Investigating the reversibility of structural modifications of Li xNi yMn zCo 1-y-zO₂ cathode materials during initial charge/discharge, at multiple length scales

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

Hwang, Sooyeon; Bak, Seong -Min; Kim, Seung Min

2015-08-11

In this work, we investigate the structural modifications occurring at the bulk, subsurface, and surface scales of Li xNi yMn zCo 1-y-zO₂ (NMC; y, z = 0.8, 0.1 and 0.4, 0.3, respectively) cathode materials during the initial charge/discharge. Various analytical tools, such as X-ray diffraction, selected-area electron diffraction, electron energy-loss spectroscopy, and high-resolution electron microscopy, are used to examine the structural properties of the NMC cathode materials at the three different scales. Cut-off voltages of 4.3 and 4.8 V are applied during the electrochemical tests as the normal and extreme conditions, respectively. The high-Ni-content NMC cathode materials exhibit unusual behaviors,more » which is deviate from the general redox reactions during the charge or discharge. The transition metal (TM) ions in the high-Ni-content NMC cathode materials, which are mostly Ni ions, are reduced at 4.8 V, even though TMs are usually oxidized to maintain charge neutrality upon the removal of Li. It was found that any changes in the crystallographic and electronic structures are mostly reversible down to the sub-surface scale, despite the unexpected reduction of Ni ions. However, after the discharge, traces of the phase transitions remain at the edges of the NMC cathode materials at the scale of a few nanometers (i.e., surface scale). This study demonstrates that the structural modifications in NMC cathode materials are induced by charge as well as discharge at multiple length scales. These changes are nearly reversible after the first cycle, except at the edges of the samples, which should be avoided because these highly localized changes can initiate battery degradation.« less

Functionalized graphene-based cathode for highly reversible lithium-sulfur batteries.

PubMed

Kim, Jin Won; Ocon, Joey D; Park, Dong-Won; Lee, Jaeyoung

2014-05-01

In this article, we highlight the salient issues in the development of lithium-sulfur battery (LSB) cathodes, present different points of view in solving them, and argue, why in the future, functionalized graphene or graphene oxide might be the ultimate solution towards LSB commercialization. As shown by previous studies and also in our recent work, functionalized graphene and graphene oxide enhance the reversibility of the charge-discharge process by trapping polysulfides in the oxygen functional groups on the graphene surface, thus minimizing polysulfide dissolution. This will be helpful for the rational design of new cathode structures based on graphene for LSBs with minimal capacity fading, low extra cost, and without the unnecessary weight increase caused by metal/metal oxide additives. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Asymmetric anode and cathode extraction structure fast recovery diode

NASA Astrophysics Data System (ADS)

Xie, Jiaqiang; Ma, Li; Gao, Yong

2018-05-01

This paper presents an asymmetric anode structure and cathode extraction fast and soft recovery diode. The device anode is partial-heavily doped and partial-lightly doped. The P+ region is introduced into the cathode. Firstly, the characteristics of the diode are simulated and analyzed. Secondly, the diode was fabricated and its characteristics were tested. The experimental results are in good agreement with the simulation results. The results show that, compared with the P–i–N diode, although the forward conduction characteristic of the diode is declined, the reverse recovery peak current is reduced by 47%, the reverse recovery time is shortened by 20% and the softness factor is doubled. In addition, the breakdown voltage is increased by 10%. Project supported by the National Natural Science Foundation of China (No. 51177133).

The first Fe-based Na+-ion cathode with two distinct types of polyanions: Fe 3P 5SiO 19

DOE PAGES

Kan, W. H.; Huq, A.; Manthiram, A.

2015-05-15

We report the synthesis, structure, and electrochemistry of the first Na +-ion cathode with two distinct types of polyanions: Fe 3P 5SiO 19. The Fe-based cathode has a reversible capacity of ca. 70 mAh g -1; ca. 1.7 Na + ions per formula can be inserted/extracted at an average voltage of 2.5 V versus Na +/Na.

Solid state cathode materials for secondary magnesium-ion batteries that are compatible with magnesium metal anodes in water-free electrolyte

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

Crowe, Adam J.; Bartlett, Bart M., E-mail: bartmb@umich.edu

2016-10-15

With high elemental abundance, large volumetric capacity, and dendrite-free metal deposition, magnesium metal anodes offer promise in beyond-lithium-ion batteries. However, the increased charge density associated with the divalent magnesium-ion (Mg{sup 2+}), relative to lithium-ion (Li{sup +}) hinders the ion-insertion and extraction processes within many materials and structures known for lithium-ion cathodes. As a result, many recent investigations incorporate known amounts of water within the electrolyte to provide temporary solvation of the Mg{sup 2+}, improving diffusion kinetics. Unfortunately with the addition of water, compatibility with magnesium metal anodes disappears due to forming an ion-insulating passivating layer. In this short review, recentmore » advances in solid state cathode materials for rechargeable magnesium-ion batteries are highlighted, with a focus on cathode materials that do not require water contaminated electrolyte solutions for ion insertion and extraction processes. - Graphical abstract: In this short review, we present candidate materials for reversible Mg-battery cathodes that are compatible with magnesium metal in water-free electrolytes. The data suggest that soft, polarizable anions are required for reversible cycling.« less

Characterization of Pulse Reverses Electroforming on Hard Gold Coating.

PubMed

Byoun, Young-Min; Noh, Young-Tai; Kim, Young-Geun; Ma, Seung-Hwan; Kim, Gwan-Hoon

2018-03-01

Effect of pulse reverse current (PRC) method on brass coatings electroplated from gold solution was investigated by various plating parameters such as plating duration, the anodic duty cycle, the anodic current density and the cathodic current density. The reversed current results in a significant change in the morphology of electrodeposits, improvement of the overall current efficiency and reduction of deposit porosity. With longer pulses, hemispherical surface features are generated, while larger grains result from shorter pulse widths. The porosity of the plated samples is found to decrease compared with results at the same time-average plating rate obtained from DC or Pulse plating. A major impediment to reducing gold later thickness is the corrosion of the underlying substrate, which is affected by the porosity of the gold layer. Both the morphology and the hydrogen evolution reaction have significant impact on porosity. PRC plating affect hydrogen gold and may oxidize hydrogen produced during the cathodic portion of the waveform. Whether the dissolution of gold and oxidation of hydrogen occur depends on the type of plating bath and the plating conditions adapted. In reversed pulse plating, the amount of excess near-surface cyanide is changed after the cathodic current is applied, and the oxidation of gold under these conditions has not been fully addressed. The effects of the current density, pulse-reverse ratio and brightener concentration of the electroplating process were investigated and optimized for suitable performance.

POWER AND THERMAL TECHNOLOGIES FOR AIR AND SPACE-SCIENTIFIC RESEARCH PROGRAM Delivery Order 0018: Single Ion Conducting Solid-State Lithium Electrochemical Technologies (Task 4)

DTIC Science & Technology

2010-08-01

a mathematical equation relates the cathode reaction reversible electric potential to the lithium content of the cathode electrode. Based on the...Transport of Lithium in the Cell Cathode Active Material The Nernst -Einstein relation linking the lithium-ion mass diffusivity and its ionic...transient, isothermal and isobaric conditions. The differential model equation describing the lithium diffusion and accumulation in a spherical, active

Ternary metal fluorides as high-energy cathodes with low cycling hysteresis

DOE PAGES

Wang, Feng; Kim, Sung -Wook; Seo, Dong -Hwa; ...

2015-03-26

In this study, transition metal fluorides are an appealing alternative to conventional intercalation compounds for use as cathodes in next-generation lithium batteries due to their extremely high capacity (3–4 times greater than the current state-of-the-art). However, issues related to reversibility, energy efficiency and kinetics prevent their practical application. Here we report on the synthesis, structural and electrochemical properties of ternary metal fluorides (M 1 yM 2 1-yF x: M 1, M 2 = Fe, Cu), which may overcome these issues. By substituting Cu into the Fe lattice, forming the solid–solution Cu yFe 1-yF 2, reversible Cu and Fe redox reactionsmore » are achieved with surprisingly small hysteresis (<150 mV). This finding indicates that cation substitution may provide a new avenue for tailoring key electrochemical properties of conversion electrodes. In conclusion, although the reversible capacity of Cu conversion fades rapidly, likely due to Cu + dissolution, the low hysteresis and high energy suggest that a Cu-based fluoride cathode remains an intriguing candidate for rechargeable lithium batteries.« less

Reversible calcium alloying enables a practical room-temperature rechargeable calcium-ion battery with a high discharge voltage

NASA Astrophysics Data System (ADS)

Wang, Meng; Jiang, Chunlei; Zhang, Songquan; Song, Xiaohe; Tang, Yongbing; Cheng, Hui-Ming

2018-06-01

Calcium-ion batteries (CIBs) are attractive candidates for energy storage because Ca2+ has low polarization and a reduction potential (-2.87 V versus standard hydrogen electrode, SHE) close to that of Li+ (-3.04 V versus SHE), promising a wide voltage window for a full battery. However, their development is limited by difficulties such as the lack of proper cathode/anode materials for reversible Ca2+ intercalation/de-intercalation, low working voltages (<2 V), low cycling stability, and especially poor room-temperature performance. Here, we report a CIB that can work stably at room temperature in a new cell configuration using graphite as the cathode and tin foils as the anode as well as the current collector. This CIB operates on a highly reversible electrochemical reaction that combines hexafluorophosphate intercalation/de-intercalation at the cathode and a Ca-involved alloying/de-alloying reaction at the anode. An optimized CIB exhibits a working voltage of up to 4.45 V with capacity retention of 95% after 350 cycles.

Reversible Intercalation of Fluoride-Anion Receptor Complexes in Graphite

NASA Technical Reports Server (NTRS)

West, William C.; Whitacre, Jay F.; Leifer, Nicole; Greenbaum, Steve; Smart, Marshall; Bugga, Ratnakumar; Blanco, Mario; Narayanan, S. R.

2007-01-01

We have demonstrated a route to reversibly intercalate fluoride-anion receptor complexes in graphite via a nonaqueous electrochemical process. This approach may find application for a rechargeable lithium-fluoride dual-ion intercalating battery with high specific energy. The cell chemistry presented here uses graphite cathodes with LiF dissolved in a nonaqueous solvent through the aid of anion receptors. Cells have been demonstrated with reversible cathode specific capacity of approximately 80 mAh/g at discharge plateaus of upward of 4.8 V, with graphite staging of the intercalant observed via in situ synchrotron X-ray diffraction during charging. Electrochemical impedance spectroscopy and B-11 nuclear magnetic resonance studies suggest that cointercalation of the anion receptor with the fluoride occurs during charging, which likely limits the cathode specific capacity. The anion receptor type dictates the extent of graphite fluorination, and must be further optimized to realize high theoretical fluorination levels. To find these optimal anion receptors, we have designed an ab initio calculations-based scheme aimed at identifying receptors with favorable fluoride binding and release properties.

Controlling hazardous reactions during voltage reversal of high energy lithium cells

NASA Technical Reports Server (NTRS)

Domeniconi, M.

1983-01-01

The roll of general cell design characteristics in preventing hazardous reactions during voltage reversal of lithium cells is discussed. Anode limited versus cathode limited design and case positive versus case negative design are addressed.

High Energy-Density and Reversibility of Iron Fluoride Cathode Enabled Via an Intercalation-Extrusion Reaction

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

Fan, Xiulin; Hu, Enyuan; Ji, Xiao

Iron fluoride, an intercalation-conversion cathode for lithium ion batteries, promises a high theoretical energy density of 1922 Wh Kg –1. However, poor electrochemical reversibility due to repeated breaking/reformation of metal-fluoride bonds poses a grand challenge for its practical application. Here we report that both a high reversibility over 1000 cycles and a high capacity of 420 mAh g –1 can be realized by concerted doping of cobalt and oxygen into iron fluoride. In the doped nanorods, an energy density of ~1000 Wh Kg –1 with a decay rate of 0.03% per cycle is achieved. The anion and cation’s co-substitutions thermodynamicallymore » reduce conversion-reaction potential and shift the reaction from less reversible intercalation-conversion reaction in iron fluoride to a highly reversible intercalation-extrusion reaction in doped material. Furthermore, the co-substitution strategy to tune the thermodynamic features of the reactions could be extended to other high energy conversion materials for improved performance.« less

High Energy-Density and Reversibility of Iron Fluoride Cathode Enabled Via an Intercalation-Extrusion Reaction

DOE PAGES

Fan, Xiulin; Hu, Enyuan; Ji, Xiao; ...

2018-05-30

Iron fluoride, an intercalation-conversion cathode for lithium ion batteries, promises a high theoretical energy density of 1922 Wh Kg –1. However, poor electrochemical reversibility due to repeated breaking/reformation of metal-fluoride bonds poses a grand challenge for its practical application. Here we report that both a high reversibility over 1000 cycles and a high capacity of 420 mAh g –1 can be realized by concerted doping of cobalt and oxygen into iron fluoride. In the doped nanorods, an energy density of ~1000 Wh Kg –1 with a decay rate of 0.03% per cycle is achieved. The anion and cation’s co-substitutions thermodynamicallymore » reduce conversion-reaction potential and shift the reaction from less reversible intercalation-conversion reaction in iron fluoride to a highly reversible intercalation-extrusion reaction in doped material. Furthermore, the co-substitution strategy to tune the thermodynamic features of the reactions could be extended to other high energy conversion materials for improved performance.« less

K-Ion Batteries Based on a P2-Type K 0.6CoO 2 Cathode

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

Kim, Haegyeom; Kim, Jae Chul; Bo, Shou-Hang

K-ion batteries are a potentially exciting and new energy storage technology that can combine high specific energy, cycle life, and good power capability, all while using abundant potassium resources. The discovery of novel cathodes is a critical step toward realizing K-ion batteries (KIBs). In this work, a layered P2-type K 0.6CoO 2 cathode is developed and highly reversible K ion intercalation is demonstrated. In situ X-ray diffraction combined with electrochemical titration reveals that P2-type K 0.6CoO 2 can store and release a considerable amount of K ions via a topotactic reaction. Despite the large amount of phase transitions as functionmore » of K content, the cathode operates highly reversibly and with good rate capability. The practical feasibility of KIBs is further demonstrated by constructing full cells with a graphite anode. This work highlights the potential of KIBs as viable alternatives for Li-ion and Na-ion batteries and provides new insights and directions for the development of next-generation energy storage systems.« less

K-Ion Batteries Based on a P2-Type K 0.6CoO 2 Cathode

DOE PAGES

Kim, Haegyeom; Kim, Jae Chul; Bo, Shou-Hang; ...

2017-05-02

K-ion batteries are a potentially exciting and new energy storage technology that can combine high specific energy, cycle life, and good power capability, all while using abundant potassium resources. The discovery of novel cathodes is a critical step toward realizing K-ion batteries (KIBs). In this work, a layered P2-type K 0.6CoO 2 cathode is developed and highly reversible K ion intercalation is demonstrated. In situ X-ray diffraction combined with electrochemical titration reveals that P2-type K 0.6CoO 2 can store and release a considerable amount of K ions via a topotactic reaction. Despite the large amount of phase transitions as functionmore » of K content, the cathode operates highly reversibly and with good rate capability. The practical feasibility of KIBs is further demonstrated by constructing full cells with a graphite anode. This work highlights the potential of KIBs as viable alternatives for Li-ion and Na-ion batteries and provides new insights and directions for the development of next-generation energy storage systems.« less

Pushing the Limits: 3D Layer-by-Layer-Assembled Composites for Cathodes with 160 C Discharge Rates.

PubMed

Mo, Runwei; Tung, Siu On; Lei, Zhengyu; Zhao, Guangyu; Sun, Kening; Kotov, Nicholas A

2015-05-26

Deficiencies of cathode materials severely limit cycling performance and discharge rates of Li batteries. The key problem is that cathode materials must combine multiple properties: high lithium ion intercalation capacity, electrical/ionic conductivity, porosity, and mechanical toughness. Some materials revealed promising characteristics in a subset of these properties, but attaining the entire set of often contrarian characteristics requires new methods of materials engineering. In this paper, we report high surface area 3D composite from reduced graphene oxide loaded with LiFePO4 (LFP) nanoparticles made by layer-by-layer assembly (LBL). High electrical conductivity of the LBL composite is combined with high ionic conductivity, toughness, and low impedance. As a result of such materials properties, reversible lithium storage capacity and Coulombic efficiency were as high as 148 mA h g(-1) and 99%, respectively, after 100 cycles at 1 C. Moreover, these composites enabled unusually high reversible charge-discharge rates up to 160 C with a storage capacity of 56 mA h g(-1), exceeding those of known LFP-based cathodes, some of them by several times while retaining high content of active cathode material. The study demonstrates that LBL-assembled composites enable resolution of difficult materials engineering tasks.

Effect of vacuum arc cathode spot distribution on breaking capacity of the arc-extinguishing chamber

NASA Astrophysics Data System (ADS)

Ding, Can; Yuan, Zhao; He, Junjia

2017-10-01

A DC circuit breaker performs a key function in breaking an intermediate-frequency (IF) current since breaking a pure IF current is equivalent to breaking a very small DC with a reverse IF current. In this study, it is found that cathode spots show a ring-shaped distribution at 2000 Hz. An arc with an uneven distribution of cathode spots has been simulated. The simulation results show that the distribution of cathode spots significantly affect the microparameter distribution of arc plasma. The current distribution on the anode side differs from that on the cathode side under the total radial electric field. Specifically, the anode current distribution is both uneven and concentrated. The applied axial magnetic field, which cannot reduce the concentrated anode current distribution effectively, might increase the concentration of the anode current. Finally, the uneven distribution of cathode spots reduces the breaking capacity of the arc-extinguishing chamber.

Structural and Chemical Evolution of Li- and Mn-rich Layered Cathode Material

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

Zheng, Jianming; Xu, Pinghong; Gu, Meng

2015-02-24

Lithium (Li)- and manganese-rich (LMR) layered-structure materials are very promising cathodes for high energy density lithium-ion batteries. However, their voltage fading mechanism and its relationships with fundamental structural changes are far from being sufficiently understood. Here we report the detailed phase transformation pathway in the LMR cathode (Li[Li0.2Ni0.2Mn0.6]O2) during cycling for the samples prepared by hydro-thermal assistant method. It is found the transformation pathway of LMR cathode is closely correlated to its initial structure and preparation conditions. The results reveal that LMR cathode prepared by HA approach experiences a phase transformation from the layered structure to a LT-LiCoO2 type defectmore » spinel-like structure (Fd-3m space group) and then to a disordered rock-salt structure (Fm-3m space group). The voltage fade can be well correlated with the Li ion insertion into octahedral sites, rather than tetrahedral sites, in both defect spinel-like structure and disordered rock-salt structure. The reversible Li insertion/removal into/from the disordered rock-salt structure is ascribed to the Li excess environment that can satisfy the Li percolating in the disordered rock-salt structure despite the increased kinetic barrier. Meanwhile, because of the presence of a great amount of oxygen vacancies, a significant decrease of Mn valence is detected in the cycled particle, which is below that anticipated for a potentially damaging Jahn-Teller distortion (+3.5). Clarification of the phase transformation pathway, cation redistribution, oxygen vacancy and Mn valence change undoubtedly provides insights into a profound understanding on the voltage fade, and capacity degradation of LMR cathode. The results also inspire us to further enhance the reversibility of LMR cathode via improving its surface structural stability.« less

High rate, long cycle life battery electrode materials with an open framework structure

DOEpatents

Wessells, Colin; Huggins, Robert; Cui, Yi; Pasta, Mauro

2015-02-10

A battery includes a cathode, an anode, and an aqueous electrolyte disposed between the cathode and the anode and including a cation A. At least one of the cathode and the anode includes an electrode material having an open framework crystal structure into which the cation A is reversibly inserted during operation of the battery. The battery has a reference specific capacity when cycled at a reference rate, and at least 75% of the reference specific capacity is retained when the battery is cycled at 10 times the reference rate.

