mn 0.54O 2. Our electrochemical studies demonstrate that the cycling performance and Coulombic efficiency aremore » significantly improved because of the additive, in particular, under elevated temperature conditions. Spectroscopic analyses revealed that the addition of 0.5 wt % TTFEB is capable of reducing the content of lithium-containing inorganic species within the cathode-electrolyte interphase layer and minimizing the reduction of tetravalent Mn4+ at the cathode surface. Furthermore, our work introduces a novel additive highly effective in improving lithium-ion battery performance, highlights the importance in preserving the surface properties of cathode materials, and provides new insights on the working mechanism of electrolyte additives.« less

Systems and methods for rebalancing redox flow battery electrolytes

DOEpatents

Pham, Ai Quoc; Chang, On Kok

2015-03-17

Various methods of rebalancing electrolytes in a redox flow battery system include various systems using a catalyzed hydrogen rebalance cell configured to minimize the risk of dissolved catalyst negatively affecting flow battery performance. Some systems described herein reduce the chance of catalyst contamination of RFB electrolytes by employing a mediator solution to eliminate direct contact between the catalyzed membrane and the RFB electrolyte. Other methods use a rebalance cell chemistry that maintains the catalyzed electrode at a potential low enough to prevent the catalyst from dissolving.

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.

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.

High performance red phosphorus electrode in ionic liquid-based electrolyte for Na-ion batteries

NASA Astrophysics Data System (ADS)

Dahbi, Mouad; Fukunishi, Mika; Horiba, Tatsuo; Yabuuchi, Naoaki; Yasuno, Satoshi; Komaba, Shinichi

2017-09-01

Electrochemical performance of the red phosphorus electrode was examined in ionic-liquid electrolyte, 0.25 mol dm-3 sodium bisfluorosulfonylamide (NaFSA) dissolved N-methyl-N-propylpyridinium-bisfluorosulfonylamide (MPPFSA), at room temperature. We compared its electrochemical performance to conventional EC/PC/DEC, EC/DEC, and PC solutions containing 1 mol dm-3 NaPF6. The electrode in NaFSA/MPPFSA demonstrated a reversible capacity of 1480 mAh g-1 and excellent capacity retention of 93% over 80 cycles, which is much better than those in the conventional electrolytes. The difference in capacity retention for the electrolytes correlates to the different solid electrolyte interphase (SEI) layer formed on the phosphorus electrode. To understand the SEI formation in NaFSA/MPPFSA and its evolution during cycling, we investigate the surface layer of the red phosphorus electrodes with hard X-ray photoelectron spectroscopy (HAXPES) and time-of-flight secondary ion mass spectrometry (TOF-SIMS). A detailed analysis of HAXPES spectra demonstrates that SEI layer consists of major inorganic and minor organic species, originating from decomposition of MPP+ and FSA-. Homogenous surface layer is formed during the first cycle in NaFSA/MPPFSA while in alkyl carbonate ester electrolytes, continuous growth of surface film up to the 20th cycle is observed. Possibility of red phosphorous electrode for battery applications with pure ionic liquid is discussed.

Effect of lithium and sodium salt on the performance of Nb2O5/rGO nanocomposite based supercapacitor

NASA Astrophysics Data System (ADS)

Ahmed, Sultan; Rafat, M.

2018-03-01

The present work reports the synthesis of Nb2O5/rGO composite using hydrothermal method and thermal annealing process. The prepared composite was found to have suitable characteristics necessary to be used as electrode material in supercapacitors. These characteristics were ascertained employing the techniques of scanning electron microscopy (SEM), x-ray diffraction (XRD), Raman spectroscopy and N2 adsorption-desorption isotherm. Further, the electrochemical performance of the prepared composite was compared in two different organic electrolytes, of lithium and sodium salt using the techniques of electrochemical impedance spectroscopy (EIS), cyclic voltammetry (CV) and charge-discharge measurements. The organic electrolyte solutions were prepared by dispersing 1 M LiClO4/NaClO4 in a mixture of ethylene carbonate/propylene carbonate (1:1 by volume). The observed results indicate that the composite of Nb2O5/rGO offers higher value of specific capacitance in sodium salt electrolyte and higher cyclic stability in lithium salt electrolyte. This is probably due to ion properties of electrolyte. Specific capacitance is observed according to efficient ion/charge diffusion/exchange and relaxation time (Li+ < Na+), while the cyclic stability is observed according to cation size (Na+ > Li+). Thus, the present study reveals the significant effect of electrolyte ions on electrochemical performance of Nb2O5/rGO composite.

Investigation on the interface between Li10GeP2S12 electrolyte and carbon conductive agents in all-solid-state lithium battery.

PubMed

Yoon, Kyungho; Kim, Jung-Joon; Seong, Won Mo; Lee, Myeong Hwan; Kang, Kisuk

2018-05-23

All-solid-state batteries are considered as one of the attractive alternatives to conventional lithium-ion batteries, due to their intrinsic safe properties benefiting from the use of non-flammable solid electrolytes in ASSBs. However, one of the issues in employing the solid-state electrolyte is the sluggish ion transport kinetics arising from the chemical and physical instability of the interfaces among solid components including electrode material, electrolyte and additive agents. In this work, we investigate the stability of the interface between carbon conductive agents and Li 10 GeP 2 S 12 in a composite cathode and its effect on the electrochemical performance of ASSBs. It is found that the inclusion of various carbon conductive agents in composite cathode leads to inferior kinetic performance of the cathode despite expectedly enhanced electrical conductivity of the composite. We observe that the poor kinetic performance is attributed to a large interfacial impedance which is gradually developed upon the inclusions of the various carbon conductive agents regardless of their physical differences. The analysis through X-ray Photoelectron Spectroscopy suggests that the carbon additives in the composite cathode stimulate the electrochemical decomposition of LGPS electrolyte degrading its surface during cycling, indicating the large interfacial resistance stems from the undesirable decomposition of the electrolyte at the interface.

Fluorinated Phosphazene Co-solvents for Improved Thermal and Safety Performance in Lithium-Ion Battery Electrolytes

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

Harry W. Rollins; Mason K. Harrup; Eric J. Dufek

2014-10-01

The safety of lithium-ion batteries is coming under increased scrutiny as they are being adopted for large format applications especially in the vehicle transportation industry and for grid-scale energy storage. The primary short-comings of lithium-ion batteries are the flammability of the liquid electrolyte and sensitivity to high voltage and elevated temperatures. We have synthesized a series of non-flammable fluorinated phosphazene liquids and blended them with conventional carbonate solvents. While the use of these phosphazenes as standalone electrolytes is highly desirable, they simply do not satisfy all of the many requirements that must be met such as high LiPF6 solubility andmore » low viscosity, thus we have used them as additives and co-solvents in blends with typical carbonates. The physical and electrochemical properties of the electrolyte blends were characterized, and then the blends were used to build 2032-type coin cells which were evaluated at constant current cycling rates from C/10 to C/1. We have evaluated the performance of the electrolytes by determining the conductivity, viscosity, flash point, vapor pressure, thermal stability, electrochemical window, cell cycling data, and the ability to form solid electrolyte interphase (SEI) films. This paper presents our results on a series of chemically similar fluorinated cyclic phosphazene trimers, the FM series, which has exhibited numerous beneficial effects on battery performance, lifetimes, and safety aspects.« less

Strongly correlated perovskite fuel cells

NASA Astrophysics Data System (ADS)

Zhou, You; Guan, Xiaofei; Zhou, Hua; Ramadoss, Koushik; Adam, Suhare; Liu, Huajun; Lee, Sungsik; Shi, Jian; Tsuchiya, Masaru; Fong, Dillon D.; Ramanathan, Shriram

2016-06-01

Fuel cells convert chemical energy directly into electrical energy with high efficiencies and environmental benefits, as compared with traditional heat engines. Yttria-stabilized zirconia is perhaps the material with the most potential as an electrolyte in solid oxide fuel cells (SOFCs), owing to its stability and near-unity ionic transference number. Although there exist materials with superior ionic conductivity, they are often limited by their ability to suppress electronic leakage when exposed to the reducing environment at the fuel interface. Such electronic leakage reduces fuel cell power output and the associated chemo-mechanical stresses can also lead to catastrophic fracture of electrolyte membranes. Here we depart from traditional electrolyte design that relies on cation substitution to sustain ionic conduction. Instead, we use a perovskite nickelate as an electrolyte with high initial ionic and electronic conductivity. Since many such oxides are also correlated electron systems, we can suppress the electronic conduction through a filling-controlled Mott transition induced by spontaneous hydrogen incorporation. Using such a nickelate as the electrolyte in free-standing membrane geometry, we demonstrate a low-temperature micro-fabricated SOFC with high performance. The ionic conductivity of the nickelate perovskite is comparable to the best-performing solid electrolytes in the same temperature range, with a very low activation energy. The results present a design strategy for high-performance materials exhibiting emergent properties arising from strong electron correlations.

Strongly correlated perovskite fuel cells

DOE PAGES

Zhou, You; Guan, Xiaofei; Zhou, Hua; ...

2016-05-16

Fuel cells convert chemical energy directly into electrical energy with high efficiencies and environmental benefits, as compared with traditional heat engines. Yttria-stabilized zirconia is perhaps the material with the most potential as an electrolyte in solid oxide fuel cells (SOFCs), owing to its stability and near-unity ionic transference number. Although there exist materials with superior ionic conductivity, they are often limited by their ability to suppress electronic leakage when exposed to the reducing environment at the fuel interface. Such electronic leakage reduces fuel cell power output and the associated chemo-mechanical stresses can also lead to catastrophic fracture of electrolyte membranes.more » Here we depart from traditional electrolyte design that relies on cation substitution to sustain ionic conduction. Instead, we use a perovskite nickelate as an electrolyte with high initial ionic and electronic conductivity. Since many such oxides are also correlated electron systems, we can suppress the electronic conduction through a filling-controlled Mott transition induced by spontaneous hydrogen incorporation. Using such a nickelate as the electrolyte in free-standing membrane geometry, we demonstrate a low-temperature micro-fabricated SOFC with high performance. The ionic conductivity of the nickelate perovskite is comparable to the best-performing solid electrolytes in the same temperature range, with a very low activation energy. The results present a design strategy for high-performance materials exhibiting emergent properties arising from strong electron correlations.« less

Investigation of lithium ion battery electrolytes containing flame retardants in combination with the film forming electrolyte additives vinylene carbonate, vinyl ethylene carbonate and fluoroethylene carbonate

NASA Astrophysics Data System (ADS)

Dagger, Tim; Grützke, Martin; Reichert, Matthias; Haetge, Jan; Nowak, Sascha; Winter, Martin; Schappacher, Falko M.

2017-12-01

In order to address the trade-off between the safety lithium ion battery (LIB) electrolytes and their electrochemical performance, synergetic effects of flame retardant additives (FRs) in combination with film forming additives (FFAs) are investigated. Triphenyl phosphate (TPP) and a silicon-containing additive (WA) are applied as FRs to improve the onset temperature of the thermal runaway of a LIB standard electrolyte (LP57: 1 M LiPF6 in EC:EMC 3:7) about 15 K and 28 K, respectively. The application of the FRs in MCMB graphite/lithium metal and NMC111/lithium metal three-electrode cells induces insufficiencies in terms of charge/discharge cycling stability and rate capability. It is investigated if the addition of FFAs can degrade the insufficiencies that are induced by the FRs. Vinylene carbonate, vinyl ethylene carbonate and fluoroethylene carbonate are added to a mixture of LP57 with 10% FR to enhance the cycling performance via improved interphase formation. Results reveal, that the rate capability of cells containing TPP or WA is especially improved by addition of 2% or 5% FEC, respectively. Postmortem analyses of the electrodes by SEM and of the electrolyte by GC-MS are performed. Direct correlations between the cycling behavior during the C-rate study and the electrolyte decomposition products are drawn.

Strongly correlated perovskite fuel cells.

PubMed

Zhou, You; Guan, Xiaofei; Zhou, Hua; Ramadoss, Koushik; Adam, Suhare; Liu, Huajun; Lee, Sungsik; Shi, Jian; Tsuchiya, Masaru; Fong, Dillon D; Ramanathan, Shriram

2016-06-09

Fuel cells convert chemical energy directly into electrical energy with high efficiencies and environmental benefits, as compared with traditional heat engines. Yttria-stabilized zirconia is perhaps the material with the most potential as an electrolyte in solid oxide fuel cells (SOFCs), owing to its stability and near-unity ionic transference number. Although there exist materials with superior ionic conductivity, they are often limited by their ability to suppress electronic leakage when exposed to the reducing environment at the fuel interface. Such electronic leakage reduces fuel cell power output and the associated chemo-mechanical stresses can also lead to catastrophic fracture of electrolyte membranes. Here we depart from traditional electrolyte design that relies on cation substitution to sustain ionic conduction. Instead, we use a perovskite nickelate as an electrolyte with high initial ionic and electronic conductivity. Since many such oxides are also correlated electron systems, we can suppress the electronic conduction through a filling-controlled Mott transition induced by spontaneous hydrogen incorporation. Using such a nickelate as the electrolyte in free-standing membrane geometry, we demonstrate a low-temperature micro-fabricated SOFC with high performance. The ionic conductivity of the nickelate perovskite is comparable to the best-performing solid electrolytes in the same temperature range, with a very low activation energy. The results present a design strategy for high-performance materials exhibiting emergent properties arising from strong electron correlations.

Ionic liquids as electrolytes for Li-ion batteries-An overview of electrochemical studies

NASA Astrophysics Data System (ADS)

Lewandowski, Andrzej; Świderska-Mocek, Agnieszka

The paper reviews properties of room temperature ionic liquids (RTILs) as electrolytes for lithium and lithium-ion batteries. It has been shown that the formation of the solid electrolyte interface (SEI) on the anode surface is critical to the correct operation of secondary lithium-ion batteries, including those working with ionic liquids as electrolytes. The SEI layer may be formed by electrochemical transformation of (i) a molecular additive, (ii) RTIL cations or (iii) RTIL anions. Such properties of RTIL electrolytes as viscosity, conductivity, vapour pressure and lithium-ion transport numbers are also discussed from the point of view of their influence on battery performance.

Imprintable, bendable, and shape-conformable polymer electrolytes for versatile-shaped lithium-ion batteries.

PubMed

Kil, Eun-Hye; Choi, Keun-Ho; Ha, Hyo-Jeong; Xu, Sheng; Rogers, John A; Kim, Mi Ri; Lee, Young-Gi; Kim, Kwang Man; Cho, Kuk Young; Lee, Sang-Young

2013-03-13

A class of imprintable, bendable, and shape-conformable polymer electrolyte with excellent electrochemical performance in a lithium battery system is reported. The material consists of a UV-cured polymer matrix, high-boiling point liquid electrolyte, and Al2 O3 nanoparticles, formulated for use in lithium-ion batteries with 3D-structured electrodes or flexible characteristics. The unique structural design and well-tuned rheological characteristics of the UV-curable electrolyte mixture, in combination with direct UV-assisted nanoimprint lithography, allow the successful fabrication of polymer electrolytes in geometries not accessible with conventional materials. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Impact of ionization equilibrium on electrokinetic flow of weak electrolytes in nanochannels

NASA Astrophysics Data System (ADS)

Ji, Ziwei; Huang, Zhuo; Chen, Bowei; He, Yuhui; Tsutsui, Makusu; Miao, Xiangshui

2018-07-01

Weak electrolyte transport in nanochannels or nanopores has been actively explored in recent experiments. In this paper, we establish a new electrokinetic model where the ionization balance effect of weak electrolytes is outlined, and performed numerical calculations for H3PO4 concentration-biased nanochannel systems. By considering the roles of local chemical equilibrium in phosphorous acid ionization, the simulation results show quantitative agreement with experimental observations. Based on the model, we predict that enhanced energy harvesting capacity could be accomplished by utilizing weak electrolytes compared to the conventional strong electrolyte approaches in a concentration gradient-based power-generating system.

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

A physical organogel electrolyte: characterized by in situ thermo-irreversible gelation and single-ion-predominent conduction

PubMed Central

Kim, Young-Soo; Cho, Yoon-Gyo; Odkhuu, Dorj; Park, Noejung; Song, Hyun-Kon

2013-01-01

Electrolytes are characterized by their ionic conductivity (σi). It is desirable that overall σi results from the dominant contribution of the ions of interest (e.g. Li+ in lithium ion batteries or LIB). However, high values of cationic transference number (t+) achieved by solid or gel electrolytes have resulted in low σi leading to inferior cell performances. Here we present an organogel polymer electrolyte characterized by a high liquid-electrolyte-level σi (~101 mS cm−1) with high t+ of Li+ (>0.8) for LIB. A conventional liquid electrolyte in presence of a cyano resin was physically and irreversibly gelated at 60°C without any initiators and crosslinkers, showing the behavior of lower critical solution temperature. During gelation, σi of the electrolyte followed a typical Arrhenius-type temperature dependency, even if its viscosity increased dramatically with temperature. Based on the Li+-driven ion conduction, LIB using the organogel electrolyte delivered significantly enhanced cyclability and thermal stability. PMID:23715177

Co-extrusion of electrolyte/anode functional layer/anode triple-layer ceramic hollow fibres for micro-tubular solid oxide fuel cells-electrochemical performance study

NASA Astrophysics Data System (ADS)

Li, Tao; Wu, Zhentao; Li, K.

2015-01-01

In this study, the effects of an anode functional layer (AFL) with controlled thickness on physical and electrochemical properties of a micro-tubular SOFC have been systematically studied. A series of electrolyte/AFL/anode triple-layer hollow fibres with controllable AFL thicknesses (16.9-52.7 μm) have been fabricated via a single-step phase-inversion assisted co-extrusion technique. Both robustness of the cell and gas-tightness of the electrolyte layer are considerably improved by introducing the AFL of this type. The fracture force of the sample with the thickest AFL (9.67 N) almost doubles when compared to the electrolyte/anode dual-layer counterpart (5.24 N). Gas-tightness of the electrolyte layer is also considerably increased as AFL contributes to better-matched sintering behaviours between different components. Moreover, the formation of an AFL simultaneously with electrolyte and anode significantly improves the cell performances. The sample with the thinnest AFL (approximately 16.9 μm, 6% of the total anode thickness) leads to a 30% (from 0.89 to 1.21 W cm-2) increase in maximum power density, due to increased triple-phase boundaries (TPB). However, further increase in TPB from a thicker AFL is less effective for improving the cell performance, due to the substantially increased fuel diffusion resistance and subsequently higher concentration polarization. This indicates that the control over the AFL thickness is critically important in avoiding offsetting the benefits of extended TPB and consequently decreased cell performances.

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.

Carbon Disulfide Cosolvent Electrolytes for High-Performance Lithium Sulfur Batteries.

PubMed

Gu, Sui; Wen, Zhaoyin; Qian, Rong; Jin, Jun; Wang, Qingsong; Wu, Meifen; Zhuo, Shangjun

2016-12-21

Development of lithium sulfur (Li-S) batteries with high Coulombic efficiency and long cycle stability remains challenging due to the dissolution and shuttle of polysulfides in electrolyte. Here, a novel additive, carbon disulfide (CS 2 ), to the organic electrolyte is reported to improve the cycling performance of Li-S batteries. The cells with the CS 2 -additive electrolyte exhibit high Coulombic efficiency and long cycle stability, showing average Coulombic efficiency >99% and a capacity retention of 88% over the entire 300 cycles. The function of the CS 2 additive is 2-fold: (1) it inhibits the migration of long-chain polysulfides to the anode by forming complexes with polysulfides and (2) it passivates electrode surfaces by inducing the protective coatings on both the anode and the cathode.

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.

Electrolytic cell-free 57Co deposition for emission Mössbauer spectroscopy

NASA Astrophysics Data System (ADS)

Zyabkin, Dmitry V.; Procházka, Vít; Miglierini, Marcel; Mašláň, Miroslav

2018-05-01

We have developed a simple, inexpensive and efficient method for an electrochemical preparation of samples for emission Mössbauer spectroscopy (EMS) and Mössbauer sources. The proposed electrolytic deposition procedure does not require any special setup, not even an electrolytic cell. It utilizes solely an electrode with a droplet of electrolyte on its surface and the second electrode sunk into the droplet. Its performance is demonstrated using two examples, a metallic glass and a Cu stripe. We present a detailed description of the deposition procedure and resulting emission Mössbauer spectra for both samples. In the case of a Cu stripe, we have performed EMS measurements at different stages of heat-treatment, which are required for the production of Mössbauer sources with the copper matrix.

Self‐Regulative Nanogelator Solid Electrolyte: A New Option to Improve the Safety of Lithium Battery

PubMed Central

Wu, Feng; Chen, Nan; Zhu, Qizhen; Tan, Guoqiang; Li, Li

2016-01-01

The lack of suitable nonflammable electrolytes has delayed battery application in electric vehicles. A new approach to improve the safety performance for lithium battery is proposed here. This technology is based on a nanogelator‐based solid electrolyte made of porous oxides and an ionic liquid. The electrolyte is fabricated using an in situ method and the porous oxides serve as a nonflammable “nanogelator” that spontaneously immobilizes the ionic liquid. The electrolyte exhibits a high liquid‐like apparent ionic conductivity of 2.93 × 10−3 S cm−1 at room temperature. The results show that the nanogelator, which possess self‐regulating ability, is able to immobilize imidazolium‐, pyrrolidinium‐, or piperidinium‐based ionic liquids, simply by adjusting the ion transport channels. Our prototype batteries made of Ti‐nanogeltor solid electrolyte outperform conventional lithium batteries made using ionic liquid and commercial organic liquid electrolytes. PMID:27774385

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

Self-Regulative Nanogelator Solid Electrolyte: A New Option to Improve the Safety of Lithium Battery.

PubMed

Wu, Feng; Chen, Nan; Chen, Renjie; Zhu, Qizhen; Tan, Guoqiang; Li, Li

2016-01-01

The lack of suitable nonflammable electrolytes has delayed battery application in electric vehicles. A new approach to improve the safety performance for lithium battery is proposed here. This technology is based on a nanogelator-based solid electrolyte made of porous oxides and an ionic liquid. The electrolyte is fabricated using an in situ method and the porous oxides serve as a nonflammable "nanogelator" that spontaneously immobilizes the ionic liquid. The electrolyte exhibits a high liquid-like apparent ionic conductivity of 2.93 × 10 -3 S cm -1 at room temperature. The results show that the nanogelator, which possess self-regulating ability, is able to immobilize imidazolium-, pyrrolidinium-, or piperidinium-based ionic liquids, simply by adjusting the ion transport channels. Our prototype batteries made of Ti-nanogeltor solid electrolyte outperform conventional lithium batteries made using ionic liquid and commercial organic liquid electrolytes.

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

Cycling performance of lithium metal polymer cells assembled with ionic liquid and poly(3-methyl thiophene)/carbon nanotube composite cathode

NASA Astrophysics Data System (ADS)

Kim, Dong-Won; Sivakkumar, S. R.; MacFarlane, Douglas R.; Forsyth, Maria; Sun, Yang-Kook

A poly(3-methylthiophene) (PMT)/multi-walled carbon nanotube (CNT) composite is synthesized by in situ chemical polymerization. The PMT/CNT composite is used as an active cathode material in lithium metal polymer cells assembled with ionic liquid (IL) electrolytes. The IL electrolyte consists of 1-ethyl-3-methylimidazolium tetrafluoroborate (EMIBF 4) and LiBF 4. A small amount of vinylene carbonate is added to the IL electrolyte to prevent the reductive decomposition of the imidazolium cation in EMIBF 4. A porous poly(vinylidene fluoride- co-hexafluoropropylene) (P(VdF- co-HFP)) film is used as a polymer membrane for assembling the cells. Electrochemical properties of the PMT/CNT composite electrode in the IL electrolyte are evaluated and the effect of vinylene carbonate on the cycling performance of the lithium metal polymer cells is investigated. The cells assembled with a non-flammable IL electrolyte and a PMT/CNT composite cathode are promising candidates for high-voltage-power sources with enhanced safety.

Simultaneous Stabilization of LiNi0.76Mn0.14Co0.10O2 Cathode and Lithium Metal Anode by LiBOB Additive.

PubMed

Zhao, Wengao; Zou, Lianfeng; Zheng, Jianming; Jia, Haiping; Song, Junhua; Engelhard, Mark H; Wang, Chongmin; Xu, Wu; Yang, Yong; Zhang, Ji-Guang

2018-05-01

The long-term cycling performance, rate capability, and voltage stability of lithium (Li) metal batteries with LiNi0.76Mn0.14Co0.10O2 (NMC76) cathodes is greatly enhanced by lithium bis(oxalato)borate (LiBOB) additive in the LiPF6-based electrolyte. With 2% LiBOB in the electrolyte, a Li||NMC76 cell is able to achieve a high capacity retention of 96.8% after 200 cycles at C/3 rate (1C = 200 mA g-1), which is the best result reported for a Ni-rich NMC cathode coupled with Li metal anode. The significantly enhanced electrochemical performance can be ascribed to the stabilization of both the NMC76-cathode/electrolyte and Li-metal-anode/electrolyte interfaces. LiBOB-containing electrolyte not only facilitates the formation of a more compact solid electrolyte interphase on the Li metal surface, it also forms a enhanced cathode electrolyte interface layer, which efficiently prevents the corrosion of the cathode interface and mitigates the formation of disordered rock-salt phase after cycling. The fundamental findings of this work highlight the importance of recognizing the dual effects of electrolyte additives in simultaneously stabilizing both cathode and anode interfaces, so as to enhance the long-term cycle life of high-energy-density battery systems. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

An experimental study on PEO polymer electrolyte based all-solid-state supercapacitor

NASA Astrophysics Data System (ADS)

Yijing, Yin

Supercapacitors are one of the most important electrochemical energy storage and conversion devices, however low ionic conductivity of solid state polymer electrolytes and the poor accessibility of the ions to the active sites in the porous electrode will cause low performance for all-solid-state supercapacitors and will limit their application. The objective of the dissertation is to improve the performance of all-solid-state supercapactor by improving electrolyte conductivity and solving accessibility problem of the ions to the active sites. The low ionic conductivity (10-8 S/cm) of poly(ethylene oxide) (PEO) limits its application as an electrolyte. Since PEO is a semicrystal polymer and the ion conduction take place mainly in the amorphous regions of the PEO/Lithium salt complex, improvements in the percentage of amorphous phase in PEO or increasing the charge carrier concentration and mobility could increase the ionic conductivity of PEO electrolyte. Hot pressing along with the additions of different lithium salts, inorganic fillers and plasticizers were applied to improve the ionic conductivity of PEO polymer electrolytes. Four electrode methods were used to evaluate the conductivity of PEO based polymer electrolytes. Results show that adding certain lithium salts, inorganic fillers, and plasticizers could improve the ionic conductivity of PEO electrolytes up 10-4 S/cm. Further hot pressing treatment could improve the ionic conductivity of PEO electrolytes up to 10-3 S/cm. The conductivity improvement after hot pressing treatment is elucidated as that the spherulite crystal phase is convert into the fringed micelle crystal phase or the amorphous phase of PEO electrolytes. PEO electrolytes were added into active carbon as a binder and an ion conductor, so as to provide electrodes with not only ion conduction, but also the accessibility of ion to the active sites of electrodes. The NaI/I 2 mediator was added to improve the conductivity of PEO electrolyte and provide pseudocapacitance for all-solid-state supercapacitors. Impedance, cyclic voltammetry, and gavalnostatic charge/discharge measurements were conducted to evaluate the electrochemical performance of PEO polymer electrolytes based all-solid-state supercapacitors. Results demonstrate that the conductivity of PEO electrolyte could be improved to 0.1 S/cm with a mediator concentration of 50wt%. A high conductivity in the PEO electrolyte with mediator is an indication of a high electron exchange rate between the mediator and mediator. The high electron exchange rates at mediator carbon interface and between mediator and mediator are essential in order to obtain a high response rate and high power. This automatically solves the accessibility problem. With the addition of NaI/I2 mediator, the specific capacitance increased more than 30 folds, specific power increased almost 20 folds, and specific energy increased around 10 folds. Further addition of filler to the electrodes along with the mediator could double the specific capacitor and specific power of the all-solid-state supercapacitor. The stability of the corresponded supercapacitor is good within 2000 cycles.

Lithium-Ion Electrolytes with Improved Safety Tolerance to High Voltage Systems

NASA Technical Reports Server (NTRS)

Smart, Marshall C. (Inventor); Prakash, Surya G. (Inventor); Bugga, Ratnakumar V. (Inventor); Krause, Frederick C. (Inventor)

2015-01-01

The invention discloses various embodiments of electrolytes for use in lithium-ion batteries, the electrolytes having improved safety and the ability to operate with high capacity anodes and high voltage cathodes. In one embodiment there is provided an electrolyte for use in a lithium-ion battery comprising an anode and a high voltage cathode. The electrolyte has a mixture of a cyclic carbonate of ethylene carbonate (EC) or mono-fluoroethylene carbonate (FEC) co-solvent, ethyl methyl carbonate (EMC), a flame retardant additive, a lithium salt, and an electrolyte additive that improves compatibility and performance of the lithium-ion battery with a high voltage cathode. The lithium-ion battery is charged to a voltage in a range of from about 2.0 V (Volts) to about 5.0 V (Volts).

Analysis of cell performance and thermal regeneration of a lithium-tin cell having an immobilized fused-salt electrolyte

NASA Technical Reports Server (NTRS)

Cairns, E. J.; Shimotake, H.

1969-01-01

Cell performance and thermal regeneration of a thermally regenerative cell uses lithium and tin and a fused-salt electrolyte. The emf of the Li-Sn cell, as a function of cathode-alloy composition, is shown to resemble that of the Na-Bi cell.

Influence of electrolytes (TEABF4 and TEMABF4) on electrochemical performance of graphite oxide derived from needle coke.

PubMed

Yang, Sunhye; Kim, Ick-Jun; Choi, In-Sik; Bae, Mi-Kyeong; Kim, Hyun-Soo

2013-05-01

The structure of needle coke was changed to graphite oxide structure after oxidation treatment with 70 wt.% of nitric acid and sodium chlorate (NaClO3), and the inter-layer distance of the oxidized needle coke was expanded to 6.9 angstroms. The first charge profile of the oxidized needle coke-cell with 1.2 M TEMABF4/acetonitrile solution displayed that the intercalation of electrolyte ions into the inter-layer occurred at 1.0 V, which value is lower than 1.3 V of the oxidized needle coke-cell with 1.2 M TEABF4/acetonitrile solution. After first charge/discharge, the cell using TEMABF4 electrolyte exhibited smaller electrode resistance of 0.05 omega, and larger specific volume capacitance of 25.5 F/ml at the two-electrode system in the potential range 0-2.5 V than those of the cell using TEABF4 electrolyte. Compared to the TEABF4 electrolyte, better electrochemical performance of the TEMABF4 electrolyte in the oxidized needle coke may be caused by the smaller cation (TEMA+) size and better ion mobility in the nanopores between inter-layers.

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.

Two-cation competition in ionic-liquid-modified electrolytes for lithium ion batteries.

PubMed

Lee, Sang-Young; Yong, Hyun Hang; Lee, Young Joo; Kim, Seok Koo; Ahn, Soonho

2005-07-21

It is a common observation that when ionic liquids are added to electrolytes the performances of lithium ion cells become poor, while the thermal safeties of the electrolytes might be improved. In this study, this behavior is investigated based on the kinetics of ionic diffusion. As a model ionic liquid, we chose butyldimethylimidazolium hexafluorophosphate (BDMIPF(6)). The common solvent was propylene carbonate (PC), and lithium hexafluorophosphate (LiPF(6)) was selected as the lithium conducting salt. Ionic diffusion coefficients are estimated by using a pulsed field gradient NMR technique. From a basic study on the model electrolytes (BDMIPF(6) in PC, LiPF(6) in PC, and BDMIPF(6) + LiPF(6) in PC), it was found that the BDMI(+) from BDMIPF(6) shows larger diffusion coefficients than the Li(+) from LiPF(6). However, the anionic (PF(6)(-)) diffusion coefficients present little difference between the model electrolytes. The higher diffusion coefficient of BDMI(+) than that of Li(+) suggests that the poor C-rate performance of lithium ion cells containing ionic liquids as an electrolyte component can be attributed to the two-cation competition between Li(+) and BDMI(+).

Honeycomb-like porous gel polymer electrolyte membrane for lithium ion batteries with enhanced safety.

PubMed

Zhang, Jinqiang; Sun, Bing; Huang, Xiaodan; Chen, Shuangqiang; Wang, Guoxiu

2014-08-29

Lithium ion batteries have shown great potential in applications as power sources for electric vehicles and large-scale energy storage. However, the direct uses of flammable organic liquid electrolyte with commercial separator induce serious safety problems including the risk of fire and explosion. Herein, we report the development of poly(vinylidene difluoride-co-hexafluoropropylene) polymer membranes with multi-sized honeycomb-like porous architectures. The as-prepared polymer electrolyte membranes contain porosity as high as 78%, which leads to the high electrolyte uptake of 86.2 wt%. The PVDF-HFP gel polymer electrolyte membranes exhibited a high ionic conductivity of 1.03 mS cm(-1) at room temperature, which is much higher than that of commercial polymer membranes. Moreover, the as-obtained gel polymer membranes are also thermally stable up to 350 °C and non-combustible in fire (fire-proof). When applied in lithium ion batteries with LiFePO4 as cathode materials, the gel polymer electrolyte demonstrated excellent electrochemical performances. This investigation indicates that PVDF-HFP gel polymer membranes could be potentially applicable for high power lithium ion batteries with the features of high safety, low cost and good performance.

Honeycomb-like porous gel polymer electrolyte membrane for lithium ion batteries with enhanced safety

NASA Astrophysics Data System (ADS)

Zhang, Jinqiang; Sun, Bing; Huang, Xiaodan; Chen, Shuangqiang; Wang, Guoxiu

2014-08-01

Lithium ion batteries have shown great potential in applications as power sources for electric vehicles and large-scale energy storage. However, the direct uses of flammable organic liquid electrolyte with commercial separator induce serious safety problems including the risk of fire and explosion. Herein, we report the development of poly(vinylidene difluoride-co-hexafluoropropylene) polymer membranes with multi-sized honeycomb-like porous architectures. The as-prepared polymer electrolyte membranes contain porosity as high as 78%, which leads to the high electrolyte uptake of 86.2 wt%. The PVDF-HFP gel polymer electrolyte membranes exhibited a high ionic conductivity of 1.03 mS cm-1 at room temperature, which is much higher than that of commercial polymer membranes. Moreover, the as-obtained gel polymer membranes are also thermally stable up to 350°C and non-combustible in fire (fire-proof). When applied in lithium ion batteries with LiFePO4 as cathode materials, the gel polymer electrolyte demonstrated excellent electrochemical performances. This investigation indicates that PVDF-HFP gel polymer membranes could be potentially applicable for high power lithium ion batteries with the features of high safety, low cost and good performance.

Honeycomb-like porous gel polymer electrolyte membrane for lithium ion batteries with enhanced safety

PubMed Central

Zhang, Jinqiang; Sun, Bing; Huang, Xiaodan; Chen, Shuangqiang; Wang, Guoxiu

2014-01-01

Lithium ion batteries have shown great potential in applications as power sources for electric vehicles and large-scale energy storage. However, the direct uses of flammable organic liquid electrolyte with commercial separator induce serious safety problems including the risk of fire and explosion. Herein, we report the development of poly(vinylidene difluoride-co-hexafluoropropylene) polymer membranes with multi-sized honeycomb-like porous architectures. The as-prepared polymer electrolyte membranes contain porosity as high as 78%, which leads to the high electrolyte uptake of 86.2 wt%. The PVDF-HFP gel polymer electrolyte membranes exhibited a high ionic conductivity of 1.03 mS cm−1 at room temperature, which is much higher than that of commercial polymer membranes. Moreover, the as-obtained gel polymer membranes are also thermally stable up to 350°C and non-combustible in fire (fire-proof). When applied in lithium ion batteries with LiFePO4 as cathode materials, the gel polymer electrolyte demonstrated excellent electrochemical performances. This investigation indicates that PVDF-HFP gel polymer membranes could be potentially applicable for high power lithium ion batteries with the features of high safety, low cost and good performance. PMID:25168687

Superior Performance of a Lithium-Sulfur Battery Enabled by a Dimethyl Trisulfide Containing Electrolyte

DOE PAGES

Chen, Shuru; Wang, Daiwei; Zhao, Yuming; ...

2018-04-26

The lithium-sulfur (Li-S) battery offers a high theoretical energy density of ≈2600 Wh/kg -1 and low cost, positioning it as a promising candidate for next-generation battery technology. However, problems including disastrous Li polysulfides dissolution and irreversible Li 2S deposition have severely retarded the development of Li-S batteries. To solve these issues, we recently reported a functional dimethyl disulfide (DMDS)-containing electrolyte that promoted an alternate electrochemical reaction pathway for sulfur cathodes by a formation of dimethyl polysulfides and Li organosulfides as intermediates and reduction products, leading to significantly boosted Li-S cell capacity with improved cycling reversibility and stability. Here in thismore » work, dimethyl trisulfide (DMTS), a primary discharge-charge intermediate in the DMDS-containing electrolyte, which is also a commercially available reagent, was further investigated as a co-solvent in functional electrolytes for Li-S batteries. Due to the higher theoretical capacity of DMTS and its better reactivity with Li 2S than DMDS, a 25 vol% DMTS-containing electrolyte enables Li-S batteries with even higher cell capacity and improved cycling performance than using previous optimal 50 vol% DMDS-containing electrolyte.« less

In Situ Raman Spectroscopic Studies on Concentration of Electrolyte Salt in Lithium-Ion Batteries by Using Ultrafine Multifiber Probes.

PubMed

Yamanaka, Toshiro; Nakagawa, Hiroe; Tsubouchi, Shigetaka; Domi, Yasuhiro; Doi, Takayuki; Abe, Takeshi; Ogumi, Zempachi

2017-03-09

Lithium-ion batteries have attracted considerable attention due to their high power density. The change in concentration of salt in the electrolyte solution in lithium-ion batteries during operation causes serious degradation of battery performance. Herein, a new method of in situ Raman spectroscopy with ultrafine multifiber probes was developed to simultaneously study the concentrations of ions at several different positions in the electrolyte solution in deep narrow spaces between the electrodes in batteries. The total amount of ions in the electrolyte solution clearly changed during operation due to the low permeability of the solid-electrolyte interphase (SEI) at the anode for Li + permeation. The permeability, which is a key factor to achieve high battery performance, was improved (enhanced) by adding film-forming additives to the electrolyte solution to modify the properties of the SEI. The results provide important information for understanding and predicting phenomena occurring in a battery and for designing a superior battery. The present method is useful for analysis in deep narrow spaces in other electrochemical devices, such as capacitors. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Superior Performance of a Lithium-Sulfur Battery Enabled by a Dimethyl Trisulfide Containing Electrolyte

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

Chen, Shuru; Wang, Daiwei; Zhao, Yuming

The lithium-sulfur (Li-S) battery offers a high theoretical energy density of ≈2600 Wh/kg -1 and low cost, positioning it as a promising candidate for next-generation battery technology. However, problems including disastrous Li polysulfides dissolution and irreversible Li 2S deposition have severely retarded the development of Li-S batteries. To solve these issues, we recently reported a functional dimethyl disulfide (DMDS)-containing electrolyte that promoted an alternate electrochemical reaction pathway for sulfur cathodes by a formation of dimethyl polysulfides and Li organosulfides as intermediates and reduction products, leading to significantly boosted Li-S cell capacity with improved cycling reversibility and stability. Here in thismore » work, dimethyl trisulfide (DMTS), a primary discharge-charge intermediate in the DMDS-containing electrolyte, which is also a commercially available reagent, was further investigated as a co-solvent in functional electrolytes for Li-S batteries. Due to the higher theoretical capacity of DMTS and its better reactivity with Li 2S than DMDS, a 25 vol% DMTS-containing electrolyte enables Li-S batteries with even higher cell capacity and improved cycling performance than using previous optimal 50 vol% DMDS-containing electrolyte.« less

Stability study of cermet-supported solid oxide fuel cells with bi-layered electrolyte

NASA Astrophysics Data System (ADS)

Zhang, Xinge; Gazzarri, Javier; Robertson, Mark; Decès-Petit, Cyrille; Kesler, Olivera

Performance and stability of five cermet-supported button-type solid oxide fuel cells featuring a bi-layered electrolyte (SSZ/SDC), an SSC cathode, and a Ni-SSZ anode, were analyzed using polarization curves, impedance spectroscopy, and post-mortem SEM observation. The cell performance degradation at 650 °C in H 2/air both with and without DC bias conditions was manifested primarily as an increase in polarization resistance, approximately at a rate of 2.3 mΩ cm 2 h -1 at OCV, suggesting a decrease in electrochemical kinetics as the main phenomenon responsible for the performance decay. In addition, the initial series resistance was about ten times higher than the calculated resistance corresponding to the electrolyte, reflecting a possible inter-reaction between the electrolyte layers that occurred during the sintering stage. In situ and ex situ sintered cathodes showed no obvious difference in cell performance or decay rate. The stability of the cells with and without electrical load was also investigated and no significant influence of DC bias was recorded. Based on the experimental results presented, we preliminarily attribute the performance degradation to electrochemical and microstructural degradation of the cathode.

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

Use of Additives to Improve Performance of Methyl Butyrate-Based Lithium-Ion Electrolytes

NASA Technical Reports Server (NTRS)

Smart, Marshall C.; Bugga, Ratnakumar V.

2011-01-01

This work addresses the need for robust rechargeable batteries that can operate well over a wide temperature range. To this end, a number of electrolyte formulations have been developed that incorporate the use of electrolyte additives to improve the high-temperature resilience, low-temperature power capability, and life characteristics of methyl butyrate-based electrolyte solutions. These electrolyte additives include mono-fluoroethylene carbonate (FEC), lithium oxalate, vinylene carbonate (VC), and lithium bis(oxalato)borate (LiBOB), which have been shown to result in improved high-temperature resilience of all carbonate-based electrolytes. Improved performance has been demonstrated of Li-ion cells with methyl butyrate-based electrolytes, including 1.20M LiPF6 in EC+EMC+MB (20:20:60 v/v %); 1.20M LiPF6 in EC+EMC+MB (20:20:60 v/v %) + 2% FEC; 1.20M LiPF6 in EC+EMC+MB (20:20:60 v/v %) + 4% FEC; 1.20M LiPF6 in EC+EMC+MB (20:20:60 v/v %) + lithium oxalate; 1.20M LiPF6 in EC+EMC+MB (20:20:60 v/v %) + 2% VC; and 1.20M LiPF6 in EC+EMC+MB (20:20:60 v/v %) + 0.10M LiBOB. These electrolytes have been shown to improve performance in MCMB-LiNiCoO2 and graphite-LiNi1/3Co1/3Mn1/3O2 experimental Li-ion cells. A number of LiPF6-based mixed carbonate electrolyte formulations have been developed that contain ester co-solvents, which have been optimized for operation at low temperature, while still providing reasonable performance at high temperature. For example, a number of ester co-solvents were investigated, including methyl propionate (MP), ethyl propionate (EP), methyl butyrate (MB), ethyl butyrate (EB), propyl butyrate (PB), and butyl butyrate (BB) in multi-component electrolytes of the following composition: 1.0M LiPF6 in ethylene carbonate (EC) + ethyl methyl carbonate (EMC) + X (20:60:20 v/v %) [where X = ester co-solvent]. ["Optimized Car bon ate and Ester-Based Li-Ion Electrolytes", NASA Tech Briefs, Vol. 32, No. 4 (April 2008), p. 56.] Focusing upon improved rate capability at low temperatures (i.e., 20 to 40 C), this approach was optimized further, resulting in the development of 1.20M LiPF6 in EC+EMC+MP (20:20:60 v/v %) and 1.20M LiPF6 in EC+EMC+EB (20:20:60 v/v %), which were demonstrated to operate well over a wide temperature range in MCMB-LiNiCoAlO2 and Li4Ti5O12(-)LiNiCoAlO2 prototype cells.