An artificial interphase enables reversible magnesium chemistry in carbonate electrolytes.

PubMed

Son, Seoung-Bum; Gao, Tao; Harvey, Steve P; Steirer, K Xerxes; Stokes, Adam; Norman, Andrew; Wang, Chunsheng; Cresce, Arthur; Xu, Kang; Ban, Chunmei

2018-05-01

Magnesium-based batteries possess potential advantages over their lithium counterparts. However, reversible Mg chemistry requires a thermodynamically stable electrolyte at low potential, which is usually achieved with corrosive components and at the expense of stability against oxidation. In lithium-ion batteries the conflict between the cathodic and anodic stabilities of the electrolytes is resolved by forming an anode interphase that shields the electrolyte from being reduced. This strategy cannot be applied to Mg batteries because divalent Mg 2+ cannot penetrate such interphases. Here, we engineer an artificial Mg 2+ -conductive interphase on the Mg anode surface, which successfully decouples the anodic and cathodic requirements for electrolytes and demonstrate highly reversible Mg chemistry in oxidation-resistant electrolytes. The artificial interphase enables the reversible cycling of a Mg/V 2 O 5 full-cell in the water-containing, carbonate-based electrolyte. This approach provides a new avenue not only for Mg but also for other multivalent-cation batteries facing the same problems, taking a step towards their use in energy-storage applications.

An artificial interphase enables reversible magnesium chemistry in carbonate electrolytes

NASA Astrophysics Data System (ADS)

Son, Seoung-Bum; Gao, Tao; Harvey, Steve P.; Steirer, K. Xerxes; Stokes, Adam; Norman, Andrew; Wang, Chunsheng; Cresce, Arthur; Xu, Kang; Ban, Chunmei

2018-05-01

Magnesium-based batteries possess potential advantages over their lithium counterparts. However, reversible Mg chemistry requires a thermodynamically stable electrolyte at low potential, which is usually achieved with corrosive components and at the expense of stability against oxidation. In lithium-ion batteries the conflict between the cathodic and anodic stabilities of the electrolytes is resolved by forming an anode interphase that shields the electrolyte from being reduced. This strategy cannot be applied to Mg batteries because divalent Mg2+ cannot penetrate such interphases. Here, we engineer an artificial Mg2+-conductive interphase on the Mg anode surface, which successfully decouples the anodic and cathodic requirements for electrolytes and demonstrate highly reversible Mg chemistry in oxidation-resistant electrolytes. The artificial interphase enables the reversible cycling of a Mg/V2O5 full-cell in the water-containing, carbonate-based electrolyte. This approach provides a new avenue not only for Mg but also for other multivalent-cation batteries facing the same problems, taking a step towards their use in energy-storage applications.

Toward Theoretically Cycling-Stable Lithium-Sulfur Battery Using a Foldable and Compositionally Heterogeneous Cathode.

PubMed

Zhong, Lei; Yang, Kai; Guan, Ruiteng; Wang, Liangbin; Wang, Shuanjin; Han, Dongmei; Xiao, Min; Meng, Yuezhong

2017-12-20

Rechargeable lithium-sulfur (Li-S) batteries have been expected for new-generation electrical energy storages, which are attributed to their high theoretical energy density, cost effectiveness, and eco-friendliness. But Li-S batteries still have some problems for practical application, such as low sulfur utilization and dissatisfactory capacity retention. Herein, we designed and fabricated a foldable and compositionally heterogeneous three-dimensional sulfur cathode with integrated sandwich structure. The electrical conductivity of the cathode is facilitated by three different dimension carbons, in which short-distance and long-distance pathways for electrons are provided by zero-dimensional ketjen black (KB), one-dimensional activated carbon fiber (ACF) and two-dimensional graphene (G). The resultant three-dimensional sulfur cathode (T-AKG/KB@S) with an areal sulfur loading of 2 mg cm -2 exhibits a high initial specific capacity, superior rate performance and a reversible discharge capacity of up to 726 mAh g -1 at 3.6 mA cm -2 with an inappreciable capacity fading rate of 0.0044% per cycle after 500 cycles. Moreover, the cathode with a high areal sulfur loading of 8 mg cm -2 also delivers a reversible discharge capacity of 938 mAh g -1 at 0.71 mA cm -2 with a capacity fading rate of 0.15% per cycle and a Coulombic efficiency of almost 100% after 50 cycles.

Reversing the direction of galvanotaxis with controlled increases in boundary layer viscosity

NASA Astrophysics Data System (ADS)

Kobylkevich, Brian M.; Sarkar, Anyesha; Carlberg, Brady R.; Huang, Ling; Ranjit, Suman; Graham, David M.; Messerli, Mark A.

2018-05-01

Weak external electric fields (EFs) polarize cellular structure and direct most migrating cells (galvanotaxis) toward the cathode, making it a useful tool during tissue engineering and for healing epidermal wounds. However, the biophysical mechanisms for sensing weak EFs remain elusive. We have reinvestigated the mechanism of cathode-directed water flow (electro-osmosis) in the boundary layer of cells, by reducing it with neutral, viscous polymers. We report that increasing viscosity with low molecular weight polymers decreases cathodal migration and promotes anodal migration in a concentration dependent manner. In contrast, increased viscosity with high molecular weight polymers does not affect directionality. We explain the contradictory results in terms of porosity and hydraulic permeability between the polymers rather than in terms of bulk viscosity. These results provide the first evidence for controlled reversal of galvanotaxis using viscous agents and position the field closer to identifying the putative electric field receptor, a fundamental, outside-in signaling receptor that controls cellular polarity for different cell types.

Reversing the direction of galvanotaxis with controlled increases in boundary layer viscosity.

PubMed

Kobylkevich, Brian M; Sarkar, Anyesha; Carlberg, Brady R; Huang, Ling; Ranjit, Suman; Graham, David M; Messerli, Mark A

2018-03-09

Weak external electric fields (EFs) polarize cellular structure and direct most migrating cells (galvanotaxis) toward the cathode, making it a useful tool during tissue engineering and for healing epidermal wounds. However, the biophysical mechanisms for sensing weak EFs remain elusive. We have reinvestigated the mechanism of cathode-directed water flow (electro-osmosis) in the boundary layer of cells, by reducing it with neutral, viscous polymers. We report that increasing viscosity with low molecular weight polymers decreases cathodal migration and promotes anodal migration in a concentration dependent manner. In contrast, increased viscosity with high molecular weight polymers does not affect directionality. We explain the contradictory results in terms of porosity and hydraulic permeability between the polymers rather than in terms of bulk viscosity. These results provide the first evidence for controlled reversal of galvanotaxis using viscous agents and position the field closer to identifying the putative electric field receptor, a fundamental, outside-in signaling receptor that controls cellular polarity for different cell types.

Enabling the high capacity of lithium-rich anti-fluorite lithium iron oxide by simultaneous anionic and cationic redox

NASA Astrophysics Data System (ADS)

Zhan, Chun; Yao, Zhenpeng; Lu, Jun; Ma, Lu; Maroni, Victor A.; Li, Liang; Lee, Eungje; Alp, Esen E.; Wu, Tianpin; Wen, Jianguo; Ren, Yang; Johnson, Christopher; Thackeray, Michael M.; Chan, Maria K. Y.; Wolverton, Chris; Amine, Khalil

2017-12-01

Anionic redox reactions in cathodes of lithium-ion batteries are allowing opportunities to double or even triple the energy density. However, it is still challenging to develop a cathode, especially with Earth-abundant elements, that enables anionic redox activity for real-world applications, primarily due to limited strategies to intercept the oxygenates from further irreversible oxidation to O2 gas. Here we report simultaneous iron and oxygen redox activity in a Li-rich anti-fluorite Li5FeO4 electrode. During the removal of the first two Li ions, the oxidation potential of O2- is lowered to approximately 3.5 V versus Li+/Li0, at which potential the cationic oxidation occurs concurrently. These anionic and cationic redox reactions show high reversibility without any obvious O2 gas release. Moreover, this study provides an insightful guide to designing high-capacity cathodes with reversible oxygen redox activity by simply introducing oxygen ions that are exclusively coordinated by Li+.

Highly improved voltage efficiency of seawater battery by use of chloride ion capturing electrode

NASA Astrophysics Data System (ADS)

Kim, Kyoungho; Hwang, Soo Min; Park, Jeong-Sun; Han, Jinhyup; Kim, Junsoo; Kim, Youngsik

2016-05-01

Cost-effective and eco-friendly battery system with high energy density is highly desirable. Herein, we report a seawater battery with a high voltage efficiency, in which a chloride ion-capturing electrode (CICE) consisting of Ag foil is utilized as the cathode. The use of Ag as the cathode leads to a sharp decrease in the voltage gaps between charge and discharge curves, based on reversible redox reaction of Ag/AgCl (at ∼2.9 V vs. Na+/Na) in a seawater catholyte during cycling. The Ag/AgCl reaction proves to be highly reversible during battery cycling. The battery employing the Ag electrode shows excellent cycling performance with a high Coulombic efficiency (98.6-98.7%) and a highly improved voltage efficiency (90.3% compared to 73% for carbonaceous cathode) during 20 cycles (total 500 h). These findings demonstrate that seawater batteries using a CICE could be used as next-generation batteries for large-scale stationary energy storage plants.

Electrochemically Driven Deactivation and Recovery in PrBaCo2 O5+δ Oxygen Electrodes for Reversible Solid Oxide Fuel Cells.

PubMed

Zhu, Lin; Wei, Bo; Wang, Zhihong; Chen, Kongfa; Zhang, Haiwu; Zhang, Yaohui; Huang, Xiqiang; Lü, Zhe

2016-09-08

The understanding of surface chemistry changes on oxygen electrodes is critical for the development of reversible solid oxide fuel cell (RSOFC). Here, we report for the first time that the electrochemical potentials can drastically affect the surface composition and hence the electrochemical activity and stability of PrBaCo2 O5+δ (PBCO) electrodes. Anodic polarization degrades the activity of the PBCO electrode, whereas the cathodic bias could recover its performance. Alternating anodic/cathodic polarization for 180 h confirms this behavior. Microstructure and chemical analysis clearly show that anodic bias leads to the accumulation and segregation of insulating nanosized BaO on the electrode surface, whereas cathodic polarization depletes the surface species. Therefore, a mechanism based on the segregation and incorporation of BaO species under electrochemical potentials is considered to be responsible for the observed deactivation and recovery process, respectively. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Method for improving fuel cell performance

DOEpatents

Uribe, Francisco A.; Zawodzinski, Thomas

2003-10-21

A method is provided for operating a fuel cell at high voltage for sustained periods of time. The cathode is switched to an output load effective to reduce the cell voltage at a pulse width effective to reverse performance degradation from OH adsorption onto cathode catalyst surfaces. The voltage is stepped to a value of less than about 0.6 V to obtain the improved and sustained performance.

Electromigration effect on intermetallic growth and Young's modulus in SAC solder joint

NASA Astrophysics Data System (ADS)

Xu, Luhua; Pang, John H. L.; Ren, Fei; Tu, K. N.

2006-12-01

Solid-state intermetallic compound (IMC) growth behavior plays and important role in solder joint reliability of electronic packaging assemblies. The directional impact of electromigration (EM) on the growth of interfacial IMCs in Ni/SAC/Ni, Cu/SAC/Ni single BGA ball solder joint, and fine pitch ball-grid-array (FPBGA) at the anode and cathode sides is reported in this study. When the solder joint was subjected to a current density of 5,000 A/cm2 at 125°C or 150°C, IMC layer growth on the anode interface was faster than that on the cathode interface, and both were faster than isothermal aging due to the Joule heating effect. The EM affects the IMC growth rate, as well as the composition and mechanical properties. The Young’s modulus and hardness were measured by the nanoindentation continuous stiffness measurement (CSM) from planar IMC surfaces after EM exposure. Different values were observed at the anode and cathode. The energy-dispersive x-ray (EDX) line scan analysis was conducted at the interface from the cathode to anode to study the presence of species; Ni was found in the anode IMC at SAC/Cu in the Ni/SAC/Cu joint, but not detected when the current was reverse. Electron-probe microanalysis (EPMA) measurement on the Ni/SAC/Ni specimen also confirmed the polarized Ni and Cu distributions in cathode and anode IMCs, which were (Ni0.57Cu0.43)3Sn4 and (Cu0.73Ni0.27)6Sn5, respectively. Thus, the Young’s moduli of the IMC are 141 and 175 GPa, respectively.

MnO2-graphene nanosheets wrapped mesoporous carbon/sulfur composite for lithium-sulfur batteries

NASA Astrophysics Data System (ADS)

Li, Zhengzheng

2018-02-01

MnO2-graphene nanosheets wrapped mesoporous carbon/sulfur (MGN@MC/S) composite is successfully synthesized derived from metal-organic frameworks and investigated as cathode for lithium-ion batteries. Used as cathode, MGN@MC/S composite possesses electronic conductivity network for redox electron transfer and strong chemical bonding to lithium polysulfides, which enables low capacity loss to be achieved. MGN@MC/S cathodes exhibit high reversible capacity of 1475 mA h g-1 at 0.1 C and an ultra-low capacity fading of 0.042% per cycle at 1 C over 450 cycles.

Spatiotemporal character of the Bobylev-Pikin flexoelectric instability in a twisted nematic bent-core liquid crystal exposed to very low frequency fields.

PubMed

Krishnamurthy, K S

2014-05-01

The Bobylev-Pikin striped-pattern state induced by a homogeneous electric field is a volume flexoelectric instability, originating in the midregion of a planarly aligned nematic liquid crystal layer. We find that the instability acquires a spatiotemporal character upon excitation by a low frequency (0.5 Hz) square wave field. This is demonstrated using a bent-core liquid crystal, initially in the 90°-twisted planar configuration. The flexoelectric modulation appears close to the cathode at each polarity reversal and, at low voltage amplitudes, decays completely as the field becomes steady. Correspondingly, at successive polarity changes, the stripe direction switches between the alignment directions at the two substrates. For large voltages, the stripes formed nearly along the alignment direction at the cathode gradually reorient toward the midplane director. These observations are generally attributed to inhomogeneous and time-dependent field conditions that come to exist after each polarity reversal. Polarity dependence of the instability is attributed to the formation of intrinsic double layers that bring about an asymmetry in surface fields. Momentary field elevation near the cathode following a voltage sign reversal and concomitant gradient flexoelectric polarization are considered the key factors in accounting for the surfacelike modulation observed at low voltages.

L-lactic acid and sodium p-toluenesulfonate co-doped polypyrrole for high performance cathode in sodium ion battery

NASA Astrophysics Data System (ADS)

Liao, Qishu; Hou, Hongying; Liu, Xianxi; Yao, Yuan; Dai, Zhipeng; Yu, Chengyi; Li, Dongdong

2018-04-01

In this work, polypyrrole (PPy) was co-doped with L-lactic acid (LA) and sodium p-toluenesulfonate (TsONa) for high performance cathode in sodium ion battery (SIB) via facile one-step electropolymerization on Fe foil. The as-synthesized LA/TsONa co-doped PPy cathode was investigated in terms of scanning electron microscope (SEM), Fourier transform infrared spectroscopy (FTIR), galvanostatic charge/discharge and cyclic voltammetry (CV). The results suggested that some oval-bud-like LA/TsONa co-doped PPy particles did form and tightly combine with the surface of Fe foil; furthermore, LA/TsONa co-doped PPy cathode also delivered higher electrochemical performances than TsONa mono-doped PPy cathode. For example, the initial specific discharge capacity was as high as about 124 mAh/g, and the reversible specific capacity still maintained at about 110 mAh/g even after 50 cycles, higher than those of TsONa mono-doped PPy cathode. The synergy effect of multi components of LA/TsONa co-doped PPy cathode should be responsible for high electrochemical performances.

Utilizing Co 2+/Co 3+ Redox Couple in P2-Layered Na 0.66Co 0.22Mn 0.44Ti 0.34O 2 Cathode for Sodium-Ion Batteries

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

Wang, Qin-Chao; Hu, Enyuan; Pan, Yang

Developing sodium-ion batteries for large-scale energy storage applications is facing big challenges of the lack of high-performance cathode materials. Here, a series of new cathode materials Na 0.66Co xMn 0.66–xTi 0.34O 2 for sodium-ion batteries are designed and synthesized aiming to reduce transition metal-ion ordering, charge ordering, as well as Na+ and vacancy ordering. An interesting structure change of Na 0.66Co xMn 0.66–xTi 0.34O 2 from orthorhombic to hexagonal is revealed when Co content increases from x = 0 to 0.33. In particular, Na 0.66Co 0.22Mn 0.44Ti 0.34O 2 with a P2-type layered structure delivers a reversible capacity of 120more » mAh g -1 at 0.1 C. When the current density increases to 10 C, a reversible capacity of 63.2 mAh g -1 can still be obtained, indicating a promising rate capability. The low valence Co 2+ substitution results in the formation of average Mn 3.7+ valence state in Na 0.66Co 0.22Mn 0.44Ti 0.34O 2, effectively suppressing the Mn3+-induced Jahn–Teller distortion, and in turn stabilizing the layered structure. X-ray absorption spectroscopy results suggest that the charge compensation of Na 0.66Co 0.22Mn 0.44Ti 0.34O 2 during charge/discharge is contributed by Co 2.2+/Co 3+ and Mn 3.3+/Mn 4+ redox couples. This is the first time that the highly reversible Co 2+/Co 3+ redox couple is observed in P2-layered cathodes for sodium-ion batteries. This finding may open new approaches to design advanced intercalation-type cathode materials.« less

Utilizing Co 2+/Co 3+ Redox Couple in P2-Layered Na 0.66Co 0.22Mn 0.44Ti 0.34O 2 Cathode for Sodium-Ion Batteries

DOE PAGES

Wang, Qin-Chao; Hu, Enyuan; Pan, Yang; ...

2017-07-06

Developing sodium-ion batteries for large-scale energy storage applications is facing big challenges of the lack of high-performance cathode materials. Here, a series of new cathode materials Na 0.66Co xMn 0.66–xTi 0.34O 2 for sodium-ion batteries are designed and synthesized aiming to reduce transition metal-ion ordering, charge ordering, as well as Na+ and vacancy ordering. An interesting structure change of Na 0.66Co xMn 0.66–xTi 0.34O 2 from orthorhombic to hexagonal is revealed when Co content increases from x = 0 to 0.33. In particular, Na 0.66Co 0.22Mn 0.44Ti 0.34O 2 with a P2-type layered structure delivers a reversible capacity of 120more » mAh g -1 at 0.1 C. When the current density increases to 10 C, a reversible capacity of 63.2 mAh g -1 can still be obtained, indicating a promising rate capability. The low valence Co 2+ substitution results in the formation of average Mn 3.7+ valence state in Na 0.66Co 0.22Mn 0.44Ti 0.34O 2, effectively suppressing the Mn3+-induced Jahn–Teller distortion, and in turn stabilizing the layered structure. X-ray absorption spectroscopy results suggest that the charge compensation of Na 0.66Co 0.22Mn 0.44Ti 0.34O 2 during charge/discharge is contributed by Co 2.2+/Co 3+ and Mn 3.3+/Mn 4+ redox couples. This is the first time that the highly reversible Co 2+/Co 3+ redox couple is observed in P2-layered cathodes for sodium-ion batteries. This finding may open new approaches to design advanced intercalation-type cathode materials.« less

Utilizing Co2+/Co3+ Redox Couple in P2-Layered Na0.66Co0.22Mn0.44Ti0.34O2 Cathode for Sodium-Ion Batteries.