Thin Film Electrodes with an Integral Current Collection Grid for Use with Solid Electrolytes

NASA Technical Reports Server (NTRS)

Ryan, M. A.; Kisor, A.; Williams, R. M.; Jeffries-Nakamura, B.; O'Connor, D.

1994-01-01

Thin film, high performance electrodes which can operate in high temperature environments are necessary for many devices which use a solid electrolyte. Electrodes of rhodium-tungsten alloy have been deposited on solid electrolyte using photolytic chemical vapor deposition (PCVD). A technique for depositing electrodes and current collection grids simultaneously has been developed using the prenucleation characteristics of PCVD. This technique makes it possible to fabricate electrodes which allow vapor transport through the thin (<1 (micro)m) portions of the electrode while integral thick grid lines improve the electronic conductivity of the electrode, thus improving overall performance.

High Performance of Supercapacitor from PEDOT:PSS Electrode and Redox Iodide Ion Electrolyte

PubMed Central

Gao, Xing; Zu, Lei; Cai, Xiaomin; Li, Ce; Lian, Huiqin; Liu, Yang; Wang, Xiaodong; Cui, Xiuguo

2018-01-01

Insufficient energy density and poor cyclic stability is still challenge for conductive polymer-based supercapacitor. Herein, high performance electrochemical system has been assembled by combining poly (3,4-ethylenedioxythiophene) (PEDOT):poly (styrene sulfonate) (PSS) redox electrode and potassium iodide redox electrolyte, which provide the maximum specific capacity of 51.3 mAh/g and the retention of specific capacity of 87.6% after 3000 cycles due to the synergic effect through a simultaneous redox reaction both in electrode and electrolyte, as well as the catalytic activity for reduction of triiodide of the PEDOT:PSS. PMID:29772662

Method of making a high performance ultracapacitor

DOEpatents

Farahmandi, C. Joseph; Dispennette, John M.

2000-07-26

A high performance double layer capacitor having an electric double layer formed in the interface between activated carbon and an electrolyte is disclosed. The high performance double layer capacitor includes a pair of aluminum impregnated carbon composite electrodes having an evenly distributed and continuous path of aluminum impregnated within an activated carbon fiber preform saturated with a high performance electrolytic solution. The high performance double layer capacitor is capable of delivering at least 5 Wh/kg of useful energy at power ratings of at least 600 W/kg.

High performance cermet electrodes

DOEpatents

Isenberg, Arnold O.; Zymboly, Gregory E.

1986-01-01

Disclosed is a method of increasing the operating cell voltage of a solid oxide electrochemical cell having metal electrode particles in contact with an oxygen-transporting ceramic electrolyte. The metal electrode is heated with the cell, and oxygen is passed through the oxygen-transporting ceramic electrolyte to the surface of the metal electrode particles so that the metal electrode particles are oxidized to form a metal oxide layer between the metal electrode particles and the electrolyte. The metal oxide layer is then reduced to form porous metal between the metal electrode particles and the ceramic electrolyte.

Mixed organic compound-ionic liquid electrolytes for lithium battery electrolyte systems

NASA Astrophysics Data System (ADS)

Montanino, M.; Moreno, M.; Carewska, M.; Maresca, G.; Simonetti, E.; Lo Presti, R.; Alessandrini, F.; Appetecchi, G. B.

2014-12-01

The thermal, transport, rheological and flammability properties of electrolyte mixtures, proposed for safer lithium-ion battery systems, were investigated as a function of the mole composition. The blends were composed of a lithium salt (LiTFSI), organic solvents (namely EC, DEC) and an ionic liquid (PYR13TFSI). The main goal is to combine the fast ion transport properties of the organic compounds with the safe issues of the non-flammable and non-volatile ionic liquids. Preliminary tests in batteries have evidenced cycling performance approaching that observed in commercial organic electrolytes.

Enhanced electrochemical performance of in situ reduced graphene oxide-polyaniline nanotubes hybrid nanocomposites using redox-additive aqueous electrolyte

NASA Astrophysics Data System (ADS)

Devi, Madhabi; Kumar, A.

2018-02-01

Reduced graphene oxide (RGO)-polyaniline nanotubes (PAniNTs) nanocomposites have been synthesized by in situ reduction of GO. The morphology and structure of the nanocomposites are characterized by HRTEM, XRD and micro-Raman spectroscopy. The electrical and electrochemical performances of the nanocomposites are investigated for different RGO concentrations by conductivity measurements, cyclic voltammetry, charge-discharge and electrochemical impedance spectroscopy. Highest gravimetric specific capacitance of 448.71 F g-1 is obtained for 40 wt.% of RGO-PAniNTs nanocomposite as compared to 194.92 F g-1 for pure PAniNTs in 1 M KCl electrolyte. To further improve the electrochemical performance of the nanocomposite electrode, KI is used as redox-additive with 1 M KCl electrolyte. Highest gravimetric specific capacitance of 876.43 F g-1 and an improved cyclic stability of 91% as compared to 79% without KI after 5000 cycles is achieved for an optimized 0.1 M KI concentration. This is attributed to the presence of different ionic species of I- ions that give rise to a number of possible redox reactions improving the pseudocapacitance of the electrode. This improved capacitive performance is compared with that of catechol redox-additive in 1 M KCl electrolyte, and that of KI and catechol redox-additives added to 1 M H2SO4 electrolyte.

Structure and Li+ ion transport in a mixed carbonate/LiPF6 electrolyte near graphite electrode surfaces: a molecular dynamics study.

PubMed

Boyer, Mathew J; Vilčiauskas, Linas; Hwang, Gyeong S

2016-10-12

Electrolyte and electrode materials used in lithium-ion batteries have been studied separately to a great extent, however the structural and dynamical properties of the electrolyte-electrode interface still remain largely unexplored despite its critical role in governing battery performance. Using molecular dynamics simulations, we examine the structural reorganization of solvent molecules (cyclic ethylene carbonate : linear dimethyl carbonate 1 : 1 molar ratio doped with 1 M LiPF 6 ) in the vicinity of graphite electrodes with varying surface charge densities (σ). The interfacial structure is found to be sensitive to the molecular geometry and polarity of each solvent molecule as well as the surface structure and charge distribution of the negative electrode. We also evaluated the potential difference across the electrolyte-electrode interface, which exhibits a nearly linear variation with respect to σ up until the onset of Li + ion accumulation onto the graphite edges from the electrolyte. In addition, well-tempered metadynamics simulations are employed to predict the free-energy barriers to Li + ion transport through the relatively dense interfacial layer, along with analysis of the Li + solvation sheath structure. Quantitative analysis of the molecular arrangements at the electrolyte-electrode interface will help better understand and describe electrolyte decomposition, especially in the early stages of solid-electrolyte-interphase (SEI) formation. Moreover, the computational framework presented in this work offers a means to explore the effects of solvent composition, electrode surface modification, and operating temperature on the interfacial structure and properties, which may further assist in efforts to engineer the electrolyte-electrode interface leading to a SEI layer that optimizes battery performance.

A Fluorinated Ether Electrolyte Enabled High Performance Prelithiated Graphite/Sulfur Batteries

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

Chen, Shuru; Yu, Zhaoxin; Gordin, Mikhail L.

Lithium/sulfur (Li/S) batteries have attracted great attention as a promising energy storage technology, but so far their practical applications are greatly hindered by issues of polysulfide shuttling and unstable lithium/electrolyte interface. To address these issues, a feasible strategy is to construct a rechargeable prelithiated graphite/sulfur batteries. In this study, a fluorinated ether of bis(2,2,2-trifluoroethyl) ether (BTFE) was reported to blend with 1,3-dioxolane (DOL) for making a multifunctional electrolyte of 1.0 M LiTFSI DOL/BTFE (1:1, v/v) to enable high performance prelithiated graphite/S batteries. First, the electrolyte significantly reduces polysulfide solubility to suppress the deleterious polysulfide shuttling and thus improves capacity retentionmore » of sulfur cathodes. Second, thanks to the low viscosity and good wettability, the fluorinated electrolyte dramatically enhances the reaction kinetics and sulfur utilization of high-areal-loading sulfur cathodes. More importantly, this electrolyte forms a stable solid-electrolyte interphase (SEI) layer on graphite surface and thus enables remarkable cyclability of graphite anodes. Lastly, by coupling prelithiated graphite anodes with sulfur cathodes with high areal capacity of ~3 mAh cm -2, we demonstrate prelithiated graphite/sulfur batteries that show high sulfur-specific capacity of ~1000 mAh g -1 and an excellent capacity retention of >65% after 450 cycles at C/10.« less

A Fluorinated Ether Electrolyte Enabled High Performance Prelithiated Graphite/Sulfur Batteries

DOE PAGES

Chen, Shuru; Yu, Zhaoxin; Gordin, Mikhail L.; ...

2017-02-03

Lithium/sulfur (Li/S) batteries have attracted great attention as a promising energy storage technology, but so far their practical applications are greatly hindered by issues of polysulfide shuttling and unstable lithium/electrolyte interface. To address these issues, a feasible strategy is to construct a rechargeable prelithiated graphite/sulfur batteries. In this study, a fluorinated ether of bis(2,2,2-trifluoroethyl) ether (BTFE) was reported to blend with 1,3-dioxolane (DOL) for making a multifunctional electrolyte of 1.0 M LiTFSI DOL/BTFE (1:1, v/v) to enable high performance prelithiated graphite/S batteries. First, the electrolyte significantly reduces polysulfide solubility to suppress the deleterious polysulfide shuttling and thus improves capacity retentionmore » of sulfur cathodes. Second, thanks to the low viscosity and good wettability, the fluorinated electrolyte dramatically enhances the reaction kinetics and sulfur utilization of high-areal-loading sulfur cathodes. More importantly, this electrolyte forms a stable solid-electrolyte interphase (SEI) layer on graphite surface and thus enables remarkable cyclability of graphite anodes. Lastly, by coupling prelithiated graphite anodes with sulfur cathodes with high areal capacity of ~3 mAh cm -2, we demonstrate prelithiated graphite/sulfur batteries that show high sulfur-specific capacity of ~1000 mAh g -1 and an excellent capacity retention of >65% after 450 cycles at C/10.« less

Gel Electrolytes with Polyamidopyridine Dendron Modified Talc for Dye-Sensitized Solar Cells.

PubMed

Santana Andrade, Marcos A; Tiihonen, Armi; Miettunen, Kati; Lund, Peter; Nogueira, Ana F; Pastore, Heloise O

2017-06-21

Organic-inorganic hybrid layered materials are proposed as additives in a quasi-solid gel electrolyte for dye-sensitized solar cells. Talcs could provide a low-cost and environmentally friendly, as well as abundant, option as gelators. Here, talcs were prepared by functionalizing an organotalc with three polyamidopyridine dendron generations, PAMPy-talc-Gn (n = 1, 2 and 3). PAMPy dendrons grow parallel to the lamellae plane and form an organized structure by intermolecular interactions. In addition, polyiodide-dendron charge-transfer complexes were prepared onto the organotalc by adsorption of iodine. In this work, the effect of the dendron generation of PAMPy-talc and the influence of polyiodide intercalation on solar cell performance and stability were investigated. The best results were reached with the use of lowest-generation PAMPy-talc (η = 4.5 ± 0.3%, V OC = 710 ± 19 mV, J sc = 10.4 ± 0.9 mA cm -2 , and FF = 61 ± 2%): 15% higher efficiency compared to similar liquid devices. While some previously studied talcs illustrate very strong absorption of the iodide from the electrolyte, in the case of PAMPy-talc such interfering effects were absent: In a 1000 h light soaking test, the PAMPy-talc cells both with and without polyiodide intercalation demonstrated stable performances. Furthermore, the color analysis of the electrolyte indicated that the color of the electrolyte remained stable after an initial period of stabilization, which is a good indication of the compound being stable and not absorbing charge carriers from the electrolyte. The performance and stability results indicate that PAMPy-talc has potential as a gelling method for electrolytes for dye solar cells.

High-Performance Flexible Solid-State Supercapacitor with an Extended Nanoregime Interface through in Situ Polymer Electrolyte Generation.

PubMed

Anothumakkool, Bihag; Torris A T, Arun; Veeliyath, Sajna; Vijayakumar, Vidyanand; Badiger, Manohar V; Kurungot, Sreekumar

2016-01-20

Here, we report an efficient strategy by which a significantly enhanced electrode-electrolyte interface in an electrode for supercapacitor application could be accomplished by allowing in situ polymer gel electrolyte generation inside the nanopores of the electrodes. This unique and highly efficient strategy could be conceived by judiciously maintaining ultraviolet-triggered polymerization of a monomer mixture in the presence of a high-surface-area porous carbon. The method is very simple and scalable, and a prototype, flexible solid-state supercapacitor could even be demonstrated in an encapsulation-free condition by using the commercial-grade electrodes (thickness = 150 μm, area = 12 cm(2), and mass loading = 7.3 mg/cm(2)). This prototype device shows a capacitance of 130 F/g at a substantially reduced internal resistance of 0.5 Ω and a high capacitance retention of 84% after 32000 cycles. The present system is found to be clearly outperforming a similar system derived by using the conventional polymer electrolyte (PVA-H3PO4 as the electrolyte), which could display a capacitance of only 95 F/g, and this value falls to nearly 50% in just 5000 cycles. The superior performance in the present case is credited primarily to the excellent interface formation of the in situ generated polymer electrolyte inside the nanopores of the electrode. Further, the interpenetrated nature of the polymer also helps the device to show a low electron spin resonance and power rate and, most importantly, excellent shelf-life in the unsealed flexible conditions. Because the nature of the electrode-electrolyte interface is the major performance-determining factor in the case of many electrochemical energy storage/conversion systems, along with the supercapacitors, the developed process can also find applications in preparing electrodes for the devices such as lithium-ion batteries, metal-air batteries, polymer electrolyte membrane fuel cells, etc.

Performance of Low Temperature Electrolytes in Experimental and Prototype Li-Ion Cells

NASA Technical Reports Server (NTRS)

Smart, M. C.; Ratnakumar, B. V.; Whitcanack, L. D.

2007-01-01

Due to their attractive properties and proven success, Li-ion batteries have become identified as the battery chemistry of choice for a number of future NASA missions. A number of these applications would be greatly benefited by improved performance of Li-ion technology over a wider operating temperature range, especially at low temperatures, such as future ESMD missions. In many cases, these technology improvements may be mission enabling, and at the very least mission enhancing. In addition to aerospace applications, the DoE has interest in developing advanced Li-ion batteries that can operate over a wide temperature range to enable terrestrial HEV applications. Thus, our focus at JPL in recent years has been to extend the operating temperature range of Li-ion batteries, especially at low temperatures. To accomplish this, the main focus of the research has been devoted to developing improved lithium-ion conducting electrolytes. In the present paper, we would like to present some of the results we have obtained with ethylene carbonate-based electrolytes optimized for low temperature in experimental MCMB-LiNixCo1_x0 2 cells. In addition to obtaining discharge and charge rate performance data at various temperatures, electrochemical measurements were performed on individual electrodes (made possible by the incorporation of Li reference electrodes), including EIS, linear polarization and Tafel polarization measurements. The combination of techniques enables the elucidation of various trends associated with electrolyte composition. In addition to investigating the behavior in experimental cells, the performance of many promising low temperature electrolytes was demonstrated in large capacity, aerospace quality Li-ion prototype cells. These cells were subjected to a number of performance tests, including discharge rate characterization, charge rate characterization, cycle life performance at various temperatures, and power characterization tests.

Yttria-stabilized zirconia solid oxide electrolyte fuel cells: Monolithic solid oxide fuel cells

NASA Astrophysics Data System (ADS)

1990-10-01

The monolithic solid oxide fuel cell (MSOFC) is currently under development for a variety of applications including coal-based power generation. The MSOFC is a design concept that places the thin components of a solid oxide fuel cell in lightweight, compact, corrugated structure, and so achieves high efficiency and excellent performance simultaneously with high power density. The MSOFC can be integrated with coal gasification plants and is expected to have high overall efficiency in the conversion of the chemical energy of coal to electrical energy. This report describes work aimed at: (1) assessing manufacturing costs for the MSOFC and system costs for a coal-based plant; (2) modifying electrodes and electrode/electrolyte interfaces to improve the electrochemical performance of the MSOFC; and (3) testing the performance of the MSOFC on hydrogen and simulated coal gas. Manufacturing costs for both the coflow and crossflow MSOFC's were assessed based on the fabrication flow charts developed by direct scaleup of tape calendering and other laboratory processes. Integrated coal-based MSOFC systems were investigated to determine capital costs and costs of electricity. Design criteria were established for a coal-fueled 200-Mw power plant. Four plant arrangements were evaluated, and plant performance was analyzed. Interfacial modification involved modification of electrodes and electrode/electrolyte interfaces to improve the MSOFC electrochemical performance. Work in the cathode and cathode/electrolyte interface was concentrated on modification of electrode porosity, electrode morphology, electrode material, and interfacial bonding. Modifications of the anode and anode/electrolyte interface included the use of additives and improvement of nickel distribution. Single cells have been tested for their electrochemical performance. Performance data were typically obtained with humidified H2 or simulated coal gas and air or oxygen.

Physiological and performance effects of carbohydrate gels consumed prior to the extra-time period of prolonged simulated soccer match-play.

PubMed

Harper, Liam D; Briggs, Marc A; McNamee, Ged; West, Daniel J; Kilduff, Liam P; Stevenson, Emma; Russell, Mark

2016-06-01

The physiological and performance effects of carbohydrate-electrolyte gels consumed before the 30min extra-time period of prolonged soccer-specific exercise were investigated. Randomised, double-blind, crossover. Eight English Premier League academy soccer players performed 120min of soccer-specific exercise on two occasions while consuming fluid-electrolyte beverages before exercise, at half-time and 90min. Carbohydrate-electrolyte (0.7±0.1gkg(-1) BM) or energy-free placebo gels were consumed ∼5min before extra-time. Blood samples were taken before exercise, at half-time and every 15min during exercise. Physical (15-m and 30-m sprint speed, 30-m sprint maintenance and countermovement jump height) and technical (soccer dribbling) performance was assessed throughout each trial. Carbohydrate-electrolyte gels improved dribbling precision (+29±20%) and raised blood glucose concentrations by 0.7±0.8mmoll(-1) during extra-time (both p<0.01). Supplementation did not affect sprint velocities (15m and 30m), 30-m sprint maintenance or dribbling speed as reductions compared to 0-15min values occurred at 105-120min irrespective of trial (all p<0.05). Plasma osmolality and blood sodium concentrations increased post-exercise vs. the opening 15min (p<0.05) but no effect of supplementation existed. Selected markers of physical performance (jump height, 30-m sprint velocity and 30-m repeated sprint maintenance) also reduced by >3% during half-time (all p<0.05). Carbohydrate-electrolyte gel ingestion raised blood glucose concentrations and improved dribbling performance during the extra-time period of simulated soccer match-play. Supplementation did not attenuate reductions in physical performance and hydration status that occurred during extra-time. Copyright © 2015 Sports Medicine Australia. Published by Elsevier Ltd. All rights reserved.

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

Micromold methods for fabricating perforated substrates and for preparing solid polymer electrolyte composite membranes

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

Mittelsteadt, Cortney; Argun, Avni; Laicer, Castro

In polymer electrolyte membrane (PEM) fuel cells and electrolyzes, attaining and maintaining high membrane conductivity and durability is crucial for performance and efficiency. The use of low equivalent weight (EW) perfluorinated ionomers is one of the few options available to improve membrane conductivity. However, excessive dimensional changes of low EW ionomers upon application of wet/dry or freeze/thaw cycles yield catastrophic losses in membrane integrity. Incorporation of ionomers within porous, dimensionally-stable perforated polymer electrolyte membrane substrates provides improved PEM performance and longevity. The present invention provides novel methods using micromolds to fabricate the perforated polymer electrolyte membrane substrates. These novel methodsmore » using micromolds create uniform and well-defined pore structures. In addition, these novel methods using micromolds described herein may be used in batch or continuous processing.« less

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.

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.

Mixed-Salt/Ester Electrolytes for Low-Temperature Li+ Cells

NASA Technical Reports Server (NTRS)

Smart, Marshall; Bugga, Ratnakumar

2006-01-01

Electrolytes comprising, variously, LiPF6 or LiPF6 plus LiBF4 dissolved at various concentrations in mixtures of alkyl carbonates and alkyl esters have been found to afford improved low-temperature performance in rechargeable lithium-ion electrochemical cells. These and other electrolytes have been investigated in a continuing effort to extend the lower limit of operating temperatures of such cells. This research at earlier stages, and the underlying physical and chemical principles, were reported in numerous previous NASA Tech Briefs articles, the most recent being Ester-Based Electrolytes for Low-Temperature Li-Ion Cells (NPO-41097), NASA Tech Briefs, Vol. 29, No. 12 (December 2005), page 59. The ingredients of the solvent mixtures include ethylene carbonate (EC), ethyl methyl carbonate (EMC), methyl butyrate (MB), and methyl propionate (MP). The electrolytes were placed in Li-ion cells containing carbon anodes and LiNi0.8Co0.2O2 cathodes, and the electrical performances of the cells were measured over a range of temperatures down to 60 C. The electrolytes that yielded the best low-temperature performances were found to consist, variously, of 1.0 M LiPF6 + 0.4 M LiBF4 or 1.4 LiPF6 in 1EC + 1EMC + 8MP or 1EC + 1EMC + 8MB, where the concentrations of the salts are given in molar units and the proportions of the solvents are by relative volume.

[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.

Polymer Electrolyte Through Enzyme Catalysis for High Performance Lithium-Ion Batteries

DTIC Science & Technology

1998-10-16

by block number) FIELD GROUP SUB-GROUP Polymer Electrolyte, Solid State, Enzyme Catalysis, Lithium - Ion Battery , Sol Gel, High Conductivity 19...excellent candidates for lithium - ion battery development. Furthermore, the processes used to achieve the final product yield very good mechanical properties...Objectives This research was initiated to investigate synthesis of improved polymer electrolytes for lithium - ion battery applications. The overall

Improved performance of lithium–sulfur battery with fluorinated electrolyte

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

Azimi, Nasim; Weng, Wei; Takoudis, Christos

An organo-fluorine compound, 1,1,2,2-tetrafluoroethyl-2,2,3,3-tetrafluoropropyl ether (TTE), was investigated for the first time as the electrolyte solvent in the lithium–sulfur battery. The new fluorinated electrolyte suppressed the deleterious shuttling effect and improved the capacity retention and coulombic efficiency in cell tests. In addition, it was found to eliminate the self-discharge of the lithium–sulfur battery.

4-Vinyl-1,3-Dioxolane-2-One as an Additive for Li-Ion Cells

NASA Technical Reports Server (NTRS)

Smart, Marshall; Bugga, Ratnakumar

2006-01-01

Electrolyte additive 4-vinyl-1,3-dioxolane-2-one has been found to be promising for rechargeable lithium-ion electrochemical cells. This and other additives, along with advanced electrolytes comprising solutions of LiPF6 in various mixtures of carbonate solvents, have been investigated in a continuing effort to improve the performances of rechargeable lithium-ion electrochemical cells, especially at low temperatures. In contrast to work by other researchers who have investigated the use of this additive to improve the high-temperature resilience of Li-ion cells, the current work involves the incorporation of 4-vinyl-1,3-dioxolane-2-one into quaternary carbonate electrolyte mixtures, previously optimized for low-temperature applications, resulting in improved low-temperature performance. The benefit afforded by 4-vinyl-1,3- dioxolane-2-one can be better understood in the light of relevant information from a number of prior NASA Tech Briefs articles about electrolytes and additives for such cells. To recapitulate: The loss of performance with decreasing temperature is attributable largely to a decrease of ionic conductivity and the increase in viscosity of the electrolyte. What is needed to extend the lower limit of operating temperature is a stable electrolyte solution with relatively small lowtemperature viscosity, a large electric permittivity, adequate coordination behavior, and appropriate ranges of solubilities of liquid and salt constituents. Whether the anode is made of graphitic or non-graphitic carbon, a film on the surface of the anode acts as a solid/electrolyte interface (SEI), the nature of which is critical to low-temperature performance. Desirably, the surface film should exert a chemically protective (passivating) effect on both the anode and the electrolyte, yet should remain conductive to lithium ions to facilitate intercalation and de-intercalation of the ions into and out of the carbon during discharging and charging, respectively. The additives investigated previously include alkyl pyrocarbonates. Those additives help to improve low-temperature performances by giving rise to the formation of SEIs having desired properties. The formation of the SEIs is believed to be facilitated by products (e.g., CO2) of the decomposition of these additives. These decomposition products are believed to react to form Li2CO3-based films on the carbon electrodes. The present additive, 4-vinyl-1,3-dioxolane-2-one, also helps to improve lowtemperature performance by contributing to the formation of SEIs having desired properties, but probably in a different manner: It is believed that, as part of the decomposition process, the compound polymerizes on the surfaces of carbon electrodes.

Development of High Conductivity Lithium-Ion Electrolytes for Low Temperature Cell Applications

NASA Technical Reports Server (NTRS)

Smart, M. C.; Ratnakumar, B. V.; Surampudi, S.

1998-01-01

NASA has continued interest in developing power sources which are capable of operating at low temperatures (-20 C and below) to enable future missions, such as the Mars Rover and Lander. Thus, under a program sponsored by the Mars Exploration Program, we have been involved in developing Li-ion batteries with improved low temperature performance. To accomplish this task, the focus of the research has been upon the development of advanced electrolyte systems with improved low temperature properties. This had led to the identification of a carbonate-based electrolyte, consisting of 1.0 M LiPF6 in EC + DEC + DMC (33:33:34), which has been shown to have excellent performance at -20 C in Li-ion AA-size prototype cells. Other groups are also actively engaged in developing electrolytes which can result in improved low temperature performance of Li-ion cells, including Polystor, Yardney, and Covalent. In addition to developing cells capable of operation at -20 C, there is continued interest in systems which can successfully operate at even lower temperatures (less than -30 C) and at high discharge rates (greater than C/2). Thus, we are currently focusing upon developing advanced electrolytes which are highly conductive at low temperatures and will result in cells capable of operation at -40 C. One approach to improve the low temperature conductivity of ethylene carbonate-based electrolytes involves adding co-solvents which will decrease the viscosity and extend the liquid range. Candidate solvent additives include formates, acetates, cyclic and aliphatic ethers, lactones, as well as other carbonates. Using this approach, we have prepared a number of electrolytes which contain methyl formate (MF), methyl acetate (MA), ethyl acetate (EA), ethyl proprionate (EP), and 1,2-dimethoxyethane (DME), some of which have been characterized and reported. Other groups have also reported electrolytes based on mixtures of carbonates and acetates. In the present study, electrolytes which have been identified to have good low temperature conductivity and stability were incorporated into lithium-graphite cells for evaluation. Using various electrochemical methods, including ac impedence and DC micropolarization techniques, the film formation characteristics of graphite electrodes in contact with various lectrolyte formulations was investigated.

New Supercapacitors Based on the Synergetic Redox Effect between Electrode and Electrolyte

PubMed Central

Zhang, You; Cui, Xiuguo; Zu, Lei; Cai, Xiaomin; Liu, Yang; Wang, Xiaodong; Lian, Huiqin

2016-01-01

Redox electrolytes can provide significant enhancement of capacitance for supercapacitors. However, more important promotion comes from the synergetic effect and matching between the electrode and electrolyte. Herein, we report a novel electrochemical system consisted of a polyanilline/carbon nanotube composite redox electrode and a hydroquinone (HQ) redox electrolyte, which exhibits a specific capacitance of 7926 F/g in a three-electrode system when the concentration of HQ in H2SO4 aqueous electrolyte is 2 mol/L, and the maximum energy density of 114 Wh/kg in two-electrode symmetric configuration. Moreover, the specific capacitance retention of 96% after 1000 galvanostatic charge/discharge cycles proves an excellent cyclic stability. These ultrahigh performances of the supercapacitor are attributed to the synergistic effect both in redox polyanilline-based electrolyte and the redox hydroquinone electrode. PMID:28773855

Effects of Propylene Carbonate Content in CsPF6-Containing Electrolytes on the Enhanced Performances of Graphite Electrode for Lithium-Ion Batteries

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

Zheng, Jianming; Yan, Pengfei; Cao, Ruiguo

2016-02-10

Cesium salt has been demonstrated as an efficient electrolyte additive in suppressing the lithium (Li) dendrite formation and directing the formation of an ultrathin and stable solid electrolyte interphase (SEI) even in propylene carbonate (PC)-ethylene carbonate (EC)-based electrolytes. Here, we further investigate the effect of PC content in the presence of CsPF6 additive (0.05 M) on the performances of graphite electrode in Li||graphite half cells and in graphite||LiNi0.80Co0.15Al0.05O2 (NCA) full cells. It is found that the performance of graphite electrode is also affected by PC content even though CsPF6 additive is present in the electrolytes. An optimal PC content ofmore » 20% by weight in the solvent mixtures is identified. The enhanced electrochemical performance of graphite electrode is attributed to the synergistic effects of the Cs+ additive and the PC solvent. The formation of a robust, ultrathin and compact SEI layer containing lithium-enriched species on the graphite electrode, directed by Cs+, effectively suppresses the PC co-intercalation and thus prevents the graphite exfoliation. This SEI layer is only permeable for de-solvated Li+ ions and allows fast Li+ ion transport through it, which therefore largely alleviates the Li dendrite formation on graphite electrode during lithiation even at high current densities. The presence of low-melting-point PC solvent also enables the sustainable operation of the graphite||NCA full cells under a wide spectrum of temperatures. The fundamental findings of this work shed light on the importance of manipulating/maintaining the electrode/electrolyte interphasial stability in a variety of energy storage devices.« less

Advanced Proton Conducting Polymer Electrolytes for Electrochemical Capacitors

NASA Astrophysics Data System (ADS)

Gao, Han

Research on solid electrochemical energy storage devices aims to provide high performance, low cost, and safe operation solutions for emerging applications from flexible consumer electronics to microelectronics. Polymer electrolytes, minimizing device sealing and liquid electrolyte leakage, are key enablers for these next-generation technologies. In this thesis, a novel proton-conducing polymer electrolyte system has been developed using heteropolyacids (HPAs) and polyvinyl alcohol for electrochemical capacitors. A thorough understanding of proton conduction mechanisms of HPAs together with the interactions among HPAs, additives, and polymer framework has been developed. Structure and chemical bonding of the electrolytes have been studied extensively to identify and elucidate key attributes affecting the electrolyte properties. Numerical models describing the proton conduction mechanism have been applied to differentiate those attributes. The performance optimization of the polymer electrolytes through additives, polymer structural modifications, and synthesis of alternative HPAs has achieved several important milestones, including: (a) high proton mobility and proton density; (b) good ion accessibility at electrode/electrolyte interface; (c) wide electrochemical stability window; and (d) good environmental stability. Specifically, high proton mobility has been addressed by cross-linking the polymer framework to improve the water storage capability at normal-to-high humidity conditions (e.g. 50-80% RH) as well as by incorporating nano-fillers to enhance the water retention at normal humidity levels (e.g. 30-60% RH). High proton density has been reached by utilizing additional proton donors (i.e. acidic plasticizers) and by developing different HPAs. Good ion accessibility has been achieved through addition of plasticizers. Electrochemical stability window of the electrolyte system has also been investigated and expanded by utilizing HPAs with different heteroatoms. The optimized polymer electrolyte demonstrated even higher proton conductivity than pure HPAs and the enabled electrochemical capacitors have demonstrated an exceptionally high rate capability of 50 Vs-1 in cyclic voltammograms and a 10 ms time constant in impedance analyses.

Gel polymer electrolyte for lithium-ion batteries comprising cyclic carbonate moieties

NASA Astrophysics Data System (ADS)

Tillmann, S. D.; Isken, P.; Lex-Balducci, A.

2014-12-01

A polymer system based on oligo (ethylene glycol) methyl ether methacrylate (OEGMA) and cyclic carbonate methacrylate (CCMA) was chosen as matrix to realize high-performance gel polymer electrolytes due to the fact that both monomers are able to interact with the liquid electrolyte, thus, retaining it inside the matrix. Additionally, OEGMA enables high flexibility, while CCMA provides mechanical stability. The polymer displays a high thermal stability up to 200 °C and a glass transition temperature below room temperature (5 °C) allowing an easy handling of the obtained films. By immobilizing the liquid electrolyte 1 M LiPF6 in EC:DMC 1:1 w:w in the polymer host a gel polymer electrolyte with a high conductivity of 2.3 mS cm-1 at 25 °C and a stable cycling behavior with high capacities and efficiencies in Li(Ni1/3Co1/3Mn1/3)O2 (NCM)/graphite full cells is obtained. The investigated gel polymer electrolyte is identified as promising electrolyte for lithium-ion batteries, because it combines good electrochemical properties comparable to that of liquid electrolytes with the safety advantage that no leakage of the flammable electrolyte solvents can occur.

Origin of Outstanding Stability in the Lithium Solid Electrolyte Materials: Insights from Thermodynamic Analyses Based on First-Principles Calculations

DOE PAGES

Zhu, Yizhou; He, Xingfeng; Mo, Yifei

2015-10-06

First-principles calculations were performed to investigate the electrochemical stability of lithium solid electrolyte materials in all-solid-state Li-ion batteries. The common solid electrolytes were found to have a limited electrochemical window. Our results suggest that the outstanding stability of the solid electrolyte materials is not thermodynamically intrinsic but is originated from kinetic stabilizations. The sluggish kinetics of the decomposition reactions cause a high overpotential leading to a nominally wide electrochemical window observed in many experiments. The decomposition products, similar to the solid-electrolyte-interphases, mitigate the extreme chemical potential from the electrodes and protect the solid electrolyte from further decompositions. With the aidmore » of the first-principles calculations, we revealed the passivation mechanism of these decomposition interphases and quantified the extensions of the electrochemical window from the interphases. We also found that the artificial coating layers applied at the solid electrolyte and electrode interfaces have a similar effect of passivating the solid electrolyte. Our newly gained understanding provided general principles for developing solid electrolyte materials with enhanced stability and for engineering interfaces in all-solid-state Li-ion batteries.« less

Development of PVA based micro-porous polymer electrolyte by a novel preferential polymer dissolution process

NASA Astrophysics Data System (ADS)

Subramania, A.; Kalyana Sundaram, N. T.; Sukumar, N.

A micro-porous polymer electrolyte based on PVA was obtained from PVA-PVC based polymer blend film by a novel preferential polymer dissolution technique. The ionic conductivity of micro-porous polymer electrolyte increases with increase in the removal of PVC content. Finally, the effect of variation of lithium salt concentration is studied for micro-porous polymer electrolyte of high ionic conductivity composition. The ionic conductivity of the micro-porous polymer electrolyte is measured in the temperature range of 301-351 K. It is observed that a 2 M LiClO 4 solution of micro-porous polymer electrolyte has high ionic conductivity of 1.5055 × 10 -3 S cm -1 at ambient temperature. Complexation and surface morphology of the micro-porous polymer electrolytes are studied by X-ray diffraction and SEM analysis. TG/DTA analysis informs that the micro-porous polymer electrolyte is thermally stable upto 277.9 °C. Chronoamperommetry and linear sweep voltammetry studies were made to find out lithium transference number and stability of micro-porous polymer electrolyte membrane, respectively. Cyclic voltammetry study was performed for carbon/micro-porous polymer electrolyte/LiMn 2O 4 cell to reveal the compatibility and electrochemical stability between electrode materials.

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

Application of nonflammable electrolyte with room temperature ionic liquids (RTILs) for lithium-ion cells

NASA Astrophysics Data System (ADS)

Nakagawa, Hiroe; Fujino, Yukiko; Kozono, Suguru; Katayama, Yoshihiro; Nukuda, Toshiyuki; Sakaebe, Hikari; Matsumoto, Hajime; Tatsumi, Kuniaki

A mixture of flammable organic solvent and nonflammable room temperature ionic liquid (RTIL) has been investigated as a new concept electrolyte to improve the safety of lithium-ion cells. This study focused on the use of N-methyl- N-propylpiperidinium bis (trifluoromethanesulfonyl) imide (PP13-TFSI) as the RTIL for the flame-retardant additive. It was found that a carbon negative electrode, both graphite and hard carbon, could be used with the mixed electrolyte. A 383562-size lithium-ion trial cell made with the mixed electrolyte showed good discharge capacity, which was equivalent to a cell with conventional organic electrolyte up to a discharge current rate of complete discharge in 1 h. Moreover, the mixed electrolyte was observed to be nonflammable at ionic liquid contents of 40 mass% or more. Thus the mixed electrolyte was found to realize both nonflammability and the good discharge performance of lithium-ion cells with carbon negative electrodes. These results indicate that RTILs have potential as a flame-retardant additive for the organic electrolytes used in lithium-ion cells.

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

Allcorn, Eric

Lithium-ion battery safety is a critical issue in the adoption of the chemistry to larger scale applications such as transportation and stationary storage. One of the critical components impacting the safety of lithium-ion batteries is their use of highly flammable organic electrolytes. In this work, brominated flame retardants (BFR’s) – an existing class of flame retardant materials – are incorporated as additives to lithium-ion battery electrolytes with the intention to reduce the electrolyte flammability and thereby improve safety. There are a few critical needs for a successful electrolyte additive: solubility in the electrolyte, electrochemical stability over the range of batterymore » operation, and minimal detrimental effects on battery performance. Those detrimental effects can take the form of electrolyte specific impacts, such as a reduction in conductivity, or electrode impacts, such as SEI-layer modification or chemical instability to the active material. In addition to these needs, the electrolyte additive also needs to achieve its intended purpose, which in this case is to reduce the flammability of the electrolyte. For the work conducted as part of this SPP agreement three separate BFR materials were provided by Albemarle to be tested by Sandia as additives in a traditional lithium-ion battery electrolyte. The provided BFR materials were tribromo-neopentyl alcohol, tetrabromo bisphenol A, and tribromoethylene. These materials were incorporated as separate 4 wt.% additives into a traditional lithium-ion battery electrolyte and compared to said traditional electrolyte, designated Gen2.« less

Tribological and Corrosion Properties of Coatings Produced by Plasma Electrolytic Oxidation on the ZA27 Alloy

NASA Astrophysics Data System (ADS)

Li, Guangyin; Mao, Yifan; Li, Zhijian; Wang, Linlin; DaCosta, Herbert

2018-05-01

In this paper, a continuous and dense coating was deposited on samples of the ZA27 alloy through the plasma electrolytic oxidation (PEO) process to improve its wear and corrosion performance. A nontoxic and environmentally friendly inorganic salt, Na2SiO3, is chosen as electrolytes with different concentrations. The effect of the concentration of Na2SiO3 aqueous solutions on the coating performances was investigated. The coatings with 3Al2O3·2SiO2 (mullite), Zn2SiO4 and Al2O3 (either crystal phase or with some amorphous SiO2 phases) were formed by the PEO processes. It was found that the coating thickness increased with the increase in electrolyte concentration. However, the wear and corrosion resistance performance of the coatings did not improve as the coating's thickness increased. This was due to the fact that the coating produced with electrolytes of 10 g/L has a porous structure with large pore size. Among all the samples, coating produced by 15 g/L Na2SiO3 has the best wear and corrosion resistance, which is attributed to its continuous and dense structure with thickness of about 47 μm.

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.

The Effect of Electrolyte Additives upon the Lithium Kinetics of Li-Ion Cells Containing MCMB and LiNi(x)Co(1-x)O2 Electrodes and Exposed to High Temperatures

NASA Technical Reports Server (NTRS)

Smart, M. C.; Ratnakumar, B. V.; Gozdz, A. S.; Mani, S.

2009-01-01

With the intent of improving the performance of lithium-ion cells at high temperatures, we have investigated the use of a number of electrolyte additives in experimental MCMB- Li(x)Ni(y)Co(1-y)O2 cells, which were exposed to temperatures as high as 80 C. In the present work, we have evaluated the use of a number of additives, namely vinylene carbonate (VC), dimethyl acetamide (DMAc), and mono-fluoroethylene carbonate (FEC), in an electrolyte solution anticipated to perform well at warm temperature (i.e., 1.0M LiPF6 in EC+EMC (50:50 v/v %). In addition, we have explored the use of novel electrolyte additives, namely lithium oxalate and lithium tetraborate. In addition to determining the capacity and power losses at various temperatures sustained as a result of high temperature cycling (cycling performed at 60 and 80 C), the three-electrode MCMB-Li(x)Ni(y)Co(1-y)O2 cells (lithium reference) enabled us to study the impact of high temperature storage upon the solid electrolyte interphase (SEI) film characteristics on carbon anodes (MCMB-based materials), metal oxide cathodes, and the subsequent impact upon electrode kinetics.

Impact of Hot Environment on Fluid and Electrolyte Imbalance, Renal Damage, Hemolysis, and Immune Activation Postmarathon

PubMed Central

Oliveira, Rodrigo Assunção; Sierra, Ana Paula Rennó; Benetti, Marino; Ghorayeb, Nabil; Sierra, Carlos A.; Kiss, Maria Augusta Peduti Dal Molin

2017-01-01

Previous studies have demonstrated the physiological changes induced by exercise exposure in hot environments. We investigated the hematological and oxidative changes and tissue damage induced by marathon race in different thermal conditions. Twenty-six male runners completed the São Paulo International Marathon both in hot environment (HE) and in temperate environment (TE). Blood and urine samples were collected 1 day before, immediately after, 1 day after, and 3 days after the marathon to analyze the hematological parameters, electrolytes, markers of tissue damage, and oxidative status. In both environments, the marathon race promotes fluid and electrolyte imbalance, hemolysis, oxidative stress, immune activation, and tissue damage. The marathon runner's performance was approximately 13.5% lower in HE compared to TE; however, in HE, our results demonstrated more pronounced fluid and electrolyte imbalance, renal damage, hemolysis, and immune activation. Moreover, oxidative stress induced by marathon in HE is presumed to be related to protein/purine oxidation instead of other oxidative sources. Fluid and electrolyte imbalance and protein/purine oxidation may be important factors responsible for hemolysis, renal damage, immune activation, and impaired performance after long-term exercise in HE. Nonetheless, we suggested that the impairment on performance in HE was not associated to the muscle damage and lipoperoxidation. PMID:29430287

Tribological and Corrosion Properties of Coatings Produced by Plasma Electrolytic Oxidation on the ZA27 Alloy

NASA Astrophysics Data System (ADS)

Li, Guangyin; Mao, Yifan; Li, Zhijian; Wang, Linlin; DaCosta, Herbert

2018-04-01

In this paper, a continuous and dense coating was deposited on samples of the ZA27 alloy through the plasma electrolytic oxidation (PEO) process to improve its wear and corrosion performance. A nontoxic and environmentally friendly inorganic salt, Na2SiO3, is chosen as electrolytes with different concentrations. The effect of the concentration of Na2SiO3 aqueous solutions on the coating performances was investigated. The coatings with 3Al2O3·2SiO2 (mullite), Zn2SiO4 and Al2O3 (either crystal phase or with some amorphous SiO2 phases) were formed by the PEO processes. It was found that the coating thickness increased with the increase in electrolyte concentration. However, the wear and corrosion resistance performance of the coatings did not improve as the coating's thickness increased. This was due to the fact that the coating produced with electrolytes of 10 g/L has a porous structure with large pore size. Among all the samples, coating produced by 15 g/L Na2SiO3 has the best wear and corrosion resistance, which is attributed to its continuous and dense structure with thickness of about 47 μm.