PubMed

Wang, Qin-Chao; Hu, Enyuan; Pan, Yang; Xiao, Na; Hong, Fan; Fu, Zheng-Wen; Wu, Xiao-Jing; Bak, Seong-Min; Yang, Xiao-Qing; Zhou, Yong-Ning

2017-11-01

Developing sodium-ion batteries for large-scale energy storage applications is facing big challenges of the lack of high-performance cathode materials. Here, a series of new cathode materials Na 0.66 Co x Mn 0.66- x Ti 0.34 O 2 for sodium-ion batteries are designed and synthesized aiming to reduce transition metal-ion ordering, charge ordering, as well as Na + and vacancy ordering. An interesting structure change of Na 0.66 Co x Mn 0.66- x Ti 0.34 O 2 from orthorhombic to hexagonal is revealed when Co content increases from x = 0 to 0.33. In particular, Na 0.66 Co 0.22 Mn 0.44 Ti 0.34 O 2 with a P2-type layered structure delivers a reversible capacity of 120 mAh g -1 at 0.1 C. When the current density increases to 10 C, a reversible capacity of 63.2 mAh g -1 can still be obtained, indicating a promising rate capability. The low valence Co 2+ substitution results in the formation of average Mn 3.7+ valence state in Na 0.66 Co 0.22 Mn 0.44 Ti 0.34 O 2 , effectively suppressing the Mn 3+ -induced Jahn-Teller distortion, and in turn stabilizing the layered structure. X-ray absorption spectroscopy results suggest that the charge compensation of Na 0.66 Co 0.22 Mn 0.44 Ti 0.34 O 2 during charge/discharge is contributed by Co 2.2+ /Co 3+ and Mn 3.3+ /Mn 4+ redox couples. This is the first time that the highly reversible Co 2+ /Co 3+ redox couple is observed in P2-layered cathodes for sodium-ion batteries. This finding may open new approaches to design advanced intercalation-type cathode materials.

A Universal Organic Cathode for Ultrafast Lithium- and Multivalent Metal Batteries.

PubMed

Fan, Xiulin; Wang, Fei; Ji, Xiao; Wang, Ruixing; Gao, Tao; Hou, Singyuk; Chen, Ji; Deng, Tao; Li, Xiaogang; Chen, Long; Luo, Chao; Wang, Luning; Wang, Chunsheng

2018-04-27

Low-cost multivalent battery chemistries (Mg 2+ , Al 3+ ) have been extensively investigated for large-scale energy storage applications. However, their commercialization is plagued by the poor power density and cycle life of cathodes. A universal polyimides@CNT (PI@CNT) cathode is now presented that can reversibly store various cations with different valences (Li + , Mg 2+ , Al 3+ ) at an extremely fast rate. The ion-coordination charge storage mechanism of PI@CNT is systemically investigated. Full cells using PI@CNT cathodes and corresponding metal anodes exhibit long cycle life (>10000 cycles), fast kinetics (>20 C), and wide operating temperature range (-40 to 50 °C), making the low-cost industrial polyimides universal cathodes for different multivalent metal batteries. The stable ion-coordinated mechanism opens a new foundation for the development of high-energy and high-power multivalent batteries. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Rechargeable Lithium/Polymer Cathode Batteries

DTIC Science & Technology

1989-06-15

rechargeable lithium batteries. PPy films prepared with P-anion and/or t.substrate precoated with niLrile butadieve rubber ( NBR ) were excellent cathode...in the polymerization and with NBR (nitrile butadiene rubber )-guided- solution gives beautiful reversibility of anion grown method(4,5). Since an...Tokyo, Japan 169 density of 2.5 mA cm- 2 (3). Moreover, PPy prepa- ration through the host polymer of NBR insulat- SCorrosion Research Center, ing film

Reinvigorating Reverse-Osmosis Membrane Technology to Stabilize the V 2 O 5 Lithium-Ion Battery Cathode

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

Wu, Ji; Byrd, Ian; Jin, Congrui

V 2O 5 is deemed as one of the most promising cathode materials for next-generation high-capacity lithium-ion batteries (LIBs). It possesses a theoretical capacity of 294 mAh g -1, which is much higher than conventional cathodes. But, there are many issues to be solved before its practical use, including poor cycle life and unsatisfactory rate performance, mainly owing to its low electronic conductivity and ionic diffusivity, as well as structural instability. Our work reports three types of V 2O 5 asymmetric membranes synthesized by using an adapted reverse-osmosis membrane technology combined with sol-gel chemistry, aiming to stabilize the cyclability andmore » improve the rate performance. V 2O 5 asymmetric membrane cathodes prepared using graphene as the conductive additives have a specific capacity of approximately 160 mAh g -1 at a current density of 100 mA g -1 with no capacity degradation after 380 cycles. It is also found that the annealing temperature and the choice of conductive additives can affect the morphology of V 2O 5 nanoparticles and the overall electrode cyclability. Furthermore, we find that a lower annealing temperature (300 vs. 400 °C) and the addition of graphene are beneficial to long-term cycling performance.« less

Reinvigorating Reverse-Osmosis Membrane Technology to Stabilize the V 2 O 5 Lithium-Ion Battery Cathode

DOE PAGES

Wu, Ji; Byrd, Ian; Jin, Congrui; ...

2017-02-27

V 2O 5 is deemed as one of the most promising cathode materials for next-generation high-capacity lithium-ion batteries (LIBs). It possesses a theoretical capacity of 294 mAh g -1, which is much higher than conventional cathodes. But, there are many issues to be solved before its practical use, including poor cycle life and unsatisfactory rate performance, mainly owing to its low electronic conductivity and ionic diffusivity, as well as structural instability. Our work reports three types of V 2O 5 asymmetric membranes synthesized by using an adapted reverse-osmosis membrane technology combined with sol-gel chemistry, aiming to stabilize the cyclability andmore » improve the rate performance. V 2O 5 asymmetric membrane cathodes prepared using graphene as the conductive additives have a specific capacity of approximately 160 mAh g -1 at a current density of 100 mA g -1 with no capacity degradation after 380 cycles. It is also found that the annealing temperature and the choice of conductive additives can affect the morphology of V 2O 5 nanoparticles and the overall electrode cyclability. Furthermore, we find that a lower annealing temperature (300 vs. 400 °C) and the addition of graphene are beneficial to long-term cycling performance.« less

Application of M-type cathodes to high-power cw klystrons

NASA Astrophysics Data System (ADS)

Isagawa, S.; Higuchi, T.; Kobayashi, K.; Miyake, S.; Ohya, K.; Yoshida, M.

1999-05-01

Two types of high-power cw klystrons have been widely used at KEK in both TRISTAN and KEKB e +e - collider projects: one is a 0.8 MW/1.0 MW tube, called YK1302/YK1303 (Philips); the other is a 1.2 MW tube, called E3786/E3732 (Toshiba). Normally, the dispenser cathodes of the `B-type' and the `S-type' have been used, respectively, but for improved versions they have been replaced by low-temperature cathodes, called the `M-type'. An Os/Ru coating was applied to the former, whereas an Ir one was applied to the latter. Until now, all upgraded tubes installing M-type cathodes, 9 and 8 in number, respectively, have worked successfully without any dropout. A positive experience concerning the lifetime under real operation conditions has been obtained. M-type cathodes are, however, more easily poisoned. One tube installing an Os/Ru-coated cathode showed a gradual, and then sudden decrease in emission during an underheating test, although the emission could fortunately be recovered by aging at the KEK test field. Once sufficiently aged, the emission of an Ir-coated cathode proved to be very high and stable, and its lifetime is expected to be very long. One disadvantage of this cathode is, however, susceptibility to gas poisoning and the necessity of long-term initial aging. New techniques, like ion milling and fine-grained tungsten top layers, were not as successful as expected from their smaller scale applications to shorten the initial aging period. A burn-in process at higher cathode loading was efficient to make the poisoned cathode active and to decrease unwanted Wehnelt emission. On top of that, the emission cooling, and thus thermal conductivity near the emitting layer could play an important role in such large-current cathodes as ours.

An artificial interphase enables reversible magnesium chemistry in carbonate electrolytes

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

Son, Seoung-Bum; Gao, Tao; Harvey, Steve P.

Magnesium-based batteries possess potential advantages over their lithium counterparts. However, reversible Mg chemistry requires a thermodynamically stable electrolyte at low potential, which is usually achieved with corrosive components and at the expense of stability against oxidation. In lithium-ion batteries the conflict between the cathodic and anodic stabilities of the electrolytes is resolved by forming an anode interphase that shields the electrolyte from being reduced. This strategy cannot be applied to Mg batteries because divalent Mg2+ cannot penetrate such interphases. Here, we engineer an artificial Mg2+-conductive interphase on the Mg anode surface, which successfully decouples the anodic and cathodic requirements formore » electrolytes and demonstrate highly reversible Mg chemistry in oxidation-resistant electrolytes. The artificial interphase enables the reversible cycling of a Mg/V2O5 full-cell in the water-containing, carbonate-based electrolyte. This approach provides a new avenue not only for Mg but also for other multivalent-cation batteries facing the same problems, taking a step towards their use in energy-storage applications.« less

Degradation of oxygen reduction reaction kinetics in porous La0.6Sr0.4Co0.2Fe0.8O3-δ cathodes due to aging-induced changes in surface chemistry

NASA Astrophysics Data System (ADS)

Baqué, Laura C.; Soldati, Analía L.; Teixeira-Neto, Erico; Troiani, Horacio E.; Schreiber, Anja; Serquis, Adriana C.

2017-01-01

The modification of surface composition after long-term operation is one of the most reported degradation mechanisms of (La,Sr)(Co,Fe)O3-δ (LSCFO) cathodes for Solid Oxide Fuel Cells (SOFCs). Nevertheless, its effect on the oxygen reduction reaction kinetics of porous LSCFO cathodes has not been yet reliably established. In this work, La- and Sr-enrichment at the LSCFO surface of porous cathodes has been induced after 50 h aging at 800 °C under air. Such cation redistribution can extend up to ∼400 nm depth under the LSCFO surface as detected by high resolution Scanning Transmission Electron Microscopy-Energy Dispersive Spectroscopy maps acquired inside the cathode pores. The observed surface chemical changes hamper the oxygen surface exchange reaction at the LSCFO/gas interface. Accordingly, a suitable Electrochemical Impedance Spectroscopy analysis revealed that the oxygen ion conductivity remains practically unaltered during the aging treatment while the oxygen surface exchange resistance increases up to 1.8 times. As a result, the cathode impedance response deteriorates within the 10-0.1 Hz frequency range during the aging treatment, resulting in a total cathode area specific resistance increase of 150%. The methodology adopted has demonstrated to be very valuable for studying the degradation of SOFC cathodes produced by the modification of surface composition.

Burning lithium in CS 2 for high-performing compact Li 2S–graphene nanocapsules for Li–S–batteries

DOE PAGES

Tan, Guoqiang; Xu, Rui; Xing, Zhenyu; ...

2017-06-12

Here, tremendous efforts have been made to design the cathode of Li–S batteries to improve their energy density and cycling life. However, challenges remain in achieving fast electronic and ionic transport while accommodating the significant cathode volumetric change, especially for the cathode with a high practical mass loading. Here we report a cathode architecture, which is constructed by burning lithium foils in a CS 2 vapour. The obtained structure features crystalline Li 2S nanoparticles wrapped by few-layer graphene (Li 2S@graphene nanocapsules). Because of the improvement on the volumetric efficiency for accommodating sulfur active species and electrical properties, the cathode designmore » enables promising electrochemical performance. More notably, at a loading of 10 mg Li2S cm –2, the electrode exhibits a high reversible capacity of 1,160 mAh g –1s, namely, an area capacity of 8.1 mAh cm –2. Li 2S@graphene cathode demonstrates a great potential for Li-ion batteries, where the Li 2S@graphene-cathode//graphite-anode cell displays a high capacity of 730 mAh g –1s as well as stable cycle performance.« less

Burning lithium in CS 2 for high-performing compact Li 2S–graphene nanocapsules for Li–S–batteries

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

Tan, Guoqiang; Xu, Rui; Xing, Zhenyu

Here, tremendous efforts have been made to design the cathode of Li–S batteries to improve their energy density and cycling life. However, challenges remain in achieving fast electronic and ionic transport while accommodating the significant cathode volumetric change, especially for the cathode with a high practical mass loading. Here we report a cathode architecture, which is constructed by burning lithium foils in a CS 2 vapour. The obtained structure features crystalline Li 2S nanoparticles wrapped by few-layer graphene (Li 2S@graphene nanocapsules). Because of the improvement on the volumetric efficiency for accommodating sulfur active species and electrical properties, the cathode designmore » enables promising electrochemical performance. More notably, at a loading of 10 mg Li2S cm –2, the electrode exhibits a high reversible capacity of 1,160 mAh g –1s, namely, an area capacity of 8.1 mAh cm –2. Li 2S@graphene cathode demonstrates a great potential for Li-ion batteries, where the Li 2S@graphene-cathode//graphite-anode cell displays a high capacity of 730 mAh g –1s as well as stable cycle performance.« less

Burning lithium in CS2 for high-performing compact Li2 S-graphene nanocapsules for Li-S batteries

NASA Astrophysics Data System (ADS)

Tan, Guoqiang; Xu, Rui; Xing, Zhenyu; Yuan, Yifei; Lu, Jun; Wen, Jianguo; Liu, Cong; Ma, Lu; Zhan, Chun; Liu, Qi; Wu, Tianpin; Jian, Zelang; Shahbazian-Yassar, Reza; Ren, Yang; Miller, Dean J.; Curtiss, Larry A.; Ji, Xiulei; Amine, Khalil

2017-07-01

Tremendous efforts have been made to design the cathode of Li-S batteries to improve their energy density and cycling life. However, challenges remain in achieving fast electronic and ionic transport while accommodating the significant cathode volumetric change, especially for the cathode with a high practical mass loading. Here we report a cathode architecture, which is constructed by burning lithium foils in a CS2 vapour. The obtained structure features crystalline Li2S nanoparticles wrapped by few-layer graphene (Li2S@graphene nanocapsules). Because of the improvement on the volumetric efficiency for accommodating sulfur active species and electrical properties, the cathode design enables promising electrochemical performance. More notably, at a loading of 10 mgLi2S cm-2, the electrode exhibits a high reversible capacity of 1,160 mAh g-1s, namely, an area capacity of 8.1 mAh cm-2. Li2S@graphene cathode demonstrates a great potential for Li-ion batteries, where the Li2S@graphene-cathode//graphite-anode cell displays a high capacity of 730 mAh g-1s as well as stable cycle performance.

On the nanostructuring and catalytic promotion of intermediate temperature solid oxide fuel cell (IT-SOFC) cathodes

NASA Astrophysics Data System (ADS)

Serra, José M.; Buchkremer, Hans-Peter

Solid oxide fuel cells (SOFCs) are highly efficient energy converters for both stationary and mobile purposes. However, their market introduction still demands the reduction of manufacture costs and one possible way to reach this goal is the decrease of the operating temperatures, which entails the improvement of the cathode electrocatalytic properties. An ideal cathode material may have mixed ionic and electronic conductivity as well as proper catalytic properties. Nanostructuring and catalytic promotion of mixed conducting perovskites (e.g. La 0.58Sr 0.4Fe 0.8Co 0.2O 3- δ) seem to be promising approaches to overcoming cathode polarization problems and are briefly illustrated here. The preparation of nanostructured cathodes with relatively high surface area and enough thermal stability enables to improve the oxygen exchange rate and therefore the overall SOFC performance. A similar effect was obtained by catalytic promoting the perovskite surface, allowing decoupling the catalytic and ionic-transport properties in the cathode design. Noble metal incorporation may improve the reversibility of the reduction cycles involved in the oxygen reduction. Under the cathode oxidizing conditions, Pd seems to be partially dissolved in the perovskite structure and as a result very well dispersed.

Selenium and selenium-sulfur cathode materials for high-energy rechargeable magnesium batteries

NASA Astrophysics Data System (ADS)

Zhao-Karger, Zhirong; Lin, Xiu-Mei; Bonatto Minella, Christian; Wang, Di; Diemant, Thomas; Behm, R. Jürgen; Fichtner, Maximilian

2016-08-01

Magnesium (Mg) is an attractive metallic anode material for next-generation batteries owing to its inherent dendrite-free electrodeposition, high capacity and low cost. Here we report a new class of Mg batteries based on both elemental selenium (Se) and selenium-sulfur solid solution (SeS2) cathode materials. Elemental Se confined into a mesoporous carbon was used as a cathode material. Coupling the Se cathode with a metallic Mg anode in a non-nucleophilic electrolyte, the Se cathode delivered a high initial volumetric discharge capacity of 1689 mA h cm-3 and a reversible capacity of 480 mA h cm-3 was retained after 50 cycles at a high current density of 2 C. The mechanistic insights into the electrochemical conversion in Mg-Se batteries were investigated by microscopic and spectroscopic methods. The structural transformation of cyclic Se8 into chainlike Sen upon battery cycling was revealed by ex-situ Raman spectroscopy. In addition, the promising battery performance with a SeS2 cathode envisages the perspective of a series of SeSn cathode materials combining the benefits of both selenium and sulfur for high energy Mg batteries.

In situ stress measurements during electrochemical cycling of lithium-rich cathodes

DOE PAGES

Nation, Leah; Li, Juchuan; James, Christine; ...

2017-08-29

Layered lithium transition metal oxides (Li 1+xM 1-xO 2, M= Ni, Mn, Co) are attractive cathode materials for lithium-ion batteries due to their high reversible capacity but suffer from structural changes and voltage fade. In this study, we use stress as a novel way to track irreversible changes in Li 1.2Mn 0.55Ni 0.125Co 0.125O 2 (LR-NMC) cathodes. A unique and unpredicted stress signature is observed during the first delithiation. Initially, a tensile stress is observed, consistent with volume contraction from lithium removal, however, the stress reverses and becomes compressive with continued charging beyond 4 V vs Li/Li +, indicating volumemore » expansion; this phenomenon is present in the first cycle only. The origin of this irreversible stress during delithiation is likely oxygen loss and the resulting cation rearrangement. Here, Raman spectroscopy provides evidence of the layered-to-spinel phase transition after cycling in the LR-NMC films, as well as recovery of the original spectra upon re-annealing in an oxygen environment.« less

In situ stress measurements during electrochemical cycling of lithium-rich cathodes

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

Nation, Leah; Li, Juchuan; James, Christine

Layered lithium transition metal oxides (Li 1+xM 1-xO 2, M= Ni, Mn, Co) are attractive cathode materials for lithium-ion batteries due to their high reversible capacity but suffer from structural changes and voltage fade. In this study, we use stress as a novel way to track irreversible changes in Li 1.2Mn 0.55Ni 0.125Co 0.125O 2 (LR-NMC) cathodes. A unique and unpredicted stress signature is observed during the first delithiation. Initially, a tensile stress is observed, consistent with volume contraction from lithium removal, however, the stress reverses and becomes compressive with continued charging beyond 4 V vs Li/Li +, indicating volumemore » expansion; this phenomenon is present in the first cycle only. The origin of this irreversible stress during delithiation is likely oxygen loss and the resulting cation rearrangement. Here, Raman spectroscopy provides evidence of the layered-to-spinel phase transition after cycling in the LR-NMC films, as well as recovery of the original spectra upon re-annealing in an oxygen environment.« less

In situ stress measurements during electrochemical cycling of lithium-rich cathodes

NASA Astrophysics Data System (ADS)

Nation, Leah; Li, Juchuan; James, Christine; Qi, Yue; Dudney, Nancy; Sheldon, Brian W.

2017-10-01

Layered lithium transition metal oxides (Li1+xM1-xO2, M = Ni, Mn, Co) are attractive cathode materials for lithium-ion batteries due to their high reversible capacity. However, they suffer from structural changes that lead to substantial voltage fade. In this study, we use stress as a novel way to track irreversible changes in Li1.2Mn0.55Ni0.125Co0.125O2 (LR-NMC) cathodes. A unique and unpredicted stress signature is observed during the first delithiation. Initially, a tensile stress is observed, consistent with volume contraction from lithium removal, however, the stress reverses and becomes compressive with continued charging beyond 4 V vs Li/Li+, indicating volume expansion; this phenomenon is present in the first cycle only. This irreversible stress during delithiation is likely to be at least partially due to oxygen loss and the resulting cation rearrangement. Raman spectroscopy provides evidence of the layered-to-spinel phase transition after cycling in the LR-NMC films, as well as recovery of the original spectra upon re-annealing in an oxygen environment.

Copper sulfates as cathode materials for Li batteries

NASA Astrophysics Data System (ADS)

Schwieger, Jonathan N.; Kraytsberg, Alexander; Ein-Eli, Yair

As lithium battery technology sets out to bridge the gap between portable electronics and the electrical automotive industry, cathode materials still stand as the bottleneck regarding performances. In the realm of highly attractive polyanion-type structures as high-voltage cathode materials, the sulfate group (SO 4) 2- possesses an acknowledged superiority over other contenders in terms of open circuit voltage arising from the inductive effect of strong covalent S-O bonds. In parallel, novel lithium insertion mechanisms are providing alternatives to traditional intercalation, enabling reversible multi-electron processes securing high capacities. Combining both of these advantageous features, we report here the successful electrochemical reactivity of copper sulfate pentahydrate (CuSO 4·5H 2O) with respect to lithium insertion via a two-electron displacement reaction entailing the extrusion of metallic copper at a dual voltage of 3.2 V and 2.7 V followed by its reversible insertion at 3.5 V and 3.8 V. At this stage, cyclability was still shown to be limited due to the irreversible degradation to a monohydrate structure owing to constitutional water loss.

Regenerable Cu-intercalated MnO2 layered cathode for highly cyclable energy dense batteries

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

Yadav, Gautam G.; Gallaway, Joshua W.; Turney, Damon E.

2017-03-06

Manganese dioxide cathodes are inexpensive and have high theoretical capacity (based on two electrons) of 617 mAh g-1, making them attractive for low-cost, energy-dense batteries. They are used in non-rechargeable batteries with anodes like zinc. Only ~10% of the theoretical capacity is currently accessible in rechargeable alkaline systems. Attempts to access the full capacity using additives have been unsuccessful. We report a class of Bi-birnessite (a layered manganese oxide polymorph mixed with bismuth oxide (Bi2O3)) cathodes intercalated with Cu2+ that deliver near-full two-electron capacity reversibly for >6,000 cycles. The key to rechargeability lies in exploiting the redox potentials of Cumore » to reversibly intercalate into the Bi-birnessite-layered structure during its dissolution and precipitation process for stabilizing and enhancing its charge transfer characteristics. This process holds promise for other applications like catalysis and intercalation of metal ions into layered structures. A large prismatic rechargeable Zn-birnessite cell delivering ~140 Wh l-1 is shown.« less

Cu2+ Dual-Doped Layer-Tunnel Hybrid Na0.6Mn1- xCu xO2 as a Cathode of Sodium-Ion Battery with Enhanced Structure Stability, Electrochemical Property, and Air Stability.

PubMed

Chen, Ting-Ru; Sheng, Tian; Wu, Zhen-Guo; Li, Jun-Tao; Wang, En-Hui; Wu, Chun-Jin; Li, Hong-Tai; Guo, Xiao-Dong; Zhong, Ben-He; Huang, Ling; Sun, Shi-Gang

2018-03-28

Sodium-ion batteries (SIBs) have been regarded as a promising candidate for large-scale renewable energy storage system. Layered manganese oxide cathode possesses the advantages of high energy density, low cost and natural abundance while suffering from limited cycling life and poor rate capacity. To overcome these weaknesses, layer-tunnel hybrid material was developed and served as the cathode of SIB, which integrated high capacity, superior cycle ability, and rate performance. In the current work, the doping of copper was adopted to suppress the Jahn-Teller effect of Mn 3+ and to affect relevant structural parameters. Multifunctions of the Cu 2+ doping were carefully investigated. It was found that the structure component ratio is varied with the Cu 2+ doping amount. Results demonstrated that Na + /vacancy rearrangement and phase transitions were suppressed during cycling without sacrificing the reversible capacity and enhanced electrochemical performances evidenced with 96 mA h g -1 retained after 250 cycles at 4 C and 85 mA h g -1 at 8 C. Furthermore, ex situ X-ray diffraction has demonstrated high reversibility of the Na 0.6 Mn 0.9 Cu 0.1 O 2 cathode during Na + extraction/insertion processes and superior air stability that results in better storage properties. This study reveals that the Cu 2+ doping could be an effective strategy to tune the properties and related performances of Mn-based layer-tunnel hybrid cathode.

A New Sealed Lithium-Peroxide Battery with a Co-Doped Li2O Cathode in a Superconcentrated Lithium Bis(fluorosulfonyl)amide Electrolyte

PubMed Central

Okuoka, Shin-ichi; Ogasawara, Yoshiyuki; Suga, Yosuke; Hibino, Mitsuhiro; Kudo, Tetsuichi; Ono, Hironobu; Yonehara, Koji; Sumida, Yasutaka; Yamada, Yuki; Yamada, Atsuo; Oshima, Masaharu; Tochigi, Eita; Shibata, Naoya; Ikuhara, Yuichi; Mizuno, Noritaka

2014-01-01

We propose a new sealed battery operating on a redox reaction between an oxide (O2−) and a peroxide (O22−) with its theoretical specific energy of 2570 Wh kg−1 (897 mAh g−1, 2.87 V) and demonstrate that a Co-doped Li2O cathode exhibits a reversible capacity over 190 mAh g−1, a high rate capability, and a good cyclability with a superconcentrated lithium bis(fluorosulfonyl)amide electrolyte in acetonitrile. The reversible capacity is largely dominated by the O2−/O22− redox reaction between oxide and peroxide with some contribution of the Co2+/Co3+ redox reaction. PMID:25023009

Nickel hydroxide positive electrode for alkaline rechargeable battery

DOEpatents

Young, Kwo; Wang, Lixin; Mays, William; Reichman, Benjamin; Chao-Ian, Hu; Wong, Diana; Nei, Jean

2018-04-03

Certain nickel hydroxide active cathode materials for use in alkaline rechargeable batteries are capable of transferring >1.3 electrons per Ni atom under reversible electrochemical conditions. The specific capacity of the nickel hydroxide active materials is for example .gtoreq.325 mAh/g. The cathode active materials exhibit an additional discharge plateau near 0.8 V vs. a metal hydride (MH) anode. Ni in an oxidation state of less than 2, such as Ni.sup.1+, is able to participate in electrochemical reactions when using the present cathode active materials. It is possible that up to 2.3 electrons, up to 2.5 electrons or more may be transferred per Ni atom under electrochemical conditions.

Nickel hydroxide positive electrode for alkaline rechargeable battery

DOEpatents

Young, Kwo; Wang, Lixin; Mays, William; Reichman, Benjamin; Chao-Ian, Hu; Wong, Diana; Nei, Jean

2018-02-20

Certain nickel hydroxide active cathode materials for use in alkaline rechargeable batteries are capable of transferring >1.3 electrons per Ni atom under reversible electrochemical conditions. The specific capacity of the nickel hydroxide active materials is for example .gtoreq.325 mAh/g. The cathode active materials exhibit an additional discharge plateau near 0.8 V vs. a metal hydride (MH) anode. Ni in an oxidation state of less than 2, such as Ni.sup.1+, is able to participate in electrochemical reactions when using the present cathode active materials. It is possible that up to 2.3 electrons, up to 2.5 electrons or more may be transferred per Ni atom under electrochemical conditions.

Effect of Current Density and Plating Time on Cu Electroplating in TSV and Low Alpha Solder Bumping

NASA Astrophysics Data System (ADS)

Jung, Do-Hyun; Sharma, Ashutosh; Kim, Keong-Heum; Choo, Yong-Chul; Jung, Jae-Pil

2015-03-01

In this study, copper filling in through-silicon via (TSV) by pulse periodic reverse electroplating and low alpha solder bumping on Cu-filled TSVs was investigated. The via diameter and depth of TSV were 60 and 120 µm, respectively. The experimental results indicated that the thickness of electrodeposited copper layer increased with increasing cathodic current density and plating time. The electroplated Cu in TSV showed a typical bottom-up filling. A defectless, complete, and fast 100% Cu-filled TSV was achieved at cathodic and anodic current densities of -8 and 16 mA/cm2 for a plating time of 4 h, respectively. A sound low alpha solder ball, Sn-1.0 wt.% Ag-0.5 wt.% Cu (SAC 105) with a diameter of 83 µm and height of 66 µm was reflow processed at 245 °C on Cu-filled TSV. The Cu/solder joint interface was subjected to high temperature aging at 85 °C for 150 h, which showed an excellent bonding characteristic with minimum Cu-Sn intermetallic compounds growth.

Electrical current mediated interconversion between graphene oxide to reduced grapene oxide

NASA Astrophysics Data System (ADS)

Teoh, H. F.; Tao, Y.; Tok, E. S.; Ho, G. W.; Sow, C. H.

2011-04-01

In this work, we demonstrate that graphene oxide (GO) can be reversibly converted to reduced-graphene-oxide (rGO) through the use of electric current. Strong electric field could cause ionization of water molecules in air to generate H+ ions at cathode, causing GO to be reduced. When the bias is reversed, the same electrode becomes positive and OH- ions are produced. According to Le Chatelier Principle, it then favors the reverse reaction, converting rGO back to GO, GO+2H++2e-=>rGO+H2O. X-ray spectroscopy and Raman spectroscopy were carried to verify the conversion reversibility in the reversed process.

LiAl xCo 1- xO 2 as 4 V cathodes for lithium ion batteries

NASA Astrophysics Data System (ADS)

Huang, Haitao; Rao, G. V. Subba; Chowdari, B. V. R.

Nominal LiAl xCo 1- xO 2 with x ranging from 0.1 to 0.3 was prepared by heating mixture of Al(OH) 3, Co 3O 4 and LiOH at 750°C in air. The effect of substitution of non-transition metal, Al, in LiCoO 2 is investigated as a 4 V cathode for lithium ion. X-ray diffraction (XRD) indicates formation of a single phase (R3¯m) within this range of substitution. When cycled between 4.5 and 2.5 V vs. Li/Li + at a current density of 1 mA cm -2, the LiAl 0.15Co 0.85O 2 cathode exhibits reversible capacity of 160 mA h g -1 initially. XRD of the cathode made at the end of 10 cycles reveals no significant change on host structure.

Surface transformation by a “cocktail” solvent enables stable cathode materials for sodium ion batteries

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

Mu, Linqin; Rahman, Muhammad Mominur; Zhang, Yan

Coating the surfaces of active materials has become an effective and indispensable path towards the stable operation of practical rechargeable batteries. Improving the affordability of coating processes can bring enormous manufacturing advantages to battery applications. Here in this paper, we report a cheap, simple and efficient method to create conformal coating layers on the primary particles of sodium layered oxide materials for improving battery performance. Mimicking the cathode–electrolyte interfacial reaction in practical cells, we create conformal coating layers via the spontaneous reaction between the oxidative cathode surfaces and a cocktail of reductive organic solvents. The conformal coating layers consist ofmore » metal–organic compounds with reduced transition metal cations, i.e., artificial cathode–electrolyte interphases (CEIs). The cells containing these coated cathode materials deliver much improved cycle life while maintaining reasonably high reversible capacity and rate capability. Furthermore, the structural stability and water resistance are enhanced, which can practically help simplify the storage protocol of cathode powders prior to battery manufacturing. The surfaces of most oxide cathode materials (e.g., lithium cathodes and sodium cathodes) are highly oxidative, and thus we expect that the present method, with tailored experimental parameters, can be readily applied to most battery systems.« less

Surface transformation by a “cocktail” solvent enables stable cathode materials for sodium ion batteries

DOE PAGES

Mu, Linqin; Rahman, Muhammad Mominur; Zhang, Yan; ...

2018-01-09

Coating the surfaces of active materials has become an effective and indispensable path towards the stable operation of practical rechargeable batteries. Improving the affordability of coating processes can bring enormous manufacturing advantages to battery applications. Here in this paper, we report a cheap, simple and efficient method to create conformal coating layers on the primary particles of sodium layered oxide materials for improving battery performance. Mimicking the cathode–electrolyte interfacial reaction in practical cells, we create conformal coating layers via the spontaneous reaction between the oxidative cathode surfaces and a cocktail of reductive organic solvents. The conformal coating layers consist ofmore » metal–organic compounds with reduced transition metal cations, i.e., artificial cathode–electrolyte interphases (CEIs). The cells containing these coated cathode materials deliver much improved cycle life while maintaining reasonably high reversible capacity and rate capability. Furthermore, the structural stability and water resistance are enhanced, which can practically help simplify the storage protocol of cathode powders prior to battery manufacturing. The surfaces of most oxide cathode materials (e.g., lithium cathodes and sodium cathodes) are highly oxidative, and thus we expect that the present method, with tailored experimental parameters, can be readily applied to most battery systems.« less

Co-intercalation of Mg(2+) and Na(+) in Na(0.69)Fe2(CN)6 as a High-Voltage Cathode for Magnesium Batteries.

PubMed

Kim, Dong-Min; Kim, Youngjin; Arumugam, Durairaj; Woo, Sang Won; Jo, Yong Nam; Park, Min-Sik; Kim, Young-Jun; Choi, Nam-Soon; Lee, Kyu Tae

2016-04-06

Thanks to the advantages of low cost and good safety, magnesium metal batteries get the limelight as substituent for lithium ion batteries. However, the energy density of state-of-the-art magnesium batteries is not high enough because of their low operating potential; thus, it is necessary to improve the energy density by developing new high-voltage cathode materials. In this study, nanosized Berlin green Fe2(CN)6 and Prussian blue Na(0.69)Fe2(CN)6 are compared as high-voltage cathode materials for magnesium batteries. Interestingly, while Mg(2+) ions cannot be intercalated in Fe2(CN)6, Na(0.69)Fe2(CN)6 shows reversible intercalation and deintercalation of Mg(2+) ions, although they have the same crystal structure except for the presence of Na(+) ions. This phenomenon is attributed to the fact that Mg(2+) ions are more stable in Na(+)-containing Na(0.69)Fe2(CN)6 than in Na(+)-free Fe2(CN)6, indicating Na(+) ions in Na(0.69)Fe2(CN)6 plays a crucial role in stabilizing Mg(2+) ions. Na(0.69)Fe2(CN)6 delivers reversible capacity of approximately 70 mA h g(-1) at 3.0 V vs Mg/Mg(2+) and shows stable cycle performance over 35 cycles. Therefore, Prussian blue analogues are promising structures for high-voltage cathode materials in Mg batteries. Furthermore, this co-intercalation effect suggests new avenues for the development of cathode materials in hybrid magnesium batteries that use both Mg(2+) and Na(+) ions as charge carriers.

Polysulfide Binding to Several Nanoscale Magnéli Phases Synthesized in Carbon for Long-Life Lithium-Sulfur Battery Cathodes.

PubMed

Zubair, Usman; Amici, Julia; Francia, Carlotta; McNulty, David; Bodoardo, Silvia; O'Dwyer, Colm

2018-06-11

In Li-S batteries, it is important to ensure efficient reversible conversion of sulfur to lithium polysulfide (LiPS). Shuttling effects caused by LiPS dissolution can lead to reduced performance and cycle life. Although carbon materials rely on physical trapping of polysulfides, polar oxide surfaces can chemically bind LiPS to improve the stability of sulfur cathodes. We show a simple synthetic method that allows high sulfur loading into mesoporous carbon preloaded with spatially localized nanoparticles of several Magnéli-phase titanium oxide (Ti n O 2n-1 ). This material simultaneously suppresses polysulfide shuttling phenomena by chemically binding Li polysulfides onto several Magnéli-phase surfaces in a single cathode and ensures physical confinement of sulfur and LiPS. The synergy between chemical immobilization of significant quantities of LiPS at the surface of several Ti n O 2n-1 phases and physical entrapment results in coulombically efficient high-rate cathodes with long cycle life and high capacity. These cathodes function efficiently at low electrolyte-to-sulfur ratios to provide high gravimetric and volumetric capacities in comparison with their highly porous carbon counterparts. Assembled coin cells have an initial discharge capacity of 1100 mAh g -1 at 0.1C and maintain a reversible capacity of 520 mAh g -1 at 0.2C for more than 500 cycles. Even at 1C, the cell loses only 0.06 % per cycle for 1000 cycles with a coulombic efficiency close to 99 %. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Tracking Electron Uptake from a Cathode into Shewanella Cells: Implications for Energy Acquisition from Solid-Substrate Electron Donors

PubMed Central

Rajeev, Pournami; Jain, Abhiney; Pirbadian, Sahand; Okamoto, Akihiro; Gralnick, Jeffrey A.; El-Naggar, Mohamed Y.; Nealson, Kenneth H.

2018-01-01

ABSTRACT While typically investigated as a microorganism capable of extracellular electron transfer to minerals or anodes, Shewanella oneidensis MR-1 can also facilitate electron flow from a cathode to terminal electron acceptors, such as fumarate or oxygen, thereby providing a model system for a process that has significant environmental and technological implications. This work demonstrates that cathodic electrons enter the electron transport chain of S. oneidensis when oxygen is used as the terminal electron acceptor. The effect of electron transport chain inhibitors suggested that a proton gradient is generated during cathode oxidation, consistent with the higher cellular ATP levels measured in cathode-respiring cells than in controls. Cathode oxidation also correlated with an increase in the cellular redox (NADH/FMNH2) pool determined with a bioluminescence assay, a proton uncoupler, and a mutant of proton-pumping NADH oxidase complex I. This work suggested that the generation of NADH/FMNH2 under cathodic conditions was linked to reverse electron flow mediated by complex I. A decrease in cathodic electron uptake was observed in various mutant strains, including those lacking the extracellular electron transfer components necessary for anodic-current generation. While no cell growth was observed under these conditions, here we show that cathode oxidation is linked to cellular energy acquisition, resulting in a quantifiable reduction in the cellular decay rate. This work highlights a potential mechanism for cell survival and/or persistence on cathodes, which might extend to environments where growth and division are severely limited. PMID:29487241

Novel strategy to mitigate cathode catalyst degradation during air/air startup cycling via the atmospheric resistive switching mechanism of a hydrogen anode with a platinum catalyst supported on tantalum-doped titanium dioxide

NASA Astrophysics Data System (ADS)

Shintani, Haruhiko; Kojima, Yuya; Kakinuma, Katsuyoshi; Watanabe, Masahiro; Uchida, Makoto

2015-10-01

We propose a new strategy for alleviating the reverse current phenomenon using a unique ;atmospheric resistive switching mechanism; (ARSM) of a metal oxide semiconductor support, such that the electrical resistivity changes depending on the gas atmosphere. The membrane-electrode assembly (MEA) using Ta-doped TiO2-supported platinum (Pt/Ta-TiO2) as the anode catalyst showed approximately one order of magnitude greater resistance in air than in hydrogen. The overpotential of the hydrogen oxidation reaction was negligible up to at least 1.5 A cm-2. The losses of electrochemically active surface area and carbon corrosion of the cathode catalyst during air/air startup cycling were significantly suppressed by the use of the Pt/Ta-TiO2 anode. The decrease in the degradation is attributed to a reduction of the reverse current due to a low oxygen reduction reaction rate at the anode, which showed high resistivity in air. These results demonstrate the effectiveness of the ARSM in mitigating cathode catalyst degradation during air/air startup cycling.

PIC simulations of post-pulse field reversal and secondary ionization in nanosecond argon discharges

NASA Astrophysics Data System (ADS)

Kim, H. Y.; Gołkowski, M.; Gołkowski, C.; Stoltz, P.; Cohen, M. B.; Walker, M.