Electrochemical studies of Copper, Tantalum and Tantalum Nitride surfaces in aqueous solutions for applications in chemical-mechanical and electrochemical-mechanical planarization

NASA Astrophysics Data System (ADS)

Sulyma, Christopher Michael

This report will investigate fundamental properties of materials involved in integrated circuit (IC) manufacturing. Individual materials (one at a time) are studied in different electrochemical environmental solutions to better understand the kinetics associated with the polishing process. Each system tries to simulate a real CMP environment in order to compare our findings with what is currently used in industry. To accomplish this, a variety of techniques are used. The voltage pulse modulation technique is useful for electrochemical processing of metal and alloy surfaces by utilizing faradaic reactions like electrodeposition and electrodissolution. A theoretical framework is presented in chapter 4 to facilitate quantitative analysis of experimental data (current transients) obtained in this approach. A typical application of this analysis is demonstrated for an experimental system involving electrochemical removal of copper surface layers, a relatively new process for abrasive-free electrochemical mechanical planarization of copper lines used in the fabrication of integrated circuits. Voltage pulse modulated electrodissolution of Cu in the absence of mechanical polishing is activated in an acidic solution of oxalic acid and hydrogen peroxide. The current generated by each applied voltage step shows a sharp spike, followed by a double-exponential decay, and eventually attains the rectangular shape of the potential pulses. For the second system in chapter 5, open-circuit potential measurements, cyclic voltammetry and Fourier transform impedance spectroscopy have been used to study pH dependent surface reactions of Cu and Ta rotating disc electrodes (RDEs) in aqueous solutions of succinic acid (SA, a complexing agent), hydrogen peroxide (an oxidizer), and ammonium dodecyl sulfate (ADS, a corrosion inhibitor for Cu). The surface chemistries of these systems are relevant for the development of a single-slurry approach to chemical mechanical planarization (CMP) of Cu lines and Ta barriers in the fabrication of semiconductor devices. It is shown that in non-alkaline solutions of H2O2, the SA-promoted surface complexes of Cu and Ta can potentially support chemically enhanced material removal in low-pressure CMP of surface topographies overlying fragile low-k dielectrics. ADS can suppress Cu dissolution without significantly affecting the surface chemistry of Ta. Chapter 6 discusses anodic corrosion of Ta, which is examined as a possible route to voltage induced removal of Ta for potential applications in electrochemical mechanical planarization (ECMP) of diffusion barriers. This strategy involves electro-oxidation of Ta in the presence of NO3- anions to form mechanically weak surface oxide films, followed by removal of the oxide layers by moderate mechanical abrasion. This NO3 - system is compared with a reference solution of Br -. In both electrolytes, the voltammetric currents of anodic oxidation exhibit oscillatory behaviors in the initial cycles of slow (5 mV s-1) voltage scans. The frequencies of these current oscillations are show signature attributes of localized pitting or general surface corrosion caused by Br- or NO3 -, respectively. Scanning electron microscopy, cyclic voltammetry, polarization resistance measurements, and time resolved Fourier transform impedance spectroscopy provide additional details about these corrosion mechanism. Apart from their relevance in the context of ECMP, the results also address certain fundamental aspects of pitting and general corrosions. The general protocols necessary to combine and analyze the results of D.C. and A.C. electrochemical measurements involving such valve metal corrosion systems are discussed in detail. In chapter 7 potassium salts of certain oxyanions (nitrate, sulfate and phosphate in particular) are shown to serve as effective surface-modifying agents in chemically enhanced, low-pressure chemical mechanical planarization (CMP) of Ta and TaN barrier layers for interconnect structures. The surface reactions that form the basis of this CMP strategy are investigated here in detail using the electrochemical techniques of cyclic voltammetry, open circuit potential analysis, polarization resistance measurements, and Fourier transform impedance spectroscopy. The results suggest that forming structurally weak oxide layers on the CMP samples is a key to achieving the goal of chemically controlled CMP of Ta/TaN at low down-pressures. (Abstract shortened by UMI.)

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

Aluminum-carbon composite electrode

DOEpatents

Farahmandi, C. Joseph; Dispennette, John M.

1998-07-07

A high performance double layer capacitor having an electric double layer formed in the interface between activated carbon and an electrolyte is disclosed. The high performance double layer capacitor includes a pair of aluminum impregnated carbon composite electrodes having an evenly distributed and continuous path of aluminum impregnated within an activated carbon fiber preform saturated with a high performance electrolytic solution. The high performance double layer capacitor is capable of delivering at least 5 Wh/kg of useful energy at power ratings of at least 600 W/kg.

Aluminum-carbon composite electrode

DOEpatents

Farahmandi, C.J.; Dispennette, J.M.

1998-07-07

A high performance double layer capacitor having an electric double layer formed in the interface between activated carbon and an electrolyte is disclosed. The high performance double layer capacitor includes a pair of aluminum impregnated carbon composite electrodes having an evenly distributed and continuous path of aluminum impregnated within an activated carbon fiber preform saturated with a high performance electrolytic solution. The high performance double layer capacitor is capable of delivering at least 5 Wh/kg of useful energy at power ratings of at least 600 W/kg. 3 figs.

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.

Research Progress towards Understanding the Unique Interfaces between Concentrated Electrolytes and Electrodes for Energy Storage Applications

PubMed Central

Lochala, Joshua A.; Kwok, Alexander; Deng, Zhiqun Daniel

2017-01-01

The electrolyte is an indispensable component in all electrochemical energy storage and conversion devices with batteries being a prime example. While most research efforts have been pursued on the materials side, the progress for the electrolyte is slow due to the decomposition of salts and solvents at low potentials, not to mention their complicated interactions with the electrode materials. The general properties of bulk electrolytes such as ionic conductivity, viscosity, and stability all affect the cell performance. However, for a specific electrochemical cell in which the cathode, anode, and electrolyte are optimized, it is the interface between the solid electrode and the liquid electrolyte, generally referred to as the solid electrolyte interphase (SEI), that dictates the rate of ion flow in the system. The commonly used electrolyte is within the range of 1–1.2 m based on the prior optimization experience, leaving the high concentration region insufficiently recognized. Recently, electrolytes with increased concentration (>1.0 m) have received intensive attention due to quite a few interesting discoveries in cells containing concentrated electrolytes. The formation mechanism and the nature of the SEI layers derived from concentrated electrolytes could be fundamentally distinct from those of the traditional SEI and thus enable unusual functions that cannot be realized using regular electrolytes. In this article, we provide an overview on the recent progress of high concentration electrolytes in different battery chemistries. The experimentally observed phenomena and their underlying fundamental mechanisms are discussed. New insights and perspectives are proposed to inspire more revolutionary solutions to address the interfacial challenges. PMID:28852621

Research Progress towards Understanding the Unique Interfaces between Concentrated Electrolytes and Electrodes for Energy Storage Applications

DOE PAGES

Zheng, Jianming; Lochala, Joshua A.; Kwok, Alexander; ...

2017-03-31

The electrolyte is an indispensable component in all electrochemical energy storage and conversion devices, for example, batteries. While most research efforts have been pursued on the materials side, the progress for the electrolyte is slow due to the decomposition of salts and solvents at low potentials, not to mention their complicated interactions with the electrode materials. The general properties of bulk electrolytes such as ionic conductivity, viscosity, and stability all affect the cell performance. However, for a specific electrochemical cell in which the cathode, anode and electrolyte are optimized, it is the interface between the solid electrode and the liquidmore » electrolyte, generally referred to as the solid electrolyte interphase (SEI), that dictates the rate of ion flow in the system. The commonly used electrolyte is within the range of 1-1.2 M based on the prior optimization experience, leaving the high concentration region insufficiently recognized. Recently, electrolytes with increased concentration (> 1.0 M) have received additional attention due to quite a few interesting discoveries in cells containing concentrated electrolytes. The formation mechanism and the nature of the SEI layers derived from concentrated electrolytes could be fundamentally different from those of the traditional SEI and thus enable unusual functions that cannot be realized using regular electrolytes. In this article, we provide an overview on the recent progress of high concentration electrolytes in different battery chemistries. The experimentally observed phenomena and their underlying fundamental mechanism are discussed. As a result, new insights and perspectives are proposed to inspire more revolutionary solutions to address the interfacial challenges.« less

Research Progress towards Understanding the Unique Interfaces between Concentrated Electrolytes and Electrodes for Energy Storage Applications.

PubMed

Zheng, Jianming; Lochala, Joshua A; Kwok, Alexander; Deng, Zhiqun Daniel; Xiao, Jie

2017-08-01

The electrolyte is an indispensable component in all electrochemical energy storage and conversion devices with batteries being a prime example. While most research efforts have been pursued on the materials side, the progress for the electrolyte is slow due to the decomposition of salts and solvents at low potentials, not to mention their complicated interactions with the electrode materials. The general properties of bulk electrolytes such as ionic conductivity, viscosity, and stability all affect the cell performance. However, for a specific electrochemical cell in which the cathode, anode, and electrolyte are optimized, it is the interface between the solid electrode and the liquid electrolyte, generally referred to as the solid electrolyte interphase (SEI), that dictates the rate of ion flow in the system. The commonly used electrolyte is within the range of 1-1.2 m based on the prior optimization experience, leaving the high concentration region insufficiently recognized. Recently, electrolytes with increased concentration (>1.0 m) have received intensive attention due to quite a few interesting discoveries in cells containing concentrated electrolytes. The formation mechanism and the nature of the SEI layers derived from concentrated electrolytes could be fundamentally distinct from those of the traditional SEI and thus enable unusual functions that cannot be realized using regular electrolytes. In this article, we provide an overview on the recent progress of high concentration electrolytes in different battery chemistries. The experimentally observed phenomena and their underlying fundamental mechanisms are discussed. New insights and perspectives are proposed to inspire more revolutionary solutions to address the interfacial challenges.

Research Progress towards Understanding the Unique Interfaces between Concentrated Electrolytes and Electrodes for Energy Storage Applications

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

Zheng, Jianming; Lochala, Joshua A.; Kwok, Alexander

The electrolyte is an indispensable component in all electrochemical energy storage and conversion devices, for example, batteries. While most research efforts have been pursued on the materials side, the progress for the electrolyte is slow due to the decomposition of salts and solvents at low potentials, not to mention their complicated interactions with the electrode materials. The general properties of bulk electrolytes such as ionic conductivity, viscosity, and stability all affect the cell performance. However, for a specific electrochemical cell in which the cathode, anode and electrolyte are optimized, it is the interface between the solid electrode and the liquidmore » electrolyte, generally referred to as the solid electrolyte interphase (SEI), that dictates the rate of ion flow in the system. The commonly used electrolyte is within the range of 1-1.2 M based on the prior optimization experience, leaving the high concentration region insufficiently recognized. Recently, electrolytes with increased concentration (> 1.0 M) have received additional attention due to quite a few interesting discoveries in cells containing concentrated electrolytes. The formation mechanism and the nature of the SEI layers derived from concentrated electrolytes could be fundamentally different from those of the traditional SEI and thus enable unusual functions that cannot be realized using regular electrolytes. In this article, we provide an overview on the recent progress of high concentration electrolytes in different battery chemistries. The experimentally observed phenomena and their underlying fundamental mechanism are discussed. As a result, new insights and perspectives are proposed to inspire more revolutionary solutions to address the interfacial challenges.« less

Alkali-Resistant Quasi-Solid-State Electrolyte for Stretchable Supercapacitors.

PubMed

Tang, Qianqiu; Wang, Wenqiang; Wang, Gengchao

2016-10-05

Research on stretchable energy-storage devices has been motivated by elastic electronics, and considerable research efforts have been devoted to the development of stretchable electrodes. However, stretchable electrolytes, another critical component in stretchable devices, have earned quite little attention, especially the alkali-resistant ones. Here, we reported a novel stretchable alkali-resistant electrolyte made of a polyolefin elastomer porous membrane supported potassium hydroxide-potassium polyacrylate (POE@KOH-PAAK). The as-prepared electrolyte shows a negligible plastic deformation even after 1000 stretching cycles at a strain of 150% as well as a high conductivity of 0.14 S cm -1 . It also exhibits excellent alkali resistance, which shows no obvious degradation of the mechanical performance after immersion in 2 M KOH for up to 2 weeks. To demonstrate its good properties, a high-performance stretchable supercapacitor is assembled using a carbon-nanotube-film-supported NiCo 2 O 4 (CNT@NiCo 2 O 4 ) as the cathode and Fe 2 O 3 (CNT@Fe 2 O 3 ) as the anode, proving great application promise of the stretchable alkali-resistant electrolyte in stretchable energy-storage devices.

Correlation of Electrolyte Volume and Electrochemical Performance in Lithium-Ion Pouch Cells with Graphite Anodes and NMC532 Cathodes

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

An, Seong Jin; Li, Jianlin; Mohanty, Debasish

2017-01-01

The work herein reports on studies aimed at exploring the correlation between electrolyte volume and electrochemical performance of full cell, pouch-cells consisting of graphite/ Li 1.02Ni 0.50Mn 0.29Co 0.19O 2 (NMC-532) as the electrodes and 1.2 M LiPF6 in ethylene carbonate:ethylmethyl carbonate (EC:EMC) as the electrolyte. It is demonstrated that a minimum electrolyte volume factor of 1.9 times the total pore volume of cell components (cathode, anode, and separator) is needed for long-term cyclability and low impedance. Less electrolyte results in an increase of the measured ohmic resistances. Increased resistance ratios for charge transfer and passivation layers at cathode, relativemore » to initial values, were 1.5–2.0 after 100 cycles. At the cathode, the resistance from charge transfer was 2–3 times higher than for passivation layers. Differential voltage analysis showed that anodes were less delithiated after discharging as the cells were cycled.« less

Effect of the Hydrofluoroether Cosolvent Structure in Acetonitrile-Based Solvate Electrolytes on the Li+ Solvation Structure and Li-S Battery Performance.

PubMed

Shin, Minjeong; Wu, Heng-Liang; Narayanan, Badri; See, Kimberly A; Assary, Rajeev S; Zhu, Lingyang; Haasch, Richard T; Zhang, Shuo; Zhang, Zhengcheng; Curtiss, Larry A; Gewirth, Andrew A

2017-11-15

We evaluate hydrofluoroether (HFE) cosolvents with varying degrees of fluorination in the acetonitrile-based solvate electrolyte to determine the effect of the HFE structure on the electrochemical performance of the Li-S battery. Solvates or sparingly solvating electrolytes are an interesting electrolyte choice for the Li-S battery due to their low polysulfide solubility. The solvate electrolyte with a stoichiometric ratio of LiTFSI salt in acetonitrile, (MeCN) 2 -LiTFSI, exhibits limited polysulfide solubility due to the high concentration of LiTFSI. We demonstrate that the addition of highly fluorinated HFEs to the solvate yields better capacity retention compared to that of less fluorinated HFE cosolvents. Raman and NMR spectroscopy coupled with ab initio molecular dynamics simulations show that HFEs exhibiting a higher degree of fluorination coordinate to Li + at the expense of MeCN coordination, resulting in higher free MeCN content in solution. However, the polysulfide solubility remains low, and no crossover of polysulfides from the S cathode to the Li anode is observed.

Tailor-Made Electrospun Multilayer Composite Polymer Electrolytes for High-Performance Lithium Polymer Batteries.

PubMed

Lim, Du-Hyun; Haridas, Anupriya K; Figerez, Stelbin Peter; Raghavan, Prasanth; Matic, Aleksandar; Ahn, Jou-Hyeon

2018-09-01

A novel tailor-made multilayer composite polymer electrolyte, consisting of two outer layers of electrospun polyacrylonitrile (PAN) and one inner layer of poly(vinyl acetate) (PVAc)/poly(methyl methacrylate) (PMMA)/poly(ethylene oxide) (PEO) fibrous membrane, was prepared using continuous electrospinning. These membranes, which are made up of fibers with diameters in the nanometer range, were stacked in layers to produce interconnected pores that result in a high porosity. Gel polymer electrolytes (GPEs) were prepared by entrapping a liquid electrolyte (1 M LiPF6 in ethylene carbonate/dimethyl carbonate) in the membranes. The composite membranes exhibited a high electrolyte uptake of 450-510%, coupled with an improved room temperature ionic conductivity of up to 4.72 mS cm-1 and a high electrochemical stability of 4.6 V versus Li/Li+. Electrochemical investigations of a composite membrane of PAN-PVAc-PAN, with a LiFePO4 cathode synthesized in-house, showed a high initial discharge capacity of 145 mAh g-1, which corresponds to 85% utilization of the active material, and displayed stable cycle performance.

Performance of intermediate temperature (600-800 °C) solid oxide fuel cell based on Sr and Mg doped lanthanum-gallate electrolyte

NASA Astrophysics Data System (ADS)

Gong, Wenquan; Gopalan, Srikanth; Pal, Uday B.

The solid electrolyte chosen for this investigation was La 0.9Sr 0.1Ga 0.8Mg 0.2O 3 (LSGM). To select appropriate electrode materials from a group of possible candidate materials, AC complex impedance spectroscopy studies were conducted between 600 and 800 °C on symmetrical cells that employed the LSGM electrolyte. Based on the results of the investigation, LSGM electrolyte supported solid oxide fuel cells (SOFCs) were fabricated with La 0.6Sr 0.4Co 0.8Fe 0.2O 3-La 0.9Sr 0.1Ga 0.8Mg 0.2O 3 (LSCF-LSGM) composite cathode and nickel-Ce 0.6La 0.4O 2 (Ni-LDC) composite anode having a barrier layer of Ce 0.6La 0.4O 2 (LDC) between the LSGM electrolyte and the Ni-LDC anode. Electrical performances of these cells were determined and the electrode polarization behavior as a function of cell current was modeled between 600 and 800 °C.

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

Facile and Reliable in Situ Polymerization of Poly(Ethyl Cyanoacrylate)-Based Polymer Electrolytes toward Flexible Lithium Batteries.

PubMed

Cui, Yanyan; Chai, Jingchao; Du, Huiping; Duan, Yulong; Xie, Guangwen; Liu, Zhihong; Cui, Guanglei

2017-03-15

Polycyanoacrylate is a very promising matrix for polymer electrolyte, which possesses advantages of strong binding and high electrochemical stability owing to the functional nitrile groups. Herein, a facile and reliable in situ polymerization strategy of poly(ethyl cyanoacrylate) (PECA) based gel polymer electrolytes (GPE) via a high efficient anionic polymerization was introduced consisting of PECA and 4 M LiClO 4 in carbonate solvents. The in situ polymerized PECA gel polymer electrolyte achieved an excellent ionic conductivity (2.7 × 10 -3 S cm -1 ) at room temperature, and exhibited a considerable electrochemical stability window up to 4.8 V vs Li/Li + . The LiFePO 4 /PECA-GPE/Li and LiNi 1.5 Mn 0.5 O 4 /PECA-GPE/Li batteries using this in-situ-polymerized GPE delivered stable charge/discharge profiles, considerable rate capability, and excellent cycling performance. These results demonstrated this reliable in situ polymerization process is a very promising strategy to prepare high performance polymer electrolytes for flexible thin-film batteries, micropower lithium batteries, and deformable lithium batteries for special purpose.

Effect of the Hydrofluoroether Cosolvent Structure in Acetonitrile-Based Solvate Electrolytes on the Li+ Solvation Structure and Li-S Battery Performance.

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

Shin, Minjeong; Wu, Heng-Liang; Narayanan, Badri

We evaluate hydrofluoroether (HFE) cosolvents with varying degrees of fluorination in the acetonitrile-based solvate electrolyte to determine the effect of the HFE structure on the electrochemical performance of the Li-S battery. Solvates or sparingly solvating electrolytes are an interesting electrolyte choice for the Li-S battery due to their low polysulfide solubility. The solvate electrolyte with a stoichiometric ratio of LiTFSI salt in acetonitrile, (MeCN)(2)-LiTFSI, exhibits limited polysulfide solubility due to the high concentration of LiTFSI. We demonstrate that the addition of highly fluorinated HFEs to the solvate yields better capacity retention compared to that of less fluorinated HFE cosolvents. Ramanmore » and NMR spectroscopy coupled with ab initio molecular dynamics simulations show that HFEs exhibiting a higher degree of fluorination coordinate to Li+ at the expense of MeCN coordination, resulting in higher free MeCN content in solution. However, the polysulfide solubility remains low, and no crossover of polysulfides from the S cathode to the Li anode is observed.« less

In situ analytical techniques for battery interface analysis.

PubMed

Tripathi, Alok M; Su, Wei-Nien; Hwang, Bing Joe

2018-02-05

Lithium-ion batteries, simply known as lithium batteries, are distinct among high energy density charge-storage devices. The power delivery of batteries depends upon the electrochemical performances and the stability of the electrode, electrolytes and their interface. Interfacial phenomena of the electrode/electrolyte involve lithium dendrite formation, electrolyte degradation and gas evolution, and a semi-solid protective layer formation at the electrode-electrolyte interface, also known as the solid-electrolyte interface (SEI). The SEI protects electrodes from further exfoliation or corrosion and suppresses lithium dendrite formation, which are crucial needs for enhancing the cell performance. This review covers the compositional, structural and morphological aspects of SEI, both artificially and naturally formed, and metallic dendrites using in situ/in operando cells and various in situ analytical tools. Critical challenges and the historical legacy in the development of in situ/in operando electrochemical cells with some reports on state-of-the-art progress are particularly highlighted. The present compilation pinpoints the emerging research opportunities in advancing this field and concludes on the future directions and strategies for in situ/in operando analysis.

Correlation of Electrolyte Volume and Electrochemical Performance in Lithium-Ion Pouch Cells with Graphite Anodes and NMC532 Cathodes

DOE PAGES

An, Seong Jin; Li, Jianlin; Mohanty, Debasish; ...

2017-04-07

The work herein reports on studies aimed at exploring the correlation between electrolyte volume and electrochemical performance of full cell, pouch-cells consisting of graphite/ Li 1.02Ni 0.50Mn 0.29Co 0.19O 2 (NMC-532) as the electrodes and 1.2 M LiPF 6 in ethylene carbonate:ethylmethyl carbonate (EC:EMC) as the electrolyte. In addition, it is demonstrated that a minimum electrolyte volume factor of 1.9 times the total pore volume of cell components (cathode, anode, and separator) is needed for long-term cyclability and low impedance. Less electrolyte results in an increase of the measured Ohmic resistances. Increased resistance ratios for charge transfer and passivation layersmore » at cathode, relative to initial values, were 1.5 2.0 after 100 cycles. At the cathode, the resistance from charge transfer was 2-3 times higher than for passivation layers. Lastly, differential voltage analysis showed that anodes were less delithiated after discharging as the cells were cycled.« less

Lithium insertion in graphite from ternary ionic liquid-lithium salt electrolytes. I. Electrochemical characterization of the electrolytes

NASA Astrophysics Data System (ADS)

Appetecchi, Giovanni B.; Montanino, Maria; Balducci, Andrea; Lux, Simon F.; Winterb, Martin; Passerini, Stefano

In this paper we report the results of chemical-physical investigation performed on ternary room temperature ionic liquid-lithium salt mixtures as electrolytes for lithium-ion battery systems. The ternary electrolytes were made by mixing N-methyl- N-propyl pyrrolidinium bis(fluorosulfonyl) imide (PYR 13FSI) and N-butyl- N-methylpyrrolidinium bis(trifluoromethanesulfonyl) imide (PYR 14TFSI) ionic liquids with lithium hexafluorophosphate (LiPF 6) or lithium bis(trifluoromethanesulfonyl)imide (LiTFSI). The mixtures were developed based on preliminary results on the cyclability of graphite electrodes in the IL-LiX binary electrolytes. The results clearly show the beneficial synergic effect of the two ionic liquids on the electrochemical properties of the mixtures.

Effect of polymer electrolyte on the performance of natural dye sensitized solar cells

NASA Astrophysics Data System (ADS)

Adel, R.; Abdallah, T.; Moustafa, Y. M.; Al-sabagh, A. M.; Talaat, H.

2015-10-01

Polymer electrolyte based on polyacrylonitrile (PAN), Ethylene Carbonate (EC) and Acetonitrile (ACN) mixed with Potassium Iodide and Iodine in liquid and thin film forms were employed in natural dye sensitized solar cells (NDSSCs). Three natural dyes; black berry, hibiscus and rose are used as the sensitizing dye. The NDSSCs used, follow the configuration: FTO/TiO2/Natural Dye/Electrolyte/ Carbon/FTO. The liquid form polymer electrolyte with black berry natural dye gives an increase of 111% in short circuit photocurrent density (Jsc), 17.5% to open circuit voltage (Voc), fill factor of 0.57 ± 0.05 and three times increase in the conversion efficiency of 0.242 ± 0.012% compared to the iodine electrolyte.

Metallization pattern on solid electrolyte or porous support of sodium battery process

DOEpatents

Kim, Jin Yong; Li, Guosheng; Lu, Xiaochuan; Sprenkle, Vincent L.; Lemmon, John P.

2016-05-31

A new battery configuration and process are detailed. The battery cell includes a solid electrolyte configured with an engineered metallization layer that distributes sodium across the surface of the electrolyte extending the active area of the cathode in contact with the anode during operation. The metallization layer enhances performance, efficiency, and capacity of sodium batteries at intermediate temperatures at or below about 200.degree. C.

Enhanced Performance of PbS-quantum-dot-sensitized Solar Cells via Optimizing Precursor Solution and Electrolytes

NASA Astrophysics Data System (ADS)

Tian, Jianjun; Shen, Ting; Liu, Xiaoguang; Fei, Chengbin; Lv, Lili; Cao, Guozhong

2016-03-01

This work reports a PbS-quantum-dot-sensitized solar cell (QDSC) with power conversion efficiency (PCE) of 4%. PbS quantum dots (QDs) were grown on mesoporous TiO2 film using a successive ion layer absorption and reaction (SILAR) method. The growth of QDs was found to be profoundly affected by the concentration of the precursor solution. At low concentrations, the rate-limiting factor of the crystal growth was the adsorption of the precursor ions, and the surface growth of the crystal became the limiting factor in the high concentration solution. The optimal concentration of precursor solution with respect to the quantity and size of synthesized QDs was 0.06 M. To further increase the performance of QDSCs, the 30% deionized water of polysulfide electrolyte was replaced with methanol to improve the wettability and permeability of electrolytes in the TiO2 film, which accelerated the redox couple diffusion in the electrolyte solution and improved charge transfer at the interfaces between photoanodes and electrolytes. The stability of PbS QDs in the electrolyte was also improved by methanol to reduce the charge recombination and prolong the electron lifetime. As a result, the PCE of QDSC was increased to 4.01%.

The oxidation of organic additives in the positive vanadium electrolyte and its effect on the performance of vanadium redox flow battery

NASA Astrophysics Data System (ADS)

Nguyen, Tam D.; Whitehead, Adam; Scherer, Günther G.; Wai, Nyunt; Oo, Moe O.; Bhattarai, Arjun; Chandra, Ghimire P.; Xu, Zhichuan J.

2016-12-01

Despite many desirable properties, the vanadium redox flow battery is limited, in the maximum operation temperature that can be continuously endured, before precipitation begins in the positive electrolyte. Many additives have been proposed to improve the thermal stability of the charged positive electrolyte. However, we have found that the apparent stability, revealed in laboratory testing, is often simply an artifact of the test method and arises from the oxidation of the additive, with corresponding partial reduction of V(V) to V(IV). This does not improve the stability of the electrolyte in an operating system. Here, we examined the oxidation of some typical organic additives with carboxyl, alcohol, and multi-functional groups, in sulfuric acid solutions containing V(V). The UV-vis measurements and titration results showed that many compounds reduced the state-of-charge (SOC) of vanadium electrolyte, for example, by 27.8, 88.5, and 81.9% with the addition of 1%wt of EDTA disodium salt, pyrogallol, and ascorbic acid, respectively. The cell cycling also indicated the effect of organic additives on the cell performance, with significant reduction in the usable charge capacity. In addition, a standard screening method for thermally stable additives was introduced, to quickly screen suitable additives for the positive vanadium electrolyte.

Effects of Anion Mobility on Electrochemical Behaviors of Lithium–Sulfur Batteries

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

Han, Kee Sung; Chen, Junzheng; Cao, Ruiguo

The electrolyte is a crucial component of lithium-sulfur (Li-S) batteries, as it controls polysulfide dissolution, charge shuttling processes, and solid-electrolyte interphase (SEI) layer formation. Experimentally, the overall performance of Li-S batteries varies with choice of solvent system and Li-salt used in the electrolyte, and a lack of predictive understanding about the effects of individual electrolyte components inhibits the rational design of electrolytes for Li-S batteries. Here we analyze the role of the counter anions of common Li salts (such as TfO-, FSI-, TFSI-, and TDI-) when dissolved in DOL/DME (1:1 vol.) for use in Li-S batteries. The evolution of ion-ionmore » and ion-solvent interactions due to vari-ous anions was analyzed using 17O NMR and pulsed-field gradient (PFG) NMR and then correlated with electrochemi-cal performance in Li-S cells. These data reveal that the for-mation of the passivation layer on the anode and the loss of active materials from the cathode (evidenced by polysulfide dissolution) are related to anion mobility and affinity with lithium polysulfide, respectively. For future electrolyte de-sign, anions with lower mobility and weaker interactions with lithium polysulfides may be superior candidates for increasing the long-term stability of Li-S batteries.« less

Ultraconcentrated Sodium Bis(fluorosulfonyl)imide-Based Electrolytes for High-Performance Sodium Metal Batteries.

PubMed

Lee, Jaegi; Lee, Yongwon; Lee, Jeongmin; Lee, Sang-Min; Choi, Jeong-Hee; Kim, Hyungsub; Kwon, Mi-Sook; Kang, Kisuk; Lee, Kyu Tae; Choi, Nam-Soon

2017-02-01

We present an ultraconcentrated electrolyte composed of 5 M sodium bis(fluorosulfonyl)imide in 1,2-dimethoxyethane for Na metal anodes coupled with high-voltage cathodes. Using this electrolyte, a very high Coulombic efficiency of 99.3% at the 120th cycle for Na plating/stripping is obtained in Na/stainless steel (SS) cells with highly reduced corrosivity toward Na metal and high oxidation durability (over 4.9 V versus Na/Na + ) without corrosion of the aluminum cathode current collector. Importantly, the use of this ultraconcentrated electrolyte results in substantially improved rate capability in Na/SS cells and excellent cycling performance in Na/Na symmetric cells without the increase of polarization. Moreover, this ultraconcentrated electrolyte exhibits good compatibility with high-voltage Na 4 Fe 3 (PO 4 ) 2 (P 2 O 7 ) and Na 0.7 (Fe 0.5 Mn 0.5 )O 2 cathodes charged to high voltages (>4.2 V versus Na/Na + ), resulting in outstanding cycling stability (high reversible capacity of 109 mAh g -1 over 300 cycles for the Na/Na 4 Fe 3 (PO 4 ) 2 (P 2 O 7 ) cell) compared with the conventional dilute electrolyte, 1 M NaPF 6 in ethylene carbonate/propylene carbonate (5/5, v/v).

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

Enhanced Performance of PbS-quantum-dot-sensitized Solar Cells via Optimizing Precursor Solution and Electrolytes.

PubMed

Tian, Jianjun; Shen, Ting; Liu, Xiaoguang; Fei, Chengbin; Lv, Lili; Cao, Guozhong

2016-03-15

This work reports a PbS-quantum-dot-sensitized solar cell (QDSC) with power conversion efficiency (PCE) of 4%. PbS quantum dots (QDs) were grown on mesoporous TiO2 film using a successive ion layer absorption and reaction (SILAR) method. The growth of QDs was found to be profoundly affected by the concentration of the precursor solution. At low concentrations, the rate-limiting factor of the crystal growth was the adsorption of the precursor ions, and the surface growth of the crystal became the limiting factor in the high concentration solution. The optimal concentration of precursor solution with respect to the quantity and size of synthesized QDs was 0.06 M. To further increase the performance of QDSCs, the 30% deionized water of polysulfide electrolyte was replaced with methanol to improve the wettability and permeability of electrolytes in the TiO2 film, which accelerated the redox couple diffusion in the electrolyte solution and improved charge transfer at the interfaces between photoanodes and electrolytes. The stability of PbS QDs in the electrolyte was also improved by methanol to reduce the charge recombination and prolong the electron lifetime. As a result, the PCE of QDSC was increased to 4.01%.

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.

Electrochemical performance and thermal stability analysis of LiNixCoyMnzO2 cathode based on a composite safety electrolyte.

PubMed

Jiang, Lihua; Wang, Qingsong; Sun, Jinhua

2018-06-05

LiNi x Co y Mn z O 2 (NCM) cathode material with high energy density is one of the best choices for power batteries. But the safety issue also becomes more prominent with higher nickel content. The improvement of thermal stability by material modification is often complex and limited. In this study, a composite safety electrolyte additive consisting of perfluoro-2-methyl-3-pentanone, N, N-Dimethylacetamide (and fluorocarbon surfactant is proved to be effective and simple in improving the thermal stability of NCM materials. Electrochemical compatibility of composite safety electrolyte with various NCM materials is investigated. Uniform interface film, lower impedance and polarization for NCM (622) cycled in composite safety electrolyte are proved to be the main reasons to ensure good cycle performance. Homemade pouch cells (NCM (622)/C) are used to verify the effectiveness for practical application, accelerating rate calorimeter and nail penetration test shows a slower temperature rise and delay of thermal runaway. For heating experiment, no fire appears for pouch cell with composite safety electrolyte. Thus, this composite safety electrolyte is effective to improve the safety of lithium ion batteries with NCM materials.(. Copyright © 2018 Elsevier B.V. All rights reserved.

Performance of Multi Walled Carbon Nanotubes Grown on Conductive Substrates as Supercapacitors Electrodes using Organic and Ionic liquid electrolytes

NASA Astrophysics Data System (ADS)

Winchester, Andrew; Ghosh, Sujoy; Turner, Ben; Zhang, X. F.; Talapatra, Saikat

2012-02-01

In this work we will present the use of Multi Walled Carbon Nanotubes (MWNT) directly grown on inconel substrates via chemical vapor deposition, as electrode materials for electrochemical double layer capacitors (EDLC). The performance of the MWNT EDLC electrodes were investigated using two electrolytes, an organic electrolyte, tetraethylammonium tetrafluoroborate in propylene carbonate (Et4NBF4 in PC), and a room temperature ionic liquid, 1-butyl-3-methylimidazolium hexafluorophosphate (BMIM-PF6). Cyclic voltammetry, galvanostatic charge-discharge, and electrochemical impedance spectroscopy measurements to obtain values for the capacitance and internal resistance of these devices will be presented and compared.

Nitrogen-doped carbon nanofibers derived from polypyrrole coated bacterial cellulose as high-performance electrode materials for supercapacitors and Li-ion batteries

DOE PAGES

Lei, Wen; Han, Lili; Xuan, Cuijuan; ...

2016-05-24

Here, nitrogen-doped carbon nanofiber (NDCN) was synthesized via carbonization of polypyrrole (PPy) coated bacterial cellulose (BC) composites, where BC serves as templates as well as precursor, and PPy serves as the nitrogen source. The synthesized NDCN was employed as electrode for both supercapacitors and Li-ion batteries. The large surface area exposed to electrolyte resulting from the 3D carbon networks leads to sufficient electrode/electrolyte interface and creates shorter transport paths of electrolyte ions and Li + ion. Besides, the three types of N dopants in NDCN improve the electronic conductivity, as well as superior electrochemical performance.

A novel small-molecule compound of lithium iodine and 3-hydroxypropionitride as a solid-state electrolyte for lithium–air batteries

DOE PAGES

Liu, Fang -Chao; Shadike, Zulipiya; Wang, Xiao -Fang; ...

2016-06-16

A novel small-molecule compound of lithium iodine and 3-hydroxypropionitrile (HPN) has been successfully synthesized. Our combined experimental and theoretical studies indicated that LiIHPN is a Li-ion conductor, which is utterly different from the I–-anion conductor of LiI(HPN) 2 reported previously. Solid-state lithium–air batteries based on LiIHPN as the electrolyte exhibit a reversible discharge capacity of more than 2100 mAh g –1 with a cyclic performance over 10 cycles. Lastly, our findings provide a new way to design solid-state electrolytes toward high-performance lithium–air batteries.

In Situ Analysis of Gas Generation in Lithium-Ion Batteries with Different Carbonate-Based Electrolytes.

PubMed

Teng, Xin; Zhan, Chun; Bai, Ying; Ma, Lu; Liu, Qi; Wu, Chuan; Wu, Feng; Yang, Yusheng; Lu, Jun; Amine, Khalil

2015-10-21

Gas generation in lithium-ion batteries is one of the critical issues limiting their safety performance and lifetime. In this work, a set of 900 mAh pouch cells were applied to systematically compare the composition of gases generated from a serial of carbonate-based composite electrolytes, using a self-designed gas analyzing system. Among electrolytes used in this work, the composite γ-butyrolactone/ethyl methyl carbonate (GBL/EMC) exhibited remarkably less gassing because of the electrochemical stability of the GBL, which makes it a promising electrolyte for battery with advanced safety and lifetime.

Lithium Ion Electrolytes and Lithium Ion Cells With Good Low Temperature Performance

NASA Technical Reports Server (NTRS)

Bugga, Ratnakumar V. (Inventor); Smart, Marshall C. (Inventor)

2014-01-01

There is provided in one embodiment of the invention an electrolyte for use in a lithium ion electrochemical cell. The electrolyte comprises a mixture of an ethylene carbonate (EC), an ethyl methyl carbonate (EMC), an ester cosolvent, and a lithium salt. The ester cosolvent comprises methyl propionate (MP), ethyl propionate (EP), methyl butyrate (MB), ethyl butyrate (EB), propyl butyrate (PB), or butyl butyrate (BB). The electrochemical cell operates in a temperature range of from about -60 C to about 60 C. In another embodiment there is provided a lithium ion electrochemical cell using the electrolyte of the invention.

Effects of adding ethanol to KOH electrolyte on electrochemical performance of titanium carbide-derived carbon

NASA Astrophysics Data System (ADS)

Xu, Jiang; Zhang, Ruijun; Chen, Peng; Ge, Shanhai

2014-01-01

Porous carbide-derived carbons (CDCs) are synthesized from TiC at different chlorination temperatures as electrode materials for electrochemical capacitors. It is found that the microstructure of the produced CDCs has significant influence on both the hydrophilicity in aqueous KOH electrolyte and the resultant electrochemical performance. Because the TiC-CDC synthesized at higher temperature (e.g. 1000 °C) contains well-ordered graphite ribbons, it shows lower hydrophilicity and specific capacitance. It is also found that addition of a small amount of ethanol to KOH electrolyte effectively improves the wettability of the CDCs synthesized at higher temperature and the corresponding specific capacitance. Compared with the CDC synthesized at 600 °C, the CDC synthesized at 1000 °C shows fast ion transport and excellent capacitive behavior in KOH electrolyte with addition of ethanol because of the existences of mesopores and high specific surface area.

Single-ion polymer electrolyte membranes enable lithium-ion batteries with a broad operating temperature range.

PubMed

Cai, Weiwei; Zhang, Yunfeng; Li, Jing; Sun, Yubao; Cheng, Hansong

2014-04-01

Conductive processes involving lithium ions are analyzed in detail from a mechanistic perspective, and demonstrate that single ion polymeric electrolyte (SIPE) membranes can be used in lithium-ion batteries with a wide operating temperature range (25-80 °C) through systematic optimization of electrodes and electrode/electrolyte interfaces, in sharp contrast to other batteries equipped with SIPE membranes that display appreciable operability only at elevated temperatures (>60 °C). The performance is comparable to that of batteries using liquid electrolyte of inorganic salt, and the batteries exhibit excellent cycle life and rate performance. This significant widening of battery operation temperatures coupled with the inherent flexibility and robustness of the SIPE membranes makes it possible to develop thin and flexible Li-ion batteries for a broad range of applications. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Co9 S8 /Co as a High-Performance Anode for Sodium-Ion Batteries with an Ether-Based Electrolyte.

PubMed

Zhao, Yingying; Pang, Qiang; Wei, Yingjin; Wei, Luyao; Ju, Yanming; Zou, Bo; Gao, Yu; Chen, Gang

2017-12-08

Co 9 S 8 has been regarded as a desirable anode material for sodium-ion batteries because of its high theoretical capacity. In this study, a Co 9 S 8 anode material containing 5.5 wt % Co (Co 9 S 8 /Co) was prepared by a solid-state reaction. The electrochemical properties of the material were studied in carbonate and ether-based electrolytes (EBE). The results showed that the material had a longer cycle life and better rate capability in EBE. This excellent electrochemical performance was attributed to a low apparent activation energy and a low overpotential for Na deposition in EBE, which improved the electrode kinetic properties. Furthermore, EBE suppressed side reactions of the electrode and electrolyte, which avoided the formation of a solid electrolyte interphase film. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

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.

Electrochemical performance of a solvent-free hybrid ceramic-polymer electrolyte based on Li7La3Zr2O12 in P(EO)15LiTFSI

NASA Astrophysics Data System (ADS)

Keller, Marlou; Appetecchi, Giovanni Battista; Kim, Guk-Tae; Sharova, Varvara; Schneider, Meike; Schuhmacher, Jörg; Roters, Andreas; Passerini, Stefano

2017-06-01

The preparation of hybrid ceramic-polymer electrolytes, consisting of 70 wt% of Li+ cation conducting Li7La3Zr2O12 (LLZO) and 30 wt% of P(EO)15LiTFSI polymer electrolyte, through a solvent-free procedure is reported. The LLZO-P(EO)15LiTFSI hybrid electrolytes exhibit remarkable improvement in terms of flexibility and processability with respect to pure LLZO ceramic electrolytes. The physicochemical and electrochemical investigation shows the effect of LLZO annealing, resulting in ion conduction gain. However, slow charge transfer at the ceramic-polymer interface is also observed especially at higher temperatures. Nevertheless, improved compatibility with lithium metal anodes and good Li stripping/plating behavior are exhibited by the LLZO-P(EO)15LiTFSI hybrid electrolytes with respect to P(EO)15LiTFSI.

Polyfluorinated boron cluster based salts: A new electrolyte for application in nonaqueous asymmetric AC/Li 4Ti 5O 12 supercapacitors

NASA Astrophysics Data System (ADS)

Ionica-Bousquet, C. M.; Muñoz-Rojas, D.; Casteel, W. J.; Pearlstein, R. M.; Kumar, G. Girish; Pez, G. P.; Palacín, M. R.

Solutions of novel fluorinated lithium dodecaborate (Li 2B 12F xH 12- x) salts have been evaluated as electrolytes in nonaqueous asymmetric supercapacitors with Li 4Ti 5O 12 as negative electrode, and activated carbon (AC) as positive electrode. The results obtained with these new electrolytes were compared with those obtained with cells built using standard 1 M LiPF 6 dissolved in ethylene carbonate and dimethyl carbonate (EC:DMC; 1:1, v/v) as electrolyte. The specific energy, rate capability, and cycling performances of nonaqueous asymmetric cells based on these new electrolyte salts were studied. Cells assembled using the new fluoroborate salts show excellent reversibility, coulombic efficiency, rate capability and improved cyclability when compared with the standard electrolyte. These features confirm the suitability of lithium-fluoro-borate based salts to be used in nonaqueous asymmetric supercapacitors.

Submicroporous/microporous and compatible/incompatible multi-functional dual-layer polymer electrolytes and their interfacial characteristics with lithium metal anode

NASA Astrophysics Data System (ADS)

Lee, Young-Gi; Kyhm, Kwangseuk; Choi, Nam-Soon; Ryu, Kwang Sun

A novel multi-functional dual-layer polymer electrolyte was prepared by impregnating the interconnected pores with an ethylene carbonate (EC)/dimethyl carbonate (DMC)/lithium hexafluorophosphate (LiPF 6) solution. An incompatible layer is based on a microporous polyethylene (PE) and a compatible layer, based on a poly(vinylidenefluoride-co-hexafluoropropylene) (P(VdF-co-HFP)) is sub-microporous and compatible with an electrolyte solution. The Li electrode/the dual-layer polymer electrolyte/Li[Ni 0.15Li 0.23M n0.62]O 2 cell showed stable cycle performance under prolonged cycle number. This behavior is due to the enhanced compatibility between the matrix polymer and the liquid electrolytes within the submicroporous compatible layer, which could lead to a controlled Li + deposition on the Li anode surface by forming homegeneous electrolyte zone near the anode.

Beneficial effect of added water on sodium metal cycling in super concentrated ionic liquid sodium electrolytes

NASA Astrophysics Data System (ADS)

Basile, Andrew; Ferdousi, Shammi A.; Makhlooghiazad, Faezeh; Yunis, Ruhamah; Hilder, Matthias; Forsyth, Maria; Howlett, Patrick C.