2018-05-01

Post-pulse electric field reversal and secondary ionization are investigated with a full kinetic treatment in argon discharges between planar electrodes on nanosecond time scales. The secondary ionization, which occurs at the falling edge of the voltage pulse, is induced by charge separation in the bulk plasma region. This process is driven by a reverse in the electric field from the cathode sheath to the formerly driven anode. Under the influence of the reverse electric field, electrons in the bulk plasma and sheath regions are accelerated toward the cathode. The electron movement manifests itself as a strong electron current generating high electron energies with significant electron dissipated power. Accelerated electrons collide with Ar molecules and an increased ionization rate is achieved even though the driving voltage is no longer applied. With this secondary ionization, in a single pulse (SP), the maximum electron density achieved is 1.5 times higher and takes a shorter time to reach using 1 kV 2 ns pulse as compared to a 1 kV direct current voltage at 1 Torr. A bipolar dual pulse excitation can increase maximum density another 50%–70% above a SP excitation and in half the time of RF sinusoidal excitation of the same period. The first field reversal is most prominent but subsequent field reversals also occur and correspond to electron temperature increases. Targeted pulse designs can be used to condition plasma density as required for fast discharge applications.

Stochastic model for the 3D microstructure of pristine and cyclically aged cathodes in Li-ion batteries

NASA Astrophysics Data System (ADS)

Kuchler, Klaus; Westhoff, Daniel; Feinauer, Julian; Mitsch, Tim; Manke, Ingo; Schmidt, Volker

2018-04-01

It is well-known that the microstructure of electrodes in lithium-ion batteries strongly affects their performance. Vice versa, the microstructure can exhibit strong changes during the usage of the battery due to aging effects. For a better understanding of these effects, mathematical analysis and modeling has turned out to be of great help. In particular, stochastic 3D microstructure models have proven to be a powerful and very flexible tool to generate various kinds of particle-based structures. Recently, such models have been proposed for the microstructure of anodes in lithium-ion energy and power cells. In the present paper, we describe a stochastic modeling approach for the 3D microstructure of cathodes in a lithium-ion energy cell, which differs significantly from the one observed in anodes. The model for the cathode data enhances the ideas of the anode models, which have been developed so far. It is calibrated using 3D tomographic image data from pristine as well as two aged cathodes. A validation based on morphological image characteristics shows that the model is able to realistically describe both, the microstructure of pristine and aged cathodes. Thus, we conclude that the model is suitable to generate virtual, but realistic microstructures of lithium-ion cathodes.

Sequential decolorization of azo dye and mineralization of decolorization liquid coupled with bioelectricity generation using a pH self-neutralized photobioelectrochemical system operated with polarity reversion.

PubMed

Sun, Jian; Hu, Yongyou; Li, Wanjun; Zhang, Yaping; Chen, Jie; Deng, Feng

2015-05-30

A novel photobioelectrochemical system (PBES) was developed by acclimating algal-bacterial biofilm in both anode and cathode using Chlorella vulgaris and indigenous wastewater bacteria as inoculums. The PBES was operated in polarity reversion mode depend on dark/light alternate reaction to achieve simultaneous pH self-neutralization, azo dye degradation (Congo red) and bioelectricity generation. The anodic accumulated acidity and cathodic accumulated alkalinity were self-neutralized after polarity reversion and hence eliminate the membrane pH gradient. The Congo red was first decolored in the dark anode and the resultant decolorization liquid was subsequently mineralized after the dark anode changing to the photo-biocathode. The presence of C. vulgaris significantly enhanced the two-stage degradation of Congo red, with 93% increases in decolorization rates and 8% increases in mineralization compared to the algae-free BES. The PBES continuously generated stable voltage output over four months under repeatedly reversion of polarity. The maximum power density produced before and after polarity reversion was 78 and 61 mW/m(2), respectively. The synergy between C. vulgaris and mixed bacteria was responsible for the successful operation of the PBES which can be potentially applied to treat wastewater containing azo dye with benefits of enhanced azo dye degradation, high net power output and buffer minimization. Copyright © 2015 Elsevier B.V. All rights reserved.

Why solid oxide cells can be reversibly operated in solid oxide electrolysis cell and fuel cell modes?

PubMed

Chen, Kongfa; Liu, Shu-Sheng; Ai, Na; Koyama, Michihisa; Jiang, San Ping

2015-12-14

High temperature solid oxide cells (SOCs) are attractive for storage and regeneration of renewable energy by operating reversibly in solid oxide electrolysis cell (SOEC) and solid oxide fuel cell (SOFC) modes. However, the stability of SOCs, particularly the deterioration of the performance of oxygen electrodes in the SOEC operation mode, is the most critical issue in the development of high performance and durable SOCs. In this study, we investigate in detail the electrochemical activity and stability of La0.8Sr0.2MnO3 (LSM) oxygen electrodes in cyclic SOEC and SOFC modes. The results show that the deterioration of LSM oxygen electrodes caused by anodic polarization can be partially or completely recovered by subsequent cathodic polarization. Using in situ assembled LSM electrodes without pre-sintering, we demonstrate that the deteriorated LSM/YSZ interface can be repaired and regenerated by operating the cells under cathodic polarization conditions. This study for the first time establishes the foundation for the development of truly reversible and stable SOCs for hydrogen fuel production and electricity generation in cyclic SOEC and SOFC operation modes.

Cathode materials review

NASA Astrophysics Data System (ADS)

Daniel, Claus; Mohanty, Debasish; Li, Jianlin; Wood, David L.

2014-06-01

The electrochemical potential of cathode materials defines the positive side of the terminal voltage of a battery. Traditionally, cathode materials are the energy-limiting or voltage-limiting electrode. One of the first electrochemical batteries, the voltaic pile invented by Alessandro Volta in 1800 (Phil. Trans. Roy. Soc. 90, 403-431) had a copper-zinc galvanic element with a terminal voltage of 0.76 V. Since then, the research community has increased capacity and voltage for primary (nonrechargeable) batteries and round-trip efficiency for secondary (rechargeable) batteries. Successful secondary batteries have been the lead-acid with a lead oxide cathode and a terminal voltage of 2.1 V and later the NiCd with a nickel(III) oxide-hydroxide cathode and a 1.2 V terminal voltage. The relatively low voltage of those aqueous systems and the low round-trip efficiency due to activation energies in the conversion reactions limited their use. In 1976, Wittingham (J. Electrochem. Soc., 123, 315) and Besenhard (J. Power Sources 1(3), 267) finally enabled highly reversible redox reactions by intercalation of lithium ions instead of by chemical conversion. In 1980, Goodenough and Mizushima (Mater. Res. Bull. 15, 783-789) demonstrated a high-energy and high-power LiCoO2 cathode, allowing for an increase of terminal voltage far beyond 3 V. Over the past four decades, the international research community has further developed cathode materials of many varieties. Current state-of-the-art cathodes demonstrate voltages beyond any known electrolyte stability window, bringing electrolyte research once again to the forefront of battery research.

Electrodeposited non-stoichiometric tungstic acid for electrochromic applications: film growth modes, crystal structure, redox behavior and stability

NASA Astrophysics Data System (ADS)

Pugolovkin, Leonid V.; Cherstiouk, Olga V.; Plyasova, Lyudmila M.; Molina, Irina Yu.; Kardash, Tatyana Yu.; Stonkus, Olga A.; Yatsenko, Dmitriy A.; Kaichev, Vasily V.; Tsirlina, Galina A.

2016-12-01

Bath composition for cathodic electrodeposition of non-stoichiometric hydrated tungstic acid with high electrochromic efficiency is optimized with account for selective electroreduction of certain isopolytungstates. XRD data for thin electrodeposited films and chemically synthesized bulk tungstic acid dihydrate are compared in the context of reversible oxidation and reduction in hydrogen atmosphere, in presence of Pt catalyst. XPS and TEM techniques are attracted to understand the nature of reversible and less reversible transformations of films in the course of their storage and operation.

Na4Mn9O18/Carbon Nanotube Composite as a High Electrochemical Performance Material for Aqueous Sodium-Ion Batteries.

PubMed

Yin, Fuxing; Liu, Zhengjun; Yang, Shuang; Shan, Zhenzhen; Zhao, Yan; Feng, Yuting; Zhang, Chengwei; Bakenov, Zhumabay

2017-10-17

The aqueous sodium-ion battery (ASIB) is one of the promising new energy storage systems owing to the abundant resources of sodium as well as efficiency and safety of electrolyte. Herein, we report an ASIB system with Na 4 Mn 9 O 18 /carbon nanotube (NMO/CNT) as cathode, metal Zn as anode and a novel Na + /Zn 2+ mixed ion as electrolyte. The NMO/CNT with microspherical structure is prepared by a simple spray-drying method. The prepared battery delivers a high reversible specific capacity and stable cyclability. Furthermore, the battery displays a stable reversible discharge capacity of 53.2 mAh g -1 even at a high current rate of 4 C after 150 cycles. Our results confirm that the NMO/CNT composite is a promising electrode cathode material for ASIBs.

M xMn 8O 16 (M = Ag or K) as promising cathode materials for secondary Mg based batteries: The role of the cation M

DOE PAGES

Huang, Jianping; Takeuchi, Esther S.; Altug S. Poyraz; ...

2016-01-01

Here, Ag xMn 8O 16 (Ag-OMS-2) and K xMn 8O 16 (K-OMS-2) were investigated as high voltage cathode materials for Mg based batteries. Both M xMn 8O 16 materials delivered high initial capacities (>180 mA h g –1), and K xMn 8O 16 showed high cycle stability with a reversible capacity of >170 mA h g –1 after 20 cycles.

High-energy lithium-ion battery using substituted LiCoPO4: From coin type to 1 Ah cell

NASA Astrophysics Data System (ADS)

Liu, D.; Zhu, W.; Kim, C.; Cho, M.; Guerfi, A.; Delp, S. A.; Allen, J. L.; Jow, T. R.; Zaghib, K.

2018-06-01

Cr, Fe and Si were added to improve the performance of olivine LiCoPO4 in cathodes for lithium-ion batteries. A substituted-LiCoPO4 in a half cell delivered a reversible capacity of 125 mAh/g at C/3 rate, with no capacity loss after over 100 cycles at 25 °C. The well-known capacity fade of LiCoPO4-based cathodes was almost completely eliminated by substituting Cr, Fe and Si.

Monitoring the Electrochemical Processes in the Lithium–Air Battery by Solid State NMR Spectroscopy

PubMed Central

2013-01-01

A multi-nuclear solid-state NMR approach is employed to investigate the lithium–air battery, to monitor the evolution of the electrochemical products formed during cycling, and to gain insight into processes affecting capacity fading. While lithium peroxide is identified by 17O solid state NMR (ssNMR) as the predominant product in the first discharge in 1,2-dimethoxyethane (DME) based electrolytes, it reacts with the carbon cathode surface to form carbonate during the charging process. 13C ssNMR provides evidence for carbonate formation on the surface of the carbon cathode, the carbonate being removed at high charging voltages in the first cycle, but accumulating in later cycles. Small amounts of lithium hydroxide and formate are also detected in discharged cathodes and while the hydroxide formation is reversible, the formate persists and accumulates in the cathode upon further cycling. The results indicate that the rechargeability of the battery is limited by both the electrolyte and the carbon cathode stability. The utility of ssNMR spectroscopy in directly detecting product formation and decomposition within the battery is demonstrated, a necessary step in the assessment of new electrolytes, catalysts, and cathode materials for the development of a viable lithium–oxygen battery. PMID:24489976

Rechargeable Batteries with High Energy Storage Activated by In-situ Induced Fluorination of Carbon Nanotube Cathode

PubMed Central

Cui, Xinwei; Chen, Jian; Wang, Tianfei; Chen, Weixing

2014-01-01

High performance rechargeable batteries are urgently demanded for future energy storage systems. Here, we adopted a lithium-carbon battery configuration. Instead of using carbon materials as the surface provider for lithium-ion adsorption and desorption, we realized induced fluorination of carbon nanotube array (CNTA) paper cathodes, with the source of fluoride ions from electrolytes, by an in-situ electrochemical induction process. The induced fluorination of CNTA papers activated the reversible fluorination/defluorination reactions and lithium-ion storage/release at the CNTA paper cathodes, resulting in a dual-storage mechanism. The rechargeable battery with this dual-storage mechanism demonstrated a maximum discharging capacity of 2174 mAh gcarbon−1 and a specific energy of 4113 Wh kgcarbon−1 with good cycling performance. PMID:24931036

Analysis of the aging/stability process of organic solar cells based on PTB7:[70]PCBM and an alternative free-vacuum deposited cathode: the effect of active layer scaling

NASA Astrophysics Data System (ADS)

Barreiro-Argüelles, Denisse; Ramos-Ortiz, Gabriel; Maldonado, José-Luis L.; Romero-Borja, Daniel; Meneses-Nava, Marco-Antonio; Pérez-Gutiérrez, Enrique

2017-08-01

The PV performance and aging/stability of organic photovoltaic (OPV) devices based on the well-known system PTB7:[70]PCBM and an alternative air-stable electrode deposited at room conditions are fully studied when the active area is scaled by a factor of 25. On the other hand, the aging/stability processes were also studied through single diode model, impedance spectroscopy and light-beam induced current (LBIC) measurements in accordance with the established ISOS-D1 (dark storage) and ISOS-L1 (illumination conditions) protocols. Results are a good indication that the alternative cathode Field's metal (FM) cathode works as an encapsulating material and provides excellent PV performance comparable with the common and costly high-vacuum evaporated Al cathode.

Scaled-down particle-in-cell simulation of cathode plasma expansion in magnetically insulated coaxial diode

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

Zhu, Danni; Zhang, Jun, E-mail: zhangjun@nudt.edu.cn; Zhong, Huihuang

2016-03-15

The expansion of cathode plasma in magnetically insulated coaxial diode (MICD) is investigated in theory and particle-in-cell (PIC) simulation. The temperature and density of the cathode plasma are about several eV and 10{sup 13}–10{sup 16 }cm{sup −3}, respectively, and its expansion velocity is of the level of few cm/μs. Through hydrodynamic theory analysis, expressions of expansion velocities in axial and radial directions are obtained. The characteristics of cathode plasma expansion have been simulated through scaled-down PIC models. Simulation results indicate that the expansion velocity is dominated by the ratio of plasma density other than the static electric field. The electric fieldmore » counteracts the plasma expansion reverse of it. The axial guiding magnetic field only reduces the radial transport coefficients by a correction factor, but not the axial ones. Both the outward and inward radial expansions of a MICD are suppressed by the much stronger guiding magnetic field and even cease.« less

Electrolytic recovery of reactor metal fuel

DOEpatents

Miller, W.E.; Tomczuk, Z.

1994-09-20

A new electrolytic process and apparatus are provided using sodium, cerium or a similar metal in alloy or within a sodium beta or beta[double prime]-alumina sodium ion conductor to electrolytically displace each of the spent fuel metals except for cesium and strontium on a selective basis from the electrolyte to an inert metal cathode. Each of the metals can be deposited separately. An electrolytic transfer of spent fuel into the electrolyte includes a sodium or cerium salt in the electrolyte with sodium or cerium alloy being deposited on the cathode during the transfer of the metals from the spent fuel. The cathode with the deposit of sodium or cerium alloy is then shunted to an anode and the reverse transfer is carried out on a selective basis with each metal being deposited separately at the cathode. The result is that the sodium or cerium needed for the process is regenerated in the first step and no additional source of these reactants is required. 2 figs.

Highly Cyclable Lithium-Sulfur Batteries with a Dual-Type Sulfur Cathode and a Lithiated Si/SiOx Nanosphere Anode.

PubMed

Lee, Sang-Kyu; Oh, Seung-Min; Park, Eunjun; Scrosati, Bruno; Hassoun, Jusef; Park, Min-Sik; Kim, Young-Jun; Kim, Hansu; Belharouak, Ilias; Sun, Yang-Kook

2015-05-13

Lithium-sulfur batteries could become an excellent alternative to replace the currently used lithium-ion batteries due to their higher energy density and lower production cost; however, commercialization of lithium-sulfur batteries has so far been limited due to the cyclability problems associated with both the sulfur cathode and the lithium-metal anode. Herein, we demonstrate a highly reliable lithium-sulfur battery showing cycle performance comparable to that of lithium-ion batteries; our design uses a highly reversible dual-type sulfur cathode (solid sulfur electrode and polysulfide catholyte) and a lithiated Si/SiOx nanosphere anode. Our lithium-sulfur cell shows superior battery performance in terms of high specific capacity, excellent charge-discharge efficiency, and remarkable cycle life, delivering a specific capacity of ∼750 mAh g(-1) over 500 cycles (85% of the initial capacity). These promising behaviors may arise from a synergistic effect of the enhanced electrochemical performance of the newly designed anode and the optimized layout of the cathode.

All-solid-state lithium organic battery with composite polymer electrolyte and pillar[5]quinone cathode.

PubMed

Zhu, Zhiqiang; Hong, Meiling; Guo, Dongsheng; Shi, Jifu; Tao, Zhanliang; Chen, Jun

2014-11-26

The cathode capacity of common lithium ion batteries (LIBs) using inorganic electrodes and liquid electrolytes must be further improved. Alternatively, all-solid-state lithium batteries comprising the electrode of organic compounds can offer much higher capacity. Herein, we successfully fabricated an all-solid-state lithium battery based on organic pillar[5]quinone (C35H20O10) cathode and composite polymer electrolyte (CPE). The poly(methacrylate) (PMA)/poly(ethylene glycol) (PEG)-LiClO4-3 wt % SiO2 CPE has an optimum ionic conductivity of 0.26 mS cm(-1) at room temperature. Furthermore, pillar[5]quinine cathode in all-solid-state battery rendered an average operation voltage of ∼2.6 V and a high initial capacity of 418 mAh g(-1) with a stable cyclability (94.7% capacity retention after 50 cycles at 0.2C rate) through the reversible redox reactions of enolate/quinonid carbonyl groups, showing favorable prospect for the device application with high capacity.

Electrolytic recovery of reactor metal fuel

DOEpatents

Miller, W.E.; Tomczuk, Z.

1993-02-03

This invention is comprised of a new electrolytic process and apparatus using sodium, cerium or a similar metal in an alloy or within a sodium beta or beta-alumina sodium ion conductor to electrolytically displace each of the spent fuel metals except for Cesium and strontium on a selective basis from the electrolyte to an inert metal cathode. Each of the metals can be deposited separately. An electrolytic transfer of spent fuel into the electrolyte includes a sodium or cerium salt in the electrolyte with sodium or cerium alloy being deposited on the cathode during the transfer of the metals from the spent fuel. The cathode with the deposit of sodium or cerium alloy is then changed to an anode and the reverse transfer is carried out on a selective basis with each metal being deposited separately at the cathode. The result is that the sodium or cerium needed for the process is regenerated in the first step and no additional source of these reactants is required.

Electrolytic recovery of reactor metal fuel

DOEpatents

Miller, William E.; Tomczuk, Zygmunt

1994-01-01

A new electrolytic process and apparatus are provided using sodium, cerium or a similar metal in alloy or within a sodium beta or beta"-alumina sodium ion conductor to electrolytically displace each of the spent fuel metals except for cesium and strontium on a selective basis from the electrolyte to an inert metal cathode. Each of the metals can be deposited separately. An electrolytic transfer of spent fuel into the electrolyte includes a sodium or cerium salt in the electrolyte with sodium or cerium alloy being deposited on the cathode during the transfer of the metals from the spent fuel. The cathode with the deposit of sodium or cerium alloy is then chanted to an anode and the reverse transfer is carried out on a selective basis with each metal being deposited separately at the cathode. The result is that the sodium or cerium needed for the process is regenerated in the first step and no additional source of these reactants is required.

A Host-Configured Lithium-Sulfur Cell Built on 3D Nickel Photonic Crystal with Superior Electrochemical Performances.

PubMed

Lin, Shengxuan; Yan, Yang; Cai, Zihe; Liu, Lin; Hu, Xiaobin

2018-04-18

The insulator of the sulfur cathode and the easy dendrites growth of the lithium anode are the main barriers for lithium-sulfur cells in commercial application. Here, a 3D NPC@S/3D NPC@Li full cell is reported based on 3D hierarchical and continuously porous nickel photonic crystal (NPC) to solve the problems of sulfur cathode and lithium anode at the same time. In this case, the 3D NPC@S cathode can not only offer a fast transfer of electron and lithium ion, but also effectively prevent the dissolution of polysulfides and the tremendous volume change during cycling, and the 3D NPC@Li anode can efficiently inhibit the growth of lithium dendrites and volume expansion, too. As a result, the cell exhibits a high reversible capacity of 1383 mAh g -1 at 0.5 C (the current density of 837 mA g -1 ), superior rate ability (the reversible capacity of 735 mAh g -1 at the extremely high current density of 16 750 mA g -1 ) with excellent coulombic efficiency of about 100% and an excellent cycle life over 500 cycles with only about 0.026% capacity loss per cycle. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Cathode materials review

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

Daniel, Claus, E-mail: danielc@ornl.gov; Mohanty, Debasish, E-mail: danielc@ornl.gov; Li, Jianlin, E-mail: danielc@ornl.gov

2014-06-16

The electrochemical potential of cathode materials defines the positive side of the terminal voltage of a battery. Traditionally, cathode materials are the energy-limiting or voltage-limiting electrode. One of the first electrochemical batteries, the voltaic pile invented by Alessandro Volta in 1800 (Phil. Trans. Roy. Soc. 90, 403-431) had a copper-zinc galvanic element with a terminal voltage of 0.76 V. Since then, the research community has increased capacity and voltage for primary (nonrechargeable) batteries and round-trip efficiency for secondary (rechargeable) batteries. Successful secondary batteries have been the lead-acid with a lead oxide cathode and a terminal voltage of 2.1 V andmore » later the NiCd with a nickel(III) oxide-hydroxide cathode and a 1.2 V terminal voltage. The relatively low voltage of those aqueous systems and the low round-trip efficiency due to activation energies in the conversion reactions limited their use. In 1976, Wittingham (J. Electrochem. Soc., 123, 315) and Besenhard (J. Power Sources 1(3), 267) finally enabled highly reversible redox reactions by intercalation of lithium ions instead of by chemical conversion. In 1980, Goodenough and Mizushima (Mater. Res. Bull. 15, 783-789) demonstrated a high-energy and high-power LiCoO{sub 2} cathode, allowing for an increase of terminal voltage far beyond 3 V. Over the past four decades, the international research community has further developed cathode materials of many varieties. Current state-of-the-art cathodes demonstrate voltages beyond any known electrolyte stability window, bringing electrolyte research once again to the forefront of battery research.« less

2013 Estorm - Invited Paper - Cathode Materials Review

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

Daniel, Claus; Mohanty, Debasish; Li, Jianlin

2014-01-01

The electrochemical potential of cathode materials defines the positive side of the terminal voltage of a battery. Traditionally, cathode materials are the energy-limiting or voltage-limiting electrode. One of the first electrochemical batteries, the voltaic pile invented by Alessandro Volta in 1800 (Phil. Trans. Roy. Soc. 90, 403 431) had a copper-zinc galvanic element with a terminal voltage of 0.76 V. Since then, the research community has increased capacity and voltage for primary (nonrechargeable) batteries and round-trip efficiency for secondary (rechargeable) batteries. Successful secondary batteries have been the lead acid with a lead oxide cathode and a terminal voltage of 2.1more » V and later the NiCd with a nickel(III) oxide hydroxide cathode and a 1.2 V terminal voltage. The relatively low voltage of those aqueous systems and the low round-trip efficiency due to activation energies in the conversion reactions limited their use. In 1976, Wittingham (J. Electrochem. Soc., 123, 315) and Besenhard (J Power Sources 1(3), 267) finally enabled highly reversible redox reactions by intercalation of lithium ions instead of by chemical conversion. In 1980, Goodenough and Mizushima (Mater. Res. Bull. 15, 783 789) demonstrated a high-energy and high-power LiCoO2 cathode, allowing for an increase of terminal voltage far beyond 3 V. Over the past four decades, the international research community has further developed cathode materials of many varieties. Current state-of-the-art cathodes demonstrate voltages beyond any known electrolyte stability window, bringing electrolyte research once again to the forefront of battery research.« less

High sulfur-containing carbon polysulfide polymer as a novel cathode material for lithium-sulfur battery.

PubMed

Zhang, Yiyong; Peng, Yueying; Wang, Yunhui; Li, Jiyang; Li, He; Zeng, Jing; Wang, Jing; Hwang, Bing Joe; Zhao, Jinbao

2017-09-12

The lithium-sulfur battery, which offers a high energy density and is environmental friendly, is a promising next generation of rechargeable energy storage system. However, despite these attractive attributes, the commercialization of lithium-sulfur battery is primarily hindered by the parasitic reactions between the Li metal anode and dissolved polysulfide species from the cathode during the cycling process. Herein, we synthesize the sulfur-rich carbon polysulfide polymer and demonstrate that it is a promising cathode material for high performance lithium-sulfur battery. The electrochemical studies reveal that the carbon polysulfide polymer exhibits superb reversibility and cycle stability. This is due to that the well-designed structure of the carbon polysulfide polymer has several advantages, especially, the strong chemical interaction between sulfur and the carbon framework (C-S bonds) inhibits the shuttle effect and the π electrons of the carbon polysulfide compound enhance the transfer of electrons and Li + . Furthermore, as-prepared carbon polysulfide polymer-graphene hybrid cathode achieves outstanding cycle stability and relatively high capacity. This work highlights the potential promise of the carbon polysulfide polymer as the cathode material for high performance lithium-sulfur battery.

Aromatic Polyimide/Graphene Composite Organic Cathodes for Fast and Sustainable Lithium-Ion Batteries

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

Lyu, Hailong; Li, Peipei; Liu, Jiurong

A composite organic cathode material based on aromatic polyimide (PI) and highly conductive graphene was prepared through a facile in situ polymerization method for application in lithium-ion batteries. The in situ polymerization generated intimate contact between PI and electronically conductive graphene, resulting in conductive composites with highly reversible redox reactions and good structure stability. The synergistic effect between PI and graphene enabled not only a high reversible capacity of 232.6 mAh g -1 at a charge–discharge rate of C/10 but also exceptionally high-rate cycling stability, that is, a high capacity of 108.9 mAh g -1 at a very high charge–dischargemore » rate of 50C with a capacity retention of 80 % after 1000 cycles. This improved electrochemical performance resulted from the combination of stable redox reversibility of PI and high electronic conductivity of the graphene additive. In conclusion, the graphene-based composite also exhibited much better performance than composites based on multi-walled carbon nanotubes and the conductive carbon black C45 in terms of specific capacity and long-term cycling stability under the same charge–discharge rates.« less

Aromatic Polyimide/Graphene Composite Organic Cathodes for Fast and Sustainable Lithium-Ion Batteries

DOE PAGES

Lyu, Hailong; Li, Peipei; Liu, Jiurong; ...

2018-01-24

A composite organic cathode material based on aromatic polyimide (PI) and highly conductive graphene was prepared through a facile in situ polymerization method for application in lithium-ion batteries. The in situ polymerization generated intimate contact between PI and electronically conductive graphene, resulting in conductive composites with highly reversible redox reactions and good structure stability. The synergistic effect between PI and graphene enabled not only a high reversible capacity of 232.6 mAh g -1 at a charge–discharge rate of C/10 but also exceptionally high-rate cycling stability, that is, a high capacity of 108.9 mAh g -1 at a very high charge–dischargemore » rate of 50C with a capacity retention of 80 % after 1000 cycles. This improved electrochemical performance resulted from the combination of stable redox reversibility of PI and high electronic conductivity of the graphene additive. In conclusion, the graphene-based composite also exhibited much better performance than composites based on multi-walled carbon nanotubes and the conductive carbon black C45 in terms of specific capacity and long-term cycling stability under the same charge–discharge rates.« less

A New CuO-Fe2 O3 -Mesocarbon Microbeads Conversion Anode in a High-Performance Lithium-Ion Battery with a Li1.35 Ni0.48 Fe0.1 Mn1.72 O4 Spinel Cathode.

PubMed

Di Lecce, Daniele; Verrelli, Roberta; Campanella, Daniele; Marangon, Vittorio; Hassoun, Jusef

2017-04-10

A ternary CuO-Fe 2 O 3 -mesocarbon microbeads (MCMB) conversion anode was characterized and combined with a high-voltage Li 1.35 Ni 0.48 Fe 0.1 Mn 1.72 O 4 spinel cathode in a lithium-ion battery of relevant performance in terms of cycling stability and rate capability. The CuO-Fe 2 O 3 -MCMB composite was prepared by using high-energy milling, a low-cost pathway that leads to a crystalline structure and homogeneous submicrometrical morphology as revealed by XRD and electron microscopy. The anode reversibly exchanges lithium ions through the conversion reactions of CuO and Fe 2 O 3 and by insertion into the MCMB carbon. Electrochemical tests, including impedance spectroscopy, revealed a conductive electrode/electrolyte interface that enabled the anode to achieve a reversible capacity value higher than 500 mAh g -1 when cycled at a current of 120 mA g -1 . The remarkable stability of the CuO-Fe 2 O 3 -MCMB electrode and the suitable characteristics in terms of delivered capacity and voltage-profile retention allowed its use in an efficient full lithium-ion cell with a high-voltage Li 1.35 Ni 0.48 Fe 0.1 Mn 1.72 O 4 cathode. The cell had a working voltage of 3.6 V and delivered a capacity of 110 mAh g cathode -1 with a Coulombic efficiency above 99 % after 100 cycles at 148 mA g cathode -1 . This relevant performances, rarely achieved by lithium-ion systems that use the conversion reaction, are the result of an excellent cell balance in terms of negative-to-positive ratio, favored by the anode composition and electrochemical features. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Towards deriving Ni-rich cathode and oxide-based anode materials from hydroxides by sharing a facile co-precipitation method.

PubMed

Qiu, Haifa; Du, Tengfei; Wu, Junfeng; Wang, Yonglong; Liu, Jian; Ye, Shihai; Liu, Sheng

2018-05-22

Although intensive studies have been conducted on layered transition metal oxide(TMO)-based cathode materials and metal oxide-based anode materials for Li-ion batteries, their precursors generally follow different or even complex synthesis routes. To share one route for preparing precursors of the cathode and anode materials, herein, we demonstrate a facile co-precipitation method to fabricate Ni-rich hydroxide precursors of Ni0.8Co0.1Mn0.1(OH)2. Ni-rich layered oxide of LiNi0.8Co0.1Mn0.1O2 is obtained by lithiation of the precursor in air. An NiO-based anode material is prepared by calcining the precursor or multi-walled carbon nanotubes (MWCNTs) incorporated precursors. The pre-addition of ammonia solution can simplify the co-precipitation procedures and the use of an air atmosphere can also make the heat treatment facile. LiNi0.8Co0.1Mn0.1O2 as the cathode material delivers a reversible capacity of 194 mA h g-1 at 40 mA g-1 and a notable cycling retention of 88.8% after 100 cycles at 200 mA g-1. This noticeable performance of the cathode arises from a decent particle morphology and high crystallinity of the layered oxides. As the anode material, the MWCNTs-incorporated oxides deliver a much higher reversible capacity of 811.1 mA h g-1 after 200 cycles compared to the pristine oxides without MWCNTs. The improvement on electrochemical performance can be attributed to synergistic effects from MWCNTs incorporation, including reinforced electronic conductivity, rich meso-pores and an alleviated volume effect. This facile and sharing method may offer an integrated and economical approach for commercial production of Ni-rich electrode materials for Li-ion batteries.

Fluorination Induced the Surface Segregation of High Voltage Spinel on Lithium-Rich Layered Cathodes for Enhanced Rate Capability in Lithium Ion Batteries.

PubMed

Jin, Yi-Chun; Duh, Jenq-Gong

2016-02-17

This study is aimed to explore the effect of fluoride doping and the associated structural transformation on lithium-rich layered cathode materials. The polymeric fluoride source is first adopted for synthesizing lithium intercalated oxide through a newly developed organic precipitation process. A heterostructured spinel/layered composite cathode material is obtained after appreciable fluorination and a superior rate capability is successfully achieved. The fluoride dopant amount and the surface spinel phase are evidenced and systematically examined by various structural spectroscopy and electrochemical analysis. It appears the reversible Ni(2+/4+) redox couple at high voltage regime around 4.8 V because of the formation of spinel LiNi1/2Mn3/2O4 phase. The mechanism of "layer to spinel" phase transformation is discussed in detail.

Electrochemical potassium-ion intercalation in NaxCoO2: a novel cathode material for potassium-ion batteries.

PubMed

Sada, Krishnakanth; Senthilkumar, Baskar; Barpanda, Prabeer

2017-07-27

Reversible electrochemical potassium-ion intercalation in P2-type Na x CoO 2 was examined for the first time. Hexagonal Na 0.84 CoO 2 platelets prepared by a solution combustion synthesis technique were found to work as an efficient host for K + intercalation. They deliver a high reversible capacity of 82 mA h g -1 , good rate capability and excellent cycling performance up to 50 cycles.

Smart nickel oxide materials for the applications of energy efficiency and storage

NASA Astrophysics Data System (ADS)

Lin, Feng

The present dissertation studies nickel oxide-based materials for the application of electrochromic windows and lithium-air batteries. The materials were fabricated via radio frequency magnetron sputtering and subsequently post-treated with thermal evaporation and ozone exposure. The strategies to improve electrochromic performance of nickel oxide materials were investigated including compositional control, morphology tuning, modification of electronic structure and interface engineering (i.e., Li2O 2, graphene). The electrochemical properties of the resulting materials were characterized in lithium ion electrolytes. Extremely high performing nickel oxide-based electrochromic materials were obtained in terms of optical modulation, switching kinetics, bleached-state transparency and durability, which promise the implementation of these materials for practical smart windows. With the aid of advanced synchrotron X-ray absorption spectroscopy, it is reported for the first time that the electrochromic effect in multicomponent nickel oxide-based materials arises from the reversible formation of hole states in the NiO6 cluster accompanying with the reversible formation of Li2O2. The reversible formation of Li2O 2 was successfully leveraged with the study of electro-catalysts and cathode materials for lithium-air batteries. The reversibility of Li 2O2 was thoroughly investigated using soft X-ray absorption spectroscopy and theoretical simulation, which substantiates the promise of using electrochromic films as electro-catalysts and/or cathode materials in lithium-air batteries.

Experimental results with fuel cell start-up and shut-down. Impact of type of carbon for cathode catalyst support

DOE PAGES

Lottin, Olivier; Dillet, Jerome; Maranzana, Gael; ...

2015-09-14

Separate testing protocols for fuel cell startups and shutdowns were developed to distinguish between their effects on reverse currents and CO 2 evolution. The internal currents and the local potentials were measured with different membrane-electrode assemblies (MEAs): we examined the influence of the type of carbon for cathode catalyst support as well as the mitigating effect of low anode Pt loading. In conclusion, significant differences were observed and the experiments also confirmed previous results that the evolved CO 2 accounts for less than 25% of the total exchanged charge.

Experimental results with fuel cell start-up and shut-down. Impact of type of carbon for cathode catalyst support

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

Lottin, Olivier; Dillet, Jerome; Maranzana, Gael

Separate testing protocols for fuel cell startups and shutdowns were developed to distinguish between their effects on reverse currents and CO 2 evolution. The internal currents and the local potentials were measured with different membrane-electrode assemblies (MEAs): we examined the influence of the type of carbon for cathode catalyst support as well as the mitigating effect of low anode Pt loading. In conclusion, significant differences were observed and the experiments also confirmed previous results that the evolved CO 2 accounts for less than 25% of the total exchanged charge.

Mesoporous Prussian blue analogues: template-free synthesis and sodium-ion battery applications.

PubMed

Yue, Yanfeng; Binder, Andrew J; Guo, Bingkun; Zhang, Zhiyong; Qiao, Zhen-An; Tian, Chengcheng; Dai, Sheng

2014-03-17

The synthesis of mesoporous Prussian blue analogues through a template-free methodology and the application of these mesoporous materials as high-performance cathode materials in sodium-ion batteries is presented. Crystalline mesostructures were produced through a synergistically coupled nanocrystal formation and aggregation mechanism. As cathodes for sodium-ion batteries, the Prussian blue analogues all show a reversible capacity of 65 mA h g-1 at low current rate and show excellent cycle stability. The reported method stands as an environmentally friendly and low-cost alternative to hard or soft templating for the fabrication of mesoporous materials.

Situ treatment of contaminated groundwater

DOEpatents

McNab, Jr., Walt W.; Ruiz, Roberto; Pico, Tristan M.

2001-01-01

A system for treating dissolved halogenated organic compounds in groundwater that relies upon electrolytically-generated hydrogen to chemically reduce the halogenated compounds in the presence of a suitable catalyst. A direct current is placed across at least a pair, or an array, of electrodes which are housed within groundwater wells so that hydrogen is generated at the cathode and oxygen at the anode. A pump is located within the well housing in which the cathode(s) is(are) located and draws in groundwater where it is hydrogenated via electrolysis, passes through a well-bore treatment unit, and then transported to the anode well(s) for reinjection into the ground. The well-bore treatment involves a permeable cylinder located in the well bore and containing a packed bed of catalyst material that facilitates the reductive dehalogenation of the halogenated organic compounds by hydrogen into environmentally benign species such as ethane and methane. Also, electro-osmatic transport of contaminants toward the cathode also contributes to contaminant mass removal. The only above ground equipment required are the transfer pipes and a direct circuit power supply for the electrodes. The electrode wells in an array may be used in pairs or one anode well may be used with a plurality of cathode wells. The DC current flow between electrode wells may be periodically reversed which controls the formation of mineral deposits in the alkaline cathode well-bore water, as well as to help rejuvenate the catalysis.

Foldable and High Sulfur Loading 3D Carbon Electrode for High-performance Li-S Battery Application

PubMed Central

He, Na; Zhong, Lei; Xiao, Min; Wang, Shuanjin; Han, Dongmei; Meng, Yuezhong

2016-01-01

Sulfur is a promising cathode material with a high theoretical capacity of 1672 mAh g−1, however, the practical energy density of Li-S battery is far away from such promising due to its low active material utilization and low sulfur loading. Moreover, the challenges of the low electrical conductivity of sulfur and the high solubility of polysulfide intermediates still hinder its practical application. Here, we report a kind of free-standing and foldable cathodes consisting of 3D activated carbon fiber matrix and sulfur cathode. The 3D activated carbon fiber matrix (ACFC) has continuous conductive framework and sufficient internal space to provide a long-distance and continuous high-speed electron pathway. It also gives a very larger internal space and tortuous cathode region to ACFC accommodate a highly sulfur loading and keeps polysulfide within the cathode. The unique structured 3D foldable sulfur cathode using a foldable ACFC as matrix delivers a reversible capacity of about 979 mAh g−1 at 0.2C, a capacity retention of 98% after 100 cycles, and 0.02% capacity attenuation per cycle. Even at an areal capacity of 6 mAh cm−2, which is 2 times higher than the values of Li-ion battery, it still maintains an excellent rate capability and cycling performance. PMID:27677602

Reversibility of Noble Metal-Catalyzed Aprotic Li-O₂ Batteries.