2018-03-01

The plating and stripping performance of sodium metal in an ionic liquid electrolyte is improved when including water as an additive. Herein we report for the first time the trend of improved cycling behavior of Na0/+ in N-methyl-N-propylpyrrolidinium bis(fluorosulfonyl)imide with 500 ppm H2O. The addition of water to this ionic liquid electrolyte promotes the breakdown of the [FSI]- anion towards beneficial SEI formation. The benefits during plating and stripping of sodium is observed as lower total polarization during symmetrical cell cycling and decreased electrode/electrolyte interface impedance. Sodium metal surfaces after cycling with 500 ppm H2O are shown to be smooth in morphology in comparison to lower additive concentrations. The outcome of adventitious moisture benefiting Na0/+ cycling in an ionic liquid, contrary to conventional electrolytes, allows flexibility in ionic liquid electrolyte design to the benefit of battery manufacturers.

Quantitative Chromatographic Determination of Dissolved Elemental Sulfur in the Non-aqueous Electrolyte for Lithium-Sulfur Batteries

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

Zheng, Dong; Yang, Xiao-Qing; Zhang, Xuran

A fast and reliable analytical method is reported for the quantitative determination of dissolved elemental sulfur in non-aqueous electrolytes for Li-S batteries. By using high performance liquid chromatography with a UV detector, the solubility of S in 12 different pure solvents and in 22 different electrolytes was determined. It was found that the solubility of elemental sulfur is dependent on the Lewis basicity, the polarity of solvents and the salt concentration in the electrolytes. In addition, the S content in the electrolyte recovered from a discharged Li-S battery was successfully determined by the proposed HPLC/UV method. Thus, the feasibility ofmore » the method to the online analysis for a Li-S battery is demonstrated. Interestingly, the S was found super-saturated in the electrolyte recovered from a discharged Li-S cell.« less

Quantitative Chromatographic Determination of Dissolved Elemental Sulfur in the Non-aqueous Electrolyte for Lithium-Sulfur Batteries

DOE PAGES

Zheng, Dong; Yang, Xiao-Qing; Zhang, Xuran; ...

2014-12-02

A fast and reliable analytical method is reported for the quantitative determination of dissolved elemental sulfur in non-aqueous electrolytes for Li-S batteries. By using high performance liquid chromatography with a UV detector, the solubility of S in 12 different pure solvents and in 22 different electrolytes was determined. It was found that the solubility of elemental sulfur is dependent on the Lewis basicity, the polarity of solvents and the salt concentration in the electrolytes. In addition, the S content in the electrolyte recovered from a discharged Li-S battery was successfully determined by the proposed HPLC/UV method. Thus, the feasibility ofmore » the method to the online analysis for a Li-S battery is demonstrated. Interestingly, the S was found super-saturated in the electrolyte recovered from a discharged Li-S cell.« less

Integrated Interface Strategy toward Room Temperature Solid-State Lithium Batteries.

PubMed

Ju, Jiangwei; Wang, Yantao; Chen, Bingbing; Ma, Jun; Dong, Shanmu; Chai, Jingchao; Qu, Hongtao; Cui, Longfei; Wu, Xiuxiu; Cui, Guanglei

2018-04-25

Solid-state lithium batteries have drawn wide attention to address the safety issues of power batteries. However, the development of solid-state lithium batteries is substantially limited by the poor electrochemical performances originating from the rigid interface between solid electrodes and solid-state electrolytes. In this work, a composite of poly(vinyl carbonate) and Li 10 SnP 2 S 12 solid-state electrolyte is fabricated successfully via in situ polymerization to improve the rigid interface issues. The composite electrolyte presents a considerable room temperature conductivity of 0.2 mS cm -1 , an electrochemical window exceeding 4.5 V, and a Li + transport number of 0.6. It is demonstrated that solid-state lithium metal battery of LiFe 0.2 Mn 0.8 PO 4 (LFMP)/composite electrolyte/Li can deliver a high capacity of 130 mA h g -1 with considerable capacity retention of 88% and Coulombic efficiency of exceeding 99% after 140 cycles at the rate of 0.5 C at room temperature. The superior electrochemical performance can be ascribed to the good compatibility of the composite electrolyte with Li metal and the integrated compatible interface between solid electrodes and the composite electrolyte engineered by in situ polymerization, which leads to a significant interfacial impedance decrease from 1292 to 213 Ω cm 2 in solid-state Li-Li symmetrical cells. This work provides vital reference for improving the interface compatibility for room temperature solid-state lithium batteries.

Promising Cell Configuration for Next-Generation Energy Storage: Li2S/Graphite Battery Enabled by a Solvate Ionic Liquid Electrolyte.

PubMed

Li, Zhe; Zhang, Shiguo; Terada, Shoshi; Ma, Xiaofeng; Ikeda, Kohei; Kamei, Yutaro; Zhang, Ce; Dokko, Kaoru; Watanabe, Masayoshi

2016-06-29

Lithium-ion sulfur batteries with a [graphite|solvate ionic liquid electrolyte|lithium sulfide (Li2S)] structure are developed to realize high performance batteries without the issue of lithium anode. Li2S has recently emerged as a promising cathode material, due to its high theoretical specific capacity of 1166 mAh/g and its great potential in the development of lithium-ion sulfur batteries with a lithium-free anode such as graphite. Unfortunately, the electrochemical Li(+) intercalation/deintercalation in graphite is highly electrolyte-selective: whereas the process works well in the carbonate electrolytes inherited from Li-ion batteries, it cannot take place in the ether electrolytes commonly used for Li-S batteries, because the cointercalation of the solvent destroys the crystalline structure of graphite. Thus, only very few studies have focused on graphite-based Li-S full cells. In this work, simple graphite-based Li-S full cells were fabricated employing electrolytes beyond the conventional carbonates, in combination with highly loaded Li2S/graphene composite cathodes (Li2S loading: 2.2 mg/cm(2)). In particular, solvate ionic liquids can act as a single-phase electrolyte simultaneously compatible with both the Li2S cathode and the graphite anode and can further improve the battery performance by suppressing the shuttle effect. Consequently, these lithium-ion sulfur batteries show a stable and reversible charge-discharge behavior, along with a very high Coulombic efficiency.

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.

Effects of Propylene Carbonate Content in CsPF 6 -Containing Electrolytes on the Enhanced Performances of Graphite Electrode for Lithium-Ion Batteries

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

Zheng, Jianming; Yan, Pengfei; Cao, Ruiguo

2016-02-15

The effects Of propylene carbonate (PC) content in CsPF6-containing electrolytes on the performances of graphite electrode in lithium half cells and in graphite parallel to LiNi0.80Co0.15Al0.05O2 (NCA) full cells are investigated. It is found that the performance of graphite electrode is significantly-affected by PC content in the CsPF6-containing electrolytes. An optimal PC content of 20% by weight in the solvent mixtures is identified. The enhanced electrochemical performance of graphite electrode can be attributed to the synergistic effects of the PC solvent and the Cs+ additive. The synergistic effects of Cs+ additive and appropriate amount of PC enable the formation ofmore » a robust, ultrathin, and compact solid electrolyte interphase (SEI) layer on the surface of graphite electrode, which is only permeable for desolvated Li+ ions and allows fast Li+ ion transport through it. Therefore, this SEI layer effectively suppresses the PC cointercalation and largely alleviates the Li dendrite formation on graphite electrode during lithiation even at relatively high current densities. The presence of low-melting-point PC solvent improves the sustainable operation of graphite parallel to NCA full cells under a wide temperature range. The fundamental findings also shed light On the importance of manipulating/maintaining the electrode/electrolyte interphasial stability in various energy-storage devices.« less

Effect of electrolytic lesion of the dorsomedial striatum on sexual behaviour and locomotor activity in rats.

PubMed

Ortiz-Pulido, R; Hernández-Briones, Z S; Tamariz-Rodríguez, A; Hernández, M E; Aranda-Abreu, G E; Coria-Avila, G A; Manzo, J; García, L I

2017-06-01

Cortical motor areas are influenced not only by peripheral sensory afferents and prefrontal association areas, but also by the basal ganglia, specifically the striatum. The dorsomedial striatum (DMS) and dorsolateral striatum are involved in both spatial and stimulus-response learning; however, each of these areas may mediate different components of learning. The aim of the study is to determine the effect of electrolytic lesion to the DMS on the learning and performance of sexual behaviour and locomotor activity in male rats. Once the subjects had learned to perform motor tests of balance, maze navigation, ramp ascent, and sexual behaviour, they underwent electrolytic lesion to the DMS. Five days later, the tests were repeated on 2 occasions and researchers compared performance latencies for each test. Average latency values for performance on the maze and balance tests were higher after the lesion. However, the average values for the ramp test and for sexual behaviour did not differ between groups. Electrolytic lesion of the DMS modifies the performance of locomotor activity (maze test and balance), but not of sexual behaviour. Copyright © 2015 Sociedad Española de Neurología. Publicado por Elsevier España, S.L.U. All rights reserved.

PC based electrolytes with LiDFOB as an alternative salt for lithium-ion batteries

NASA Astrophysics Data System (ADS)

Knight, Brandon M.

Lithium-ion batteries (LIBs) have been greatly sought after as a source of renewable energy storage. LIBs have a wide range of applications including but not limited portable electronic devices, electric vehicles, and power tools. As a direct result of their commercial viability an insatiable hunger for knowledge, advancement within the field of LIBs has been omnipresent for the last two decades. However, there are set backs evident within the LIB field; most notably the limitations of standard electrolyte formulations and LiPF6 lithium salt. The standard primary carbonate of ethylene carbonate (EC) has a very limited operating range due to its innate physical properties, and the LiPF6 salt is known to readily decompose to form HF which can further degrade LIB longevity. The goal of our research is to explore the use of a new primary salt LiDFOB in conjunction with a propylene carbonate based electrolyte to establish a more flexible electrolyte formulation by constructing coin cells and cycling them under various conditions to give a clear understanding of each formulation inherent performance capabilities. Our studies show that 1.2M LiDFOB in 3:7 PC/EMC + 1.5% VC is capable of performing comparably to the standard 1.2M LiPF6 in 3:7 EC/EMC at 25°C and the PC electrolyte also illustrates performance superior to the standard at 55°C. The degradation of lithium manganese spinel electrodes, including LiNi 0.5Mn1.5O4, is an area of great concern within the field of lithium ion batteries (LIBs). Manganese containing cathode materials frequently have problems associated with Mn dissolution which significantly reduces the cycle life of LIB. Thus the stability of the cathode material is paramount to the performance of Mn spinel cathode materials in LIBs. In an effort to gain a better understanding of the stability of LiNi0.5 Mn1.5O4 in common LiPF6/carbonate electrolytes, samples were stored at elevated temperature in the presence of electrolyte. Then after storage both the electrolyte solution and uncharged cathode particles were analyzed. The solid cathode particles were analyzed via scanning electron microscopy (SEM) whereas the electrolyte solution was analyzed using inductively coupled plasma mass spectroscopy (ICP-MS). The SEM analysis assists with elucidation of changes to the surfaces of the cathode particles. The ICP-MS of the electrolyte allows the determination of the extent of Mn and Ni dissolution. Samples of LiNi0.5Mn1.5O4 with different crystal surface facets were prepared to investigate the role of particle morphology in Mn and Ni dissolution. The factors affecting Mn and Ni dissolution and methods to inhibit dissolution will be discussed.

Thermally responsive polymer electrolytes for inherently safe electrochemical energy storage

NASA Astrophysics Data System (ADS)

Kelly, Jesse C.

Electrochemical double layer capacitors (EDLCs), supercapacitors and Li-ion batteries have emerged as premier candidates to meet the rising demands in energy storage; however, such systems are limited by thermal hazards, thermal runaway, fires and explosions, all of which become increasingly more dangerous in large-format devices. To prevent such scenarios, thermally-responsive polymer electrolytes (RPEs) that alter properties in electrochemical energy storage devices were designed and tested. These RPEs will be used to limit or halt device operation when temperatures increase beyond a predetermined threshold, therefore limiting further heating. The development of these responsive systems will offer an inherent safety mechanism in electrochemical energy storage devices, while preserving the performance, lifetimes, and versatility that large-format systems require. Initial work focused on the development of a model system that demonstrated the concept of RPEs in an electrochemical device. Aqueous electrolyte solutions of polymers exhibiting properties that change in response to temperature were developed for applications in EDLCs and supercapacitors. These "smart materials" provide a means to control electrochemical systems where polymer phase separation at high temperatures affects electrolyte properties and inhibits device performance. Aqueous RPEs were synthesized using N-isopropylacrylamide, which governs the thermal properties, and fractions of acrylic acid or vinyl sulfonic acids, which provide ions to the solution. The molecular properties of these aqueous RPEs, specifically the ionic composition, were shown to influence the temperature-dependent electrolyte properties and the extent to which these electrolytes control the energy storage characteristics of a supercapacitor device. Materials with high ionic content provided the highest room temperature conductivity and electrochemical activity; however, RPEs with low ionic content provided the highest "on-off" ratio in electrochemical activity at elevated temperatures. Overall, solution pH and conductivity were altered by an order of magnitude and device performance (ability to store charge) decreased by over 70%. After demonstration of a model responsive electrolyte in an aqueous system, ionic liquid (IL) based electrolytes were developed as a means of controlling the electrochemical performance in the non-aqueous environments that batteries, specifically Li-ion, require. Here, two systems were developed: (1) an electrolyte comprising poly(ethylene oxide) (PEO), the IL, [EMIM][BF4], and a lithium salt and (2) an electrolyte comprising poly(benzyl methacrylate) (PBzMA), the IL, [EMIM][TFSI], and a lithium salt. In each system, the polymer-IL phase separation inhibited device operation at elevated temperatures. For the PEO/IL electrolyte, the thermally induced liquid-liquid phase separation was shown to decrease the ionic conductivity, thereby affecting the concentration of ions at the electrode. Additionally, an increasing charge transfer resistance associated with the phase separated polymer coating the porous electrode was shown to limit electrochemical activity significantly. For the PBzMA/IL electrolyte, the solid-liquid phase separation did not show a change in conductivity, but did cause a drastic increase in charge transfer resistance, effectively shutting off Li-ion battery operation at high temperatures. Such responsive mixtures provide a transformative approach to regulating electrochemical processes, which is necessary to achieve inherently safe operation in large format energy storage with EDLCs, supercapacitors and Li-ion batteries.

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.

Evaluation of Ca3Co2O6 as cathode material for high-performance solid-oxide fuel cell

PubMed Central

Wei, Tao; Huang, Yun-Hui; Zeng, Rui; Yuan, Li-Xia; Hu, Xian-Luo; Zhang, Wu-Xing; Jiang, Long; Yang, Jun-You; Zhang, Zhao-Liang

2013-01-01

A cobalt-based thermoelectric compound Ca3Co2O6 (CCO) has been developed as new cathode material with superior performance for intermediate-temperature (IT) solid-oxide fuel cell (SOFC). Systematic evaluation has been carried out. Measurement of thermal expansion coefficient (TEC), thermal-stress (σ) and interfacial shearing stress (τ) with the electrolyte show that CCO matches well with several commonly-used IT electrolytes. Maximum power density as high as 1.47 W cm−2 is attained at 800°C, and an additional thermoelectric voltage of 11.7 mV is detected. The superior electrochemical performance, thermoelectric effect, and comparable thermal and mechanical behaviors with the electrolytes make CCO to be a promising cathode material for SOFC. PMID:23350032

Mesopore- and Macropore-Dominant Nitrogen-Doped Hierarchically Porous Carbons for High-Energy and Ultrafast Supercapacitors in Non-Aqueous Electrolytes.

PubMed

Shao, Rong; Niu, Jin; Liang, Jingjing; Liu, Mengyue; Zhang, Zhengping; Dou, Meiling; Huang, Yaqin; Wang, Feng

2017-12-13

Non-aqueous electrolytes (e.g., organic and ionic liquid electrolytes) can undergo high working voltage to improve the energy densities of supercapacitors. However, the large ion sizes, high viscosities, and low ionic conductivities of organic and ionic liquid electrolytes tend to cause the low specific capacitances, poor rate, and cycling performance of supercapacitors based on conventional micropore-dominant activated carbon electrodes, limiting their practical applications. Herein, we propose an effective strategy to simultaneously obtain high power and energy densities in non-aqueous electrolytes via using a cattle bone-derived porous carbon as an electrode material. Because of the unique co-activation of KOH and hydroxyapatite (HA) within the cattle bone, nitrogen-doped hierarchically porous carbon (referred to as NHPC-HA/KOH) is obtained and possesses a mesopore- and macropore-dominant porosity with an ultrahigh specific surface area (2203 m 2 g -1 ) of meso- and macropores. The NHPC-HA/KOH electrodes exhibit superior performance with specific capacitances of 224 and 240 F g -1 at 5 A g -1 in 1.0 M TEABF 4 /AN and neat EMIMBF 4 electrolyte, respectively. The symmetric supercapacitor using NHPC-HA/KOH electrodes can deliver integrated high energy and power properties (48.6 W h kg -1 at 3.13 kW kg -1 in 1.0 M TEABF 4 /AN and 75 W h kg -1 at 3.75 kW kg -1 in neat EMIMBF 4 ), as well as superior cycling performance (over 89% of the initial capacitance after 10 000 cycles at 10 A g -1 ).

A F-doped tree-like nanofiber structural poly-m-phenyleneisophthalamide separator for high-performance lithium-sulfur batteries

NASA Astrophysics Data System (ADS)

Deng, Nanping; Wang, Yan; Yan, Jing; Ju, Jingge; Li, Zongjie; Fan, Lanlan; Zhao, Huijuan; Kang, Weimin; Cheng, Bowen

2017-09-01

In this study, F-doped tree-like nanofiber structural poly-m-phenyleneisophthalamide (PMIA) membranes are prepared via one-step electrospinning approach and their application performance as separators for lithium-sulfur batteries are discussed. The F-doped PMIA membrane can be regarded as matrix to form gel polymer electrolyte. The F doping endows the PMIA membranes with extraordinary high electrolyte uptake, excellent ability of preserving the liquid electrolyte and forceful chemisorption to polysulfides. And the tree-like structure effectively blocks polysulfides by the physical confinement. The lithium-sulfur cell with the F-doped PMIA separator exhibits high first-cycle discharge capacity of 1222.5 mAh g-1 and excellent cycling stability with good capacity retention of 745.7 mAh g-1 and coulombic efficiency of 97.97% after 800 cycles. The remarkable performance can be ascribed to the suppressed shuttle effects through both the physical trapping of polysulfides by the gel polymer electrolyte based on matrix with F-doped PMIA membrane and the tree-like structure in a working cell.

The Role of Electrolyte Upon the SEI Formation Characteristics and Low Temperature Performance of Lithium-Ion Cells With Graphite Anodes

NASA Technical Reports Server (NTRS)

Smart, M.; Ratnakumar, B.; Greenbaum, S.; Surampudi, S.

1998-01-01

Quarternary lithium-ion battery electrolyte solutions containing ester co-solvents in mixtures of carbonates have been demonstrated to have high conductivity at low temperatures (<-20 degrees Celcius).

Safer Electrolytes for Lithium-Ion Batteries: State of the Art and Perspectives.

PubMed

Kalhoff, Julian; Eshetu, Gebrekidan Gebresilassie; Bresser, Dominic; Passerini, Stefano

2015-07-08

Lithium-ion batteries are becoming increasingly important for electrifying the modern transportation system and, thus, hold the promise to enable sustainable mobility in the future. However, their large-scale application is hindered by severe safety concerns when the cells are exposed to mechanical, thermal, or electrical abuse conditions. These safety issues are intrinsically related to their superior energy density, combined with the (present) utilization of highly volatile and flammable organic-solvent-based electrolytes. Herein, state-of-the-art electrolyte systems and potential alternatives are briefly surveyed, with a particular focus on their (inherent) safety characteristics. The challenges, which so far prevent the widespread replacement of organic carbonate-based electrolytes with LiPF6 as the conducting salt, are also reviewed herein. Starting from rather "facile" electrolyte modifications by (partially) replacing the organic solvent or lithium salt and/or the addition of functional electrolyte additives, conceptually new electrolyte systems, including ionic liquids, solvent-free, and/or gelled polymer-based electrolytes, as well as solid-state electrolytes, are also considered. Indeed, the opportunities for designing new electrolytes appear to be almost infinite, which certainly complicates strict classification of such systems and a fundamental understanding of their properties. Nevertheless, these innumerable opportunities also provide a great chance of developing highly functionalized, new electrolyte systems, which may overcome the afore-mentioned safety concerns, while also offering enhanced mechanical, thermal, physicochemical, and electrochemical performance. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Electrolyte Engineering: Optimizing High-Rate Double-Layer Capacitances of Micropore- and Mesopore-Rich Activated Carbon.

PubMed

Chen, Ting-Hao; Yang, Cheng-Hsien; Su, Ching-Yuan; Lee, Tai-Chou; Dong, Quan-Feng; Chang, Jeng-Kuei

2017-09-22

Various types of electrolyte cations as well as binary cations are used to optimize the capacitive performance of activated carbon (AC) with different pore structures. The high-rate capability of micropore-rich AC, governed by the mobility of desolvated cations, can outperform that of mesopore-rich AC, which essentially depends on the electrolyte conductivity. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

High efficiency solid state dye sensitized solar cells with graphene-polyethylene oxide composite electrolytes.

PubMed

Akhtar, M Shaheer; Kwon, Soonji; Stadler, Florian J; Yang, O Bong

2013-06-21

Novel and highly effective composite electrolytes were prepared by combining the two dimensional graphene (Gra) and polyethylene oxide (PEO) for the solid electrolyte of dye sensitized solar cells (DSSCs). Gra sheets were uniformly coated by the polymer layer through the ester carboxylate bonding between oxygenated species on Gra sheets and PEO. The Gra-PEO composite electrolyte showed the large scale generation of iodide ions in a redox couple. From rheological analysis, the decrease in viscosity after the addition of LiI and I2 in the Gra-PEO electrolyte might be explained by the dipolar interactions being severely disrupted by the ionic interactions of Li(+), I(-), and I3(-) ions. A composite electrolyte with 0.5 wt% Gra presented a higher ionic conductivity (3.32 mS cm(-1)) than those of PEO and other composite electrolytes at room temperature. A high overall conversion efficiency (∼5.23%) with a very high short circuit current (JSC) of 18.32 mA cm(-2), open circuit voltage (VOC) of 0.592 V and fill factor (FF) of 0.48 was achieved in DSSCs fabricated with the 0.5 wt% Gra-PEO composite electrolyte. This enhanced photovoltaic performance might be attributed to the large scale formation of iodide ions in the redox electrolyte and the relatively high ionic conductivity.

Nanoclay gelation approach toward improved dye-sensitized solar cell efficiencies: an investigation of charge transport and shift in the TiO2 conduction band.

PubMed

Wang, Xiu; Kulkarni, Sneha A; Ito, Bruno Ieiri; Batabyal, Sudip K; Nonomura, Kazuteru; Wong, Chee Cheong; Grätzel, Michael; Mhaisalkar, Subodh G; Uchida, Satoshi

2013-01-23

Nanoclay minerals play a promising role as additives in the liquid electrolyte to form a gel electrolyte for quasi-solid-state dye-sensitized solar cells, because of the high chemical stability, unique swelling capability, ion exchange capacity, and rheological properties of nanoclays. Here, we report the improved performance of a quasi-solid-state gel electrolyte that is made from a liquid electrolyte and synthetic nitrate-hydrotalcite nanoclay. Charge transport mechanisms in the gel electrolyte and nanoclay interactions with TiO(2)/electrolyte interface are discussed in detail. The electrochemical analysis reveals that the charge transport is solely based on physical diffusion at the ratio of [PMII]:[I(2)] = 10:1 (where PMII is 1-propyl-3-methylimidazolium iodide). The calculated physical diffusion coefficient shows that the diffusion of redox ions is not affected much by the viscosity of nanoclay gel. The addition of nitrate-hydrotalcite clay in the electrolyte has the effect of buffering the protonation process at the TiO(2)/electrolyte interface, resulting in an upward shift in the conduction band and a boost in open-circuit voltage (V(OC)). Higher V(OC) values with undiminished photocurrent is achieved with nitrate-hydrotalcite nanoclay gel electrolyte for organic as well as for inorganic dye (D35 and N719) systems. The efficiency for hydrotalcite clay gel electrolyte solar cells is increased by 10%, compared to that of the liquid electrolyte. The power conversion efficiency can reach 10.1% under 0.25 sun and 9.6% under full sun. This study demonstrates that nitrate-hydrotalcite nanoclay in the electrolyte not only solidifies the liquid electrolyte to prevent solvent leakage, but also facilitates the improvement in cell efficiency.

Reduction of Electrolyte Components on a Coated Si Anode of Lithium-Ion Batteries.

PubMed

Gomez-Ballesteros, Jose L; Balbuena, Perla B

2017-07-20

Surface modification of Si anodes in Li-ion batteries by deposition of a thin alucone coating has demonstrated an effective way to help maintain a stable anode/electrolyte interface and good battery performance. In this work, we investigate the interactions and reactivity of the film with electrolyte components using ab initio molecular dynamics simulations. Adsorption of solvent molecules (ethylene carbonate, EC) and salt (LiPF 6 ) and reduction by two mechanisms depending on the Li content of the film (yielding open EC adsorbed on the film or C 2 H 4 + CO 3 2- ) take place near the film/electrolyte and film/anode interfaces. Reaction products incorporate into the structure of the film and create a new kind of solid-electrolyte interphase layer.

Reduction of Electrolyte Components on a Coated Si Anode of Lithium-Ion Batteries

DOE PAGES

Gomez-Ballesteros, Jose L.; Balbuena, Perla B.

2017-07-07

Surface modification of Si anodes in Li-ion batteries by deposition of a thin alucone coating has demonstrated an effective way to help maintain a stable anode/electrolyte interface and good battery performance. In this paper, we investigate the interactions and reactivity of the film with electrolyte components using ab initio molecular dynamics simulations. Adsorption of solvent molecules (ethylene carbonate, EC) and salt (LiPF 6), and reduction by two mechanisms depending on the Li content of the film (yielding open EC adsorbed on the film or C 2H 4 + CO 3 2-) take place near the film/electrolyte and film/anode interfaces. Finally,more » reactions products incorporate to the structure of the film and create a new kind of solid-electrolyte interphase layer.« less

Electrochemical characteristics of Li/LiMn 2O 4 cells using gel polymer electrolytes

NASA Astrophysics Data System (ADS)

Kim, Dong-Won; Ko, Jang-Myoun; Chun, Jong-Han

Gel polymer electrolytes composed of acrylonitrile-methylmethacrylate (AM) copolymer and 1 M LiClO 4-ethylene carbonate (EC)/propylene carbonate (PC) are prepared. The ionic conductivity reaches 1.9×10 -3 S cm -1 in a gel polymer electrolyte with 20 wt.% of AM copolymer and 80 wt.% of LiClO 4-EC/PC at room temperature. These systems showed no solvent exudation from the matrix polymer due to enhanced compatibility between AM copolymer and organic liquid electrolyte. A Li/gel polymer electrolyte/LiMn 2O 4 cell has a reversible capacity of 132 mAh g -1 in the voltage range of 3.0-4.3 V at the C/5 rate and shows good cycling performance with a coulombic efficiency >99%.

Molecular interactions in high conductive gel electrolytes based on low molecular weight gelator.

PubMed

Bielejewski, Michał; Łapiński, Andrzej; Demchuk, Oleg

2017-03-15

Organic ionic gel (OIG) electrolytes, also known as gel electrolytes or ionogels are one example of modern functional materials with the potential to use in wide range of electrochemical applications. The functionality of OIGs arises from the thermally reversible solidification of electrolytes or ionic liquids and their superior ionic conductivity. To understand and to predict the properties of these systems it is important to get the knowledge about the interactions on molecular level between the solid gelator matrix and the electrolyte solution. This paper reports the spectroscopic studies (FT-IR, UV-Vis and Raman) of the gel electrolyte based on low molecular weight gelator methyl-4,6-O-(p-nitrobenzylidene)-α-d-glucopyranoside and solution of quaternary ammonium salt, tetramethylammonium bromide. The solidification process was based on sol-gel technique. Below characteristic temperature, defined as gel to sol phase transition temperature, T gs , the samples were solid-like and showed high conductivity values of the same order as observed for pure liquid electrolytes. The investigations were performed for a OIGs in a wide range of molar concentrations of the electrolyte solution. Copyright © 2016 Elsevier Inc. All rights reserved.

Cross-linked Composite Gel Polymer Electrolyte using Mesoporous Methacrylate-Functionalized SiO2 Nanoparticles for Lithium-Ion Polymer Batteries

PubMed Central

Shin, Won-Kyung; Cho, Jinhyun; Kannan, Aravindaraj G.; Lee, Yoon-Sung; Kim, Dong-Won

2016-01-01

Liquid electrolytes composed of lithium salt in a mixture of organic solvents have been widely used for lithium-ion batteries. However, the high flammability of the organic solvents can lead to thermal runaway and explosions if the system is accidentally subjected to a short circuit or experiences local overheating. In this work, a cross-linked composite gel polymer electrolyte was prepared and applied to lithium-ion polymer cells as a safer and more reliable electrolyte. Mesoporous SiO2 nanoparticles containing reactive methacrylate groups as cross-linking sites were synthesized and dispersed into the fibrous polyacrylonitrile membrane. They directly reacted with gel electrolyte precursors containing tri(ethylene glycol) diacrylate, resulting in the formation of a cross-linked composite gel polymer electrolyte with high ionic conductivity and favorable interfacial characteristics. The mesoporous SiO2 particles also served as HF scavengers to reduce the HF content in the electrolyte at high temperature. As a result, the cycling performance of the lithium-ion polymer cells with cross-linked composite gel polymer electrolytes employing methacrylate-functionalized mesoporous SiO2 nanoparticles was remarkably improved at elevated temperatures. PMID:27189842

Preparation and electrochemical characterization of gel polymer electrolyte based on electrospun polyacrylonitrile nonwoven membranes for lithium batteries

NASA Astrophysics Data System (ADS)

Raghavan, Prasanth; Manuel, James; Zhao, Xiaohui; Kim, Dul-Sun; Ahn, Jou-Hyeon; Nah, Changwoon

Electrospun membranes of polyacrylonitrile are prepared, and the electrospinning parameters are optimized to get fibrous membranes with uniform bead-free morphology. The polymer solution of 16 wt.% in N, N-dimethylformamide at an applied voltage of 20 kV results in the nanofibrous membrane with average fiber diameter of 350 nm and narrow fiber diameter distribution. Gel polymer electrolytes are prepared by activating the nonwoven membranes with different liquid electrolytes. The nanometer level fiber diameter and fully interconnected pore structure of the host polymer membranes facilitate easy penetration of the liquid electrolyte. The gel polymer electrolytes show high electrolyte uptake (>390%) and high ionic conductivity (>2 × 10 -3 S cm -1). The cell fabricated with the gel polymer electrolytes shows good interfacial stability and oxidation stability >4.7 V. Prototype coin cells with gel polymer electrolytes based on a membrane activated with 1 M LiPF 6 in ethylene carbonate/dimethyl carbonate or propylene carbonate are evaluated for discharge capacity and cycle property in Li/LiFePO 4 cells at room temperature. The cells show remarkably good cycle performance with high initial discharge properties and low capacity fade under continuous cycling.

Two Players Make a Formidable Combination: In Situ Generated Poly(acrylic anhydride-2-methyl-acrylic acid-2-oxirane-ethyl ester-methyl methacrylate) Cross-Linking Gel Polymer Electrolyte toward 5 V High-Voltage Batteries.

PubMed

Ma, Yue; Ma, Jun; Chai, Jingchao; Liu, Zhihong; Ding, Guoliang; Xu, Gaojie; Liu, Haisheng; Chen, Bingbing; Zhou, Xinhong; Cui, Guanglei; Chen, Liquan

2017-11-29

Electrochemical performance of high-voltage lithium batteries with high energy density is limited because of the electrolyte instability and the electrode/electrolyte interfacial reactivity. Hence, a cross-linking polymer network of poly(acrylic anhydride-2-methyl-acrylic acid-2-oxirane-ethyl ester-methyl methacrylate) (PAMM)-based electrolyte was introduced via in situ polymerization inspired by "shuangjian hebi", which is a statement in a traditional Chinese Kungfu story similar to the synergetic effect of 1 + 1 > 2. A poly(acrylic anhydride) and poly(methyl methacrylate)-based system is very promising as electrolyte materials for lithium-ion batteries, in which the anhydride and acrylate groups can provide high voltage resistance and fast ionic conductivity, respectively. As a result, the cross-linking PAMM-based electrolyte possesses a significant comprehensive enhancement, including electrochemical stability window exceeding 5 V vs Li + /Li, an ionic conductivity of 6.79 × 10 -4 S cm -1 at room temperature, high mechanical strength (27.5 MPa), good flame resistance, and excellent interface compatibility with Li metal. It is also demonstrated that this gel polymer electrolyte suppresses the negative effect resulting from dissolution of Mn 2+ ions at 25 and 55 °C. Thus, the LiNi 0.5 Mn 1.5 O 4 /Li and LiNi 0.5 Mn 1.5 O 4 /Li 4 Ti 5 O 12 cells using the optimized in situ polymerized cross-linking PAMM-based gel polymer electrolyte deliver stable charging/discharging profiles and excellent rate performance at room temperature and even at 55 °C. These findings suggest that the cross-linking PAMM is an intriguing candidate for 5 V class high-voltage gel polymer electrolyte toward high-energy lithium-on batteries.

High‐Performance Lithium‐Oxygen Battery Electrolyte Derived from Optimum Combination of Solvent and Lithium Salt

PubMed Central

Ahn, Su Mi; Suk, Jungdon; Kim, Do Youb; Kim, Hwan Kyu

2017-01-01

Abstract To fabricate a sustainable lithium‐oxygen (Li‐O2) battery, it is crucial to identify an optimum electrolyte. Herein, it is found that tetramethylene sulfone (TMS) and lithium nitrate (LiNO3) form the optimum electrolyte, which greatly reduces the overpotential at charge, exhibits superior oxygen efficiency, and allows stable cycling for 100 cycles. Linear sweep voltammetry (LSV) and differential electrochemical mass spectrometry (DEMS) analyses reveal that neat TMS is stable to oxidative decomposition and exhibit good compatibility with a lithium metal. But, when TMS is combined with typical lithium salts, its performance is far from satisfactory. However, the TMS electrolyte containing LiNO3 exhibits a very low overpotential, which minimizes the side reactions and shows high oxygen efficiency. LSV‐DEMS study confirms that the TMS‐LiNO3 electrolyte efficiently produces NO2 −, which initiates a redox shuttle reaction. Interestingly, this NO2 −/NO2 redox reaction derived from the LiNO3 salt is not very effective in solvents other than TMS. Compared with other common Li‐O2 solvents, TMS seems optimum solvent for the efficient use of LiNO3 salt. Good compatibility with lithium metal, high dielectric constant, and low donicity of TMS are considered to be highly favorable to an efficient NO2 −/NO2 redox reaction, which results in a high‐performance Li‐O2 battery. PMID:29051863

High Performance Hybrid Energy Storage with Potassium Ferricyanide Redox Electrolyte.

PubMed

Lee, Juhan; Choudhury, Soumyadip; Weingarth, Daniel; Kim, Daekyu; Presser, Volker

2016-09-14

We demonstrate stable hybrid electrochemical energy storage performance of a redox-active electrolyte, namely potassium ferricyanide in aqueous media in a supercapacitor-like setup. Challenging issues associated with such a system are a large leakage current and high self-discharge, both stemming from ion redox shuttling through the separator. The latter is effectively eliminated when using an ion exchange membrane instead of a porous separator. Other critical factors toward the optimization of a redox-active electrolyte system, especially electrolyte concentration and volume of electrolyte, have been studied by electrochemical methods. Finally, excellent long-term stability is demonstrated up to 10 000 charge/discharge cycles at 1.2 and 1.8 V, with a broad maximum stability window of up to 1.8 V cell voltage as determined via cyclic voltammetry. An energy capacity of 28.3 Wh/kg or 11.4 Wh/L has been obtained from such cells, taking the nonlinearity of the charge-discharge profile into account. The power performance of our cell has been determined to be 7.1 kW/kg (ca. 2.9 kW/L or 1.2 kW/m(2)). These ratings are higher compared to the same cell operated in aqueous sodium sulfate. This hybrid electrochemical energy storage system is believed to find a strong foothold in future advanced energy storage applications.

Interfacial Chemistry Regulation via a Skin-Grafting Strategy Enables High-Performance Lithium-Metal Batteries

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

Gao, Yue; Zhao, Yuming; Li, Yuguang C.

The lithium (Li) metal anode suffers severe interfacial instability from its high reactivity toward liquid electrolytes, especially carbonate-based electrolytes, resulting in poor electrochemical performance of batteries that use 4 V high-capacity cathodes. In this paper, we report a new skin-grafting strategy that stabilizes the Li metal–liquid electrolyte interface by coating the Li metal surface with poly((N-2,2-dimethyl-1,3-dioxolane-4-methyl)-5-norbornene-exo-2,3-dicarboximide), a chemically and electrochemically active polymer layer. This layer, composed of cyclic ether groups with a stiff polycyclic main chain, serves as a grafted polymer skin on the Li metal anode not only to incorporate ether-based polymeric components into the solid-electrolyte interphase (SEI) butmore » also to accommodate Li deposition/dissolution under the skin in a dendrite/moss-free manner. Consequently, a Li-metal battery employing a Li metal anode with the grafted skin paired with LiNi 0.5Co 0.2Mn 0.3O 2 cathode has a 90.0% capacity retention after 400 charge/discharge cycles and a capacity of 1.2 mAh/cm 2 in a carbonate-based electrolyte. Finally, this proof-of-concept study provides a new direction for regulating the interfacial chemistry of Li metal anodes and for enabling high-performance Li-metal batteries.« less

Interfacial Chemistry Regulation via a Skin-Grafting Strategy Enables High-Performance Lithium-Metal Batteries

DOE PAGES

Gao, Yue; Zhao, Yuming; Li, Yuguang C.; ...

2017-10-06

The lithium (Li) metal anode suffers severe interfacial instability from its high reactivity toward liquid electrolytes, especially carbonate-based electrolytes, resulting in poor electrochemical performance of batteries that use 4 V high-capacity cathodes. In this paper, we report a new skin-grafting strategy that stabilizes the Li metal–liquid electrolyte interface by coating the Li metal surface with poly((N-2,2-dimethyl-1,3-dioxolane-4-methyl)-5-norbornene-exo-2,3-dicarboximide), a chemically and electrochemically active polymer layer. This layer, composed of cyclic ether groups with a stiff polycyclic main chain, serves as a grafted polymer skin on the Li metal anode not only to incorporate ether-based polymeric components into the solid-electrolyte interphase (SEI) butmore » also to accommodate Li deposition/dissolution under the skin in a dendrite/moss-free manner. Consequently, a Li-metal battery employing a Li metal anode with the grafted skin paired with LiNi 0.5Co 0.2Mn 0.3O 2 cathode has a 90.0% capacity retention after 400 charge/discharge cycles and a capacity of 1.2 mAh/cm 2 in a carbonate-based electrolyte. Finally, this proof-of-concept study provides a new direction for regulating the interfacial chemistry of Li metal anodes and for enabling high-performance Li-metal batteries.« less

Ester-Based Electrolytes for Low-Temperature Li-Ion Cells

NASA Technical Reports Server (NTRS)

Smart, Marshall; Bugga, Ratnakumar

2005-01-01

Electrolytes comprising LiPF6 dissolved at a concentration of 1.0 M in five different solvent mixtures of alkyl carbonates have been found to afford improved performance in rechargeable lithium-ion electrochemical cells at temperatures as low as -70 C. These and other electrolytes have been investigated in continuing research directed toward extending the lower limit of practical operating temperatures of Li-ion cells. This research at earlier stages, and the underlying physical and chemical principles, were reported in numerous previous NASA Tech Briefs articles, the most recent being Low-EC-Content Electrolytes for Low-Temperature Li-Ion Cells (NPO-30226), NASA Tech Briefs, Vol. 27, No. 1 (January 2003), page 46. The ingredients of the present solvent mixtures are ethylene carbonate (EC), ethyl methyl carbonate (EMC), methyl butyrate (MB), methyl propionate (MP), ethyl propionate (EP), ethyl butyrate (EB), and ethyl valerate (EV). In terms of volume proportions of these ingredients, the present solvent mixtures are 1EC + 1EMC + 8MB, 1EC + 1EMC + 8EB, 1EC + 1EMC + 8MP, 1EC + 1EMC + 8EV, and 1EC + 9EMC. These electrolytes were placed in Liion cells containing carbon anodes and LiNi0.8Co0.2O2 cathodes, and the low-temperature electrical performances of the cells were measured. The cells containing the MB and MP mixtures performed best.

High-Performance Lithium-Oxygen Battery Electrolyte Derived from Optimum Combination of Solvent and Lithium Salt.

PubMed

Ahn, Su Mi; Suk, Jungdon; Kim, Do Youb; Kang, Yongku; Kim, Hwan Kyu; Kim, Dong Wook

2017-10-01

To fabricate a sustainable lithium-oxygen (Li-O 2 ) battery, it is crucial to identify an optimum electrolyte. Herein, it is found that tetramethylene sulfone (TMS) and lithium nitrate (LiNO 3 ) form the optimum electrolyte, which greatly reduces the overpotential at charge, exhibits superior oxygen efficiency, and allows stable cycling for 100 cycles. Linear sweep voltammetry (LSV) and differential electrochemical mass spectrometry (DEMS) analyses reveal that neat TMS is stable to oxidative decomposition and exhibit good compatibility with a lithium metal. But, when TMS is combined with typical lithium salts, its performance is far from satisfactory. However, the TMS electrolyte containing LiNO 3 exhibits a very low overpotential, which minimizes the side reactions and shows high oxygen efficiency. LSV-DEMS study confirms that the TMS-LiNO 3 electrolyte efficiently produces NO 2 - , which initiates a redox shuttle reaction. Interestingly, this NO 2 - /NO 2 redox reaction derived from the LiNO 3 salt is not very effective in solvents other than TMS. Compared with other common Li-O 2 solvents, TMS seems optimum solvent for the efficient use of LiNO 3 salt. Good compatibility with lithium metal, high dielectric constant, and low donicity of TMS are considered to be highly favorable to an efficient NO 2 - /NO 2 redox reaction, which results in a high-performance Li-O 2 battery.

Effect of ethylene glycol bis (propionitrile) ether (EGBE) on the performance and interfacial chemistry of lithium-rich layered oxide cathode

NASA Astrophysics Data System (ADS)

Hong, Pengbo; Xu, Mengqing; Zheng, Xiongwen; Zhu, Yunmin; Liao, Youhao; Xing, Lidan; Huang, Qiming; Wan, Huaping; Yang, Yongjun; Li, Weishan

2016-10-01

Ethylene glycol bis (propionitrile) ether (EGBE) is used as an electrolyte additive to improve the cycling stability and rate capability of Li/Li1.2Mn0.54Ni0.13Co0.13O2 cells at high operating voltage (4.8 V). After 150 cycles, cells with 1.0 wt% of EGBE containing electrolyte have remarkable cycling performance, 89.0% capacity retention; while the cells with baseline electrolyte only remain 67.4% capacity retention. Linear sweep voltammetry (LSV) and computation results demonstrate that EGBE preferably oxidizes on the cathode surface compared to the LiPF6/carbonate electrolyte. In order to further understand the effects of EGBE on Li1.2Mn0.54Ni0.13Co0.13O2 cathode upon cycling at high voltage, electrochemical behaviors and ex-situ surface analysis of Li1.2Mn0.54Ni0.13Co0.13O2 are investigated via electrochemical impedance spectroscopy (EIS), scanning electron spectroscopy (SEM), X-ray photoelectron spectroscopy (XPS), transmission electron microscopy (TEM), and inductive coupled plasma spectroscopy (ICP-MS). The improved cycling performance can be attributed to more stable and robust surface layer yield via incorporation of EGBE, which mitigates the oxidation of electrolyte on the cathode electrode, and also inhibits the dissolution of bulk transition metal ions as well upon cycling at high voltage.

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.

Functionally Graded Bismuth Oxide/Zirconia Bilayer Electrolytes for High-Performance Intermediate-Temperature Solid Oxide Fuel Cells (IT-SOFCs).

PubMed

Joh, Dong Woo; Park, Jeong Hwa; Kim, Doyeub; Wachsman, Eric D; Lee, Kang Taek

2017-03-15

A functionally graded Bi 1.6 Er 0.4 O 3 (ESB)/Y 0.16 Zr 0.84 O 1.92 (YSZ) bilayer electrolyte is successfully developed via a cost-effective screen printing process using nanoscale ESB powders on the tape-cast NiO-YSZ anode support. Because of the highly enhanced oxygen incorporation process at the cathode/electrolyte interface, a novel bilayer solid oxide fuel cell (SOFC) yields extremely high power density of ∼2.1 W cm -2 at 700 °C, which is a 2.4 times increase compared to that of the YSZ single electrolyte SOFC.

Electrolyte salts for nonaqueous electrolytes

DOEpatents

Amine, Khalil; Zhang, Zhengcheng; Chen, Zonghai

2012-10-09

Metal complex salts may be used in lithium ion batteries. Such metal complex salts not only perform as an electrolyte salt in a lithium ion batteries with high solubility and conductivity, but also can act as redox shuttles that provide overcharge protection of individual cells in a battery pack and/or as electrolyte additives to provide other mechanisms to provide overcharge protection to lithium ion batteries. The metal complex salts have at least one aromatic ring. The aromatic moiety may be reversibly oxidized/reduced at a potential slightly higher than the working potential of the positive electrode in the lithium ion battery. The metal complex salts may also be known as overcharge protection salts.

Review on solid electrolytes for all-solid-state lithium-ion batteries

NASA Astrophysics Data System (ADS)

Zheng, Feng; Kotobuki, Masashi; Song, Shufeng; Lai, Man On; Lu, Li

2018-06-01

All-solid-state (ASS) lithium-ion battery has attracted great attention due to its high safety and increased energy density. One of key components in the ASS battery (ASSB) is solid electrolyte that determines performance of the ASSB. Many types of solid electrolytes have been investigated in great detail in the past years, including NASICON-type, garnet-type, perovskite-type, LISICON-type, LiPON-type, Li3N-type, sulfide-type, argyrodite-type, anti-perovskite-type and many more. This paper aims to provide comprehensive reviews on some typical types of key solid electrolytes and some ASSBs, and on gaps that should be resolved.

Ether-based nonflammable electrolyte for room temperature sodium battery

NASA Astrophysics Data System (ADS)

Feng, Jinkui; Zhang, Zhen; Li, Lifei; Yang, Jian; Xiong, Shenglin; Qian, Yitai

2015-06-01

Safety problem is one of the key points that hinder the development of room temperature sodium batteries. In this paper, four well-known nonflammable organic compounds, Trimethyl Phosphate (TMP), Tri(2,2,2-trifluoroethyl) phosphite (TFEP), Dimethyl Methylphosphonate (DMMP), Methyl nonafluorobuyl Ether (MFE), are investigated as nonflammable solvents in sodium batteries for the first time. Among them, MFE is stable towards sodium metal at room temperature. The electrochemical properties and electrode compatibility of MFE based electrolyte are investigated. Both Prussian blue cathode and carbon nanotube anode show good electrochemical performance retention in this electrolyte. The results suggest that MFE is a promising option as nonflammable electrolyte additive for sodium batteries.

Carbon dioxide electrolysis with solid oxide electrolyte cells for oxygen recovery in life support systems

NASA Technical Reports Server (NTRS)

Isenberg, Arnold O.; Cusick, Robert J.

1988-01-01

The direct electrochemical reduction of carbon dioxide (CO2) is achieved without catalysts and at sufficiently high temperatures to avoid carbon formation. The tubular electrolysis cell consists of thin layers of anode, electrolyte, cathode and cell interconnection. The electrolyte is made from yttria-stabilized zirconia which is an oxygen ion conductor at elevated temperatures. Anode and cell interconnection materials are complex oxides and are electronic conductors. The cathode material is a composite metal-ceramic structure. Cell performance characteristics have been determined using varying feed gas compositions and degrees of electrochemical decomposition. Cell test data are used to project the performance of a three-person CO2-electrolysis breadboard system.

Enhanced fatigue performance of porous coated Ti6Al4V biomedical alloy

NASA Astrophysics Data System (ADS)

Apachitei, I.; Leoni, A.; Riemslag, A. C.; Fratila-Apachitei, L. E.; Duszczyk, J.

2011-05-01

Biofunctional coatings are necessary to improve integration of titanium implants in the host tissue but they may be detrimental for the implant fatigue properties. This study presents an attempt towards enhancement of the in vitro fatigue strength of plasma electrolytic oxidation coated Ti6Al4V alloy by applying shot peening process prior to coating. The electrolytic oxidation was performed in calcium acetate and calcium glycerophosphate electrolytes that allowed formation of porous oxide coatings with high surface free energy and apatite like ability. A deformed surface layer coupled with induced residual compressive stresses seem to affect oxide growth rate and fatigue behavior of the titanium alloy.

Li-Ion Cells Employing Electrolytes With Methyl Propionate and Ethyl Butyrate Co-Solvents

NASA Technical Reports Server (NTRS)

Smart, Marshall C.; Bugga, Ratnakumar V.

2011-01-01

Future NASA missions aimed at exploring Mars and the outer planets require rechargeable batteries that can operate at low temperatures to satisfy the requirements of such applications as landers, rovers, and penetrators. A number of terrestrial applications, such as hybrid electric vehicles (HEVs) and electric vehicles (EVs) also require energy storage devices that can operate over a wide temperature range (i.e., -40 to +70 C), while still providing high power capability and long life. Currently, the state-of-the-art lithium-ion system has been demonstrated to operate over a wide range of temperatures (-30 to +40 C); however, the rate capability at the lower temperatures is very poor. These limitations at very low temperatures are due to poor electrolyte conductivity, poor lithium intercalation kinetics over the electrode surface layers, and poor ionic diffusion in the electrode bulk. Two wide-operating-temperature-range electrolytes have been developed based on advances involving lithium hexafluorophosphate-based solutions in carbonate and carbonate + ester solvent blends, which have been further optimized in the context of the technology and targeted applications. The approaches employed include further optimization of electrolytes containing methyl propionate (MP) and ethyl butyrate (EB), which are effective co-solvents, to widen the operating temperature range beyond the baseline systems. Attention was focused on further optimizing ester-based electrolyte formulations that have exhibited the best performance at temperatures ranging from -60 to +60 C, with an emphasis upon improving the rate capability at -20 to -40 C. This was accomplished by increasing electrolyte salt concentration to 1.20M and increasing the ester content to 60 percent by volume to increase the ionic conductivity at low temperatures. Two JPL-developed electrolytes 1.20M LiPF6 in EC+EMC+MP (20:20:60 v/v %) and 1.20M LiPF6 in EC+EMC+EB (20:20:60 v/v %) operate effectively over a wide temperature range in MCMB-LiNiCoAlO2 and Li4Ti5O12-LiNi-CoAlO2 prototype cells. These electrolytes have enabled high rate performance at low temperature (i.e., up to 2.0C rates at -50 C and 5.0C rates at -40 C), and good cycling performance over a wide temperature range (i.e., from -40 to +70 C). Current efforts are focused upon improving the high temperature resilience of the methyl propionatebased system through the use of electrolyte additives, which are envisioned to improve the nature of the solid electrolyte interphase (SEI) layers.

LiGa(OTf)(sub 4) as an Electrolyte Salt for Li-Ion Cells

NASA Technical Reports Server (NTRS)

Reddy, V. Prakash; Prakash, G. K. Syria; Hu, Jinbo; Yan, Ping; Smart, Marshall; Bugga, ratnakumar; Chin, Keith; Surampudi, Subarao

2008-01-01

Lithium tetrakis(trifluoromethane sulfo - nato)gallate [abbreviated "LiGa(OTf)4" (wherein "OTf" signifies trifluoro - methanesulfonate)] has been found to be promising as an electrolyte salt for incorporation into both liquid and polymer electrolytes in both rechargeable and non-rechargeable lithium-ion electrochemical cells. This and other ingredients have been investigated in continuing research oriented toward im proving the performances of rechargeable lithium-ion electrochemical cells, especially at low temperatures. This research at earlier stages, and the underlying physical and chemical principles, were reported in numerous previous NASA Tech Briefs articles. As described in more detail in those articles, lithiumion cells most commonly contain nonaqueous electrolyte solutions consisting of lithium hexafluorophosphate (LiPF6) dissolved in mixtures of cyclic and linear alkyl carbonates, including ethylene carbonate (EC), propylene carbonate (PC), dimethyl carbonate (DMC), diethyl carbonate (DEC), and ethyl methyl carbonate (EMC). Although such LiPF6-based electrolyte solutions are generally highly ionically conductive and electrochemically stable, as needed for good cell performance, there is interest in identifying alternate lithium electrolyte salts that, relative to LiPF6, are more resilient at high temperature and are less expensive. Experiments have been performed on LiGa(OTf)4 as well as on several other candidate lithium salts in pursuit of this interest. As part of these experiments, LiGa(OTf)4 was synthesized by the reaction of Ga(OTf)3 with an equimolar portion of LiOTf in a solvent consisting of anhydrous acetonitrile. Evaporation of the solvent yielded LiGa(OTf)4 as a colorless crystalline solid. The LiGa(OTf)4 and the other salts were incorporated into solutions with PC and DMC. The resulting electrolyte solutions exhibited reasonably high ionic conductivities over a relatively wide temperature range down to 40 C (see figure). In cyclic voltammetry measurements, LiGa(OTf)4 and the other salts exhibited acceptably high electrochemical stability over the relatively wide potential window of 0 to 5 V versus Li+/Li. 13C nuclear-magneticresonance measurements yielded results that suggested that in comparison with the other candidate salts, LiGa(OTf)4 exhibits less ion pairing. Planned further development will include optimization of the salt and solvent contents of such electrolyte solutions and incorporation of LiGa(OTf)4 into gel and solid-state polymer electrolytes. Of the salts, LiGa(OTf)4 is expected to be especially desirable for incorporation into lithium polymer electrolytes, wherein decreased ion pairing is advantageous and the large delocalized anions can exert a plasticizing effect.

Study on characteristics of PVDF/nano-clay composite polymer electrolyte using PVP as pore-forming agent

NASA Astrophysics Data System (ADS)

Dyartanti, Endah R.; Purwanto, Agus; Widiasa, I. Nyoman; Susanto, Heru

2016-02-01

Polyvinylidene fluoride (PVDF) based polymer electrolytes have a high dielectric constant, which can assist in greater ionization of lithium salts. The main advantages of PVDF are its durability in long battery operation and its ability to be a good ion conductor. However, the limitation of this polymer is its crystalline molecular structure. Dispersing nano-particles in the polymer matrix may improve the characteristics of the PVDF polymer. This paper aims to investigate the impact of nano-clay addition on the characteristics of PVDF polymer to be used as a polymer electrolyte membrane. In addition, the effect of poly(vinyl pyrrolidone) (PVP) is also investigated. The membrane was prepared by phase separation method whereas the polymer electrolyte membranes was prepared by immersing into 1 M lithium hexafluorophosphate (LiPF6) in ethylene carbonate/dimethyl carbonate (EC/DMC) electrolytes for 1 h. The membranes were characterized by scanning electron microscope (SEM), porosity and electrolyte uptake and performance in battery cell. The results showed that both nano-clay and PVP have significant impacts on the improvement of PVDF membranes to be used as polymer electrolyte.

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.

Electrode-electrolyte interface model of tripolar concentric ring electrode and electrode paste.

PubMed

Nasrollaholhosseini, Seyed Hadi; Steele, Preston; Besio, Walter G

2016-08-01

Electrodes are used to transform ionic currents to electrical currents in biological systems. Modeling the electrode-electrolyte interface could help to optimize the performance of the electrode interface to achieve higher signal to noise ratios. There are previous reports of accurate models for single-element biomedical electrodes. In this paper we develop a model for the electrode-electrolyte interface for tripolar concentric ring electrodes (TCRE) that are used to record brain signals.

Floating gate transistors as biosensors (Conference Presentation)

NASA Astrophysics Data System (ADS)

Frisbie, C. Daniel

2016-11-01

Electrolyte gated transistors (EGTs) are a sub-class of thin film transistors that are extremely promising for biological sensing applications. These devices employ a solid electrolyte as the gate insulator; the very large capacitance of the electrolyte results in low voltage operation and high transconductance or gain. This talk will describe the fabrication of floating gate EGTs and their use as ricin sensors. The critical performance metrics for EGTs compared with other types of TFTs will also be reviewed.

Flexible, High-Wettability and Fire-Resistant Separators Based on Hydroxyapatite Nanowires for Advanced Lithium-Ion Batteries.

PubMed

Li, Heng; Wu, Dabei; Wu, Jin; Dong, Li-Ying; Zhu, Ying-Jie; Hu, Xianluo

2017-11-01

Separators play a pivotal role in the electrochemical performance and safety of lithium-ion batteries (LIBs). The commercial microporous polyolefin-based separators often suffer from inferior electrolyte wettability, low thermal stability, and severe safety concerns. Herein, a novel kind of highly flexible and porous separator based on hydroxyapatite nanowires (HAP NWs) with excellent thermal stability, fire resistance, and superior electrolyte wettability is reported. A hierarchical cross-linked network structure forms between HAP NWs and cellulose fibers (CFs) via hybridization, which endows the separator with high flexibility and robust mechanical strength. The high thermal stability of HAP NW networks enables the separator to preserve its structural integrity at temperatures as high as 700 °C, and the fire-resistant property of HAP NWs ensures high safety of the battery. In particular, benefiting from its unique composition and highly porous structure, the as-prepared HAP/CF separator exhibits near zero contact angle with the liquid electrolyte and high electrolyte uptake of 253%, indicating superior electrolyte wettability compared with the commercial polyolefin separator. The as-prepared HAP/CF separator has unique advantages of superior electrolyte wettability, mechanical robustness, high thermal stability, and fire resistance, thus, is promising as a new kind of separator for advanced LIBs with enhanced performance and high safety. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Li-Doped Ionic Liquid Electrolytes: From Bulk Phase to Interfacial Behavior

NASA Technical Reports Server (NTRS)

Haskins, Justin B.; Lawson, John W.

2016-01-01

Ionic liquids have been proposed as candidate electrolytes for high-energy density, rechargeable batteries. We present an extensive computational analysis supported by experimental comparisons of the bulk and interfacial properties of a representative set of these electrolytes as a function of Li-salt doping. We begin by investigating the bulk electrolyte using quantum chemistry and ab initio molecular dynamics to elucidate the solvation structure of Li(+). MD simulations using the polarizable force field of Borodin and coworkers were then performed, from which we obtain an array of thermodynamic and transport properties. Excellent agreement is found with experiments for diffusion, ionic conductivity, and viscosity. Combining MD simulations with electronic structure computations, we computed the electrochemical window of the electrolytes across a range of Li(+)-doping levels and comment on the role of the liquid environment. Finally, we performed a suite of simulations of these Li-doped electrolytes at ideal electrified interfaces to evaluate the differential capacitance and the equilibrium Li(+) distribution in the double layer. The magnitude of differential capacitance is in good agreement with our experiments and exhibits the characteristic camel-shaped profile. In addition, the simulations reveal Li(+) to be highly localized to the second molecular layer of the double layer, which is supported by additional computations that find this layer to be a free energy minimum with respect to Li(+) translation.

Thermostable gel polymer electrolyte based on succinonitrile and ionic liquid for high-performance solid-state supercapacitors

NASA Astrophysics Data System (ADS)

Pandey, Gaind P.; Liu, Tao; Hancock, Cody; Li, Yonghui; Sun, Xiuzhi Susan; Li, Jun

2016-10-01

A flexible, free-standing, thermostable gel polymer electrolyte based on plastic crystalline succinonitrile (SN) and ionic liquid 1-butyl-3-methylimidazolium tetrafluoroborate (BMImBF4) entrapped in copolymer poly(vinylidene fluoride-co-hexafluoropropylene) (PVdF-HFP) is prepared and optimized for application in solvent-free solid-state supercapacitors. The synthesized gel polymer electrolyte exhibits a high ionic conductivity over a wide temperature range (from ∼5 × 10-4 S cm-1 at -30 °C up to ∼1.5 × 10-2 S cm-1 at 80 °C) with good electrochemical stability window (-2.9 to 2.5 V). Thermal studies confirm that the SN containing gel polymer electrolyte remains stable in the same gel phase over a wide temperature range from -30 to 90 °C. The electric double layer capacitors (EDLCs) have been fabricated using activated carbon as active materials and new gel polymer electrolytes. Electrochemical performance of the EDLCs is assessed through cyclic voltammetry, galvanostatic charge-discharge cycling and impedance spectroscopy. The EDLC cells with the proper SN-containing gel polymer electrolyte has been found to give high specific capacitance 176 F g-1 at 0.18 A g-1 and 138 F g-1 at 8 A g-1. These solid-state EDLC cells show good cycling stability and the capability to retain ∼80% of the initial capacitance after 10,000 cycles.

Suppressed Sr segregation and performance of directly assembled La0.6Sr0.4Co0.2Fe0.8O3-δ oxygen electrode on Y2O3-ZrO2 electrolyte of solid oxide electrolysis cells

NASA Astrophysics Data System (ADS)

Ai, Na; He, Shuai; Li, Na; Zhang, Qi; Rickard, William D. A.; Chen, Kongfa; Zhang, Teng; Jiang, San Ping

2018-04-01

Active and stable oxygen electrode is probably the most important in the development of solid oxide electrolysis cells (SOECs) technologies. Herein, we report the successful development of mixed ionic and electronic conducting (MIEC) La0.6Sr0.4Co0.2Fe0.8O3-δ (LSCF) perovskite oxides directly assembled on barrier-layer-free yttria-stabilized zirconia (YSZ) electrolyte as highly active and stable oxygen electrodes of SOECs. Electrolysis polarization effectively induces the formation of electrode/electrolyte interface, similar to that observed under solid oxide fuel cell (SOFC) operation conditions. However, in contrast to the significant performance decay under SOFC operation conditions, the cell with directly assembled LSCF oxygen electrodes shows excellent stability, tested for 300 h at 0.5 A cm-2 and 750 °C under SOEC operation conditions. Detailed microstructure and phase analysis reveal that Sr segregation is inevitable for LSCF electrode, but anodic polarization substantially suppresses Sr segregation and migration to the electrode/electrolyte interface, leading to the formation of stable and efficient electrode/electrolyte interface for water and CO2 electrolysis under SOECs operation conditions. The present study demonstrates the feasibility of using directly assembled MIEC cobaltite based oxygen electrodes on barrier-layer-free YSZ electrolyte of SOECs.

Self-standing gel polymer electrolyte for improving supercapacitor thermal and electrochemical stability

NASA Astrophysics Data System (ADS)

Dagousset, Laure; Pognon, Grégory; Nguyen, Giao T. M.; Vidal, Frédéric; Jus, Sébastien; Aubert, Pierre-Henri

2018-07-01

Electrochemical energy storage is a very active research topic. However, the use of liquid electrolyte in such systems as supercacitors presents several drawbacks on security and packaging. One way to overcome these issues is to design supercapacitors using solid-state electrolytes. We report here the one-pot synthesis and the characterization of self-standing gel polymer electrolyte (SGPE) composed of semi-Interpenetrating Polymer Networks (semi-IPN) based on poly(ethylene oxide) (PEO) network and non cross-linked nitrile butadiene rubber (NBR), self-containing EMITFSI/γ-Butyrolactone (50/50 wt%/wt%) binary mixtures. The SGPE under the form of a thin film are then used as solid electrolyte and also as separator in supercapacitors with Single Wall Carbon Nanotubes (SWCNTs) bucky paper as electrodes. Thermal characterization revealed the suitability of all synthesized membrane in wide range of operating temperature. Electrochemical stabilities of SGPE were close to that of a cellulose separator system (ESW∼3.2-3.6 V) at 20 °C, and were relatively higher than a cellulose system at 100 °C: 2.1-2.5 V and 1.8 V respectively. Furthermore, floating experiments at 100 °C (holding voltage at 2 V) revealed the exceptionally high stability of SGPE, with a residual capacitance of 93% after 500 h. This high electrochemical performance demonstrated the potential of semi-IPN SGPE as separator/electrolyte for high performance supercapacitors.

Ethoxy (pentafluoro) cyclotriphosphazene (PFPN) as a multi-functional flame retardant electrolyte additive for lithium-ion batteries

NASA Astrophysics Data System (ADS)

Li, Xi; Li, Weikang; Chen, Lai; Lu, Yun; Su, Yuefeng; Bao, Liying; Wang, Jing; Chen, Renjie; Chen, Shi; Wu, Feng

2018-02-01

With the wide application of lithium-ion batteries (LiBs), safety performance is an important constraint on the commercialization of large-scale, high-capacity LIBs. The main reason for the safety problem is that the electrolyte of LiBs is highly flammable, especially under high temperature and high voltage. It is an effective method to improve the safety of cells by mixing flame retardant with conventional electrolyte comprising of LiPF6 and carbonates. Herein, ethoxy (pentafluoro) cyclotriphosphazene (PFPN) is studied as a high efficiency flame retardant. Adding 5 vol% of PFPN results in a non-flammable electrolyte with self-extinguishing time (SET) of 12.38 s g-1 and critical oxygen index (COI) of 22.9, without compromising the capacity of cathode material. The initial discharge capacity of the LiCoO2 electrode with 5% PFPN is 150.7 mAh g-1, with a capacity retention of 99.14% after 30 cycles at 0.1 C. The results show that 5 vol% is the best adding amount of PFPN for electrolyte, which can modify the solid electrolyte interface (SEI). Moreover, PFPN reduces charge transfer resistance of the cells, resulting decreased electrode polarization and enhanced electrochemistry performances at low temperature. These results have confirmed that PFPN has the potential to be a multi-function additive for commercial LIBs production.

Exploratory studies on some electrochemical cell systems

NASA Astrophysics Data System (ADS)

Chaudhuri, Srikumar; Guha, D.

Exploratory studies were conducted on cell systems with different metal anodes, and iodine and sulphur mixed with graphite powder in a polymer matrix as cathodes, using different electrolytes in non-aqueous and aqueous media as ionic charge carriers. The electrical conductance of the electrolyte solutions in aqueous and non-aqueous solvents, the open circuit voltage (OCV) and short circuit current (SCC) for the different cell systems were measured. To date, the non-aqueous solvents used in our studies were dimethylformamide, formamide, dioxan, and nitrobenzene, and the electrolytes used were potassium iodide, caustic potash, cetyltrimethylammonium bromide (CTAB), sodium lauryl sulphate (SLS) and calcium chloride. These electrolytes were used in both non-aqueous and aqueous media. In general, aqueous electrolyte solutions gave a better performance than non-aqueous electrolyte solutions. Of the aqueous electrolytes, the highest conductance was shown by potassium chloride solution in water (conductance=0.0334 mho). However, the best OCV and SCC were shown by aluminium as anode and iodine as cathode with a saturated solution of caustic potash in water. The OCV was 1.85 V and the SCC was 290 mA cm -2. The highest conductance among the non-aqueous systems was shown by caustic potash in formamide. (Conductance=0.013 mho.) The best OCV and SCC, however, were shown by a zinc anode and iodine cathode with saturated potassium chloride in formamide, having an OCV of 1.55 V and an SCC of 150 mA cm -2. Further studies are in progress to obtain detailed performance data and recharging characteristics of some of the more promising systems reported here.

N-doped structures and surface functional groups of reduced graphene oxide and their effect on the electrochemical performance of supercapacitor with organic electrolyte

NASA Astrophysics Data System (ADS)

Li, Shin-Ming; Yang, Shin-Yi; Wang, Yu-Sheng; Tsai, Hsiu-Ping; Tien, Hsi-Wen; Hsiao, Sheng-Tsung; Liao, Wei-Hao; Chang, Chien-Liang; Ma, Chen-Chi M.; Hu, Chi-Chang

2015-03-01

Nitrogen-doped reduced graphene oxide (N-rGO) has been synthesized using a simple, efficient method combining instant thermal exfoliation and covalent bond transformation from a melamine-graphene oxide mixture. The capacitive performance of N-rGO has been tested in both aqueous (0.5 M H2SO4) and organic (1 M tetraethyl-ammonium tetrafluoroborate (TEABF4) in propylene carbonate (PC)) electrolytes, which are compared with those obtained from thermal-reduced graphene oxide (T-rGO) and chemical-reduced graphene oxide (C-rGO). The contributions of scan-rate-independent (double-layer-like) and scan-rate-dependent (pseudo-capacitance-like) capacitance of all reduced graphene oxides in both aqueous and organic electrolytes were evaluated and compared. The results show that relatively rich oxygen-containing functional groups on C-rGO form significant ion-diffusion barrier, resulting in worse electrochemical responses in organic electrolyte. By contrast, the N-doped structures, large surface area, and lower density of oxygen-containing groups make N-rGO become a promising electrode material for organic electric double-layer capacitors (EDLCs). The capacitance rate-retention of N-rGO reaches 71.1% in 1 M TEABF4/PC electrolyte when the scan rate is elevated to 200 mVs-1, demonstrating that N-rGO improves the relatively low-power drawback of EDLCs in organic electrolytes. The specific energy and power of a symmetric N-rGO cell in the organic electrolyte reach 25 Wh kg-1 and 10 kW kg-1, respectively.

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.

Innovative polymer nanocomposite electrolytes: nanoscale manipulation of ion channels by functionalized graphenes.

PubMed

Choi, Bong Gill; Hong, Jinkee; Park, Young Chul; Jung, Doo Hwan; Hong, Won Hi; Hammond, Paula T; Park, Hoseok

2011-06-28

The chemistry and structure of ion channels within the polymer electrolytes are of prime importance for studying the transport properties of electrolytes as well as for developing high-performance electrochemical devices. Despite intensive efforts on the synthesis of polymer electrolytes, few studies have demonstrated enhanced target ion conduction while suppressing unfavorable ion or mass transport because the undesirable transport occurs through an identical pathway. Herein, we report an innovative, chemical strategy for the synthesis of polymer electrolytes whose ion-conducting channels are physically and chemically modulated by the ionic (not electronic) conductive, functionalized graphenes and for a fundamental understanding of ion and mass transport occurring in nanoscale ionic clusters. The functionalized graphenes controlled the state of water by means of nanoscale manipulation of the physical geometry and chemical functionality of ionic channels. Furthermore, the confinement of bound water within the reorganized nanochannels of composite membranes was confirmed by the enhanced proton conductivity at high temperature and the low activation energy for ionic conduction through a Grotthus-type mechanism. The selectively facilitated transport behavior of composite membranes such as high proton conductivity and low methanol crossover was attributed to the confined bound water, resulting in high-performance fuel cells.

Enhanced lithium battery with polyethylene oxide-based electrolyte containing silane-Al2 O3 ceramic filler.

PubMed

Zewde, Berhanu W; Admassie, Shimelis; Zimmermann, Jutta; Isfort, Christian Schulze; Scrosati, Bruno; Hassoun, Jusef

2013-08-01

A solid polymer electrolyte prepared by using a solvent-free, scalable technique is reported. The membrane is formed by low-energy ball milling followed by hot-pressing of dry powdered polyethylene oxide polymer, LiCF3 SO3 salt, and silane-treated Al2 O3 (Al2 O3 -ST) ceramic filler. The effects of the ceramic fillers on the properties of the ionically conducting solid electrolyte membrane are characterized by using electrochemical impedance spectroscopy, XRD, differential scanning calorimeter, SEM, and galvanostatic cycling in lithium cells with a LiFePO4 cathode. We demonstrate that the membrane containing Al2 O3 -ST ceramic filler performs well in terms of ionic conductivity, thermal properties, and lithium transference number. Furthermore, we show that the lithium cells, which use the new electrolyte together with the LiFePO4 electrode, operate within 65 and 90 °C with high efficiency and long cycle life. Hence, the Al2 O3 -ST ceramic can be efficiently used as a ceramic filler to enhance the performance of solid polymer electrolytes in lithium batteries. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

High-temperature solid electrolyte interphases (SEI) in graphite electrodes

NASA Astrophysics Data System (ADS)

Rodrigues, Marco-Tulio F.; Sayed, Farheen N.; Gullapalli, Hemtej; Ajayan, Pulickel M.

2018-03-01

Thermal fragility of the solid electrolyte interphase (SEI) is a major source of performance decay in graphite anodes, and efforts to overcome the issues offered by extreme environments to Li-ion batteries have had limited success. Here, we demonstrate that the SEI can be extensively reinforced by carrying the formation cycles at elevated temperatures. Under these conditions, decomposition of the ionic liquid present in the electrolyte favored the formation of a thicker and more protective layer. Cells in which the solid electrolyte interphase was cast at 90 °C were significantly less prone to self-discharge when exposed to high temperature, with no obvious damages to the formed SEI. This additional resilience was accomplished at the expense of rate capability, as charge transfer became growingly inefficient in these systems. At slower rates, however, cells that underwent SEI formation at 90 °C presented superior performances, as a result of improved Li+ transport through the SEI, and optimal wetting of graphite by the electrolyte. This work analyzes different graphite hosts and ionic liquids, showing that this effect is more pervasive than anticipated, and offering the unique perspective that, for certain systems, temperature can actually be an asset for passivation.

Holey graphene nanosheets with surface functional groups as high-performance supercapacitors in ionic-liquid electrolyte.

PubMed

Yang, Cheng-Hsien; Huang, Po-Ling; Luo, Xu-Feng; Wang, Chueh-Han; Li, Chi; Wu, Yi-Hsuan; Chang, Jeng-Kuei

2015-05-22

Pores and surface functional groups are created on graphene nanosheets (GNSs) to improve supercapacitor properties in a butylmethylpyrrolidinium-dicyanamide (BMP-DCA) ionic liquid (IL) electrolyte. The GNS electrode exhibits an optimal capacitance of 330 F g(-1) and a satisfactory rate capability within a wide potential range of 3.3 V at 25 °C. Pseudocapacitive effects are confirmed using X-ray photoelectron spectroscopy. Under the same conditions, carbon nanotube and activated carbon electrodes show capacitances of 80 and 81 F g(-1) , respectively. Increasing the operation temperature increases the conductivity and decreases the viscosity of the IL electrolyte, further improving cell performance. At 60 °C, a symmetric-electrode GNS supercapacitor with the IL electrolyte is able to deliver maximum energy and power densities of 140 Wh kg(-1) and 52.5 kW kg(-1) (based on the active material on both electrodes), respectively, which are much higher than the 20 Wh kg(-1) and 17.8 kW kg(-1) obtained for a control cell with a conventional organic electrolyte. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

The effect of various electrolyte cations on electrochemical performance of polypyrrole/RGO based supercapacitors.

PubMed

Zhu, Jianbo; Xu, Youlong; Wang, Jie; Lin, Jun; Sun, Xiaofei; Mao, Shengchun

2015-11-21

In this work, polypyrrole/graphene doped by p-toluenesulfonic is prepared as an active material for supercapacitors, and its capacitance performance is investigated in various aqueous electrolytes including HCl, LiCl, NaCl, and KCl with a concentration of 3 M, respectively. A rising trend of capacitance is observed according to the cationic mobility (Li(+) < Na(+) < K(+) < H(+)), which is due to its effect on the ionic conductivity, efficient ion/charge diffusion/exchange and relaxation time. On the other hand, long-term cycling stability is in the following order: KCl < NaCl < LiCl < HCl, corresponding to the decreasing tendency of cation size (K(+) > Na(+) > Li(+) > H(+)). The reason can be attributed to the fact that the insertion/de-insertion of large size cation brings a significant doping level decrease and an over-oxidation increase during the charging-discharging cycles. Hence, we not only obtain good capacitance performance (280.3 F g(-1) at 5 mV s(-1)), superior rate capability (225.8 F g(-1) at 500 mV s(-1)) and high cycling stability (92.0% capacitance retention after 10,000 cycles at 1 A g(-1)) by employing 3 M HCl as an electrolyte, but also reveal that the electrolyte cations have a significant effect on the supercapacitors' electrochemical performance.

High Rate Performance Nanocomposite Electrode of Mesoporous Manganese Dioxide/Silver Nanowires in KI Electrolytes.

PubMed

Jiang, Yanhua; Cui, Xiuguo; Zu, Lei; Hu, Zhongkai; Gan, Jing; Lian, Huiqin; Liu, Yang; Xing, Guangjian

2015-10-13

In recent years, manganese dioxide has become a research hotspot as an electrode material because of its low price. However, it has also become an obstacle to industrialization due to its low ratio of capacitance and the low rate performance which is caused by the poor electrical conductivity. In this study, a KI solution with electrochemical activity was innovatively applied to the electrolyte, and we systematically investigated the rate performance of the mesoporous manganese dioxide and the composite electrode with silver nanowires in supercapacitors. The results showed that when mesoporous manganese dioxide and mesoporous manganese dioxide/silver nanowires composite were used as electrodes, the strength of the current was amplified five times (from 0.1 to 0.5 A/g), the remaining rates of specific capacitance were 95% (from 205.5 down to 197.1 F/g) and 92% (from 208.1 down to 191.7 F/g) in the KI electrolyte, and the rate performance was much higher than which in an Na₂SO₄ electrolyte with a remaining rate of 25% (from 200.3 down to 49.1 F/g) and 60% (from 187.2 down to 113.1 F/g). The morphology and detail structure were investigated by Scanning electron microscopy, X-ray diffraction, Fourier transform infrared spectrometry and Nitrogen adsorption-desorption isotherms. The electrochemical performance was assessed by cyclic voltammograms, galvanostatic charge/discharge and electrochemical impedance spectroscopy.

Graphene Oxide Sponge as Nanofillers in Printable Electrolytes in High-Performance Quasi-Solid-State Dye-Sensitized Solar Cells.

PubMed

Venkatesan, Shanmuganathan; Surya Darlim, Elmer; Tsai, Ming-Hsiang; Teng, Hsisheng; Lee, Yuh-Lang

2018-04-04

A graphene oxide sponge (GOS) is utilized for the first time as a nanofiller (NF) in printable electrolytes (PEs) based on poly(ethylene oxide) and poly(vinylidene fluoride) for quasi-solid-state dye-sensitized solar cells (QS-DSSCs). The effects of the various concentrations of GOS NFs on the ion diffusivity and conductivity of electrolytes and the performance of the QS-DSSCs are studied. The results show that the presence of GOS NFs significantly increases the diffusivity and conductivity of the PEs. The introduction of 1.5 wt % of GOS NFs decreases the charge-transfer resistance at the Pt-counter electrode/electrolyte interface ( R pt ) and increases the recombination resistance at the photoelectrode/electrolyte interface ( R ct ). QS-DSSC utilizing 1.5 wt % GOS NFs can achieve an energy conversion efficiency (8.78%) higher than that found for their liquid counterpart and other reported polymer gel electrolytes/GO NFs based DSSCs. The high energy conversion efficiency is a consequence of the increase in both the open-circuit potential ( V oc ) and fill factor with a slight decrease in current density ( J sc ). The cell efficiency can retain 86% of its initial value after a 500 h stability test at 60 °C under dark conditions. The long-term stability of the QS-DSSC with GOS NFs is higher than that without NFs. This result indicates that the GOS NFs do not cause dye-desorption from the photoanode in a long-term stability test, which infers a superior performance of GOS NFs as compared to TiO 2 NFs in terms of increasing the efficiency and long-term stability of QS-DSSCs.

Oligo(ethylene glycol)-functionalized disiloxanes as electrolytes for lithium-ion batteries

NASA Astrophysics Data System (ADS)

Zhang, Zhengcheng; Dong, Jian; West, Robert; Amine, Khalil

Functionalized disiloxane compounds were synthesized by attaching oligo(ethylene glycol) chains, -(CH 2CH 2O)- n, n = 2-7, via hydrosilation, dehydrocoupling, and nucleophilic substitution reactions and were examined as non-aqueous electrolyte solvents in lithium-ion cells. The compounds were fully characterized by 1H, 13C, and 29Si nuclear magnetic resonance (NMR) spectroscopy. Upon doping with lithium bis(oxalato)borate (LiBOB) or LiPF 6, the disiloxane electrolytes showed conductivities up to 6.2 × 10 -4 S cm -1 at room temperature. The thermal behavior of the electrolytes was studied by differential scanning calorimetry, which revealed very low glass transition temperatures before and after LiBOB doping and much higher thermal stability compared to organic carbonate electrolytes. Cyclic voltammetry measurements showed that disiloxane-based electrolytes with 0.8 M LiBOB salt concentration are stable to 4.7 V. The LiBOB/disiloxane combinations were found to be good electrolytes for lithium-ion cells; unlike LiPF 6, LiBOB can provide a good passivation film on the graphite anode. The LiPF 6/disiloxane electrolyte was enabled in lithium-ion cells by adding 1 wt% vinyl ethylene carbonate (VEC). Full cell performance tests with LiNi 0.80Co 0.15Al 0.05O 2 as the cathode and mesocarbon microbead (MCMB) graphite as the anode show stable cyclability. The results demonstrate that disiloxane-based electrolytes have considerable potential as electrolytes for use in lithium-ion batteries.

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 (

A comparative study of quasi-solid nanoclay gel electrolyte and liquid electrolyte dye sensitized solar cells

NASA Astrophysics Data System (ADS)

Main, Laura

Dye sensitized solar cells (DSSCs) are currently being explored as a cheaper alternative to the more common silicon (Si) solar cell technology. In addition to the cost advantages, DSSCs show good performance in low light conditions and are not sensitive to varying angles of incident light like traditional Si cells. One of the major challenges facing DSSCs is loss of the liquid electrolyte, through evaporation or leakage, which lowers stability and leads to increased degradation. Current research with solid-state and quasi-solid DSSCs has shown success regarding a reduction of electrolyte loss, but at a cost of lower conversion efficiency output. The research work presented in this paper focuses on the effects of using nanoclay material as a gelator in the electrolyte of the DSSC. The data showed that the quasi-solid cells are more stable than their liquid electrolyte counterparts, and achieved equal or better I-V characteristics. The quasi-solid cells were fabricated with a gel electrolyte that was prepared by adding 7 wt% of Nanoclay, Nanomer® (1.31PS, montmorillonite clay surface modified with 15-35% octadecylamine and 0.5-5 wt% aminopropyltriethoxysilane, Aldrich) to the iodide/triiodide liquid electrolyte, (Iodolyte AN-50, Solaronix). Various gel concentrations were tested in order to find the optimal ratio of nanoclay to liquid. The gel electrolyte made with 7 wt% nanoclay was more viscous, but still thin enough to allow injection with a standard syringe. Batches of cells were fabricated with both liquid and gel electrolyte and were evaluated at STC conditions (25°C, 100 mW/cm2) over time. The gel cells achieved efficiencies as high as 9.18% compared to the 9.65% achieved by the liquid cells. After 10 days, the liquid cell decreased to 1.75%, less than 20% of its maximum efficiency. By contrast, the gel cell's efficiency increased for two weeks, and did not decrease to 20% of maximum efficiency until 45 days. After several measurements, the liquid cells showed visible signs of leakage through the sealant, whereas the gel cells did not. This resistance to leakage likely contributed to the improved performance of the quasi-solid cells over time, and is a significant advantage over liquid electrolyte DSSCs.

Novel choline-based ionic liquids as safe electrolytes for high-voltage lithium-ion batteries

NASA Astrophysics Data System (ADS)

Yong, Tianqiao; Zhang, Lingzhi; Wang, Jinglun; Mai, Yongjin; Yan, Xiaodan; Zhao, Xinyue

2016-10-01

Three choline-based ionic liquids functionalized with trimethylsilyl, allyl, and cynoethyl groups are synthesized in an inexpensive route as safe electrolytes for high-voltage lithium-ion batteries. The thermal stabilities, viscosities, conductivities, and electrochemical windows of these ILs are reported. Hybrid electrolytes were formulated by doping with 0.6 M LiPF6/0.4 M lithium oxalydifluoroborate (LiODFB) as salts and dimethyl carbonate (DMC) as co-solvent. By using 0.6 M LiPF6/0.4 M LiODFB trimethylsilylated choline-based IL (SN1IL-TFSI)/DMC as electrolyte, LiCoO2/graphite full cell showed excellent cycling performance with a capacity of 152 mAh g-1 and 99% capacity retention over 90 cycles at a cut-off voltage of 4.4 V. The propagation rate of SN1IL-TFSI)/DMC electrolyte is only one quarter of the commercial electrolyte (1 M LiPF6 EC/DEC/DMC, v/v/v = 1/1/1), suggesting a better safety feature.

A Key concept in Magnesium Secondary Battery Electrolytes.

PubMed

Bertasi, Federico; Hettige, Chaminda; Sepehr, Fatemeh; Bogle, Xavier; Pagot, Gioele; Vezzù, Keti; Negro, Enrico; Paddison, Stephen J; Greenbaum, Steve G; Vittadello, Michele; Di Noto, Vito

2015-09-21

A critical roadblock toward practical Mg-based energy storage technologies is the lack of reversible electrolytes that are safe and electrochemically stable. Here, we report on high-performance electrolytes based on 1-ethyl-3-methylimidazolium chloride (EMImCl) doped with AlCl3 and highly amorphous δ-MgCl2 . The phase diagram of the electrolytes reveals the presence of four thermal transitions that strongly depend on salt content. High-level density functional theory (DFT)-based electronic structure calculations substantiate the structural and vibrational assignment of the coordination complexes. A 3D chloride-concatenated dynamic network model accounts for the outstanding redox behaviour and the electric and magnetic properties, providing insight into the conduction mechanism of the electrolytes. Mg anode cells assembled using the electrolytes were cyclically discharged at a high rate (35 mA g(-1) ), exhibiting an initial capacity of 80 mA h g(-1) and a steady-state voltage of 2.3 V. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

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

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.

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.

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.

MgCl 2 : The Key Ingredient to Improve Chloride Containing Electrolytes for Rechargeable Magnesium-Ion Batteries

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

Pan, Baofei; Huang, Jinhua; Sa, Niya

The effect of MgCl2 on a series of chloride containing magnesium electrolytes was investigated. In the presence of extra MgCl2, the electrochemical properties of Grignard reagents (RMgCl, R = Ph, Et, iPr) were significantly improved, and the advance of MgCl2 was further demonstrated in Mg-Mo6S8 rechargeable batteries with improved capacities and much smaller over-potentials. MgCl2 was then further proven to be powerful reagent to improve the performance of well-established strong Lewis acid derived magnesium electrolytes including the “all-phenyl” complex (APC) and alkoxide-based magnesium electrolytes. The results suggest that MgCl2 salt is a very important species to benefit all chloride containingmore » electrolytes for rechargeable magnesium-ion batteries.« less

An advanced model framework for solid electrolyte intercalation batteries.

PubMed

Landstorfer, Manuel; Funken, Stefan; Jacob, Timo

2011-07-28

Recent developments of solid electrolytes, especially lithium ion conductors, led to all solid state batteries for various applications. In addition, mathematical models sprout for different electrode materials and battery types, but are missing for solid electrolyte cells. We present a mathematical model for ion flux in solid electrolytes, based on non-equilibrium thermodynamics and functional derivatives. Intercalated ion diffusion within the electrodes is further considered, allowing the computation of the ion concentration at the electrode/electrolyte interface. A generalized Frumkin-Butler-Volmer equation describes the kinetics of (de-)intercalation reactions and is here extended to non-blocking electrodes. Using this approach, numerical simulations were carried out to investigate the space charge region at the interface. Finally, discharge simulations were performed to study different limitations of an all solid state battery cell. This journal is © the Owner Societies 2011

[EFFECTS OF INGESTING CARBOHYDRATE-PROTEIN SUPPLEMENTS DURING EXERCISE ON ENDURANCE PERFORMANCE: A SYSTEMATIC REVIEW].