PubMed

Ma, Shunchao; Wu, Yang; Wang, Jiawei; Zhang, Yelong; Zhang, Yantao; Yan, Xinxiu; Wei, Yang; Liu, Peng; Wang, Jiaping; Jiang, Kaili; Fan, Shoushan; Xu, Ye; Peng, Zhangquan

2015-12-09

The aprotic Li-O2 battery has attracted a great deal of interest because, theoretically, it can store far more energy than today's batteries. Toward unlocking the energy capabilities of this neotype energy storage system, noble metal-catalyzed high surface area carbon materials have been widely used as the O2 cathodes, and some of them exhibit excellent electrochemical performances in terms of round-trip efficiency and cycle life. However, whether these outstanding electrochemical performances are backed by the reversible formation/decomposition of Li2O2, i.e., the desired Li-O2 electrochemistry, remains unclear due to a lack of quantitative assays for the Li-O2 cells. Here, noble metal (Ru and Pd)-catalyzed carbon nanotube (CNT) fabrics, prepared by magnetron sputtering, have been used as the O2 cathode in aprotic Li-O2 batteries. The catalyzed Li-O2 cells exhibited considerably high round-trip efficiency and prolonged cycle life, which could match or even surpass some of the best literature results. However, a combined analysis using differential electrochemical mass spectrometry and Fourier transform infrared spectroscopy, revealed that these catalyzed Li-O2 cells (particularly those based on Pd-CNT cathodes) did not work according to the desired Li-O2 electrochemistry. Instead the presence of noble metal catalysts impaired the cells' reversibility, as evidenced by the decreased O2 recovery efficiency (the ratio of the amount of O2 evolved during recharge/that consumed in the preceding discharge) coupled with increased CO2 evolution during charging. The results reported here provide new insights into the O2 electrochemistry in the aprotic Li-O2 batteries containing noble metal catalysts and exemplified the importance of the quantitative assays for the Li-O2 reactions in the course of pursuing truly rechargeable Li-O2 batteries.

Synthesis, Structure, and Electrochemical Performance of High Capacity Li 2Cu 0.5Ni 0.5O 2 Cathodes

DOE PAGES

Ruther, Rose E; Zhou, Hui; Dhital, Chetan; ...

2015-09-08

Orthorhombic Li 2NiO 2, Li 2CuO 2, and solid solutions thereof have been studied as potential cathode materials for lithium-ion batteries due to their high theoretical capacity and relatively low cost. While neither endmember shows good cycling stability, the intermediate composition, Li 2Cu 0.5Ni 0.5O 2, yields reasonably high reversible capacities. A new synthetic approach and detailed characterization of this phase and the parent Li 2CuO 2 are presented. The cycle life of Li 2Cu 0.5Ni 0.5O 2 is shown to depend critically on the voltage window. The formation of Cu 1+ at low voltage and oxygen evolution at highmore » voltage limit the electrochemical reversibility. In situ X-ray absorption spectroscopy (XAS), in situ Raman spectroscopy, and gas evolution measurements are used to follow the chemical and structural changes that occur as a function of cell voltage.« less

Layered P2-Na 2/3 Co 1/2 Ti 1/2 O 2 as a high-performance cathode material for sodium-ion batteries

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

Sabi, Noha; Doubaji, Siham; Hashimoto, Kazuki

Layered oxides are regarded as promising cathode materials for sodium-ion batteries. We present Na2/3Co1/2Ti1/2O2 as a potential new cathode material for sodium-ion batteries. The crystal features and morphology of the pristine powder were characterized by X-ray diffraction (XRD) and scanning electron microscopy (SEM). The cathode material is evaluated in galvanostatic charge-discharge and galvanostatic intermittent titration tests, as well as ex-situ X-ray diffraction analysis. Synthesized by a high-temperature solid state reaction, Na2/3Co1/2Ti1/2O2 crystallizes in P2-type structure with P6(3)/mmc space group. The material presents reversible electrochemical behavior and delivers a specific discharge capacity of 100 mAh g(-1) when tested in Na halfmore » cells between 2.0 and 4.2 V (vs. Na+/Na), with capacity retention of 98% after 50 cycles. Furthermore, the electrochemical cycling of this titanium-containing material evidenced a reduction of the potential jumps recorded in the NaxCoO2 parent phase, revealing a positive impact of Ti substitution for Co. The ex-situ XRD measurements confirmed the reversibility and stability of the material. No structural changes were observed in the XRD patterns, and the P2-type structure was stable during the charge/discharge process between 2.0 and 4.2 V vs. Na+/Na. These outcomes will contribute to the progress of developing low cost electrode materials for sodium-ion batteries. (C) 2017 Elsevier B.V. All rights reserved.« less

Structural Evolution of Reversible Mg Insertion into a Bilayer Structure of V 2 O 5 · n H 2 O Xerogel Material

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

Sa, Niya; Kinnibrugh, Tiffany L.; Wang, Hao

Functional multivalent intercalation cathodes represent one of the largest hurdles in the development of Mg batteries. While there are many reports of Mg cathodes, many times the evidence of intercalation chemistry is only circumstantial. In this work, direct evidence of Mg intercalation into a bilayer structure of V2O5·nH2O xerogel is confirmed, and the nature of the Mg intercalated species is reported. The interlayer spacing of V2O5·nH2O contracts upon Mg intercalation and expands for Mg deintercalation due to the strong electrostatic interaction between the divalent cation and the cathode. A combination of NMR, pair distribution function (PDF) analysis, and X-ray absorptionmore » near edge spectroscopy (XANES) confirmed reversible Mg insertion into the V2O5·nH2O material, and structural evolution of Mg intercalation leads to the formation of multiple new phases. Structures of V2O5·nH2O with Mg intercalation were further supported by the first principle simulations. A solvent cointercalated Mg in V2O5·nH2O is observed for the first time, and the 25Mg magic angle spinning nuclear magnetic resonance (MAS NMR) spectroscopy was used to elucidate the structure obtained upon electrochemical cycling. Specifically, existence of a well-defined Mg–O environment is revealed for the Mg intercalated structures. Information reported here reveals the fundamental Mg ion intercalation mechanism in a bilayer structure of V2O5·nH2O material and provides insightful design metrics for future Mg cathodes.« less

Minimal RED cell pairs markedly improve electrode kinetics and power production in microbial reverse electrodialysis cells.

PubMed

Cusick, Roland D; Hatzell, Marta; Zhang, Fang; Logan, Bruce E

2013-12-17

Power production from microbial reverse electrodialysis cell (MRC) electrodes is substantially improved compared to microbial fuel cells (MFCs) by using ammonium bicarbonate (AmB) solutions in multiple RED cell pair stacks and the cathode chamber. Reducing the number of RED membranes pairs while maintaining enhanced electrode performance could help to reduce capital costs. We show here that using only a single RED cell pair (CP), created by operating the cathode in concentrated AmB, dramatically increased power production normalized to cathode area from both acetate (Acetate: from 0.9 to 3.1 W/m(2)-cat) and wastewater (WW: 0.3 to 1.7 W/m(2)), by reducing solution and charge transfer resistances at the cathode. A second RED cell pair increased RED stack potential and reduced anode charge transfer resistance, further increasing power production (Acetate: 4.2 W/m(2); WW: 1.9 W/m(2)). By maintaining near optimal electrode power production with fewer membranes, power densities normalized to total membrane area for the 1-CP (Acetate: 3.1 W/m(2)-mem; WW: 1.7 W/m(2)) and 2-CP (Acetate: 1.3 W/m(2)-mem; WW: 0.6 W/m(2)) reactors were much higher than previous MRCs (0.3-0.5 W/m(2)-mem with acetate). While operating at peak power, the rate of wastewater COD removal, normalized to reactor volume, was 30-50 times higher in 1-CP and 2-CP MRCs than that in a single chamber MFC. These findings show that even a single cell pair AmB RED stack can significantly enhance electrical power production and wastewater treatment.

Electrochemically influenced cation inter-diffusion and Co 3O 4 formation on La 0.6Sr 0.4CoO 3 infiltrated into SOFC cathodes

DOE PAGES

Song, Xueyan; Lee, Shiwoo; Chen, Yun; ...

2015-06-18

Nanosized LSC electrocatalyst was infiltrated into a porous scaffold cathode composed of Sm 2O 3-doped CeO 2 (SDC) and La 0.6Sr 0.4Co 0.2Fe 0.8O 3-δ (LSCF) in a commercial button solid oxide fuel cell (SOFC). To understand the stability of cathodes infiltrated with LSC, the infiltrated composite cells were subjected to both electrochemical operating and thermal aging states at 750 °C for 1500 h. Nanostructure and local chemistry evolution of La 0.6Sr 0.4CoO 3 (LSC) infiltrated cathodes upon operation and aging were investigated by transmission electron microscopy. After operation, the LSC remained a cubic perovskite, and the crystal grains exhibitmore » comparable size to as-infiltrated LSC grains. Inter-diffusion of Fe from the LSCF to a Fe-incorporated LSC layer developed on the LSCF backbone. However, only sharp interfaces were observed between LSC and SDC backbone in the as-infiltrated cathode and such interfaces remain after operation. The infiltrated LSC on the SDC backbone also retains granular particle morphology. Furthermore, newly grown Co 3O 4 nanocrystals were found in the operated cathode. After thermal aging, on the other hand, cation inter-diffusion across the interfaces of the infiltrate particles and the cathode backbones is less than that from the operated cells. Lastly, the following hypothesis is proposed: Co 3O 4 forms on LSC arising from local charge balancing between cobalt and oxygen vacancies.« less

LiCaFeF6: A zero-strain cathode material for use in Li-ion batteries

NASA Astrophysics Data System (ADS)

de Biasi, Lea; Lieser, Georg; Dräger, Christoph; Indris, Sylvio; Rana, Jatinkumar; Schumacher, Gerhard; Mönig, Reiner; Ehrenberg, Helmut; Binder, Joachim R.; Geßwein, Holger

2017-09-01

A new zero-strain LiCaFeF6 cathode material for reversible insertion and extraction of lithium ions is presented. LiCaFeF6 is synthesized by a solid-state reaction and processed to a conductive electrode composite via high-energy ball-milling. In the first cycle, a discharge capacity of 112 mAh g-1 is achieved in the voltage range from 2.0 V to 4.5 V. The electrochemically active redox couple is Fe3+/Fe2+ as confirmed by Mössbauer spectroscopy and X-ray absorption spectroscopy. The compound has a trigonal colquiriite-type crystal structure (space group P 3 bar 1 c). By means of in situ and ex situ XRD as well as X-ray absorption fine structure spectroscopy a reversible response to Li uptake/release is found. For an uptake of 0.8 mol Li per formula unit only minimal changes occur in the lattice parameters causing a total change in unit cell volume of less than 0.5%. The spatial distribution of cations in the crystal structure as well as the linkage between their corresponding fluorine octahedra is responsible for this very small structural response. With its zero-strain behaviour this material is expected to exhibit only negligible mechanical degradation. It may be used as a cathode material in future lithium-ion batteries with strongly improved safety and cycle life.

Graphite|LiFePO4 lithium-ion battery working at the heat engine coolant temperature

NASA Astrophysics Data System (ADS)

Lewandowski, Andrzej; Kurc, Beata; Swiderska-Mocek, Agnieszka; Kusa, Natalia

2014-11-01

Electrochemical properties of the graphite anode and the LiFePO4 cathode, working together with the 1 M LiPF6 in TMS (sulpholane) at 90 °C have been studied. The general aim of the investigation was to demonstrate a potential application for a Li-ion cell working in the cooling system of a car heat engine (90 °C). Electrodes were characterized with the use of electrochemical impedance spectroscopy (EIS), scanning electron microscopy (SEM) as well as galvanostatic charging/discharging tests. SEM images of both electrodes after charging/discharging processes were covered with a film (electrochemical SEI formation). The charge transfer resistance at 90 °C, Rct, of the C6Li|Li+ anode and the LiFePO4 cathode was 24 Ω and 110 Ω, respectively. Reversible capacity of the LiC6 anode after 10-20 cycles, at a low current rate was close to the theoretical value of 370 mAh g-1 however an increasing current rate decreased to ca. 200 mAh g-1 (for 1C). The reversibility of the process was close to 95%. The capacity of the LiFePO4 cathode was ca. 150 mAh g-1, almost independent of the current rate and close to the theoretical value of 170 mAh g-1.

A high-voltage rechargeable magnesium-sodium hybrid battery

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

Li, Yifei; An, Qinyou; Cheng, Yingwen

2017-04-01

Growing global demand of safe and low-cost energy storage technology triggers strong interests in novel battery concepts beyond state-of-art Li-ion batteries. Here we report a high-voltage rechargeable Mg–Na hybrid battery featuring dendrite-free deposition of Mg anode and Na-intercalation cathode as a low-cost and safe alternative to Li-ion batteries for large-scale energy storage. A prototype device using a Na3V2(PO4)3 cathode, a Mg anode, and a Mg–Na dual salt electrolyte exhibits the highest voltage (2.60 V vs. Mg) and best rate performance (86% capacity retention at 10C rate) among reported hybrid batteries. Synchrotron radiation-based X-ray absorption near edge structure (XANES), atomic-pair distributionmore » function (PDF), and high-resolution X-ray diffraction (HRXRD) studies reveal the chemical environment and structural change of Na3V2(PO4)3 cathode during the Na ion insertion/deinsertion process. XANES study shows a clear reversible shift of vanadium K-edge and HRXRD and PDF studies reveal a reversible two-phase transformation and V–O bond length change during cycling. The energy density of the hybrid cell could be further improved by developing electrolytes with a higher salt concentration and wider electrochemical window. This work represents a significant step forward for practical safe and low-cost hybrid batteries.« less

A high-voltage rechargeable magnesium-sodium hybrid battery

DOE PAGES

Li, Yifei; An, Qinyou; Cheng, Yingwen; ...

2017-02-13

There is a growing global demand for safe and low-cost energy storage technology which triggers strong interests in novel battery concepts beyond state-of-art Li-ion batteries. We report a high-voltage rechargeable Mg–Na hybrid battery featuring dendrite-free deposition of Mg anode and Na-intercalation cathode as a low-cost and safe alternative to Li-ion batteries for large-scale energy storage. A prototype device using a Na 3V 2(PO 4) 3 cathode, a Mg anode, and a Mg–Na dual salt electrolyte exhibits the highest voltage (2.60 V vs. Mg) and best rate performance (86% capacity retention at 10 C rate) among reported hybrid batteries. Synchrotron radiation-basedmore » X-ray absorption near edge structure (XANES), atomic-pair distribution function (PDF), and high-resolution X-ray diffraction (HRXRD) studies reveal the chemical environment and structural change of Na 3V 2(PO 4) 3 cathode during the Na ion insertion/deinsertion process. XANES study shows a clear reversible shift of vanadium K-edge and HRXRD and PDF studies reveal a reversible two-phase transformation and V–O bond length change during cycling. The energy density of the hybrid cell could be further improved by developing electrolytes with a higher salt concentration and wider electrochemical window. Our work represents a significant step forward for practical safe and low-cost hybrid batteries.« less

Electrochemical and thermal studies of lithium ion batteries

NASA Astrophysics Data System (ADS)

Lu, Wenquan

The structural, electrochemical, and thermal characteristics of carbonaceous anodes and LiNi0.8Co0.2O2 cathode in Li-ion cells were investigated using various electrochemical and calorimetric techniques. The electrode-electrolyte interface was investigated for various carbonaceous materials such as graphite with different shapes, surface modified graphite with copper, and novel carbon material derived from sepiolite template. The structural and morphological properties were determined using XRD, TGA, SEM, BET techniques. The electrochemical characteristics were studied using conventional electrochemical techniques such as galvanostatic charge/discharge cycling, cyclic voltammetry, and impedance (AC and DC) methods. It was observed that the electrochemical active surface area instead of the BET area plays a critical role in the irreversible capacity loss associated with the carbonaceous anodes. It was also found that the exfoliation of carbon anodes especially in PC based electrolyte could be significantly reduced by protective copper coating of the natural graphite. LiNi0.8Co0.2O2 cathode material was found to possess high energy density and excellent cycling characteristics. The structural and electrochemical properties of LiNi0.8Co 0.2O2 synthesized by sol-gel and solid-state methods were studied. Results of the AC impedance spectroscopy carried out on LiNi 0.8Co0.2O2 cathodes revealed that the charge transfer resistance is a function of the state of charge. The solid state Li + diffusion was calculated to be around 10-13 cm2/s in the oxide particle by Warburg impedance method. In addition, the cell fabricated with LiNi0.8Co0.2O 2 cathode showed excellent energy and power performance under static and dynamic load conditions that prevail in Electric and Hybrid Vehicles. Thermal properties of the LiNi0.8Co0.2O2 cathode, carbonaceous anodes, and Li-ion cells fabricated with these electrodes were also investigated using isothermal microcalorimetry (IMC), differential scanning calorimetry (DSC) and accelerated rate calorimetry (ARC). Isothermal micro-calorimeter was used to investigate the thermal behavior of the Li-ion cell and its electrodes. The overall heat changes during charge-discharge processes were explained in terms of the irreversible (resistive) and reversible (entropic) heats. It was observed that the reversible heat strongly depends on the structural or phase change occurring in the electrodes during Li-ion insertion and extraction reactions. It was also found that the contribution of the reversible heat to the overall cell heat generation rate was significant only at low cycling rates.

New Redox Polymers that Exhibit Reversible Cleavage of Sulfur Bonds as Cathode Materials.

PubMed

Baloch, Marya; Ben Youcef, Hicham; Li, Chunmei; Garcia-Calvo, Oihane; Rodriguez, Lide M; Shanmukaraj, Devaraj; Rojo, Teofilo; Armand, Michel

2016-11-23

Two new cathode materials based on redox organosulfur polymers were synthesized and investigated for rechargeable lithium batteries as a proof-of-concept study. These cathodes offered good cycling performance owing to the absence of polysulfide solubility, which plagues Li/S systems. Herein, an aliphatic polyamine or a conjugated polyazomethine was used as the base to tether the redox-active species. The activity comes from the cleavage and formation of S-S or N-S bonds, which is made possible by the rigid conjugated backbone. The synthesized polymers were characterized through FTIR spectroscopy and thermogravimetric analysis (TGA). Galvanostatic measurements were performed to evaluate the discharge/charge cycles and characterize the performance of the lithium-based cells, which displayed initial discharge capacities of approximately 300 mA h g -1 at C/5 over 100 cycles with approximately 98 % Coulombic efficiency. © 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Synthesis of Li2MnSiO4-graphene composite and its electrochemical performances as a cathode material for lithium ion batteries.

PubMed

Kim, Jeonghyun; Song, Taeseup; Park, Hyunjung; Yuh, Junhan; Paik, Ungyu

2014-10-01

The Li2MnSiO4 is a promising candidate as a cathode for lithium ion batteries due to its large theoretical capacity of 330 mA h g(-1) and high thermal stability. However, the problems related to low electronic conductivity and large irreversible capacity at the first cycle limits its practical use as a Li-ion cathode material. We have developed a carbon coated Li2MnSiO4-graphene composite electrode to overcome these problems. Our designed electrode exhibits high reversible capacity of 301 mA h g(-1), with a high initial coulombic efficiency, and a discharge capacity at current rate of 0.5 C, that is double value of carbon coated Li2MnSiO4-carbon black composite electrode. These significant improvements are attributed to fast electron transport along the graphene sheet.

Efficient reversible electrodes for solid oxide electrolyzer cells

DOEpatents

Elangovan, Singaravelu [South Jordan, UT; Hartvigsen, Joseph J [Kaysville, UT

2011-07-12

An electrolyzer cell is disclosed which includes a cathode to reduce an oxygen-containing molecule, such as H2O, CO2, or a combination thereof, to produce an oxygen ion and a fuel molecule, such as H2, CO, or a combination thereof. An electrolyte is coupled to the cathode to transport the oxygen ion to an anode. The anode is coupled to the electrolyte to receive the oxygen ion and produce oxygen gas therewith. In one embodiment, the anode may be fabricated to include an electron-conducting phase having a perovskite crystalline structure or structure similar thereto. This perovskite may have a chemical formula of substantially (Pr(1-x)Lax)(z-y)A'yBO(3-.differential.), wherein 0.ltoreq.x.ltoreq.0.5, 0.ltoreq.y.ltoreq.0.5, and 0.8.ltoreq.z.ltoreq.1.1. In another embodiment, the cathode includes an electron-conducting phase that contains nickel oxide intermixed with magnesium oxide.