PubMed

Espino-González, Ever; Muñoz-Daw, María de Jesús; Candia-Lujan, Ramon

2015-11-01

sports drinks aid to improve physical performance significantly because of its content of carbohydrate, electrolytes and water. However, in recent decades it has been found that drinking a sports drink with protein during exercise improves endurance performance, produces lower losses of body weight induced by dehydration and helps to reduce post-exercise muscle damage compared to a drink only with carbohydrate and electrolytes. the aim of this study was to analyze the main studies about the effectiveness of a supplement intake with carbohydrate, protein and electrolytes during exercise. studies were identified by searching Google Scholar, EBSCO, PubMed and Scopus using the following search terms: Carbohydrate-protein and performance and Added protein and sports drink. The methodological quality of the trials was evaluated, and It was considered that the intake of the supplement has been during exercise. twenty articles were included in this study. Thirteen obtained results were the intake of sports drinks with protein produced significant improvements on endurance performance compared to beverages with carbohydrates and electrolytes alone, or a placebo. increase the caloric content of sports drinks to add protein was probably a better strategy than reduce the carbohydrate content to match the amount of calories. protein intake during exercise demonstrated an ergogenic effect on endurance performance when assessed by time to exhaustion. However, we need more evidence to prove this possible ergogenic effect of protein. Copyright AULA MEDICA EDICIONES 2014. Published by AULA MEDICA. All rights reserved.

Molecularly Engineered Ru(II) Sensitizers Compatible with Cobalt(II/III) Redox Mediators for Dye-Sensitized Solar Cells.

PubMed

Wu, Kuan-Lin; Huckaba, Aron J; Clifford, John N; Yang, Ya-Wen; Yella, Aswani; Palomares, Emilio; Grätzel, Michael; Chi, Yun; Nazeeruddin, Mohammad Khaja

2016-08-01

Thiocyanate-free isoquinazolylpyrazolate Ru(II) complexes were synthesized and applied as sensitizers in dye-sensitized solar cells (DSCs). Unlike most other successful Ru sensitizers, Co-based electrolytes were used, and resulting record efficiency of 9.53% was obtained under simulated sunlight with an intensity of 100 mW cm(-2). Specifically, dye 51-57dht.1 and an electrolyte based on Co(phen)3 led to measurement of a JSC of 13.89 mA cm(-2), VOC of 900 mV, and FF of 0.762 to yield 9.53% efficiency. The improved device performances were achieved by the inclusion of 2-hexylthiophene units onto the isoquinoline subunits, in addition to lengthening the perfluoroalkyl chain on the pyrazolate chelating group, which worked to increase light absorption and decrease recombination effects when using the Co-based electrolyte. As this study shows, Ru(II) sensitizers bearing sterically demanding ligands can allow successful utilization of important Co electrolytes and high performance.

Supercritical carbon dioxide extraction of electrolyte from spent lithium ion batteries and its characterization by gas chromatography with chemical ionization

NASA Astrophysics Data System (ADS)

Mönnighoff, Xaver; Friesen, Alex; Konersmann, Benedikt; Horsthemke, Fabian; Grützke, Martin; Winter, Martin; Nowak, Sascha

2017-06-01

The aging products of the electrolyte from a commercially available state-of-the-art 18650-type cell were investigated. During long term cycling a huge difference in their performance and lifetime at different temperatures was observed. By interpretation of a strong capacity fading of cells cycled at 20 °C compared to cells cycled at 45 °C a temperature depending aging mechanism was determined. To investigate the influence of the electrolyte on this fading, the electrolyte was extracted by supercritical fluid extraction (SFE) and then analyzed by gas chromatography (GC) with electron impact (EI) ionization and mass selective detection. To obtain more information with regard to the identification of unknown decomposition products further analysis with positive chemical ionization (PCI) and negative chemical ionization (NCI) was performed. 17 different volatile organic aging products were detected and identified. So far, seven of them were not yet known in literature and several formation pathways were postulated taking previously published literature into account.

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

Vijayakumar, M.; Nie, Zimin; Walter, Eric D.

Redox flow battery (RFB) is a promising candidate for energy storage component in designing resilient grid scale power supply due to the advantage of the separation of power and energy. However, poorly understood chemical and thermal stability issues of electrolytes currently limit the performance of RFB. Designing of high performance stable electrolytes requires comprehensive knowledge about the molecular level solvation structure and dynamics of their redox active species. The molecular level understanding of detrimental V2O5 precipitation process led to successful designing of mixed acid based electrolytes for vanadium redox flow batteries (VRFB). The higher stability of mixed acid based electrolytesmore » is attributed to the choice of hydrochloric acid as optimal co-solvent, which provides chloride anions for ligand exchange process in vanadium solvation structure. The role of chloride counter anion on solvation structure and dynamics of vanadium species were studied using combined magnetic resonance spectroscopy and DFT based theoretical methods. Finally, the solvation phenomenon of multiple vanadium species and their impact on VRFB electrolyte chemical stability were discussed.« less

Kinetic-Dominated Charging Mechanism within Representative Aqueous Electrolyte-based Electric Double-Layer Capacitors.

PubMed

Yang, Huachao; Yang, Jinyuan; Bo, Zheng; Chen, Xia; Shuai, Xiaorui; Kong, Jing; Yan, Jianhua; Cen, Kefa

2017-08-03

The chemical nature of electrolytes has been demonstrated to play a pivotal role in the charge storage of electric double-layer capacitors (EDLCs), whereas primary mechanisms are still partially resolved but controversial. In this work, a systematic exploration into EDL structures and kinetics of representative aqueous electrolytes is performed with numerical simulation and experimental research. Unusually, a novel charging mechanism exclusively predominated by kinetics is recognized, going beyond traditional views of manipulating capacitances preferentially via interfacial structural variations. Specifically, strikingly distinctive EDL structures stimulated by diverse ion sizes, valences, and mixtures manifest a virtually identical EDL capacitance, where the dielectric nature of solvents attenuates ionic effects on electrolyte redistributions, in stark contradiction with solvent-free counterpart and traditional Helmholtz theory. Meanwhile, corresponding kinetics evolve conspicuously with ionic species, intimately correlated with ion-solvent interactions. The achieved mechanisms are subsequently illuminated by electrochemical measurements, highlighting the crucial interplay between ions and solvents in regulating EDLC performances.

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

Tan, Guoqiang; Wu, Feng; Zhan, Chun

The development of safe, stable, and long-life Li-ion batteries is being intensively pursued to enable the electrification of transportation and intelligent grid applications. Here, we report a new solid-state Li-ion battery technology, using a solid nanocomposite electrolyte composed of porous silica matrices with in situ immobilizing Li+ conducting ionic liquid, anode material of MCMB, and cathode material of LiCoO 2, LiNi 1/3Co 1/3Mn 1/3O 2, or LiFePO 4. An injection printing method is used for the electrode/electrolyte preparation. Solid nanocomposite electrolytes exhibit superior performance to the conventional organic electrolytes with regard to safety and cycle-life. They also have a transparentmore » glassy structure with high ionic conductivity and good mechanical strength. Solid-state full cells tested with the various cathodes exhibited high specific capacities, long cycling stability, and excellent high temperature performance. This solid-state battery technology will provide new avenues for the rational engineering of advanced Li-ion batteries and other electrochemical devices.« less

Precursor-route ZnO films from a mixed casting solvent for high performance aqueous electrolyte-gated transistors.

PubMed

Althagafi, Talal M; Algarni, Saud A; Al Naim, Abdullah; Mazher, Javed; Grell, Martin

2015-12-14

We significantly improved the performance of precursor-route semiconducting zinc oxide (ZnO) films in electrolyte-gated thin film transistors (TFTs). We find that the organic precursor to ZnO, zinc acetate (ZnAc), dissolves more readily in a 1 : 1 mixture of ethanol (EtOH) and acetone than in pure EtOH, pure acetone, or pure isopropanol. XPS and SEM characterisation show improved morphology of ZnO films converted from a mixed solvent cast ZnAc precursor compared to the EtOH cast precursor. When gated with a biocompatible electrolyte, phosphate buffered saline (PBS), ZnO thin film transistors (TFTs) derived from mixed solvent cast ZnAc give 4 times larger field effect current than similar films derived from ZnAc cast from pure EtOH. The sheet resistance at VG = VD = 1 V is 30 kΩ □(-1), lower than for any organic TFT, and lower than for any electrolyte-gated ZnO TFT reported to date.

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

Redox flow batteries with serpentine flow fields: Distributions of electrolyte flow reactant penetration into the porous carbon electrodes and effects on performance

NASA Astrophysics Data System (ADS)

Ke, Xinyou; Prahl, Joseph M.; Alexander, J. Iwan D.; Savinell, Robert F.

2018-04-01

Redox flow batteries with flow field designs have been demonstrated to boost their capacities to deliver high current density and power density in medium and large-scale energy storage applications. Nevertheless, the fundamental mechanisms involved with improved current density in flow batteries with serpentine flow field designs have been not fully understood. Here we report a three-dimensional model of a serpentine flow field over a porous carbon electrode to examine the distributions of pressure driven electrolyte flow penetrations into the porous carbon electrodes. We also estimate the maximum current densities associated with stoichiometric availability of electrolyte reactant flow penetrations through the porous carbon electrodes. The results predict reasonably well observed experimental data without using any adjustable parameters. This fundamental work on electrolyte flow distributions of limiting reactant availability will contribute to a better understanding of limits on electrochemical performance in flow batteries with serpentine flow field designs and should be helpful to optimizing flow batteries.

Lifetime estimates for sterilizable silver-zinc battery separators

NASA Technical Reports Server (NTRS)

Cuddihy, E. F.; Walmsley, D. E.; Moacanin, J.

1972-01-01

The lifetime of separator membranes currently employed in the electrolyte environment of silver-zinc batteries was estimated at 3 to 5 years. The separator membranes are crosslinked polyethylene film containing grafted poly (potassium acrylate)(PKA), the latter being the hydrophilic agent which promotes electrolyte ion transport. The lifetime was estimated by monitoring the rate of loss of PKA from the separators, caused by chemical attack of the electrolyte, and relating this loss rate to a known relationship between battery performance and PKA concentration in the separators.

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.

Alkaline polymer electrolyte membranes for fuel cell applications.

PubMed

Wang, Yan-Jie; Qiao, Jinli; Baker, Ryan; Zhang, Jiujun

2013-07-07

In this review, we examine the most recent progress and research trends in the area of alkaline polymer electrolyte membrane (PEM) development in terms of material selection, synthesis, characterization, and theoretical approach, as well as their fabrication into alkaline PEM-based membrane electrode assemblies (MEAs) and the corresponding performance/durability in alkaline polymer electrolyte membrane fuel cells (PEMFCs). Respective advantages and challenges are also reviewed. To overcome challenges hindering alkaline PEM technology advancement and commercialization, several research directions are then proposed.

A stable perovskite electrolyte in moist air for Li-ion batteries.

PubMed

Li, Yutao; Xu, Henghui; Chien, Po-Hsiu; Wu, Nan; Xin, Sen; Xue, Leigang; Park, Kyusung; Hu, Yan-Yan; Goodenough, John B

2018-05-07

Solid-oxide Li+ electrolytes of a rechargeable cell are generally sensitive to moisture in the air, H+ exchanges for the mobile Li+ of the electrolyte and forms insulating surface phases at the electrolyte interfaces and in the grain boundaries of a polycrystalline membrane. These surface phases dominate the total interfacial resistance of a conventional rechargeable cell having a solid-electrolyte separator. We report a new perovskite Li+ solid electrolyte, Li0.38Sr0.44Ta0.7Hf0.3O2.95F0.05, having a Li-ion conductivity σLi = 4.8×10-4 S cm-1 at 25 oC that does not react with water having 3≤pH≤14. The solid electrolyte with a thin Li+-conducting polymer on its surface to prevent reduction of Ta5+ is wet by metallic lithium and provides low-impedance dendrite-free plating/stripping of a lithium anode. It is also stable on contact with a composite polymer cathode. With this solid electrolyte, we demonstrate excellent cycling performance of an all-solid-state Li/LiFePO4 cell, a Li-S cell with a polymer-gel cathode, and a supercapacitor. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Charge carrier dynamics in PMMA-LiClO4 based polymer electrolytes plasticized with different plasticizers

NASA Astrophysics Data System (ADS)

Pal, P.; Ghosh, A.

2017-07-01

We have studied the charge carrier dynamics in poly(methylmethacrylate)-LiClO4 polymer electrolytes plasticized with different plasticizers such as ethylene carbonate (EC), propylene carbonate (PC), polyethylene glycol (PEG), and dimethyl carbonate (DMC). We have measured the broadband complex conductivity spectra of these electrolytes in the frequency range of 0.01 Hz-3 GHz and in the temperature range of 203 K-363 K and analyzed the conductivity spectra in the framework of the random barrier model by taking into account the contribution of the electrode polarization observed at low frequencies and/or at high temperatures. It is observed that the temperature dependences of the ionic conductivity and relaxation time follow the Vogel-Tammann-Fulcher relation for all plasticized electrolytes. We have also performed the scaling of the conductivity spectra, which indicates that the charge carrier dynamics is almost independent of temperature and plasticizers in a limited frequency range. The existence of nearly constant loss in these electrolytes has been observed at low temperatures and/or high frequencies. We have studied the dielectric relaxation in these electrolytes using electric modulus formalism and obtained the stretched exponent and the decay function. We have observed less cooperative ion dynamics in electrolytes plasticized with DMC compared to electrolytes plasticized with EC, PC, and PEG.

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.

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.

Hydrofluoroether electrolytes for lithium-ion batteries: Reduced gas decomposition and nonflammable

NASA Astrophysics Data System (ADS)

Nagasubramanian, Ganesan; Orendorff, Christopher J.

2011-10-01

The optimum combination of high energy density at the desired power sets lithium-ion battery technology apart from the other well known secondary battery chemistries. However, this is besieged by thermal instability of the electrolyte. This "Achilles heel" still remains a significant safety issue and unless this propensity is improved the promise of widespread adoption of Li-ion batteries for Transportation application may not be realized. With this in mind we launched a systematic study to evaluate fluoro solvents that are known to be nonflammable, for thermal and electrochemical performances. We investigated hydro-fluoro-ethers (HFE) (1) 2-trifluoromethyl-3-methoxyperfluoropentane {TMMP} and (2) 2-trifluoro-2-fluoro-3-difluoropropoxy-3-difluoro-4-fluoro-5-trifluoropentane {TPTP} in Sandia-built cells. Thermal properties under near abuse conditions that exist in thermal runaway environment and the electrochemical characteristics for these electrolytes were measured. In the thermal ramp (TR) measurement, EC:DEC:TPTP-1 M LiBETI (or TFSI or LiPF6) electrolytes exhibited no ignition/fire. Similar behavior was observed for the EC:DEC:TMMP-1 M LiBETI. Further, in ARC studies the HFE electrolytes generated less gas by 50% compared to the EC:EMC-1.2 M LiPF6 {CAR-1} electrolyte. Although in all cases the HFEs generated less gas, the onset of gas generation appears to depend on the salt. For the LiBETI and TFSI containing HFEs the onset is pushed out by ∼80 °C and for the LiPF6 the onset is comparable to that of the CAR-1. The solution ionic conductivity of these HFE electrolytes was lower (4-5 times) than that of the CAR-1 electrolyte however, the electrochemical performance was comparable. For example, full cells in 2032 type coin cells containing LiMN0.33Ni0.33Co0.33O2 cathode and carbon anode showed around 5 mA h capacity and the computed specific capacity was ∼154 mA h for all the electrolytes. In half-cells against lithium the cathode and anode gave specific capacity on the order of 170 mA h and 340 mA h respectively. These electrolytes when tested in 18,650 cells containing the above cathode and anode also showed comparable capacity. Further, the voltage stability window was not compromised by the HFEs. ARC measurements on 18,650 full cells showed less gas generation for the HFE electrolytes compared to CAR-1 electrolyte.

Highly Stable Sr-Free Cobaltite-Based Perovskite Cathodes Directly Assembled on a Barrier-Layer-Free Y2 O3 -ZrO2 Electrolyte of Solid Oxide Fuel Cells.

PubMed

Ai, Na; Li, Na; Rickard, William D A; Cheng, Yi; Chen, Kongfa; Jiang, San Ping

2017-03-09

Direct assembly is a newly developed technique in which a cobaltite-based perovskite (CBP) cathode can be directly applied to a barrier-layer-free Y 2 O 3 -ZrO 2 (YSZ) electrolyte with no high-temperature pre-sintering steps. Solid oxide fuel cells (SOFCs) based on directly assembled CBPs such as La 0.6 Sr 0.4 Co 0.2 Fe 0.8 O 3-δ show high performance initially but degrade rapidly under SOFC operation conditions at 750 °C owing to Sr segregation and accumulation at the electrode/electrolyte interface. Herein, the performance and interface of Sr-free CBPs such as LaCoO 3-δ (LC) and Sm 0.95 CoO 3-δ (SmC) and their composite cathodes directly assembled on YSZ electrolyte was studied systematically. The LC electrode underwent performance degradation, most likely owing to cation demixing and accumulation of La on the YSZ electrolyte under polarization at 500 mA cm -2 and 750 °C. However, the performance and stability of LC electrodes could be substantially enhanced by the formation of LC-gadolinium-doped ceria (GDC) composite cathodes. Replacement of La by Sm increased the cell stability, and doping of 5 % Pd to form Sm 0.95 Co 0.95 Pd 0.05 O 3-δ (SmCPd) significantly improved the electrode activity. An anode-supported YSZ-electrolyte cell with a directly assembled SmCPd-GDC composite electrode exhibited a peak power density of 1.4 W cm -2 at 750 °C, and an excellent stability at 750 °C for over 240 h. The higher stability of SmC as compared to that of LC is most likely a result of the lower reactivity of SmC with YSZ. This study demonstrates the new opportunities in the design and development of intermediate-temperature SOFCs based on the directly assembled high-performance and durable Sr-free CBP cathodes. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Novel approaches for fabrication of thin film layers for solid oxide electrolyte fuel cells

NASA Technical Reports Server (NTRS)

Murugesamoorthi, K. A.; Srinivasan, S.; Cocke, D. L.; Appleby, A. J.

1990-01-01

The main objectives of the SOFC (solid oxide fuel cell) project are to (1) identify viable and cost-effective techniques to prepare cell components for stable MSOFCs (monolithic SOFCs); (2) fabricate half and single cells; and (3) evaluate their performances. The approach used to fabricate stable MSOFCs is as follows: (1) the electrolyte layer is prepared in the form of a honeycomb structure by alloy oxidation and other cell components are deposited on it; (2) the electrolyte and anode layers are deposited on the cathode layer, which has a porous, honeycomb structure; and (3) the electrolyte and cathode layers are deposited on the anode layer. The current status of the project is reported.

High optical and switching performance electrochromic devices based on a zinc oxide nanowire with poly(methyl methacrylate) gel electrolytes

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

Chun, Young Tea; Chu, Daping, E-mail: dpc31@cam.ac.uk; Neeves, Matthew

2014-11-10

High performance electrochromic devices have been fabricated and demonstrated utilizing a solid polymer electrolyte and zinc oxide (ZnO) nanowire (NW) array counter electrode. The poly(methyl methacrylate) based polymer electrolyte was spin coated upon hydrothermally grown ZnO NW array counter electrodes, while electron beam evaporated NiO{sub x} thin films formed the working electrodes. Excellent optical contrast and switching speeds were observed in the fabricated devices with active areas of 2 cm{sup 2}, exhibiting an optical contrast of 73.11% at the wavelength of 470 nm, combined with a fast switching time of 0.2 s and 0.4 s for bleaching and coloration, respectively.

Recent Progresses and Development of Advanced Atomic Layer Deposition towards High-Performance Li-Ion Batteries

PubMed Central

Lu, Wei; Liang, Longwei; Sun, Xuan; Sun, Xiaofei; Wu, Chen; Hou, Linrui; Sun, Jinfeng

2017-01-01

Electrode materials and electrolytes play a vital role in device-level performance of rechargeable Li-ion batteries (LIBs). However, electrode structure/component degeneration and electrode-electrolyte sur-/interface evolution are identified as the most crucial obstacles in practical applications. Thanks to its congenital advantages, atomic layer deposition (ALD) methodology has attracted enormous attention in advanced LIBs. This review mainly focuses upon the up-to-date progress and development of the ALD in high-performance LIBs. The significant roles of the ALD in rational design and fabrication of multi-dimensional nanostructured electrode materials, and finely tailoring electrode-electrolyte sur-/interfaces are comprehensively highlighted. Furthermore, we clearly envision that this contribution will motivate more extensive and insightful studies in the ALD to considerably improve Li-storage behaviors. Future trends and prospects to further develop advanced ALD nanotechnology in next-generation LIBs were also presented. PMID:29036916

Development of safe, green and high performance ionic liquids-based batteries (ILLIBATT project)

NASA Astrophysics Data System (ADS)

Balducci, A.; Jeong, S. S.; Kim, G. T.; Passerini, S.; Winter, M.; Schmuck, M.; Appetecchi, G. B.; Marcilla, R.; Mecerreyes, D.; Barsukov, V.; Khomenko, V.; Cantero, I.; De Meatza, I.; Holzapfel, M.; Tran, N.

This manuscript presents the work carried out within the European project ILLIBATT, which was dedicated to the development of green, safe and high performance ionic liquids-based lithium batteries. Different types of ionic liquids-based electrolytes were developed in the project, based on different ionic liquids and polymers. Using these electrolytes, the performance of several anodic and cathodic materials has been tested and promising results have been obtained. Also, electrodes were formulated using water soluble binders. Using these innovative components, lithium-ion and lithium-metal battery prototypes (0.7-0.8 Ah) have been assembled and cycled between 100% and 0% SOC. The results of these tests showed that such ionic liquids-based prototypes are able to display high capacity, high coulombic efficiency and high cycle life. Moreover, safety tests showed that the introduction of these alternative electrolytes positively contribute to the safety of the batteries.

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.

Electrochemical performance investigations on the hydrogen depolarized CO2 concentrator

NASA Technical Reports Server (NTRS)

Aylward, J. R.

1976-01-01

An extensive investigation of anode and cathode polarization in complete cells and half cells was conducted to determine the factors affecting HDC electrode polarization and the nature of this polarization. Matrix-electrolyte-electrode interactions and cell electrolyte composition were also investigated. The electrodes were found to have normal performance capabilities. The HDC anode polarization characteristics were correlated with a theoretical kinetic analysis; and, except for some quantitative details, a rather complete understanding of the causes for HDC electrode polarization was formulated. One of the important finding resulting from the kinetic analysis was that platinum appears to catalyze the decomposition of carbonic acid to carbon dioxide and water. It was concluded that the abnormal voltage performance of the One Man ARS HDC cells was caused by insufficient cell electrolyte volume under normal operating conditions due to deficiencies in the reservoir to cell interfacing.

On direct and indirect methanol fuel cells for transportation applications

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

Gottesfield, S.

1996-04-01

Research on direct oxidation methanol fuel cells (DMFCs) and polymer electrolyte fuel cells (PEFCs) is discussed. Systems considered for transportation applications are addressed. The use of platinum/ruthenium anode electrocatalysts and platinum cathode electrocatalysts in polymer electrolyte DMFCs has resulted in significant performance enhancements.

Effect of aluminum anodizing in phosphoric acid electrolyte on adhesion strength and thermal performance

NASA Astrophysics Data System (ADS)

Lee, Sulki; Kim, Donghyun; Kim, Yonghwan; Jung, Uoochang; Chung, Wonsub

2016-01-01

This study examined the adhesive bond strength and thermal performance of the anodized aluminum 6061 in phosphoric acid electrolyte to improve the adhesive bond strength and thermal performance for use in metal core printed circuit boards (MCPCB). The electrolyte temperature and applied voltage were altered to generate varied pore structures. The thickness, porosity and pore diameter of the anodized layer were measured. The pore morphologies were affected most by temperature, which was the driving force for ion transportation. The mechanism of adhesive bond was penetration of the epoxy into the pores. The optimal anodization conditions for maximum adhesive bond strength, 27 MPa, were 293 K and 100V. The maximum thermal conductivity of the epoxy-treated anodized layer was 1.6 W/m·K at 273 K. Compared with the epoxy-treated Al layer used for conventional MCPCBs, the epoxy-treated anodized layer showed advanced thermal performance due to a low difference of thermal resistance and high heat dissipation.

Theoretical performance of hydrogen-bromine rechargeable SPE fuel cell. [Solid Polymer Electrolyte

NASA Technical Reports Server (NTRS)

Savinell, R. F.; Fritts, S. D.

1988-01-01

A mathematical model was formulated to describe the performance of a hydrogen-bromine fuel cell. Porous electrode theory was applied to the carbon felt flow-by electrode and was coupled to theory describing the solid polymer electrolyte (SPE) system. Parametric studies using the numerical solution to this model were performed to determine the effect of kinetic, mass transfer, and design parameters on the performance of the fuel cell. The results indicate that the cell performance is most sensitive to the transport properties of the SPE membrane. The model was also shown to be a useful tool for scale-up studies.

Electrode effects on temporal changes in electrolyte pH and redox potential for water treatment

PubMed Central

Ciblak, Ali; Mao, Xuhui; Padilla, Ingrid; Vesper, Dorothy; Alshawabkeh, Iyad; Alshawabkeh, Akram N.

2012-01-01

The performance of electrochemical remediation methods could be optimized by controlling the physicochemical conditions of the electrochemical redox system. The effects of anode type (reactive or inert), current density and electrolyte composition on the temporal changes in pH and redox potential of the electrolyte were evaluated in divided and mixed electrolytes. Two types of electrodes were used: iron as a reactive electrode and mixed metal oxide coated titanium (MMO) as an inert electrode. Electric currents of 15, 30, 45 and 60 mA (37.5 mA L−1, 75 mA L−1, 112.5 mA L−1 and 150 mA L−1) were applied. Solutions of NaCl, Na2SO4 and NaHCO3 were selected to mimic different wastewater or groundwater composition. Iron anodes resulted in highly reducing electrolyte conditions compared to inert anodes. Electrolyte pH was dependent on electrode type, electrolyte composition and current density. The pH of mixed-electrolyte was stable when MMO electrodes were used. When iron electrodes were used, the pH of electrolyte with relatively low current density (37.5 mA L−1) did not show significant changes but the pH increased sharply for relatively high current density (150 mA L−1). Sulfate solution showed more basic and relatively more reducing electrolyte condition compared to bicarbonate and chloride solution. The study shows that a highly reducing environment could be achieved using iron anodes in divided or mixed electrolytes and the pH and redox potential could be optimized by using appropriate current and polarity reversal. PMID:22416866

Molecular simulations of electrolyte structure and dynamics in lithium-sulfur battery solvents

NASA Astrophysics Data System (ADS)

Park, Chanbum; Kanduč, Matej; Chudoba, Richard; Ronneburg, Arne; Risse, Sebastian; Ballauff, Matthias; Dzubiella, Joachim

2018-01-01

The performance of modern lithium-sulfur (Li/S) battery systems critically depends on the electrolyte and solvent compositions. For fundamental molecular insights and rational guidance of experimental developments, efficient and sufficiently accurate molecular simulations are thus in urgent need. Here, we construct a molecular dynamics (MD) computer simulation model of representative state-of-the art electrolyte-solvent systems for Li/S batteries constituted by lithium-bis(trifluoromethane)sulfonimide (LiTFSI) and LiNO3 electrolytes in mixtures of the organic solvents 1,2-dimethoxyethane (DME) and 1,3-dioxolane (DOL). We benchmark and verify our simulations by comparing structural and dynamic features with various available experimental reference systems and demonstrate their applicability for a wide range of electrolyte-solvent compositions. For the state-of-the-art battery solvent, we finally calculate and discuss the detailed composition of the first lithium solvation shell, the temperature dependence of lithium diffusion, as well as the electrolyte conductivities and lithium transference numbers. Our model will serve as a basis for efficient future predictions of electrolyte structure and transport in complex electrode confinements for the optimization of modern Li/S batteries (and related devices).

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.

A facile prestrain-stick-release assembly of stretchable supercapacitors based on highly stretchable and sticky hydrogel electrolyte

NASA Astrophysics Data System (ADS)

Tang, Qianqiu; Chen, Mingming; Wang, Gengchao; Bao, Hua; Saha, Petr

2015-06-01

A facile prestrain-stick-release assembly strategy for the stretchable supercapacitor device is developed based on a novel Na2SO4-aPUA/PAAM hydrogel electrolyte, saving the stretchable rubber base conventionally used. The Na2SO4-aPUA/PAAM hydrogel electrolyte exhibits high stretchability (>1000%), electrical conductivity (0.036 S cm-1) and stickiness. Due to the unique features of the hydrogel electrolyte, the carbon nanotube@MnO2 film electrodes can be firmly stuck to two sides of the prestrained hydrogel electrolyte. Then, by releasing the hydrogel electrolyte, homogenous buckles are formed for the film electrodes to get a full stretchable supercapacitor device. Besides, the high stickiness of the hydrogel electrolyte ensures its strong adhesion with the film electrodes, facilitating ion and electronic transfer of the supercapacitor. As a result, excellent electrochemical performance is achieved with the specific capacitance of 478.6 mF cm-2 at 0.5 mA cm-2 (corresponding to 201.1 F g-1) and capacitance retention of 91.5% after 3000 charging-discharging cycles under 150% strain, which is the best for the stretchable supercapacitors.

Study on characteristics of PVDF/nano-clay composite polymer electrolyte using PVP as pore-forming agent

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

Dyartanti, Endah R., E-mail: heru.susanto@undip.ac.id, E-mail: endah-rd@uns.ac.id; Department of Chemical Engineering, Diponegoro University, Semarang; Purwanto, Agus

2016-02-08

Polyvinylidene fluoride (PVDF) based polymer electrolytes have a high dielectric constant, which can assist in greater ionization of lithium salts. The main advantages of PVDF are its durability in long battery operation and its ability to be a good ion conductor. However, the limitation of this polymer is its crystalline molecular structure. Dispersing nano-particles in the polymer matrix may improve the characteristics of the PVDF polymer. This paper aims to investigate the impact of nano-clay addition on the characteristics of PVDF polymer to be used as a polymer electrolyte membrane. In addition, the effect of poly(vinyl pyrrolidone) (PVP) is alsomore » investigated. The membrane was prepared by phase separation method whereas the polymer electrolyte membranes was prepared by immersing into 1 M lithium hexafluorophosphate (LiPF{sub 6}) in ethylene carbonate/dimethyl carbonate (EC/DMC) electrolytes for 1 h. The membranes were characterized by scanning electron microscope (SEM), porosity and electrolyte uptake and performance in battery cell. The results showed that both nano-clay and PVP have significant impacts on the improvement of PVDF membranes to be used as polymer electrolyte.« less

New Insights into the Compositional Dependence of Li-Ion Transport in Polymer-Ceramic Composite Electrolytes.

PubMed

Zheng, Jin; Hu, Yan-Yan

2018-01-31

Composite electrolytes are widely studied for their potential in realizing improved ionic conductivity and electrochemical stability. Understanding the complex mechanisms of ion transport within composites is critical for effectively designing high-performance solid electrolytes. This study examines the compositional dependence of the three determining factors for ionic conductivity, including ion mobility, ion transport pathways, and active ion concentration. The results show that with increase in the fraction of ceramic Li 7 La 3 Zr 2 O 12 (LLZO) phase in the LLZO-poly(ethylene oxide) composites, ion mobility decreases, ion transport pathways transit from polymer to ceramic routes, and the active ion concentration increases. These changes in ion mobility, transport pathways, and concentration collectively explain the observed trend of ionic conductivity in composite electrolytes. Liquid additives alter ion transport pathways and increase ion mobility, thus enhancing ionic conductivity significantly. It is also found that a higher content of LLZO leads to improved electrochemical stability of composite electrolytes. This study provides insight into the recurring observations of compositional dependence of ionic conductivity in current composite electrolytes and pinpoints the intrinsic limitations of composite electrolytes in achieving fast ion conduction.

A comparative study of nano-SiO2 and nano-TiO2 fillers on proton conductivity and dielectric response of a silicotungstic acid-H3PO4-poly(vinyl alcohol) polymer electrolyte.

PubMed

Gao, Han; Lian, Keryn

2014-01-08

The effects of nano-SiO2 and nano-TiO2 fillers on a thin film silicotungstic acid (SiWA)-H3PO4-poly(vinyl alcohol) (PVA) proton conducting polymer electrolyte were studied and compared with respect to their proton conductivity, environmental stability, and dielectric properties, across a temperature range from 243 to 323 K. Three major effects of these fillers have been identified: (a) barrier effect; (b) intrinsic dielectric constant effect; and (c) water retention effect. Dielectric analyses were used to differentiate these effects on polymer electrolyte-enabled capacitors. Capacitor performance was correlated to electrolyte properties through dielectric constant and dielectric loss spectra. Using a single-ion approach, proton density and proton mobility of each polymer electrolyte were derived as a function of temperature. The results allow us to deconvolute the different contributions to proton conductivity in SiWA-H3PO4-PVA-based electrolytes, especially in terms of the effects of fillers on the dynamic equilibrium of free protons and protonated water in the electrolytes.

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

Ionic Liquids as Electrolytes for Electrochemical Double-Layer Capacitors: Structures that Optimize Specific Energy.

PubMed

Mousavi, Maral P S; Wilson, Benjamin E; Kashefolgheta, Sadra; Anderson, Evan L; He, Siyao; Bühlmann, Philippe; Stein, Andreas

2016-02-10

Key parameters that influence the specific energy of electrochemical double-layer capacitors (EDLCs) are the double-layer capacitance and the operating potential of the cell. The operating potential of the cell is generally limited by the electrochemical window of the electrolyte solution, that is, the range of applied voltages within which the electrolyte or solvent is not reduced or oxidized. Ionic liquids are of interest as electrolytes for EDLCs because they offer relatively wide potential windows. Here, we provide a systematic study of the influence of the physical properties of ionic liquid electrolytes on the electrochemical stability and electrochemical performance (double-layer capacitance, specific energy) of EDLCs that employ a mesoporous carbon model electrode with uniform, highly interconnected mesopores (3DOm carbon). Several ionic liquids with structurally diverse anions (tetrafluoroborate, trifluoromethanesulfonate, trifluoromethanesulfonimide) and cations (imidazolium, ammonium, pyridinium, piperidinium, and pyrrolidinium) were investigated. We show that the cation size has a significant effect on the electrolyte viscosity and conductivity, as well as the capacitance of EDLCs. Imidazolium- and pyridinium-based ionic liquids provide the highest cell capacitance, and ammonium-based ionic liquids offer potential windows much larger than imidazolium and pyridinium ionic liquids. Increasing the chain length of the alkyl substituents in 1-alkyl-3-methylimidazolium trifluoromethanesulfonimide does not widen the potential window of the ionic liquid. We identified the ionic liquids that maximize the specific energies of EDLCs through the combined effects of their potential windows and the double-layer capacitance. The highest specific energies are obtained with ionic liquid electrolytes that possess moderate electrochemical stability, small ionic volumes, low viscosity, and hence high conductivity, the best performing ionic liquid tested being 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide.

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.

Fabrication and Performance of Zirconia Electrolysis Cells for Cabon Dioxide Reduction for Mars In Situ Resource Utilization Applications

NASA Technical Reports Server (NTRS)

Minh, N. Q.; Chung, B. W.; Doshi, R.; Lear, G. R.; Montgomery, K.; Ong, E. T.

1999-01-01

Use of the Martian atmosphere (95% CO2) to produce oxygen (for propellant and life support) can significantly lower the required launch mass and dramatically reduce the total cost for Mars missions. Zirconia electrolysis cells are one of the technologies being considered for oxygen generation from carbon dioxide in Mars In Situ Resource Utilization (ISRU) production plants. The attractive features of the zirconia cell for this application include simple operation and lightweight, low volume system. A zirconia electrolysis cell is an all-solid state device, based on oxygen-ion conducting zirconia electrolytes, that electrochemically reduces carbon dioxide to oxygen and carbon monoxide. The cell consists of two porous electrodes (the anode and cathode) separated by a dense zirconia electrolyte. Typical zirconia cells contain an electrolyte layer which is 200 to 400 micrometer thick. The electrical conductivity requirement for the electrolyte necessitates an operating temperature of 9000 to 10000C. Recently, the fabrication of zirconia cells by the tape calendering has been evaluated. This fabrication process provides a simple means of making cells having very thin electrolytes (5 to 30 micrometers). Thin zirconia electrolytes reduce cell ohmic losses, permitting efficient operation at lower temperatures (8000C or below). Thus, tape-calendered cells provides not only the potential of low temperature operation but also the flexibility in operating temperatures. This paper describes the fabrication of zirconia cells by the tape calendering method and discusses the performance results obtained to date.

Can ionophobic nanopores enhance the energy storage capacity of electric-double-layer capacitors containing nonaqueous electrolytes?

DOE PAGES

Lian, Cheng; Univ. of California, Riverside, CA; Liu, Honglai; ...

2016-08-22

The ionophobicity effect of nanoporous electrodes on the capacitance and the energy storage capacity of nonaqueous-electrolyte supercapacitors is studied by means of the classical density functional theory (DFT). It has been hypothesized that ionophobic nanopores may create obstacles in charging, but they store energy much more efficiently than ionophilic pores. In this paper, we find that, for both ionic liquids and organic electrolytes, an ionophobic pore exhibits a charging behavior different from that of an ionophilic pore, and that the capacitance–voltage curve changes from a bell shape to a two-hump camel shape when the pore ionophobicity increases. For electric-double-layer capacitorsmore » containing organic electrolytes, an increase in the ionophobicity of the nanopores leads to a higher capacity for energy storage. Without taking into account the effects of background screening, the DFT predicts that an ionophobic pore containing an ionic liquid does not enhance the supercapacitor performance within the practical voltage ranges. However, by using an effective dielectric constant to account for ion polarizability, the DFT predicts that, like an organic electrolyte, an ionophobic pore with an ionic liquid is also able to increase the energy stored when the electrode voltage is beyond a certain value. We find that the critical voltage for an enhanced capacitance in an ionic liquid is larger than that in an organic electrolyte. Finally, our theoretical predictions provide further understanding of how chemical modification of porous electrodes affects the performance of supercapacitors.« less

In-situ preparation of poly(ethylene oxide)/Li3PS4 hybrid polymer electrolyte with good nanofiller distribution for rechargeable solid-state lithium batteries

NASA Astrophysics Data System (ADS)

Chen, Shaojie; Wang, Junye; Zhang, Zhihua; Wu, Linbin; Yao, Lili; Wei, Zhenyao; Deng, Yonghong; Xie, Dongjiu; Yao, Xiayin; Xu, Xiaoxiong

2018-05-01

Nano-sized fillers in a polymer matrix with good distribution can play a positive role in improving polymer electrolytes in the aspects of ionic conductivity, mechanical property and electrochemical performance of Li-ion cells. Herein, polyethylene oxide (PEO)/Li3PS4 hybrid polymer electrolyte is prepared via a new in-situ approach. The ionic conductivities of the novel hybrid electrolytes with variable proportions are measured, and the optimal electrolyte of PEO-2%vol Li3PS4 presents a considerable ionic conductivity of 8.01 × 10-4 S cm-1 at 60 °C and an electrochemical window up to 5.1 V. The tests of DSC and EDXS reveal that the Li3PS4 nanoparticles with better distribution, as active fillers scattering in the PEO, exhibit a positive effect on the transference of lithium ion and electrochemical interfacial stabilities. Finally, the assembled solid-state LiFePO4/Li battery presents a decent cycling performance (80.9% retention rate after 325 cycles at 60 °C) and excellent rate capacities with 153, 143, 139 and 127 mAh g-1 at the discharging rate of 0.1 C, 0.2 C, 0.5 C and 1 C at 60 °C. It is fully proved that it is an advanced strategy to preparing the new organic/inorganic hybrid electrolytes for lithium-ion batteries applications.

Modulation of solid electrolyte interphase of lithium-ion batteries by LiDFOB and LiBOB electrolyte additives

NASA Astrophysics Data System (ADS)

Huang, Shiqiang; Wang, Shuwei; Hu, Guohong; Cheong, Ling-Zhi; Shen, Cai

2018-05-01

Solid-electrolyte interphase (SEI) layer is an organic-inorganic composite layer that allows Li+ transport across but blocks electron flow across and prevents solvent diffusing to electrode surface. Morphology, thickness, mechanical and chemical properties of SEI are important for safety and cycling performance of lithium-ion batteries. Herein, we employ a combination of in-situ AFM and XPS to investigate the effects of two electrolyte additives namely lithium difluoro(oxalate)borate (LiDFOB) and lithium bis(oxalato)borate (LiBOB) on SEI layer. LiDFOB is found to result in a thin but hard SEI layer containing more inorganic species (LiF and LiCO3); meanwhile LiBOB promotes formation of a thick but soft SEI layer containing more organic species such as ROCO2Li. Findings from present study will help development of electrolyte additives that promote formation of good SEI layer.

Fluid and electrolyte needs for training, competition, and recovery.

PubMed

Shirreffs, Susan M; Sawka, Michael N

2011-01-01

Fluids and electrolytes (sodium) are consumed by athletes, or recommended to athletes, for a number of reasons, before, during, and after exercise. These reasons are generally to sustain total body water, as deficits (hypohydration) will increase cardiovascular and thermal strain and degrade aerobic performance. Vigorous exercise and warm/hot weather induce sweat production, which contains both water and electrolytes. Daily water (4-10 L) and sodium (3500-7000 mg) losses in active athletes during hot weather exposure can induce water and electrolyte deficits. Both water and sodium need to be replaced to re-establish "normal" total body water (euhydration). This replacement can be by normal eating and drinking practices if there is no urgency for recovery. But if rapid recovery (<24 h) is desired or severe hypohydration (>5% body mass) is encountered, aggressive drinking of fluids and consuming electrolytes should be encouraged to facilitate recovery for subsequent competition.

High Voltage LiNi 0.5 Mn 0.3 Co 0.2 O 2 /Graphite Cell Cycled at 4.6 V with a FEC/HFDEC-Based Electrolyte

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

He, Meinan; Su, Chi-Cheung; Feng, Zhenxing

2017-04-26

A high voltage LiNi0.5Mn0.3Co0.2O2/graphite cell with a fluorinated electrolyte formulation 1.0 m LiPF6 fluoroethylene carbonate/bis(2,2,2-trifluoroethyl) carbonate is reported and its electrochemical performance is evaluated at cell voltage of 4.6 V. Comparing with its nonfluorinated electrolyte counterpart, the reported fluorinated one shows much improved Coulombic efficiency and capacity retention when a higher cut-off voltage (4.6 V) is applied. Scanning electron microscopy/energy dispersive X-ray spectroscopy and X-ray photoelectron spectroscopy data clearly demonstrate the superior oxidative stability of the new electrolyte. The structural stability of the bulk cathode materials cycled with different electrolytes is extensively studied by X-ray absorption near edge structure andmore » X-ray diffraction.« less

Novel Stable Gel Polymer Electrolyte: Toward a High Safety and Long Life Li-Air Battery.

PubMed

Yi, Jin; Liu, Xizheng; Guo, Shaohua; Zhu, Kai; Xue, Hailong; Zhou, Haoshen

2015-10-28

Nonaqueous Li-air battery, as a promising electrochemical energy storage device, has attracted substantial interest, while the safety issues derived from the intrinsic instability of organic liquid electrolytes may become a possible bottleneck for the future application of Li-air battery. Herein, through elaborate design, a novel stable composite gel polymer electrolyte is first proposed and explored for Li-air battery. By use of the composite gel polymer electrolyte, the Li-air polymer batteries composed of a lithium foil anode and Super P cathode are assembled and operated in ambient air and their cycling performance is evaluated. The batteries exhibit enhanced cycling stability and safety, where 100 cycles are achieved in ambient air at room temperature. The feasibility study demonstrates that the gel polymer electrolyte-based polymer Li-air battery is highly advantageous and could be used as a useful alternative strategy for the development of Li-air battery upon further application.

Monolithic All-Phosphate Solid-State Lithium-Ion Battery with Improved Interfacial Compatibility.

PubMed

Yu, Shicheng; Mertens, Andreas; Tempel, Hermann; Schierholz, Roland; Kungl, Hans; Eichel, Rüdiger-A

2018-06-22

High interfacial resistance between solid electrolyte and electrode of ceramic all-solid-state batteries is a major reason for the reduced performance of these batteries. A solid-state battery using a monolithic all-phosphate concept based on screen printed thick LiTi 2 (PO 4 ) 3 anode and Li 3 V 2 (PO 4 ) 3 cathode composite layers on a densely sintered Li 1.3 Al 0.3 Ti 1.7 (PO 4 ) 3 solid electrolyte has been realized with competitive cycling performance. The choice of materials was primarily based on the (electro-)chemical and mechanical matching of the components instead of solely focusing on high-performance of individual components. Thus, the battery utilized a phosphate backbone in combination with tailored morphology of the electrode materials to ensure good interfacial matching for a durable mechanical stability. Moreover, the operating voltage range of the active materials matches with the intrinsic electrochemical window of the electrolyte which resulted in high electrochemical stability. A highly competitive discharge capacity of 63.5 mAh g -1 at 0.39 C after 500 cycles, corresponding to 84% of the initial discharge capacity, was achieved. The analysis of interfacial charge transfer kinetics confirmed the structural and electrical properties of the electrodes and their interfaces with the electrolyte, as evidenced by the excellent cycling performance of the all-phosphate solid-state battery. These interfaces have been studied via impedance analysis with subsequent distribution of relaxation times analysis. Moreover, the prepared solid-state battery could be processed and operated in air atmosphere owing to the low oxygen sensitivity of the phosphate materials. The analysis of electrolyte/electrode interfaces after cycling demonstrates that the interfaces remained stable during cycling.

Qualitative Investigation of the Decomposition of Organic Solvent Based Lithium Ion Battery Electrolytes with LC-IT-TOF-MS.

PubMed

Schultz, Carola; Vedder, Sven; Winter, Martin; Nowak, Sascha

2016-11-15

The development of a novel high performance liquid chromatography (HPLC) method hyphenated to an ion-trap time-of-flight mass spectrometer (IT-TOF-MS) for the separation and identification of constituents from common organic carbonate solvent-based electrolyte systems in lithium ion batteries (LIBs) is presented in this work. The method development was conducted for the qualitative structural elucidation of electrolyte main constituents with a special focus on the aging products of these components. The determination of their limits of detection was performed as well. Four different LiPF 6 -based LIB electrolytes were investigated in this study. The selected aging procedures for the electrolytes were thermal aging (storage at 60 °C for 2 weeks, storage at 60 °C in the presence of 2 vol % water contamination for 2 weeks) and electrochemical aging for 100 cycles at 2C. After thermal aging, several aging products were identified. The formation of organic phosphate aging products and several organofluorophosphates aging products was observed after thermal aging with water. Additionally, the content of carbonate aging products increased. After electrochemical aging, several carbonate aging products were detected. Electrochemical aging at 60 °C leads to the additional generation of organofluorophosphate aging products.

Effect of the Anion Activity on the Stability of Li Metal Anodes in Lithium-Sulfur Batteries

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

Cao, Ruiguo; Chen, Junzheng; Han, Kee Sung

2016-03-29

With the significant progress made in the development of cathodes in lithium-sulfur (Li-S) batteries, the stability of Li metal anodes becomes a more urgent challenge in these batteries. Here we report the systematic investigation of the stability of the anode/electrolyte interface in Li-S batteries with concentrated electrolytes containing various lithium salts. It is found that Li-S batteries using LiTFSI-based electrolytes are more stable than those using LiFSI-based electrolytes. The decreased stability is because the N-S bond in the FSI- anion is fairly weak and the scission of this bond leads to the formation of lithium sulfate (LiSOx) in the presencemore » of polysulfide species. In contrast, even the weakest bond (C-S) in the TFSI- anion is stronger than the N-S bond in the FSI- anion. In the LiTFSI-based electrolyte, the lithium metal anode tends to react with polysulfide to form lithium sulfide (LiSx) which is more reversible than LiSOx formed in the LiTFSI-based electrolyte. This fundamental difference in the bond strength of the salt anions in the presence of polysulfide species leads to a large difference in the stability of the anode-electrolyte interface and performance of the Li-S batteries with electrolytes composed of these salts. Therefore, anion selection is one of the key parameters in the search for new electrolytes for stable operation of Li-S batteries.« less

High Rate Performance Nanocomposite Electrode of Mesoporous Manganese Dioxide/Silver Nanowires in KI Electrolytes

PubMed Central

Jiang, Yanhua; Cui, Xiuguo; Zu, Lei; Hu, Zhongkai; Gan, Jing; Lian, Huiqin; Liu, Yang; Xing, Guangjian

2015-01-01

In recent years, manganese dioxide has become a research hotspot as an electrode material because of its low price. However, it has also become an obstacle to industrialization due to its low ratio of capacitance and the low rate performance which is caused by the poor electrical conductivity. In this study, a KI solution with electrochemical activity was innovatively applied to the electrolyte, and we systematically investigated the rate performance of the mesoporous manganese dioxide and the composite electrode with silver nanowires in supercapacitors. The results showed that when mesoporous manganese dioxide and mesoporous manganese dioxide/silver nanowires composite were used as electrodes, the strength of the current was amplified five times (from 0.1 to 0.5 A/g), the remaining rates of specific capacitance were 95% (from 205.5 down to 197.1 F/g) and 92% (from 208.1 down to 191.7 F/g) in the KI electrolyte, and the rate performance was much higher than which in an Na2SO4 electrolyte with a remaining rate of 25% (from 200.3 down to 49.1 F/g) and 60% (from 187.2 down to 113.1 F/g). The morphology and detail structure were investigated by Scanning electron microscopy, X-ray diffraction, Fourier transform infrared spectrometry and Nitrogen adsorption-desorption isotherms. The electrochemical performance was assessed by cyclic voltammograms, galvanostatic charge/discharge and electrochemical impedance spectroscopy. PMID:28347086

Performance of electrolyte measurements assessed by a trueness verification program.

PubMed

Ge, Menglei; Zhao, Haijian; Yan, Ying; Zhang, Tianjiao; Zeng, Jie; Zhou, Weiyan; Wang, Yufei; Meng, Qinghui; Zhang, Chuanbao

2016-08-01

In this study, we analyzed frozen sera with known commutabilities for standardization of serum electrolyte measurements in China. Fresh frozen sera were sent to 187 clinical laboratories in China for measurement of four electrolytes (sodium, potassium, calcium, and magnesium). Target values were assigned by two reference laboratories. Precision (CV), trueness (bias), and accuracy [total error (TEa)] were used to evaluate measurement performance, and the tolerance limit derived from the biological variation was used as the evaluation criterion. About half of the laboratories used a homogeneous system (same manufacturer for instrument, reagent and calibrator) for calcium and magnesium measurement, and more than 80% of laboratories used a homogeneous system for sodium and potassium measurement. More laboratories met the tolerance limit of imprecision (coefficient of variation [CVa]) than the tolerance limits of trueness (biasa) and TEa. For sodium, calcium, and magnesium, the minimal performance criterion derived from biological variation was used, and the pass rates for total error were approximately equal to the bias (<50%). For potassium, the pass rates for CV and TE were more than 90%. Compared with the non homogeneous system, the homogeneous system was superior for all three quality specifications. The use of commutable proficiency testing/external quality assessment (PT/EQA) samples with values assigned by reference methods can monitor performance and provide reliable data for improving the performance of laboratory electrolyte measurement. The homogeneous systems were superior to the non homogeneous systems, whereas accuracy of assigned values of calibrators and assay stability remained challenges.

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

K. Gering

An important feature of the DUALFOIL model for simulation of lithium-ion cells [1,2] is rigorous accounting for non-ideal electrolyte properties. Unfortunately, data are available on only a few electrolytes [3,4]. However, K. Gering has developed a model for estimation of electrolyte properties [5] and recently generated complete property sets (density, conductivity, activity coefficient, diffusivity, transport number) as a function of temperature and salt concentration. Here we use these properties in an enhanced version of the DUALFOIL model called DISTNP, available in Battery Design Studio [6], to examine the effect of different electrolytes on cell performance. Specifically, the behavior of amore » high energy LiCoO2/graphite 18650-size cell is simulated. The ability of Battery Design Studio to si« less

Advances in the high performance polymer electrolyte membranes for fuel cells.

PubMed

Zhang, Hongwei; Shen, Pei Kang

2012-03-21

This critical review tersely and concisely reviews the recent development of the polymer electrolyte membranes and the relationship between their properties and affecting factors like operation temperature. In the first section, the advantages and shortcomings of the corresponding polymer electrolyte membrane fuel cells are analyzed. Then, the limitations of Nafion membranes and their alternatives to large-scale commercial applications are discussed. Secondly, the concepts and approaches of the alternative proton exchange membranes for low temperature and high temperature fuel cells are described. The highlights of the current scientific achievements are given for various aspects of approaches. Thirdly, the progress of anion exchange membranes is presented. Finally, the perspectives of future trends on polymer electrolyte membranes for different applications are commented on (400 references).

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.

Electrical conductivity studies on (1-x)[PVA/PVP]: x[MgCl2{6H2O}] blend polymer electrolytes

NASA Astrophysics Data System (ADS)

Basha, S. K. Shahenoor; Reddy, K. Veera Bhadra; Rao, M. C.

2018-05-01

Blend polymer electrolytes of polyvinyl alcohol and polyvinyl pyrrolidone were prepared with different molecular wt% ratios of MgCl2.6H2O by solution cast technique. Electrical conductivity measurements for the prepared films were performed using Keithley electrometer model 6514 and the maximum ionic conductivity was found to be 1.01x10-3 S/cm at 373 K for the prepared composition of 35PVA/35PVP:30MgCl2.6H2O. The maximum ionic conductivity of polymer electrolyte has been used in fabrication of electrochemical cell with the configuration of Mg+/(PVA/PVP+MgCl2.6H2O)/(I2+C+electrolyte).

Three-dimensional ionic conduction in the strained electrolytes of solid oxide fuel cells

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

Han, Yupei; Zou, Minda; Lv, Weiqiang

2016-05-07

Flexible power sources including fuel cells and batteries are the key to realizing flexible electronic devices with pronounced foldability. To understand the bending effects in these devices, theoretical analysis on three-dimensional (3-D) lattice bending is necessary. In this report, we derive a 3-D analytical model to analyze the effects of electrolyte crystal bending on ionic conductivity in flexible solid-state batteries/fuel cells. By employing solid oxide fuel cells as a materials' platform, the intrinsic parameters of bent electrolyte materials, including lattice constant, Young's modulus, and Poisson ratio, are evaluated. Our work facilitates the rational design of highly efficient flexible electrolytes formore » high-performance flexible device applications.« less

Combination of an electrolytic pretreatment unit with secondary water reclamation processes

NASA Technical Reports Server (NTRS)

Wells, G. W.; Bonura, M. S.

1973-01-01

The design and fabrication of a flight concept prototype electrolytic pretreatment unit (EPU) and of a contractor-furnished air evaporation unit (AEU) are described. The integrated EPU and AEU potable water recovery system is referred to as the Electrovap and is capable of processing the urine and flush water of a six-man crew. Results of a five-day performance verification test of the Electrovap system are presented and plans are included for the extended testing of the Electrovap to produce data applicable to the combination of electrolytic pretreatment with most final potable water recovery systems. Plans are also presented for a program to define the design requirements for combining the electrolytic pretreatment unit with a reverse osmosis final processing unit.

Theory of electrohydrodynamic instabilities in electrolytic cells

NASA Technical Reports Server (NTRS)

Bruinsma, R.; Alexander, S.

1990-01-01

The paper develops the theory of the hydrodynamic stability of an electrolytic cell as a function of the imposed electric current. A new electrohydrodynamic instability is encountered when the current is forced to exceed the Nernst limit. The convection is driven by the volume force exerted by the electric field on space charges in the electrolyte. This intrinsic instability is found to be easily masked by extrinsic convection sources such as gravity or stirring. A linear stability analysis is performed and a dimensionless number Le is derived whose value determines the convection pattern.

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.

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.

Multistage Mechanism of Lithium Intercalation into Graphite Anodes in the Presence of the Solid Electrolyte Interface.

PubMed

Dinkelacker, Franz; Marzak, Philipp; Yun, Jeongsik; Liang, Yunchang; Bandarenka, Aliaksandr S

2018-04-25

A so-called solid electrolyte interface (SEI) in a lithium-ion battery largely determines the performance of the whole system. However, it is one of the least understood objects in these types of batteries. SEIs are formed during the initial charge-discharge cycles, prevent the organic electrolytes from further decomposition, and at the same time govern lithium intercalation into the graphite anodes. In this work, we use electrochemical impedance spectroscopy and atomic force microscopy to investigate the properties of a SEI film and an electrified "graphite/SEI/electrolyte interface". We reveal a multistage mechanism of lithium intercalation and de-intercalation in the case of graphite anodes covered by SEI. On the basis of this mechanism, we propose a relatively simple model, which perfectly explains the impedance response of the "graphite/SEI/electrolyte" interface at different temperatures and states of charge. From the whole data obtained in this work, it is suggested that not only Li + but also negatively charged species, such as anions from the electrolyte or functional groups of the SEI, likely interact with the surface of the graphite anode.

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.

Hierarchical porous carbons prepared by an easy one-step carbonization and activation of phenol-formaldehyde resins with high performance for supercapacitors

NASA Astrophysics Data System (ADS)

Zheng, Zhoujun; Gao, Qiuming

Hierarchical porous carbons are prepared by an easy one-step process of carbonization and activation derived from phenol-formaldehyde resins, in which potassium hydroxide acts as both the catalyst of polymerization and the activation reagent. The simple one-step preparation saves the cost of carbons and leads to high yield. The porous carbons have high surface areas with abundant pore structures. The plenty of micropores and small mesopores increase the capacitance and make the electrolyte ions diffuse fast into the pores. These hierarchical porous carbons show high performance for supercapacitors possessing of the optimized capacitance of 234 F g -1 in aqueous electrolyte and 137 F g -1 in organic electrolyte with high capacitive retention.

Thiocyanates as attractive redox-active electrolytes for high-energy and environmentally-friendly electrochemical capacitors.

PubMed

Gorska, Barbara; Bujewska, Paulina; Fic, Krzysztof

2017-03-15

This manuscript reports on the novel insight into the development of high voltage carbon/carbon electrochemical capacitors operating in aqueous solutions of alkali metals and ammonium thiocyanates (KSCN, NaSCN, LiSCN, and NH 4 SCN). The effect of salt concentration, electrode porosity and current collectors on the capacitance value, system stability, and power performance has been investigated. Therefore, thiocyanate-based electrolytes were recognized as cheap and highly conductive electrolytic solutions (up to 401 mS cm -1 for NH 4 SCN at RT) allowing a cell voltage of 1.6 V in a symmetric carbon/carbon system to be achieved. At the same time, they display an attractive redox activity, enhancing the energy of the device with a good performance during cycling.

Performance assessment of polymer based electrodes for in vitro electrophysiological sensing: the role of the electrode impedance

NASA Astrophysics Data System (ADS)

Medeiros, Maria C. R.; Mestre, Ana L. G.; Inácio, Pedro M. C.; Santos, José M. L.; Araujo, Inês M.; Bragança, José; Biscarini, Fabio; Gomes, Henrique L.

2016-09-01

Conducting polymer electrodes based on poly(3,4-ethylenedioxythiophene) polystyrene sulfonate (PEDOT:PSS) are used to record extracellular signals from autonomous cardiac contractile cells and glioma cell cultures. The performance of these conducting polymer electrodes is compared with Au electrodes. A small-signal impedance analysis shows that in the presence of an electrolyte, both Au and polymer electrodes establish high capacitive double-layers. However, the polymer/electrolyte interfacial resistance is 3 orders of magnitude lower than the resistance of the metal/electrolyte interface. The polymer low interfacial resistance minimizes the intrinsic thermal noise and increases the system sensitivity. However, when measurements are carried out in current mode a low interfacial resistance partially acts as a short circuit of the interfacial capacitance, this affects the signal shape.

Development of Lithium Dimethyl Phosphate as an Electrolyte Additive for Lithium Ion Batteries

DOE PAGES

Milien, Mickdy S.; Tottempudi, Usha; Son, Miyoung; ...

2016-04-27

The novel electrolyte additive lithium dimethyl phosphate (LiDMP) has been synthesized and characterized. Incorporation of LiDMP (0.1% wt) into LiPF 6 in ethylene carbonate (EC) / ethyl methyl carbonate (EMC) (3:7 wt) results in improved rate performance and reduced impedance for graphite / LiNi 1/3Mn 1/3Co 1/3O 2 cells. Ex-situ surface analysis of the electrodes suggests that incorporation of LiDMP results in a modification of the solid electrolyte interphase (SEI) on the anode. A decrease in the concentration of lithium alkyl carbonates and an increase in the concentration of lithium fluoro phosphates are observed. The change in the anode SEImore » structure is responsible for the increased rate performance and decreased cell impedance.« less

Substituted Quaternary Ammonium Salts Improve Low-Temperature Performance of Double-Layer Capacitors

NASA Technical Reports Server (NTRS)

Brandon, Erik J.; Smart, Marshall C.; West, William C.

2011-01-01

Double-layer capacitors are unique energy storage devices, capable of supporting large current pulses as well as a very high number of charging and discharging cycles. The performance of doublelayer capacitors is highly dependent on the nature of the electrolyte system used. Many applications, including for electric and fuel cell vehicles, back-up diesel generators, wind generator pitch control back-up power systems, environmental and structural distributed sensors, and spacecraft avionics, can potentially benefit from the use of double-layer capacitors with lower equivalent series resistances (ESRs) over wider temperature limits. Higher ESRs result in decreased power output, which is a particular problem at lower temperatures. Commercially available cells are typically rated for operation down to only 40 C. Previous briefs [for example, Low Temperature Supercapacitors (NPO-44386), NASA Tech Briefs, Vol. 32, No. 7 (July 2008), p. 32, and Supercapacitor Electrolyte Solvents With Liquid Range Below 80 C (NPO-44855), NASA Tech Briefs, Vol. 34, No. 1 (January 2010), p. 44] discussed the use of electrolytes that employed low-melting-point co-solvents to depress the freezing point of traditional acetonitrile-based electrolytes. Using these modified electrolyte formulations can extend the low-temperature operational limit of double-layer capacitors beyond that of commercially available cells. This previous work has shown that although the measured capacitance is relatively insensitive to temperature, the ESR can rise rapidly at low temperatures, due to decreased electrolyte conductance within the pores of the high surface- area carbon electrodes. Most of these advanced electrolyte systems featured tetraethylammonium tetrafluoroborate (TEATFB) as the salt. More recent work at JPL indicates the use of the asymmetric quaternary ammonium salt triethylmethylammonium tetrafluoroborate (TEMATFB) or spiro-(l,l')-bipyrrolidium tetrafluoroborate (SBPBF4) in a 1:1 by volume solvent mixture of acetonitrile (AN) and methyl formate (MF) enables double-layer capacitor cells to operate well below -40 C with a relatively low ESR. Typically, a less than twofold increase in ESR is observed at -65 C relative to room-temperature values, when these modified electrolyte blends are used in prototype cells. Double-layer capacitor coin cells filled with these electrolytes have displayed the lowest measured ESR for an organic electrolyte to date at low temperature (based on a wide range of electrolyte screening studies at JPL). The cells featured high-surface-area (approximately equal to 2,500 m/g) carbon electrodes that were 0.50 mm thick and 1.6 cm in diameter, and coated with a thin layer of platinum to reduce cell resistance. A polyethylene separator was used to electrically isolate the electrodes.

The influence of a 12% carbohydrate-electrolyte beverage on self-paced soccer-specific exercise performance.

PubMed

Harper, Liam D; Stevenson, Emma J; Rollo, Ian; Russell, Mark

2017-12-01

To assess the physiological and performance effects of a 12% carbohydrate-electrolyte beverage consumed at practically applicable time-points (i.e., before each half) throughout simulated soccer match-play. Randomised, counterbalanced, crossover. Fed players (n=15) performed 90-min of soccer-specific exercise (including self-paced exercise at the end of each half). Players consumed carbohydrate-electrolyte (CHO; 60g×500ml -1 , Na + 205mg×500ml -1 ), placebo-electrolyte (PL) or water (Wat) beverages at the end of the warm-up (250ml) and half-time (250ml plus ad-libitum water). Blood was drawn before each half and every 15-min during exercise. Physical (15-m sprinting, countermovement jumps, self-paced distance, acceleration/deceleration count), technical (dribbling) and cognitive (memory, attention, decision-making) performance was assessed. Ratings of perceived exertion (RPE) and abdominal discomfort were measured. Against Wat and PL, CHO increased (all p<0.05) mean accelerations >1.5m·s -2 during self-paced exercise (>+25%) and dribbling speed from 60-min onwards (>+3%). Mean sprinting speed improved (+2.7%) in CHO versus Wat. Blood glucose increased before and during each half in CHO versus PL and Wat (all p<0.05). A 27% decline in glycaemia occurred at 60-min in CHO. RPE was comparable between trials. Cognition reduced post-exercise (p<0.05); this decline was not attenuated by CHO. Abdominal discomfort increased during exercise but was similar between trials. Using more realistic fluid ingestion timings than have been examined previously, consuming a 12% carbohydrate-electrolyte beverage increased blood glucose, self-paced exercise performance, and improved dribbling speed in the final 30-min of exercise compared to water and placebo. Carbohydrates did not attenuate post-exercise reductions in cognition. Copyright © 2017 Sports Medicine Australia. Published by Elsevier Ltd. All rights reserved.

Design and research on discharge performance for aluminum-air battery

NASA Astrophysics Data System (ADS)

Liu, Zu; Zhao, Junhong; Cai, Yanping; Xu, Bin

2017-01-01

As a kind of clean energy, the research of aluminum air battery is carried out because aluminum-air battery has advantages of high specific energy, silence and low infrared. Based on the research on operating principle of aluminum-air battery, a novel aluminum-air battery system was designed composed of aluminum-air cell and the circulation system of electrolyte. A system model is established to analyze the polarization curve, the constant current discharge performance and effect of electrolyte concentration on the performance of monomer. The experimental results show that the new energy aluminum-air battery has good discharge performance, which lays a foundation for its application.

30 CFR 75.1910 - Nonpermissible diesel-powered equipment; electrical system design and performance requirements.

Code of Federal Regulations, 2010 CFR

2010-07-01

... chemical reaction to electrolyte must be provided on battery connections to prevent battery terminals from... materials. Insulating materials that may be subject to chemical reaction with electrolyte must be treated to resist such action; and (o) Drainage holes must be provided in the bottom of each battery box. ...

Textile Inspired Lithium-Oxygen Battery Cathode with Decoupled Oxygen and Electrolyte Pathways.

PubMed

Xu, Shaomao; Yao, Yonggang; Guo, Yuanyuan; Zeng, Xiaoqiao; Lacey, Steven D; Song, Huiyu; Chen, Chaoji; Li, Yiju; Dai, Jiaqi; Wang, Yanbin; Chen, Yanan; Liu, Boyang; Fu, Kun; Amine, Khalil; Lu, Jun; Hu, Liangbing

2018-01-01

The lithium-air (Li-O 2 ) battery has been deemed one of the most promising next-generation energy-storage devices due to its ultrahigh energy density. However, in conventional porous carbon-air cathodes, the oxygen gas and electrolyte often compete for transport pathways, which limit battery performance. Here, a novel textile-based air cathode is developed with a triple-phase structure to improve overall battery performance. The hierarchical structure of the conductive textile network leads to decoupled pathways for oxygen gas and electrolyte: oxygen flows through the woven mesh while the electrolyte diffuses along the textile fibers. Due to noncompetitive transport, the textile-based Li-O 2 cathode exhibits a high discharge capacity of 8.6 mAh cm -2 , a low overpotential of 1.15 V, and stable operation exceeding 50 cycles. The textile-based structure can be applied to a range of applications (fuel cells, water splitting, and redox flow batteries) that involve multiple phase reactions. The reported decoupled transport pathway design also spurs potential toward flexible/wearable Li-O 2 batteries. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

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.

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.

New Ether-functionalized Morpholinium- and Piperidinium-based Ionic Liquids as Electrolyte Components in Lithium and Lithium-Ion Batteries.

PubMed

Navarra, Maria Assunta; Fujimura, Kanae; Sgambetterra, Mirko; Tsurumaki, Akiko; Panero, Stefania; Nakamura, Nobuhumi; Ohno, Hiroyuki; Scrosati, Bruno

2017-06-09

Here, two ionic liquids, N-ethoxyethyl-N-methylmorpholinium bis(trifluoromethanesulfonyl)imide (M 1,2O2 TFSI) and N-ethoxyethyl-N-methylpiperidinium bis(trifluoromethanesulfonyl)imide (P 1,2O2 TFSI) were synthesized and compared. Fundamental relevant properties, such as thermal and electrochemical stability, density, and ionic conductivity were analyzed to evaluate the effects caused by the presence of the ether bond in the side chain and/or in the organic cation ring. Upon lithium salt addition, two electrolytes suitable for lithium batteries applications were found. Higher conducting properties of the piperidinium-based electrolyte resulted in enhanced cycling performances when tested with LiFePO 4 (LFP) cathode in lithium cells. When mixing the P 1,2O2 TFSI/LiTFSI electrolyte with a tailored alkyl carbonate mixture, the cycling performance of both Li and Li-ion cells greatly improved, with prolonged cyclability delivering very stable capacity values, as high as the theoretical one in the case of Li/LFP cell configurations. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Demonstrating the potential of yttrium-doped barium zirconate electrolyte for high-performance fuel cells.

PubMed

Bae, Kiho; Jang, Dong Young; Choi, Hyung Jong; Kim, Donghwan; Hong, Jongsup; Kim, Byung-Kook; Lee, Jong-Ho; Son, Ji-Won; Shim, Joon Hyung

2017-02-23

In reducing the high operating temperatures (≥800 °C) of solid-oxide fuel cells, use of protonic ceramics as an alternative electrolyte material is attractive due to their high conductivity and low activation energy in a low-temperature regime (≤600 °C). Among many protonic ceramics, yttrium-doped barium zirconate has attracted attention due to its excellent chemical stability, which is the main issue in protonic-ceramic fuel cells. However, poor sinterability of yttrium-doped barium zirconate discourages its fabrication as a thin-film electrolyte and integration on porous anode supports, both of which are essential to achieve high performance. Here we fabricate a protonic-ceramic fuel cell using a thin-film-deposited yttrium-doped barium zirconate electrolyte with no impeding grain boundaries owing to the columnar structure tightly integrated with nanogranular cathode and nanoporous anode supports, which to the best of our knowledge exhibits a record high-power output of up to an order of magnitude higher than those of other reported barium zirconate-based fuel cells.

Development of many-body polarizable force fields for Li-battery applications: 2. LiTFSI-doped Oligoether, polyether, and carbonate-based electrolytes.

PubMed

Borodin, Oleg; Smith, Grant D

2006-03-30

A quantum chemistry study of Li(+) interactions with ethers, carbonates, alkanes, and a trifluoromethanesulfonylimide anion (TFSI(-)) was performed at the MP2, B3LYP, and HF levels using the aug-cc-pvDz basis set for solvents and TFSI(-) anion, and [8s4p3d/5s3p2d]-type basis set for Li. A classical many-polarizable force field was developed for the LiTFSI salt interacting with ethylene carbonate (EC), gamma-butyrolactone (GBL), dimethyl carbonate (DMC), acetone, oligoethers, n-alkanes, and perfluoroalkanes. Molecular dynamics (MD) simulations were performed for EC/LiTFSI, PC/LiTFSI, GBL/LiTFSI, DMC/LiTFSI, 1,2-dimethoxyethane/LiTFSI, pentaglyme/LiTFSI, and poly(ethylene oxide) (MW = 2380)/LiTFSI electrolytes at temperatures from 298 to 423 K and salt concentrations from 0.3 to 5 M. The ion and solvent self-diffusion coefficients, electrolyte conductivity, electrolyte density, LiTFSI apparent molar volumes, and structure of the Li(+) cation environment predicted by MD simulations were found in good agreement with experimental data.

Enhancing long-term photostability of BiVO4 photoanodes for solar water splitting by tuning electrolyte composition

NASA Astrophysics Data System (ADS)

Lee, Dong Ki; Choi, Kyoung-Shin

2018-01-01

As the performance of photoelectrodes used for solar water splitting continues to improve, enhancing the long-term stability of the photoelectrodes becomes an increasingly crucial issue. In this study, we report that tuning the composition of the electrolyte can be used as a strategy to suppress photocorrosion during solar water splitting. Anodic photocorrosion of BiVO4 photoanodes involves the loss of V5+ from the BiVO4 lattice by dissolution. We demonstrate that the use of a V5+-saturated electrolyte, which inhibits the photooxidation-coupled dissolution of BiVO4, can serve as a simple yet effective method to suppress anodic photocorrosion of BiVO4. The V5+ species in the solution can also incorporate into the FeOOH/NiOOH oxygen-evolution catalyst layer present on the BiVO4 surface during water oxidation, further enhancing water-oxidation kinetics. The effect of the V5+ species in the electrolyte on both the long-term photostability of BiVO4 and the performance of the FeOOH/NiOOH oxygen-evolution catalyst layer is systematically elucidated.

Influence of Polar Organic Solvents in an Ionic Liquid Containing Lithium Bis(fluorosulfonyl)amide: Effect on the Cation-Anion Interaction, Lithium Ion Battery Performance, and Solid Electrolyte Interphase.

PubMed

Lahiri, Abhishek; Li, Guozhu; Olschewski, Mark; Endres, Frank

2016-12-14

Ionic liquid-organic solvent mixtures have recently been investigated as potential battery electrolytes. However, contradictory results with these mixtures have been shown for battery performance. In this manuscript, we studied the influence of the addition of polar organic solvents into the ionic liquid electrolyte 1 M lithium bis(fluorosulfonyl)amide (LiFSI)-1-butyl-1-methylpyrrolidinium bis(fluorosulfonyl)amide ([Py 1,4 ]FSI) and tested it for lithium ion battery applications. From infrared and Raman spectroscopy, clear changes in the lithium solvation and cation-anion interactions in the ionic liquid were observed on addition of organic solvents. From the lithiation/delithiation studies on electrodeposited Ge, the storage capacity for the ionic liquid-highly polar organic solvent (acetonitrile) mixture was found to be the highest at low C-rates (0.425 C) compared to using an ionic liquid alone and ionic liquid-less polar solvent (dimethyl carbonate) mixtures. Furthermore, XPS and AFM were used to evaluate the solid electrolyte interphase (SEI) and to correlate its stability with Li storage capacity.

Electrolytes as Cathode Interlayers in Inverted Organic Solar Cells: Influence of the Cations on Bias-Dependent Performance.

PubMed

Li, Yaru; Liu, Xiaohui; Li, Xiaodong; Zhang, Wenjun; Xing, Feifei; Fang, Junfeng

2017-03-08

The performance of organic solar cells (OSCs) with edetate electrolytes depends on external bias, and ions are speculated to be responsible for this phenomenon. To clarify the detailed relationship between the ions of electrolytes and the bias-dependent behaviors of devices, this work introduces four edetate cathode interlayers (EDTA-X, X = nH(4-n)Na, n = 0, 1, 2, and 4) containing different kinds and number of cations into inverted OSCs. The results show that the devices initial and saturated (after external bias treatment) power conversion efficiencies (PCEs) both decrease with the increase in the number of H + . Moreover, the bias-dependent degrees increase with the increase in H + number; with that, the PCE increment of EDTA-4H device is 53.4%, while that of the EDTA-4Na device is almost unchanged. The electrical impedance spectroscopy and capacitance-voltage tests reveal that the interfacial recombination is greatly suppressed by external bias treatment, which is not a result of the decreased density of defect states. The results indicate that the ion's motion, specifically the H + motion, under external electrical field is responsible for the bias-dependent behavior, which is conducive to the design of new efficient electrolytic interlayers without bias-dependent performance.

The Electrochemical Performance of Silicon Nanoparticles in Concentrated Electrolyte.

PubMed

Chang, Zeng-Hua; Wang, Jian-Tao; Wu, Zhao-Hui; Gao, Min; Wu, Shuai-Jin; Lu, Shi-Gang

2018-06-11

Silicon is a promising material for anodes in energy-storage devices. However, excessive growth of a solid-electrolyte interphase (SEI) caused by the severe volume change during the (de)lithiation processes leads to dramatic capacity fading. Here, we report a super-concentrated electrolyte composed of lithium bis(fluorosulfonyl)imide (LiFSI) and propylene carbonate (PC) with a molar ratio of 1:2 to improve the cycling performance of silicon nanoparticles (SiNPs). The SiNP electrode shows a remarkably improved cycling performance with an initial delithiation capacity of approximately 3000 mAh g -1 and a capacity of approximately 2000 mAh g -1 after 100 cycles, exhibiting about 6.8 times higher capacity than the cells with dilute electrolyte LiFSI-(PC) 8 . Raman spectra reveal that most of the PC solvent and FSI anions are complexed by Li + to form a specific solution structure like a fluid polymeric network. The reduction of FSI anions starts to play an important role owing to the increased concentration of contact ion pairs (CIPs) or aggregates (AGGs), which contribute to the formation of a more mechanically robust and chemically stable complex SEI layer. The complex SEI layer can effectively suppress the morphology evolution of silicon particles and self-limit the excessive growth, which mitigates the crack propagation of the silicon electrode and the deterioration of the kinetics. This study will provide a new direction for screening cycling-stable electrolytes for silicon-based electrodes. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

DMAC and NMP as Electrolyte Additives for Li-Ion Cells

NASA Technical Reports Server (NTRS)

Smart, Marshall; Bugga, Ratnakumar; Lucht, Brett

2008-01-01

Dimethyl acetamide (DMAC) and N-methyl pyrrolidinone (NMP) have been found to be useful as high-temperature-resilience-enhancing additives to a baseline electrolyte used in rechargeable lithium-ion electrochemical cells. The baseline electrolyte, which was previously formulated to improve low-temperature performance, comprises LiPF6 dissolved at a concentration of 1.0 M in a mixture comprising equal volume proportions of ethylene carbonate, diethyl carbonate, and dimethyl carbonate. This and other electrolytes comprising lithium salts dissolved in mixtures of esters (including alkyl carbonates) have been studied in continuing research directed toward extending the lower limits of operating temperatures and, more recently, enhancing the high-temperature resilience of such cells. This research at earlier stages, and the underlying physical and chemical principles, were reported in numerous previous NASA Tech Briefs articles. Although these electrolytes provide excellent performance at low temperatures (typically as low as -40 C), when the affected Li-ion cells are subjected to high temperatures during storage and cycling, there occur irreversible losses of capacity accompanied by power fade and deterioration of low-temperature performance. The term "high-temperature resilience" signifies, loosely, the ability of a cell to resist such deterioration, retaining as much as possible of its initial charge/discharge capacity during operation or during storage in the fully charged condition at high temperature. For the purposes of the present development, a temperature is considered to be high if it equals or exceeds the upper limit (typically, 30 C) of the operating-temperature range for which the cells in question are generally designed.

Design rules and reality check for carbon-based ultracapacitors

NASA Astrophysics Data System (ADS)

Eisenmann, Erhard T.

1995-04-01

Design criteria for carbon-based Ultracapacitors have been determined for specified energy and power requirements, using the geometry of the components and such material properties as density, porosity and conductivity as parameters, while also considering chemical compatibility. This analysis shows that the weights of active and inactive components of the capacitor structure must be carefully balanced for maximum energy and power density. When applied to nonaqueous electrolytes, the design rules for a 5 Wh/kg device call for porous carbon with a specific capacitance of about 30 F/cu cm. This performance is not achievable with pure, electrostatic double layer capacitance. Double layer capacitance is only 5 to 30% of that observed in aqueous electrolyte. Tests also showed that nonaqueous electrolytes have a diminished capability to access micropores in activated carbon, in one case yielding a capacitance of less than 1 F/cu cm for carbon that had 100 F/cu cm in aqueous electrolyte. With negative results on nonaqueous electrolytes dominating the present study, the obvious conclusion is to concentrate on aqueous systems. Only aqueous double layer capacitors offer adequate electrostatic charging characteristics which is the basis for high power performance. There arc many opportunities for further advancing aqueous double layer capacitors, one being the use of highly activated carbon films, as opposed to powders, fibers and foams. While the manufacture of carbon films is still costly, and while the energy and power density of the resulting devices may not meet the optimistic goals that have been proposed, this technology could produce true double layer capacitors with significantly improved performance and large commercial potential.

Numerical investigation and thermodynamic analysis of the effect of electrolyte flow rate on performance of all vanadium redox flow batteries

NASA Astrophysics Data System (ADS)

Khazaeli, Ali; Vatani, Ali; Tahouni, Nassim; Panjeshahi, Mohammad Hassan

2015-10-01

In flow batteries, electrolyte flow rate plays a crucial role on the minimizing mass transfer polarization which is at the compensation of higher pressure drop. In this work, a two-dimensional numerical method is applied to investigate the effect of electrolyte flow rate on cell voltage, maximum depth of discharge and pressure drop a six-cell stack of VRFB. The results show that during the discharge process, increasing electrolyte flow rate can raise the voltage of each cell up to 50 mV on average. Moreover, the maximum depth of discharge dramatically increases with electrolyte flow rate. On the other hand, the pressure drop also positively correlates with electrolyte flow rate. In order to investigate all these effects simultaneously, average energy and exergy efficiencies are introduced in this study for the transient process of VRFB. These efficiencies give insight into choosing an appropriate strategy for the electrolyte flow rate. Finally, the energy efficiency of electricity storage using VRFB is investigated and compared with other energy storage systems. The results illustrate that this kind of battery has at least 61% storage efficiency based on the second law of thermodynamics, which is considerably higher than that of their counterparts.

Formation of Reversible Solid Electrolyte Interface on Graphite Surface from Concentrated Electrolytes

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

Lu, Dongping; Tao, Jinhui; Yan, Pengfei

2017-02-10

Interfacial phenomena have always been key determinants for the performance of energy storage technologies. The solid electrolyte interfacial (SEI) layer, pervasive on the surfaces of battery electrodes for numerous chemical couples, directly affects the ion transport, charge transfer and lifespan of the entire energy system. Almost all SEI layers, however, are unstable resulting in the continuous consumption of the electrolyte. Typically, this leads to the accumulation of degradation products on/restructuring of the electrode surface and thus increased cell impedance, which largely limits the long-term operation of the electrochemical reactions. Herein, a completely new SEI formation mechanism has been discovered, inmore » which the electrolyte components reversibly self-assemble into a protective surface coating on a graphite electrode upon changing the potential. In contrast to the established wisdom regarding the necessity of employing the solvent ethylene carbonate (EC) to form a protective SEI layer on graphite, a wide range of EC-free electrolytes are demonstrated for the reversible intercalation/deintercalation of Li+ cations within a graphite lattice, thereby providing tremendous flexibility in electrolyte tailoring for battery couples. This novel finding is broadly applicable and provides guidance for how to control interfacial reactions through the relationship between ion aggregation and solvent decomposition at polarized interfaces.« less

Enhanced performance of dicationic ionic liquid electrolytes by organic solvents.

PubMed

Li, Song; Zhang, Pengfei; Fulvio Pasquale, F; Hillesheim Patrick, C; Feng, Guang; Dai, Sheng; Cummings Peter, T

2014-07-16

The use of dicationic ionic liquid (DIL) electrolytes in supercapacitors is impeded by the slow dynamics of DILs, whereas the addition of organic solvents into DIL electrolytes improves ion transport and then enhances the power density of supercapacitors. In this work, the influences of organic solvents on the conductivity of DILs and the electrical double layer (EDL) of DIL-based supercapacitors are investigated using classical molecular dynamics simulation. Two types of organic solvents, acetonitrile (ACN) and propylene carbonate (PC), were used to explore the effects of different organic solvents on the EDL structure and capacitance of DIL/organic solvent-based supercapacitors. Firstly, it was found that the conductivity of DIL electrolytes was greatly enhanced in the presence of the organic solvent ACN. Secondly, a stronger adsorption of PC on graphite results in different EDL structures formed by DIL/ACN and DIL/PC electrolytes. The expulsion of co-ions from EDLs was observed in DIL/organic solvent electrolytes rather than neat DILs and this feature is more evident in DIL/PC. Furthermore, the bell-shaped differential capacitance-electric potential curve was not essentially changed by the presence of organic solvents. Comparing DIL/organic solvent electrolytes with neat DILs, the capacitance is slightly increased by organic solvents, which is in agreement with experimental observation.

Self-Assembled Polymeric Ionic Liquid-Functionalized Cellulose Nano-crystals: Constructing 3D Ion-conducting Channels Within Ionic Liquid-based Composite Polymer Electrolytes.

PubMed

Shi, Qing Xuan; Xia, Qing; Xiang, Xiao; Ye, Yun Sheng; Peng, Hai Yan; Xue, Zhi Gang; Xie, Xiao Lin; Mai, Yiu-Wing

2017-09-04

Composite polymeric and ionic liquid (IL) electrolytes are some of the most promising electrolyte systems for safer battery technology. Although much effort has been directed towards enhancing the transport properties of polymer electrolytes (PEs) through nanoscopic modification by incorporating nano-fillers, it is still difficult to construct ideal ion conducting networks. Here, a novel class of three-dimensional self-assembled polymeric ionic liquid (PIL)-functionalized cellulose nano-crystals (CNC) confining ILs in surface-grafted PIL polymer chains, able to form colloidal crystal polymer electrolytes (CCPE), is reported. The high-strength CNC nano-fibers, decorated with PIL polymer chains, can spontaneously form three-dimensional interpenetrating nano-network scaffolds capable of supporting electrolytes with continuously connected ion conducting networks with IL being concentrated in conducting domains. These new CCPE have exceptional ionic conductivities, low activation energies (close to bulk IL electrolyte with dissolved Li salt), high Li + transport numbers, low interface resistances and improved interface compatibilities. Furthermore, the CCPE displays good electrochemical properties and a good battery performance. This approach offers a route to leak-free, non-flammable and high ionic conductivity solid-state PE in energy conversion devices. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Renal Function of Rats in Response to 37 Days of Head-Down Tilt

NASA Technical Reports Server (NTRS)

Wang, Tommy J.; Wade, Charles E.; Dalton, Bonnie P. (Technical Monitor)

2001-01-01

Spaceflight induces changes in human renal function, suggesting similar changes may occur in rats. Since rats continue to be the prime mammalian model for study in space, the effects of chronic microgravity on rat renal function should be clarified. Acute studies in rats using the ground-based microgravity simulation model, head-down tilt (HDT), have shown increases in glomerular filtration rate (GFR), electrolyte excretion, and a diuresis. However, long term effects of HDT have not been studied extensively. This study was performed to elucidate rat renal function following long-term simulated microgravity. Chronic exposure to HDT will cause an increase in GFR and electrolyte excretion in rats, similar to acute exposures, and lead to a decrease in the fractional excretion of filtered electrolytes. Experimental animals (HDT, n=10) were tail-suspended for 37 days and renal function compared to ambulatory controls (AMB, n=10). On day 37 of HDT, GFR, osmolal clearance, and electrolyte excretion were decreased, while plasma osmolality and free water clearance were increased. Urine output remained similar between groups. The fractional excretion of the filtered electrolytes was unchanged except for a decrease in the percentage of filtered calcium excreted. Chronic exposure to HDT results in decreased GFR and electrolyte excretion, but the fractional excretion of filtered electrolytes remained primarily unaffected.

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).

Degradation Mechanisms at the Li10GeP2S12/LiCoO2 Cathode Interface in an All-Solid-State Lithium-Ion Battery.

PubMed

Zhang, Wenbo; Richter, Felix H; Culver, Sean P; Leichtweiss, Thomas; Lozano, Juan G; Dietrich, Christian; Bruce, Peter G; Zeier, Wolfgang G; Janek, Jürgen

2018-06-20

All-solid-state batteries (ASSBs) show great potential for providing high power and energy densities with enhanced battery safety. While new solid electrolytes (SEs) have been developed with high enough ionic conductivities, SSBs with long operational life are still rarely reported. Therefore, on the way to high-performance and long-life ASSBs, a better understanding of the complex degradation mechanisms, occurring at the electrode/electrolyte interfaces is pivotal. While the lithium metal/solid electrolyte interface is receiving considerable attention due to the quest for high energy density, the interface between the active material and solid electrolyte particles within the composite cathode is arguably the most difficult to solve and study. In this work, multiple characterization methods are combined to better understand the processes that occur at the LiCoO 2 cathode and the Li 10 GeP 2 S 12 solid electrolyte interface. Indium and Li 4 Ti 5 O 12 are used as anode materials to avoid the instability problems associated with Li-metal anodes. Capacity fading and increased impedances are observed during long-term cycling. Postmortem analysis with scanning transmission electron microscopy, electron energy loss spectroscopy, X-ray diffraction, and X-ray photoelectron spectroscopy show that electrochemically driven mechanical failure and degradation at the cathode/solid electrolyte interface contribute to the increase in internal resistance and the resulting capacity fading. These results suggest that the development of electrochemically more stable SEs and the engineering of cathode/SE interfaces are crucial for achieving reliable SSB performance.

Dual phase polymer gel electrolyte based on non-woven poly(vinylidenefluoride-co-hexafluoropropylene)–layered clay nanocomposite fibrous membranes for lithium ion batteries

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

Shubha, Nageswaran; Prasanth, Raghavan; Energy Research Institute - NTU

2013-02-15

Graphical abstract: Display Omitted Highlights: ► P(VdF-co-HFP)–clay nanocomposite based electrospun membranes are prepared. ► The membranes are used as polymer gel electrolyte (PGE) in lithium ion batteries. ► The composite PGE shows ionic conductivity of 5.5 mS cm{sup −1} at room temperature. ► Li/PGE/LiFePO{sub 4} cell delivers initial discharge capacity of 160 mAh g{sup −1}. ► The use of prepared electrolyte significantly improved the cell performance. -- Abstract: A new approach for fabricating polymer gel electrolytes (PGEs) based on electrospun poly(vinylidenefluoride-co-hexafluoropropylene) (P(VdF-co-HFP)) incorporated with layered nanoclay has been employed to enhance the ionic conductivity and electrochemical properties of P(VdF-co-HFP) withoutmore » compromising its mechanical strength. The effect of layered nanoclay on properties of membranes has been evaluated by X-ray diffraction (XRD), differential scanning calorimetry (DSC) and thermal gravimetric analysis (TGA). Surface morphology of the membranes has been studied using field-emission scanning electron microscopy (FE-SEM). Polymer gel electrolytes are prepared by soaking the fibrous membrane into 1 M LiPF{sub 6} in EC/DEC. The electrochemical studies show that incorporation of layered nanoclay into the polymer matrix greatly enhanced the ionic conductivity and compatibility with lithium electrodes. The charge–discharge properties and cycling performance of Li/LiFePO{sub 4} cells comprising nanocomposite polymer gel electrolytes have been evaluated at room temperature.« less

Edge-selenated graphene nanoplatelets as durable metal-free catalysts for iodine reduction reaction in dye-sensitized solar cells

PubMed Central

Ju, Myung Jong; Jeon, In-Yup; Kim, Hong Mo; Choi, Ji Il; Jung, Sun-Min; Seo, Jeong-Min; Choi, In Taek; Kang, Sung Ho; Kim, Han Seul; Noh, Min Jong; Lee, Jae-Joon; Jeong, Hu Young; Kim, Hwan Kyu; Kim, Yong-Hoon; Baek, Jong-Beom

2016-01-01

Metal-free carbon-based electrocatalysts for dye-sensitized solar cells (DSSCs) are sufficiently active in Co(II)/Co(III) electrolytes but are not satisfactory in the most commonly used iodide/triiodide (I−/I3−) electrolytes. Thus, developing active and stable metal-free electrocatalysts in both electrolytes is one of the most important issues in DSSC research. We report the synthesis of edge-selenated graphene nanoplatelets (SeGnPs) prepared by a simple mechanochemical reaction between graphite and selenium (Se) powders, and their application to the counter electrode (CE) for DSSCs in both I−/I3− and Co(II)/Co(III) electrolytes. The edge-selective doping and the preservation of the pristine graphene basal plane in the SeGnPs were confirmed by various analytical techniques, including atomic-resolution transmission electron microscopy. Tested as the DSSC CE in both Co(bpy)32+/3+ (bpy = 2,2′-bipyridine) and I−/I3− electrolytes, the SeGnP-CEs exhibited outstanding electrocatalytic performance with ultimately high stability. The SeGnP-CE–based DSSCs displayed a higher photovoltaic performance than did the Pt-CE–based DSSCs in both SM315 sensitizer with Co(bpy)32+/3+ and N719 sensitizer with I−/I3− electrolytes. Furthermore, the I3− reduction mechanism, which has not been fully understood in carbon-based CE materials to date, was clarified by an electrochemical kinetics study combined with density functional theory and nonequilibrium Green’s function calculations. PMID:27386557

Use of phosphoranimines to reduce organic carbonate content in Li-ion battery electrolytes

DOE PAGES

Dufek, Eric J.; Klaehn, John R.; McNally, Joshua S.; ...

2016-05-09

In this study, the use of phosphoranimines (PAs), a class of linear, monomeric phosphazenes, as electrolytes for Li-ion battery applications has been investigated as a route to improve safety and stability for Li-ion batteries. Of the potential PAs for use in battery applications, this work focuses on the initial synthetic preparation and analysis of N-trimethylsilyl-P,P-bis((2-methoxyethoxy)ethoxy)-P-ethylphosphoranimine (PA-5). PA-5 has high LiPF6 solubility in excess of 2 M, high thermal stability with a melting point below -80°C and high thermal stability as a neat compound to at least 250°C. As part of electrolyte blends, the inclusion of PA-5 shifts the onset ofmore » thermal degradation by close to 40°C at 35% loading and by 20°C at a 10% loading, improves the low temperature performance of the electrolyte, and when used as a primary solvent leads to increases in the flash point (by 20°C) when compared to more traditional EC:EMC blends. Cycling capabilities of full-coin cells with graphite negative electrodes and Li 1+w[Ni 0.5Mn 0.3Co 0.2] 1-wO 2 positive electrodes using PA-5:EC:EMC electrolyte blends are comparable with the performance seen for traditional EC:EMC blends. Analysis of the impact of the use of additives such as vinylene carbonate in PA-5:EC:EMC blended electrolyte results in enhanced capacity retention and improved coulombic efficiency.« less

Identification and formation mechanism of individual degradation products in lithium-ion batteries studied by liquid chromatography/electrospray ionization mass spectrometry and atmospheric solid analysis probe mass spectrometry.

PubMed

Takeda, Sahori; Morimura, Wataru; Liu, Yi-Hung; Sakai, Tetsuo; Saito, Yuria

2016-08-15

Improvement of lithium ion batteries (LIBs) in terms of performance and robustness requires good understanding of the reaction processes. The analysis of the individual degradation products in LIB electrolytes and on the surface of the electrodes provides vital information in this regard. In this study, mass spectrometric analytical methods were utilized for the identification of the individual degradation products. The degradation products in the electrolytes recovered from cycle-tested cells were separated by liquid chromatography (LC) and their mass spectrometric analysis was conducted by electrospray ionization mass spectrometry (ESI-MS). For identification of degradation products on the surface of electrodes, atmospheric solid analysis probe (ASAP)-MS analysis was conducted by time-of-flight mass spectrometry with an ASAP probe and an atmospheric pressure chemical ionization source. The degradation products in the electrolytes, namely carbonate oligomers and organophosphates, were identified simultaneously by LC/ESI-MS. Their formation mechanisms were estimated, which explain their different compositions at different temperatures. One degradation product was found on the anode surface by ASAP-MS, and its formation mechanism was explained similarly to those in the electrolyte. The results suggest that the electrolyte degradation is correlated with the formation of a solid electrolyte interphase, which is an important factor in the performance of LIBs. We expect that further investigation of the degradation products by LC/ESI-MS and ASAP-MS will be helpful for studying their degradation processes in LIBs. Copyright © 2016 John Wiley & Sons, Ltd. Copyright © 2016 John Wiley & Sons, Ltd.

Tolerability, safety, and efficacy of PEG 3350 as a 1-day bowel preparation in children.

PubMed

Walia, Ritu; Steffen, Rita; Feinberg, Lisa; Worley, Sarah; Mahajan, Lori

2013-02-01

The aim of the study was to evaluate the tolerability, safety, and efficacy of polyethylene glycol (PEG) 3350 without electrolytes as a 1-day bowel preparation for colonoscopy in children. A prospective study of 45 children undergoing colonoscopy prescribed PEG 3350 without electrolytes mixed with a commercial electrolyte beverage was performed. Patients <45 kg received 136 g of PEG 3350 without electrolytes mixed in 32 ounces of Gatorade. Patients ≥ 45 kg were given 255 g of PEG 3350 without electrolytes in 64 ounces of Gatorade A basic metabolic panel was performed at the time of the clinic visit and just before colonoscopy. Patients completed a survey related to bowel preparation. Endoscopists graded bowel preparation and noted the proximal extent of the examination. A total of 44 patients (14 ± 3 years) completed the study. One patient was excluded due to protocol breach. All subjects reported the preparation was easy (61%) or tolerable (39%). Adverse events included nausea (34%), abdominal pain (23%), vomiting (16%), abdominal distension (20%), bloating (23%), and dizziness (7%). Although significant changes in serum glucose and CO2 were noted, no therapeutic interventions were indicated. Significant changes in sodium, potassium chloride, blood urea nitrogen, or creatinine did not occur. Colonic preparation was rated as excellent in 23%, good in 52%, fair in 23%, and poor in 2% of patients. Intubation of the ileum was successful in 100%. One-day bowel preparation with high dose PEG 3350 mixed with commercial electrolyte solution is tolerable, safe, and effective in children before colonoscopy.

Development and In Situ Characterization of New Electrolyte and Electrode materials for Rechargeable Lithium Batteries

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

Yang, X -Q; Xing, X K; Daroux, M

The object of this project is to develop new electrolyte and cathode materials for rechargeable lithium batteries, especially for lithium ion and lithium polymer batteries. Enhancing performance, reducing cost, and replacing toxic materials by environmentally benign materials, are strategic goals of DOE in lithium battery research. This proposed project will address these goals on two important material studies, namely the new electrolytes and new cathode materials. For the new electrolyte materials, aza based anion receptors as additives, organic lithium salts and plasticizers which have been developed by BNL team under Energy Research programs of DOE, will be evaluated by Gouldmore » for potential use in commercial battery cells. All of these three types of compounds are aimed to enhance the conductivity and lithium transference number of lithium battery electrolytes and reduce the use of toxic salts in these electrolytes. BNL group will be working closely with Gould to further develop these compounds for commercialization. For the cathode material studies, BNL efforts wi U be focused on developing new superior characterization methclds, especially in situ techniques utilize the unique user facility of DOE at BNL, namely the National Synchrotrons Light Source (NSLS). In situ x-ray absorption and x-ray diftlaction spectroscopy will be used to study the relationship between performance and the electronic and structural characteristics of intercalation compounds such as LiNi0 2, LiCo0 2, and LiMn 20 4 spinel. The study will be focused on LiMn 20 4 spinel materials. Gould team will contribute their expertise in choosing the most promising compounds, providing overall performance requirements, and will use the results of this study to guide their procedure for quality control. The knowledge gained through this project will not only benefit Gould and BNL, but will be very valuable to the scientific community in battery research.« less

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).

Ion Pairing and Diffusion in Magnesium Electrolytes Based on Magnesium Borohydride.

PubMed

Samuel, Devon; Steinhauser, Carl; Smith, Jeffrey G; Kaufman, Aaron; Radin, Maxwell D; Naruse, Junichi; Hiramatsu, Hidehiko; Siegel, Donald J

2017-12-20

One obstacle to realizing a practical, rechargeable magnesium-ion battery is the development of efficient Mg electrolytes. Electrolytes based on simple Mg(BH 4 ) 2 salts suffer from poor salt solubility and/or low conductivity, presumably due to strong ion pairing. Understanding the molecular-scale processes occurring in these electrolytes would aid in overcoming these performance limitations. Toward this goal, the present study examines the solvation, agglomeration, and transport properties of a family of Mg electrolytes based on the Mg(BH 4 ) 2 salt using classical molecular dynamics. These properties were examined across five different solvents (tetrahydrofuran and the glymes G1-G4) and at four salt concentrations ranging from the dilute limit up to 0.4 M. Significant and irreversible salt agglomeration was observed in all solvents at all nondilute Mg(BH 4 ) 2 concentrations. The degree of clustering observed in these divalent Mg systems is much larger than that reported for electrolytes containing monovalent cations, such as Li. The salt agglomeration rate and diffusivity of Mg 2+ were both observed to correlate with solvent self-diffusivity: electrolytes using longer- (shorter-) chain solvents had the lowest (highest) Mg 2+ diffusivity and agglomeration rates. Incorporation of Mg 2+ into Mg 2+ -BH 4 - clusters significantly reduces the diffusivity of Mg 2+ by restricting displacements to localized motion within largely immobile agglomerates. Consequently, diffusion is increasingly impeded with increasing Mg(BH 4 ) 2 concentration. These data are consistent with the solubility limitations observed experimentally for Mg(BH 4 ) 2 -based electrolytes and highlight the need for strategies that minimize salt agglomeration in electrolytes containing divalent cations.

High-performance transistors for bioelectronics through tuning of channel thickness

PubMed Central

Rivnay, Jonathan; Leleux, Pierre; Ferro, Marc; Sessolo, Michele; Williamson, Adam; Koutsouras, Dimitrios A.; Khodagholy, Dion; Ramuz, Marc; Strakosas, Xenofon; Owens, Roisin M.; Benar, Christian; Badier, Jean-Michel; Bernard, Christophe; Malliaras, George G.

2015-01-01

Despite recent interest in organic electrochemical transistors (OECTs), sparked by their straightforward fabrication and high performance, the fundamental mechanism behind their operation remains largely unexplored. OECTs use an electrolyte in direct contact with a polymer channel as part of their device structure. Hence, they offer facile integration with biological milieux and are currently used as amplifying transducers for bioelectronics. Ion exchange between electrolyte and channel is believed to take place in OECTs, although the extent of this process and its impact on device characteristics are still unknown. We show that the uptake of ions from an electrolyte into a film of poly(3,4-ethylenedioxythiophene) doped with polystyrene sulfonate (PEDOT:PSS) leads to a purely volumetric capacitance of 39 F/cm3. This results in a dependence of the transconductance on channel thickness, a new degree of freedom that we exploit to demonstrate high-quality recordings of human brain rhythms. Our results bring to the forefront a transistor class in which performance can be tuned independently of device footprint and provide guidelines for the design of materials that will lead to state-of-the-art transistor performance. PMID:26601178

Magnetic Cobalt Ferrite Nanocrystals For an Energy Storage Concentration Cell.

PubMed

Dai, Qilin; Patel, Ketan; Donatelli, Greg; Ren, Shenqiang

2016-08-22

Energy-storage concentration cells are based on the concentration gradient of redox-active reactants; the increased entropy is transformed into electric energy as the concentration gradient reaches equilibrium between two half cells. A recyclable and flow-controlled magnetic electrolyte concentration cell is now presented. The hybrid inorganic-organic nanocrystal-based electrolyte, consisting of molecular redox-active ligands adsorbed on the surface of magnetic nanocrystals, leads to a magnetic-field-driven concentration gradient of redox molecules. The energy storage performance of concentration cells is dictated by magnetic characteristics of cobalt ferrite nanocrystal carriers. The enhanced conductivity and kinetics of redox-active electrolytes could further induce a sharp concentration gradient to improve the energy density and voltage switching of magnetic electrolyte concentration cells. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

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.

Performance of carbon-carbon supercapacitors based on organic, aqueous and ionic liquid electrolytes

NASA Astrophysics Data System (ADS)

Lewandowski, Andrzej; Olejniczak, Angelika; Galinski, Maciej; Stepniak, Izabela

Properties of capacitors working with the same carbon electrodes (activated carbon cloth) and three types of electrolytes: aqueous, organic and ionic liquids were compared. Capacitors filled with ionic liquids worked at a potential difference of 3.5 V, their solutions in AN and PC were charged up to the potential difference of 3 V, classical organic systems to 2.5 V and aqueous to 1 V. Cyclic voltammetry, galvanostatic charging/discharging and impedance spectroscopy were used to characterize these capacitors. The highest specific energy was recorded for the device working with ionic liquids, while the highest power is characteristic for the device filled with aqueous H 2SO 4 electrolyte. Aqueous electrolytes led to energy density an order of magnitude lower in comparison to that characteristic of ionic liquids.

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

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

Reduced graphene oxide aerogel with high-rate supercapacitive performance in aqueous electrolytes

NASA Astrophysics Data System (ADS)

Si, Weijiang; Wu, Xiaozhong; Zhou, Jin; Guo, Feifei; Zhuo, Shuping; Cui, Hongyou; Xing, Wei

2013-05-01

Reduced graphene oxide aerogel (RGOA) is synthesized successfully through a simultaneous self-assembly and reduction process using hypophosphorous acid and I2 as reductant. Nitrogen sorption analysis shows that the Brunauer-Emmett-Teller surface area of RGOA could reach as high as 830 m2 g-1, which is the largest value ever reported for graphene-based aerogels obtained through the simultaneous self-assembly and reduction strategy. The as-prepared RGOA is characterized by a variety of means such as scanning electron microscopy, transmission electron microscopy, X-ray diffraction, Raman spectroscopy, and X-ray photoelectron spectroscopy. Electrochemical tests show that RGOA exhibits a high-rate supercapacitive performance in aqueous electrolytes. The specific capacitance of RGOA is calculated to be 211.8 and 278.6 F g-1 in KOH and H2SO4 electrolytes, respectively. The perfect supercapacitive performance of RGOA is ascribed to its three-dimensional structure and the existence of oxygen-containing groups.

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.

Reduced graphene oxide aerogel with high-rate supercapacitive performance in aqueous electrolytes.

PubMed

Si, Weijiang; Wu, Xiaozhong; Zhou, Jin; Guo, Feifei; Zhuo, Shuping; Cui, Hongyou; Xing, Wei

2013-05-21

Reduced graphene oxide aerogel (RGOA) is synthesized successfully through a simultaneous self-assembly and reduction process using hypophosphorous acid and I2 as reductant. Nitrogen sorption analysis shows that the Brunauer-Emmett-Teller surface area of RGOA could reach as high as 830 m2 g-1, which is the largest value ever reported for graphene-based aerogels obtained through the simultaneous self-assembly and reduction strategy. The as-prepared RGOA is characterized by a variety of means such as scanning electron microscopy, transmission electron microscopy, X-ray diffraction, Raman spectroscopy, and X-ray photoelectron spectroscopy. Electrochemical tests show that RGOA exhibits a high-rate supercapacitive performance in aqueous electrolytes. The specific capacitance of RGOA is calculated to be 211.8 and 278.6 F g-1 in KOH and H2SO4 electrolytes, respectively. The perfect supercapacitive performance of RGOA is ascribed to its three-dimensional structure and the existence of oxygen-containing groups.

Highly Conductive Aromatic Functionalized Multi-Walled Carbon Nanotube for Inkjet Printable High Performance Supercapacitor Electrodes

PubMed Central

Attri, Pankaj

2015-01-01

We report the functionalization of multiwalled carbon nanotubes (MWCNT) via the 1,3-dipolar [3+2] cycloaddition of aromatic azides, which resulted in a detangled CNT as shown by transmission electron microscopy (TEM). Carboxylic moieties (-COOH) on aromatic azide result in highly stable aqueous dispersion (max. conc. ~ 10 mg/mL H2O), making the suitable for inkjet printing. Printed patterns on polyethylene terephthalate (PET) flexible substrate exhibit low sheet resistivity ~65 Ω. cm, which is attributed to enhanced conductivity. Fabricated Supercapacitors (SC) assembled using these printed substrates exhibit good electrochemical performance in organic as well as aqueous electrolytes. High energy and power density (57.8 Wh/kg and 0.85 kW/kg) in 1M H2SO4 aqueous electrolyte demonstrate the excellent performance of the proposed supercapacitor. Capacitive retention varies from ~85–94% with columbic efficiency ~95% after 1000 charge/discharge cycles in different electrolytes, demonstrating the excellent potential of the device for futuristic power applications. PMID:26153688

Performance of strontium- and magnesium-doped lanthanum gallate electrolyte with lanthanum-doped ceria as a buffer layer for IT-SOFCs

NASA Astrophysics Data System (ADS)

Lee, Dokyol; Han, Ju-Hyeong; Kim, Eun-Gu; Song, Rak-Hyun; Shin, Dong-Ryul

La 0.8Sr 0.2Ga 0.8Mg 0.2O 2.8 (LSGM8080) powder, showing the highest electrical conductivity among LSGMs of various compositions, is synthesized using the glycine nitrate process (GNP) and used as the electrolyte for an intermediate-temperature solid oxide fuel cell (IT-SOFC). The LDC (Ce 0.55La 0.45O 1.775) powder is synthesized by a solid-state reaction and employed as the material for a buffer layer to prevent the reaction between the anode and electrolyte materials. The LDC also serves as the skeleton material for the anode. An anode-supported single cell with an active area of 1 cm 2 is constructed for performance evaluation. A single-cell test is performed at 750 and 800 °C. The maximum power density of the cell 459 and 664 mW cm -2 at 750 and 800 °C, respectively.

An Innovative Carbonate Fuel Cell Matrix, Abstract #188

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

Hilmi, Abdelkader; Surendranath, Arun; Yuh, Chao-Yi

2015-05-28

The electrolyte matrix in direct carbonate fuel cell (DFC) is a microporous ceramic structure sandwiched between the electrodes to isolate the fuel from the oxidant, store electrolyte and facilitate ionic transport. FCE has advanced DFC electrolyte matrix over the years and demonstrated that the matrix meets the requirements for greater than 5 year life based on accelerated tests and field stack operations. However, development of advanced designs and materials that can further increase the performance and extend cell life will enable accelerated MCFC deployment. This paper will report the progress on the development of an unique and innovative matrix designmore » that offers numerous benefits to the carbonate fuel cell performance and durability. In addition, this paper will also review parameters that affect matrix material stability and approaches to extend cell life.« less

Millimeter-wave irradiation heating for operation of doped CeO2 electrolyte-supported single solid oxide fuel cell

NASA Astrophysics Data System (ADS)

Che Abdullah, Salmie Suhana Binti; Teranishi, Takashi; Hayashi, Hidetaka; Kishimoto, Akira

2018-01-01

High operation temperature of solid oxide fuel cell (SOFC) results in high cell and operation cost, time consuming and fast cell degradation. Developing high performance SOFC that operates at lower temperature is required. Here we demonstrate 24 GHz microwave as a rapid heating source to replace conventional heating method for SOFC operation using 20 mol% Sm doped CeO2 electrolyte-supported single cell. The tested cell shows improvement of 62% in maximum power density at 630 °C under microwave heating. This improvement governs by bulk conductivity of the electrolyte. Investigation of ionic transference number reveals that the value is unchanged under microwave irradiation, confirming the charge carrier is dominated by oxygen ion species. This work shows a potential new concept of high performance as well as cost and energy effective SOFC.

Thermally Deposited Palladium-Tungsten Carbide and Platinum-Tungsten Carbide Counter Electrodes for a High Performance Dye-Sensitized Solar Cell Based on Organic T-/T₂ Electrolyte.

PubMed

Towannang, Madsakorn; Thiangkaew, Anongnad; Maiaugree, Wasan; Ratchaphonsaenwong, Kunthaya; Jarernboon, Wirat; Pimanpang, Samuk; Amornkitbamrung, Vittaya

2018-02-01

Tungsten carbide (WC) particles (~1 μm) were dispersed in DI water and dropped onto conductive glass. The resulting WC films were used as dye-sensitized solar cell (DSSC) counter electrodes. The performance of the WC DSSC based on the organic thiolate/disulfide (T-/T2) electrolyte was ~0.78%. The cell efficiency was greatly improved after decorating palladium (Pd) or platinum (Pt) nanoparticles on WC particles with a promising efficiency of ~2.15% for Pd-WC DSSC and ~4.62% for Pt-WC DSSC. The efficiency improvement of the composited (Pd-WC and Pt-WC) cells is attributed to co-functioning catalysts, the large electrode interfacial area and a low charge-transfer resistance at the electrolyte/counter electrode interface.

Allylic ionic liquid electrolyte-assisted electrochemical surface passivation of LiCoO2 for advanced, safe lithium-ion batteries.

PubMed

Mun, Junyoung; Yim, Taeeun; Park, Jang Hoon; Ryu, Ji Heon; Lee, Sang Young; Kim, Young Gyu; Oh, Seung M

2014-08-29

Room-temperature ionic liquid (RTIL) electrolytes have attracted much attention for use in advanced, safe lithium-ion batteries (LIB) owing to their nonvolatility, high conductivity, and great thermal stability. However, LIBs containing RTIL-electrolytes exhibit poor cyclability because electrochemical side reactions cause problematic surface failures of the cathode. Here, we demonstrate that a thin, homogeneous surface film, which is electrochemically generated on LiCoO2 from an RTIL-electrolyte containing an unsaturated substituent on the cation (1-allyl-1-methylpiperidinium bis(trifluoromethanesulfonyl)imide, AMPip-TFSI), can avert undesired side reactions. The derived surface film comprised of a high amount of organic species from the RTIL cations homogenously covered LiCoO2 with a <25 nm layer and helped suppress unfavorable thermal reactions as well as electrochemical side reactions. The superior performance of the cell containing the AMPip-TFSI electrolyte was further elucidated by surface, electrochemical, and thermal analyses.

Allylic ionic liquid electrolyte-assisted electrochemical surface passivation of LiCoO2 for advanced, safe lithium-ion batteries

NASA Astrophysics Data System (ADS)

Mun, Junyoung; Yim, Taeeun; Park, Jang Hoon; Ryu, Ji Heon; Lee, Sang Young; Kim, Young Gyu; Oh, Seung M.

2014-08-01

Room-temperature ionic liquid (RTIL) electrolytes have attracted much attention for use in advanced, safe lithium-ion batteries (LIB) owing to their nonvolatility, high conductivity, and great thermal stability. However, LIBs containing RTIL-electrolytes exhibit poor cyclability because electrochemical side reactions cause problematic surface failures of the cathode. Here, we demonstrate that a thin, homogeneous surface film, which is electrochemically generated on LiCoO2 from an RTIL-electrolyte containing an unsaturated substituent on the cation (1-allyl-1-methylpiperidinium bis(trifluoromethanesulfonyl)imide, AMPip-TFSI), can avert undesired side reactions. The derived surface film comprised of a high amount of organic species from the RTIL cations homogenously covered LiCoO2 with a <25 nm layer and helped suppress unfavorable thermal reactions as well as electrochemical side reactions. The superior performance of the cell containing the AMPip-TFSI electrolyte was further elucidated by surface, electrochemical, and thermal analyses.

Design of aqueous redox-enhanced electrochemical capacitors with high specific energies and slow self-discharge.

PubMed

Chun, Sang-Eun; Evanko, Brian; Wang, Xingfeng; Vonlanthen, David; Ji, Xiulei; Stucky, Galen D; Boettcher, Shannon W

2015-08-04

Electrochemical double-layer capacitors exhibit high power and long cycle life but have low specific energy compared with batteries, limiting applications. Redox-enhanced capacitors increase specific energy by using redox-active electrolytes that are oxidized at the positive electrode and reduced at the negative electrode during charging. Here we report characteristics of several redox electrolytes to illustrate operational/self-discharge mechanisms and the design rules for high performance. We discover a methyl viologen (MV)/bromide electrolyte that delivers a high specific energy of ∼14 Wh kg(-1) based on the mass of electrodes and electrolyte, without the use of an ion-selective membrane separator. Substituting heptyl viologen for MV increases stability, with no degradation over 20,000 cycles. Self-discharge is low, due to adsorption of the redox couples in the charged state to the activated carbon, and comparable to cells with inert electrolyte. An electrochemical model reproduces experiments and predicts that 30-50 Wh kg(-1) is possible with optimization.

Design of aqueous redox-enhanced electrochemical capacitors with high specific energies and slow self-discharge

PubMed Central

Chun, Sang-Eun; Evanko, Brian; Wang, Xingfeng; Vonlanthen, David; Ji, Xiulei; Stucky, Galen D.; Boettcher, Shannon W.

2015-01-01

Electrochemical double-layer capacitors exhibit high power and long cycle life but have low specific energy compared with batteries, limiting applications. Redox-enhanced capacitors increase specific energy by using redox-active electrolytes that are oxidized at the positive electrode and reduced at the negative electrode during charging. Here we report characteristics of several redox electrolytes to illustrate operational/self-discharge mechanisms and the design rules for high performance. We discover a methyl viologen (MV)/bromide electrolyte that delivers a high specific energy of ∼14 Wh kg−1 based on the mass of electrodes and electrolyte, without the use of an ion-selective membrane separator. Substituting heptyl viologen for MV increases stability, with no degradation over 20,000 cycles. Self-discharge is low, due to adsorption of the redox couples in the charged state to the activated carbon, and comparable to cells with inert electrolyte. An electrochemical model reproduces experiments and predicts that 30–50 Wh kg−1 is possible with optimization. PMID:26239891

Characterization of commercial supercapacitors for low temperature applications

NASA Astrophysics Data System (ADS)

Iwama, E.; Taberna, P. L.; Azais, P.; Brégeon, L.; Simon, P.

2012-12-01

Electrochemical characterizations at low temperature and floating tests have been performed on 600F commercial supercapacitor (SC) for acetonitrile (AN)-based and AN + methyl acetate (MA) mixed electrolytes. From -40 to +20 °C, AN electrolyte showed slightly higher capacitance than those of AN + MA mixed electrolytes (25 and 33 vol.% of MA). At -55 °C, however, AN electrolyte did not cycle at all, while MA mixed electrolyte normally cycled with a slight decrease in their capacitance. From electrochemical impedance spectroscopy measurements, the whole resistance for AN-based cells at -55 °C was found to be about 10,000 times higher than that of +20 °C, while a 40-fold increase in the cell resistance was obtained for the MA mixture between 20 and -55 °C. From the results of floating tests at 2.7 V and 60 °C for 1 month, the 25 vol.% MA mixture showed no change and slight decreased but stable capacitance.

Enabling electrolyte compositions for columnar silicon anodes in high energy secondary batteries

NASA Astrophysics Data System (ADS)

Piwko, Markus; Thieme, Sören; Weller, Christine; Althues, Holger; Kaskel, Stefan

2017-09-01

Columnar silicon structures are proven as high performance anodes for high energy batteries paired with low (sulfur) or high (nickel-cobalt-aluminum oxide, NCA) voltage cathodes. The introduction of a fluorinated ether/sulfolane solvent mixture drastically improves the capacity retention for both battery types due to an improved solid electrolyte interface (SEI) on the surface of the silicon electrode which reduces irreversible reactions normally causing lithium loss and rapid capacity fading. For the lithium silicide/sulfur battery cycling stability is significantly improved as compared to a frequently used reference electrolyte (DME/DOL) reaching a constant coulombic efficiency (CE) as high as 98%. For the silicon/NCA battery with higher voltage, the addition of only small amounts of fluoroethylene carbonate (FEC) to the novel electrolyte leads to a stable capacity over at least 50 cycles and a CE as high as 99.9%. A high volumetric energy density close to 1000 Wh l-1 was achieved with the new electrolyte taking all inactive components of the stack into account for the estimation.

Synthesis of One-Dimensional and Hyperbranched Nanomaterials for Lithium-Ion Battery Solid Electrolytes

NASA Astrophysics Data System (ADS)

Yang, Ting

Lithium-ion batteries can fail and catch fire when overcharged, exposed to high temperatures or short-circuited due to the highly flammable organic liquid used in the electrolyte. Using inorganic solid electrolyte materials can potentially improve the safety factor. Additionally, nanostructured electrolyte materials may further enhanced performance by taking advantage of their large aspect ratio. In this work, the synthesis of two promising nanostructured solid electrolyte materials was explored. Amorphous lithium niobate nanowires were synthesized through the decomposition of a niobium-containing complex in a structure-directing solvent using a reflux method. Lithium lanthanum titanate was obtained via solid state reaction with titanium oxide nanowires as the titanium precursor, but the nanowire morphology could not be preserved due to high temperature sintering. Hyperbranched potassium lanthanum titanate was synthesized through hydrothermal route. This was the first time that hyperbranched nanowires with perovskite structure were made without any catalyst or substrate. This result has the potential to be applied to other perovskite materials.

Towards the next generation of solid oxide fuel cells operating below 600 °c with chemically stable proton-conducting electrolytes.

PubMed

Fabbri, Emiliana; Bi, Lei; Pergolesi, Daniele; Traversa, Enrico

2012-01-10

The need for reducing the solid oxide fuel cell (SOFC) operating temperature below 600 °C is imposed by cost reduction, which is essential for widespread SOFC use, but might also disclose new applications. To this aim, high-temperature proton-conducting (HTPC) oxides have gained widespread interest as electrolyte materials alternative to oxygen-ion conductors. This Progress Report describes recent developments in electrolyte, anode, and cathode materials for protonic SOFCs, addressing the issue of chemical stability, processability, and good power performance below 600 °C. Different fabrication methods are reported for anode-supported SOFCs, obtained using state-of-the-art, chemically stable proton-conducting electrolyte films. Recent findings show significant improvements in the power density output of cells based on doped barium zirconate electrolytes, pointing out towards the feasibility of the next generation of protonic SOFCs, including a good potential for the development of miniaturized SOFCs as portable power supplies. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Allylic ionic liquid electrolyte-assisted electrochemical surface passivation of LiCoO2 for advanced, safe lithium-ion batteries

PubMed Central

Mun, Junyoung; Yim, Taeeun; Park, Jang Hoon; Ryu, Ji Heon; Lee, Sang Young; Kim, Young Gyu; Oh, Seung M.

2014-01-01

Room-temperature ionic liquid (RTIL) electrolytes have attracted much attention for use in advanced, safe lithium-ion batteries (LIB) owing to their nonvolatility, high conductivity, and great thermal stability. However, LIBs containing RTIL-electrolytes exhibit poor cyclability because electrochemical side reactions cause problematic surface failures of the cathode. Here, we demonstrate that a thin, homogeneous surface film, which is electrochemically generated on LiCoO2 from an RTIL-electrolyte containing an unsaturated substituent on the cation (1-allyl-1-methylpiperidinium bis(trifluoromethanesulfonyl)imide, AMPip-TFSI), can avert undesired side reactions. The derived surface film comprised of a high amount of organic species from the RTIL cations homogenously covered LiCoO2 with a <25 nm layer and helped suppress unfavorable thermal reactions as well as electrochemical side reactions. The superior performance of the cell containing the AMPip-TFSI electrolyte was further elucidated by surface, electrochemical, and thermal analyses. PMID:25168309

Accessing the bottleneck in all-solid state batteries, lithium-ion transport over the solid-electrolyte-electrode interface.

PubMed

Yu, Chuang; Ganapathy, Swapna; Eck, Ernst R H van; Wang, Heng; Basak, Shibabrata; Li, Zhaolong; Wagemaker, Marnix

2017-10-20

Solid-state batteries potentially offer increased lithium-ion battery energy density and safety as required for large-scale production of electrical vehicles. One of the key challenges toward high-performance solid-state batteries is the large impedance posed by the electrode-electrolyte interface. However, direct assessment of the lithium-ion transport across realistic electrode-electrolyte interfaces is tedious. Here we report two-dimensional lithium-ion exchange NMR accessing the spontaneous lithium-ion transport, providing insight on the influence of electrode preparation and battery cycling on the lithium-ion transport over the interface between an argyrodite solid-electrolyte and a sulfide electrode. Interfacial conductivity is shown to depend strongly on the preparation method and demonstrated to drop dramatically after a few electrochemical (dis)charge cycles due to both losses in interfacial contact and increased diffusional barriers. The reported exchange NMR facilitates non-invasive and selective measurement of lithium-ion interfacial transport, providing insight that can guide the electrolyte-electrode interface design for future all-solid-state batteries.

Miniaturized Amperometric Solid Electrolyte Carbon Dioxide Sensors

NASA Technical Reports Server (NTRS)

Hunter, G. W.; Xu, J. C.; Liu, C. C.; Hammond, J. W.; Ward, B.; Lukco, D.; Lampard, P.; Artale, M.; Androjna, D.

2006-01-01

A miniaturized electrochemical carbon dioxide (CO2) sensor using Na3Z r2Si2PO12 (NASICON) as a solid electrolyte has been fabricated and de monstrated. Microfabrication techniques were used for sensor fabricat ion to yield a sensing area around 1.0 mm x 1.1 mm. The NASICON solid electrolyte and the Na2CO3/BaCO3 (1:1.7 molar ratio) auxiliary elect rolyte were deposited by sputtering in between and on top of the inte rdigitated finger-shaped platinum electrodes. This structure maximize s the length of the three-phase boundary (electrode, solid electrolyt e, and auxiliary electrolyte), which is critical for gas sensing. The robust CO2 sensor operated up to 600 C in an amperometric mode and a ttempts were made to optimize sensor operating parameters. Concentrat ions of CO2 between 0.02% and 4% were detected and the overall sensor performance was evaluated. Linear response of sensor current output to ln[CO2 concentration] ranging from 0.02% to 1% was achieved.

Ethylene carbonate-free fluoroethylene carbonate-based electrolyte works better for freestanding Si-based composite paper anodes for Li-ion batteries

NASA Astrophysics Data System (ADS)

Yao, K.; Zheng, J. P.; Liang, R.

2018-03-01

Fluoroethylene carbonate (FEC)-based electrolytes using FEC as the co-solvent (50 wt%) are investigated and compared with the electrolyte using FEC as the additive (10 wt%) for freestanding Si-carbon nanotubes (CNTs) composite paper anodes for Li-ion batteries. The ethylene carbonate (EC)-free FEC-based electrolyte is found to achieve higher specific capacity and better capacity retention in terms of long-term cycling. After 500 cycles, the capacity retention of the cell using diethyl carbonate (DEC)-FEC (1:1 w/w) is increased by 88% and 60% compared to the cells using EC-DEC-FEC (45:45:10 w/w/w) and EC-FEC (1:1 w/w), respectively. Through SEM-EDX and XPS analyses, a possible reaction route of formation of fluorinated semicarbonates and polyolefins from FEC is proposed. The inferior cell performance related to the EC-containing electrolytes is likely due to the formation of more polyolefins, which do not favor Li ion migration.

Facile preparation, optical and electrochemical properties of layer-by-layer V2O5 quadrate structures

NASA Astrophysics Data System (ADS)

Zhang, Yifu; Zheng, Jiqi; Wang, Qiushi; Hu, Tao; Tian, Fuping; Meng, Changgong

2017-03-01

Layer-by-layer V2O5 structures self-assembly by quadrate sheets like "multilayer cake" were successfully synthesized using NH4VO3 as the vanadium sources by a facile hydrothermal route and combination of the calcination. The structure and composition were characterized by field emission scanning electron microscopy, energy-dispersive X-ray spectrometer, X-ray powder diffraction, Raman and Fourier transform infrared spectroscopy. The optical properties of the as-obtained V2O5 layer-by-layer structures were investigated by the Ultraviolet-visible spectroscopy and photoluminescence spectrum. The electrochemical properties of the as-obtained V2O5 layer-by-layer structures as electrodes in supercapacitor device were measured by cyclic voltammetry (CV) and galvanostatic charge-discharge (GCD) both in the aqueous and organic electrolyte. The specific capacitance is 347 F g-1 at 1 A g-1 in organic electrolyte, which is improved by 46% compared with 238 F g-1 in aqueous electrolyte. During the cycle performance, the specific capacitances of V2O5 layer-by-layer structures after 100 cycles are 30% and 82% of the initial discharge capacity in the aqueous and organic electrolyte, respectively, indicating the cycle performance is significantly improved in organic electrolyte. Our results turn out that layer-by-layer V2O5 structures are an ideal material for supercapacitor electrode in the present work.

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

Lian, Cheng; Univ. of California, Riverside, CA; Liu, Honglai

The ionophobicity effect of nanoporous electrodes on the capacitance and the energy storage capacity of nonaqueous-electrolyte supercapacitors is studied by means of the classical density functional theory (DFT). It has been hypothesized that ionophobic nanopores may create obstacles in charging, but they store energy much more efficiently than ionophilic pores. In this paper, we find that, for both ionic liquids and organic electrolytes, an ionophobic pore exhibits a charging behavior different from that of an ionophilic pore, and that the capacitance–voltage curve changes from a bell shape to a two-hump camel shape when the pore ionophobicity increases. For electric-double-layer capacitorsmore » containing organic electrolytes, an increase in the ionophobicity of the nanopores leads to a higher capacity for energy storage. Without taking into account the effects of background screening, the DFT predicts that an ionophobic pore containing an ionic liquid does not enhance the supercapacitor performance within the practical voltage ranges. However, by using an effective dielectric constant to account for ion polarizability, the DFT predicts that, like an organic electrolyte, an ionophobic pore with an ionic liquid is also able to increase the energy stored when the electrode voltage is beyond a certain value. We find that the critical voltage for an enhanced capacitance in an ionic liquid is larger than that in an organic electrolyte. Finally, our theoretical predictions provide further understanding of how chemical modification of porous electrodes affects the performance of supercapacitors.« less

Molecular dynamics simulation of polymer electrolytes based on poly(ethylene oxide) and ionic liquids. I. Structural properties.

PubMed

Costa, Luciano T; Ribeiro, Mauro C C

2006-05-14

Molecular dynamics (MD) simulations have been performed for prototype models of polymer electrolytes in which the salt is an ionic liquid based on 1-alkyl-3-methylimidazolium cations and the polymer is poly(ethylene oxide), PEO. The MD simulations were performed by combining the previously proposed models for pure ionic liquids and polymer electrolytes containing simple inorganic ions. A systematic investigation of ionic liquid concentration, temperature, and the 1-alkyl- chain length, [1,3-dimethylimidazolium]PF6, and [1-butyl-3-methylimidazolium]PF6, effects on resulting equilibrium structure is provided. It is shown that the ionic liquid is dispersed in the polymeric matrix, but ionic pairs remain in the polymer electrolyte. Imidazolium cations are coordinated by both the anions and the oxygen atoms of PEO chains. Probability density maps of occurrences of nearest neighbors around imidazolium cations give a detailed physical picture of the environment experienced by cations. Conformational changes on PEO chains upon addition of the ionic liquid are identified. The equilibrium structure of simulated systems is also analyzed in reciprocal space by using the static structure factor, S(k). Calculated S(k) display a low wave-vector peak, indicating that spatial correlation in an extended-range order prevail in the ionic liquid polymer electrolytes. Long-range correlations are assigned to nonuniform distribution of ionic species within the simulation box.

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.

Performance improvement of gel- and solid-state dye-sensitized solar cells by utilization the blending effect of poly (vinylidene fluoride-co-hexafluropropylene) and poly (acrylonitrile-co-vinyl acetate) co-polymers

NASA Astrophysics Data System (ADS)

Venkatesan, Shanmugam; Obadja, Nesia; Chang, Ting-Wei; Chen, Li-Tung; Lee, Yuh-Lang

2014-12-01

Poly (vinylidene fluoride-co-hexafluropropylene) (PVDF-HFP) and poly (acrylonitrile-co-vinyl acetate) (PAN-VA) are used as gelator to prepare gel- and solid-state polymer electrolytes for dye sensitized solar cells (DSSCs) applications. The electrolytes prepared using PVDF-HFP have higher conductivities than those prepared using PAN-VA. In blended polymers, the conductivities of the electrolytes increase with increasing composition of PVDF-HFP; at 75% PVDF-HFP, conductivity of the blended polymer surpassed that of pure polymers. It is also found that the viscosity of the electrolyte prepared by PAN-VA (1.2 kPaS) is much lower than that by PVDF-HFP (11 kPaS). Therefore, increasing PAN-VA composition can decrease the viscosity of the electrolyte, improving the penetration of electrolytes in the TiO2 matrix. By controlling the ratio of PVDF-HFP/PAN-VA, the conductivity and viscosity of the electrolyte can be regulated and an optimal ratio based on the conversion efficiency of the gel- and solid state DSSCs is obtained at the ratio of 3/1. The highest efficiency achieved by the gel- and solid-state cells using the blending polymers are 6.3% and 4.88%, respectively, which are higher than those prepared using pure polymers (5.53% and 4.56%, respectively). The introduction of TiO2 fillers to the solid electrolyte can further increase the cell efficiency to 5.34%.

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