Building Honeycomb-Like Hollow Microsphere Architecture in a Bubble Template Reaction for High-Performance Lithium-Rich Layered Oxide Cathode Materials.

PubMed

Chen, Zhaoyong; Yan, Xiaoyan; Xu, Ming; Cao, Kaifeng; Zhu, Huali; Li, Lingjun; Duan, Junfei

2017-09-13

In the family of high-performance cathode materials for lithium-ion batteries, lithium-rich layered oxides come out in front because of a high reversible capacity exceeding 250 mAh g -1 . However, the long-term energy retention and high energy densities for lithium-rich layered oxide cathode materials require a stable structure with large surface areas. Here we propose a "bubble template" reaction to build "honeycomb-like" hollow microsphere architecture for a Li 1.2 Mn 0.52 Ni 0.2 Co 0.08 O 2 cathode material. Our material is designed with ca. 8-μm-sized secondary particles with hollow and highly exposed porous structures that promise a large flexible volume to achieve superior structure stability and high rate capability. Our preliminary electrochemical experiments show a high capacity of 287 mAh g -1 at 0.1 C and a capacity retention of 96% after 100 cycles at 1.0 C. Furthermore, the rate capability is superior without any other modifications, reaching 197 mAh g -1 at 3.0 C with a capacity retention of 94% after 100 cycles. This approach may shed light on a new material engineering for high-performance cathode materials.

Thin film buried anode battery

DOEpatents

Lee, Se-Hee [Lakewood, CO; Tracy, C Edwin [Golden, CO; Liu, Ping [Denver, CO

2009-12-15

A reverse configuration, lithium thin film battery (300) having a buried lithium anode layer (305) and process for making the same. The present invention is formed from a precursor composite structure (200) made by depositing electrolyte layer (204) onto substrate (201), followed by sequential depositions of cathode layer (203) and current collector (202) on the electrolyte layer. The precursor is subjected to an activation step, wherein a buried lithium anode layer (305) is formed via electroplating a lithium anode layer at the interface of substrate (201) and electrolyte film (204). The electroplating is accomplished by applying a current between anode current collector (201) and cathode current collector (202).

Electrode erosion in arc discharges at atmospheric pressure

NASA Technical Reports Server (NTRS)

Hardy, T. L.

1985-01-01

An experimental investigation was performed in an effort to measure and increase lifetime of electrodes in an arcjet thruster. The electrode erosion of various anode and cathode materials was measured after tests in an atmospheric pressure nitrogen arc discharge at powers less than 1 kW. A free-burning arc configuration and a constricted arc configuration were used to test the materials. Lanthanum hexboride and thoriated tungsten had low cathode erosion rates while thoriated tungsten and pure tungsten had the lowest anode erosion rates of the materials tested. Anode cooling, reverse gas flow, an external magnetic fields were all found to reduce electrode mass loss.

High voltage and high specific capacity dual intercalating electrode Li-ion batteries

NASA Technical Reports Server (NTRS)

Blanco, Mario (Inventor); West, William C. (Inventor)

2010-01-01

The present invention provides high capacity and high voltage Li-ion batteries that have a carbonaceous cathode and a nonaqueous electrolyte solution comprising LiF salt and an anion receptor that binds the fluoride ion. The batteries can comprise dual intercalating electrode Li ion batteries. Methods of the present invention use a cathode and electrode pair, wherein each of the electrodes reversibly intercalate ions provided by a LiF salt to make a high voltage and high specific capacity dual intercalating electrode Li-ion battery. The present methods and systems provide high-capacity batteries particularly useful in powering devices where minimizing battery mass is important.

Direct Investigation of Mg Intercalation into the Orthorhombic V 2O 5 Cathode Using Atomic-Resolution Transmission Electron Microscopy [Direct Investigation of Mg intercalation into orthorhombic V 2O 5 cathode using Atomic Resolution Electron Microscopy Methods

DOE PAGES

Mukherjee, Arijita; Sa, Niya; Phillips, Patrick J.; ...

2017-02-13

Batteries based on Mg metal anode can promise much higher specific volumetric capacity and energy density compared to Li-ion systems and are, at the same time, safer and more cost-effective. While previous experimental reports have claimed reversible Mg intercalation into beyond Chevrel phase cathodes, they provide limited evidence of true Mg intercalation other than electrochemical data. Transmission electron microscopy techniques provide unique capabilities to directly image Mg intercalation and quantify the redox reaction within the cathode material. Here, we present a systematic study of Mg insertion into orthorhombic V 2O 5, combining aberration-corrected scanning transmission electron microscopy (STEM) imaging, electronmore » energy-loss spectroscopy (EELS), and energy-dispersive X-ray spectroscopy (EDX) analysis. We compare the results from an electrochemically cycled V 2O 5 cathode in a prospective full cell with Mg metal anode with a chemically synthesized MgV 2O 5 sample. Results suggest that the electrochemically cycled orthorhombic V 2O 5 cathode shows a local formation of the theoretically predicted ϵ-Mg0.5V2O5 phase; however, the intercalation levels of Mg are lower than predicted. Lastly, this phase is different from the chemically synthesized sample, which is found to represent the δ-MgV 2O 5 phase.« less

Systematic aging of commercial LiFePO4|Graphite cylindrical cells including a theory explaining rise of capacity during aging

NASA Astrophysics Data System (ADS)

Lewerenz, Meinert; Münnix, Jens; Schmalstieg, Johannes; Käbitz, Stefan; Knips, Marcus; Sauer, Dirk Uwe

2017-03-01

The contribution introduces a new theory explaining the capacity increase that is often observed in early stages of life of lithium-ion batteries. This reversible and SOC-depending capacity rise is explained by the passive electrode effect in this work. The theory assumes a slow, compensating flow of active lithium between the passive and the active part of the anode, where the passive part represents the geometric excess anode with respect to the cathode. The theory is validated using a systematic test of 50 cylindrical 8 Ah LiFePO4|Graphite battery cells analyzed during cyclic and calendaric aging. The cyclic aging has been performed symmetrically at 40 °C cell temperature, varying current rates and DODs. The calendar aging is executed at three temperatures and up to four SOCs. The aging is dominated by capacity fade while the increase of internal resistance is hardly influenced. Surprisingly shallow cycling between 45 and 55% SOC shows stronger aging than aging at higher DOD and tests at 4 C exhibit less aging than aging at lower C-rates. Aging mechanisms at 60 °C seem to deviate from those at 40 °C or lower. The data of this aging matrix is used for further destructive and non-destructive characterization in future contributions.

An Airborne Programmable Digital to Video Converter Interface and Operation Manual.

DTIC Science & Technology

1981-02-01

Identify by block number) SCAN CONVERTER VIDEO DISPLAY TELEVISION DISPLAY 20. ABSTRACT (Continue on reverse oide If necessary and Identify by block...programmable cathode ray tube (CRT) controller which is accessed by the CPU to permit operation in a wide variety of modes. The Alphanumeric Generator

The Li-ion rechargeable battery: a perspective.

PubMed

Goodenough, John B; Park, Kyu-Sung

2013-01-30

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

Long-Term Cr Poisoning Effect on LSCF-GDC Composite Cathodes Sintered at Different Temperatures

DOE PAGES

Xiong, Chunyan; Taillon, Joshua A.; Pellegrinelli, Christopher; ...

2016-07-19

Here, the impact of sintering temperature on Cr-poisoning of solid oxide fuel cell (SOFC) cathodes was systematically studied. La 0.6Sr 0.4Fe 0.8Co 0.2O 3-δ - Ce 0.9Gd 0.1O 2-δ symmetric cells were aged at 750°C in synthetic air with the presence of Crofer 22 APU, a common high temperature interconnect, over 200 hours and electrochemical impedance spectroscopy (EIS) was used to determine the degradation process. Both the ohmic resistance (R Ω) and polarization resistance (R P) of LSCF-GDC cells, extracted from EIS spectra, for different sintering temperatures increase as a function of aging time. Furthermore, the Cr-related degradation rate increasesmore » with decreased cathode sintering temperature. The polarization resistance of cathode sintered at lower temperature (950°C) increases dramatically while aging with the presence of Cr and also significantly decreases the oxygen partial pressure dependence after aging. The degradation rate shows a positive correlation to the concentration of Cr. The results indicate that decreased sintering temperature increases the total surface area, leading to more available sites for Sr-Cr-O nucleation and thus greater Cr degradation.« less

Amorphous MoS3 as the sulfur-equivalent cathode material for room-temperature Li-S and Na-S batteries.

PubMed

Ye, Hualin; Ma, Lu; Zhou, Yu; Wang, Lu; Han, Na; Zhao, Feipeng; Deng, Jun; Wu, Tianpin; Li, Yanguang; Lu, Jun

2017-12-12

Many problems associated with Li-S and Na-S batteries essentially root in the generation of their soluble polysulfide intermediates. While conventional wisdom mainly focuses on trapping polysulfides at the cathode using various functional materials, few strategies are available at present to fully resolve or circumvent this long-standing issue. In this study, we propose the concept of sulfur-equivalent cathode materials, and demonstrate the great potential of amorphous MoS 3 as such a material for room-temperature Li-S and Na-S batteries. In Li-S batteries, MoS 3 exhibits sulfur-like behavior with large reversible specific capacity, excellent cycle life, and the possibility to achieve high areal capacity. Most remarkably, it is also fully cyclable in the carbonate electrolyte under a relatively high temperature of 55 °C. MoS 3 can also be used as the cathode material of even more challenging Na-S batteries to enable decent capacity and good cycle life. Operando X-ray absorption spectroscopy (XAS) experiments are carried out to track the structural evolution of MoS 3 It largely preserves its chain-like structure during repetitive battery cycling without generating any free polysulfide intermediates.

Synthesis cathode material LiNi0.80Co0.15Al0.05O2 with two step solid-state method under air stream

NASA Astrophysics Data System (ADS)

Xia, Shubiao; Zhang, Yingjie; Dong, Peng; Zhang, Yannan

2014-01-01

A facile generic strategy of solid-state reaction under air atmosphere is employed to prepare LiNi0.8Co0.15Al0.05O2 layer structure micro-sphere as cathodes for Li-ion batteries. The impurity phase has been eliminated wholly without changing the R-3m space group of LiNi0.8Co0.15Al0.05O2. The electrochemical performance of LiNi0.8Co0.15Al0.05O2 cathodes depend on the sintering step, temperature, particle size and uniformity. The sample pre-sintered at 540 °C for 12 h and then sintered at 720 °C for 28 h exhibits the best electrochemical performance, which delivers a reversible capacity of 180.4, 165.8, 154.7 and 135.6 mAhg-1 at 0.2 C, 1 C, 2 C and 5 C, respectively. The capacity retention keeps over 87% after 76 cycles at 1 C. This method is simple, cheap and mass-productive, and thus suitable to large scale production of NCA cathodes directly used for lithium ion batteries.

Amorphous MoS3 as the sulfur-equivalent cathode material for room-temperature Li–S and Na–S batteries

PubMed Central

Ye, Hualin; Ma, Lu; Zhou, Yu; Wang, Lu; Han, Na; Zhao, Feipeng; Deng, Jun; Wu, Tianpin; Li, Yanguang; Lu, Jun

2017-01-01

Many problems associated with Li–S and Na–S batteries essentially root in the generation of their soluble polysulfide intermediates. While conventional wisdom mainly focuses on trapping polysulfides at the cathode using various functional materials, few strategies are available at present to fully resolve or circumvent this long-standing issue. In this study, we propose the concept of sulfur-equivalent cathode materials, and demonstrate the great potential of amorphous MoS3 as such a material for room-temperature Li–S and Na–S batteries. In Li–S batteries, MoS3 exhibits sulfur-like behavior with large reversible specific capacity, excellent cycle life, and the possibility to achieve high areal capacity. Most remarkably, it is also fully cyclable in the carbonate electrolyte under a relatively high temperature of 55 °C. MoS3 can also be used as the cathode material of even more challenging Na–S batteries to enable decent capacity and good cycle life. Operando X-ray absorption spectroscopy (XAS) experiments are carried out to track the structural evolution of MoS3. It largely preserves its chain-like structure during repetitive battery cycling without generating any free polysulfide intermediates. PMID:29180431

A Sheet-like Carbon Matrix Hosted Sulfur as Cathode for High-performance Lithium-Sulfur Batteries

PubMed Central

Lu, Songtao; Chen, Yan; Zhou, Jia; Wang, Zhida; Wu, Xiaohong; Gu, Jian; Zhang, Xiaoping; Pang, Aimin; Jiao, Zilong; Jiang, Lixiang

2016-01-01

Lithium-sulfur (Li-S) batteries are a promising candidate of next generation energy storage systems owing to its high theoretical capacity and energy density. However, to date, its commercial application was hindered by the inherent problems of sulfur cathode. Additionally, with the rapid decline of non-renewable resources and active appeal of green chemistry, the intensive research of new electrode materials was conducted worldwide. We have obtained a sheet-like carbon material (shaddock peel carbon sheets SPCS) from organic waste shaddock peel, which can be used as the conductive carbon matrix for sulfur-based cathodes. Furthermore, the raw materials are low-cost, truly green and recyclable. As a result, the sulfur cathode made with SPCS (SPCS-S), can deliver a high reversible capacity of 722.5 mAh g−1 at 0.2 C after 100 cycles with capacity recuperability of ~90%, demonstrating that the SPCS-S hybrid is of great potential as the cathode for rechargeable Li-S batteries. The high electrochemical performance of SPCS-S hybrid could be attributed to the sheet-like carbon network with large surface area and high conductivity of the SPCS, in which the carbon sheets enable the uniform distribution of sulfur, better ability to trap the soluble polysulfides and accommodate volume expansion/shrinkage of sulfur during repeated charge/discharge cycles. PMID:26842015

Carbon black as an alternative cathode material for electrical energy recovery and transfer in a microbial battery.

PubMed

Zhang, Xueqin; Guo, Kun; Shen, Dongsheng; Feng, Huajun; Wang, Meizhen; Zhou, Yuyang; Jia, Yufeng; Liang, Yuxiang; Zhou, Mengjiao

2017-08-01

Rather than the conventional concept of viewing conductive carbon black (CB) to be chemically inert in microbial electrochemical cells (MECs), here we confirmed the redox activity of CB for its feasibility as an electron sink in the microbial battery (MB). Acting as the cathode of a MB, the solid-state CB electrode showed the highest electron capacity equivalent of 18.58 ± 0.46 C/g for the unsintered one and the lowest capacity of 2.29 ± 0.48 C/g for the one sintered under 100% N 2 atmosphere. The capacity vibrations of CBs were strongly in coincidence with the abundances of C=O moiety caused by different pretreatments and it implied one plausible mechanism based on CB's surface functionality for its electron capturing. Once subjected to electron saturation, CB could be completely regenerated by different strategies in terms of electrochemical discharging or donating electrons to biologically-catalyzed nitrate reduction. Surface characterization also revealed that CB's regeneration fully depended on the reversible shift of C=O moiety, further confirming the functionality-based mechanism for CB's feasibility as the role of MB's cathode. Moreover, resilience tests demonstrated that CB cathode was robust for the multi-cycles charging-discharging operations. These results imply that CB is a promising alternative material for the solid-state cathode in MBs.

A Sheet-like Carbon Matrix Hosted Sulfur as Cathode for High-performance Lithium-Sulfur Batteries.

PubMed

Lu, Songtao; Chen, Yan; Zhou, Jia; Wang, Zhida; Wu, Xiaohong; Gu, Jian; Zhang, Xiaoping; Pang, Aimin; Jiao, Zilong; Jiang, Lixiang

2016-02-04

Lithium-sulfur (Li-S) batteries are a promising candidate of next generation energy storage systems owing to its high theoretical capacity and energy density. However, to date, its commercial application was hindered by the inherent problems of sulfur cathode. Additionally, with the rapid decline of non-renewable resources and active appeal of green chemistry, the intensive research of new electrode materials was conducted worldwide. We have obtained a sheet-like carbon material (shaddock peel carbon sheets SPCS) from organic waste shaddock peel, which can be used as the conductive carbon matrix for sulfur-based cathodes. Furthermore, the raw materials are low-cost, truly green and recyclable. As a result, the sulfur cathode made with SPCS (SPCS-S), can deliver a high reversible capacity of 722.5 mAh g(-1) at 0.2 C after 100 cycles with capacity recuperability of ~90%, demonstrating that the SPCS-S hybrid is of great potential as the cathode for rechargeable Li-S batteries. The high electrochemical performance of SPCS-S hybrid could be attributed to the sheet-like carbon network with large surface area and high conductivity of the SPCS, in which the carbon sheets enable the uniform distribution of sulfur, better ability to trap the soluble polysulfides and accommodate volume expansion/shrinkage of sulfur during repeated charge/discharge cycles.

A Sheet-like Carbon Matrix Hosted Sulfur as Cathode for High-performance Lithium-Sulfur Batteries

NASA Astrophysics Data System (ADS)

Lu, Songtao; Chen, Yan; Zhou, Jia; Wang, Zhida; Wu, Xiaohong; Gu, Jian; Zhang, Xiaoping; Pang, Aimin; Jiao, Zilong; Jiang, Lixiang

2016-02-01

Lithium-sulfur (Li-S) batteries are a promising candidate of next generation energy storage systems owing to its high theoretical capacity and energy density. However, to date, its commercial application was hindered by the inherent problems of sulfur cathode. Additionally, with the rapid decline of non-renewable resources and active appeal of green chemistry, the intensive research of new electrode materials was conducted worldwide. We have obtained a sheet-like carbon material (shaddock peel carbon sheets SPCS) from organic waste shaddock peel, which can be used as the conductive carbon matrix for sulfur-based cathodes. Furthermore, the raw materials are low-cost, truly green and recyclable. As a result, the sulfur cathode made with SPCS (SPCS-S), can deliver a high reversible capacity of 722.5 mAh g-1 at 0.2 C after 100 cycles with capacity recuperability of ~90%, demonstrating that the SPCS-S hybrid is of great potential as the cathode for rechargeable Li-S batteries. The high electrochemical performance of SPCS-S hybrid could be attributed to the sheet-like carbon network with large surface area and high conductivity of the SPCS, in which the carbon sheets enable the uniform distribution of sulfur, better ability to trap the soluble polysulfides and accommodate volume expansion/shrinkage of sulfur during repeated charge/discharge cycles.

High performance C/S composite cathodes with conventional carbonate-based electrolytes in Li-S battery.

PubMed

Zheng, Shiyou; Han, Pan; Han, Zhuo; Zhang, Huijuan; Tang, Zhihong; Yang, Junhe

2014-04-29

High stable C/S composites are fabricated by a novel high-temperature sulfur infusion into micro-mesoporous carbon method following with solvent cleaning treatment. The C/S composite cathodes show high Coulombic efficiency, long cycling stability and good rate capability in the electrolyte of 1.0 M LiPF6 + EC/DEC (1:1 v/v), for instance, the reversible capacity of the treated C/S-50 (50% S) cathode retains around 860 mAh/g even after 500 cycles and the Coulombic efficiency is close to 100%, which demonstrates the best electrochemical performance of carbon-sulfur composite cathodes using the carbonate-based electrolyte reported to date. It is believed that the chemical bond of C-S is responsible for the superior electrochemical properties in Li-S battery, that is, the strong interaction between S and carbon matrix significantly improves the conductivity of S, effectively buffers the structural strain/stress caused by the large volume change during lithiation/delithiation, completely eliminates the formation of high-order polysulfide intermediates, and substantially avoids the shuttle reaction and the side reaction between polysulfide anions and carbonate solvent, and thus enables the C/S cathode to use conventional carbonate-based electrolytes and achieve outstanding electrochemical properties in Li-S battery. The results may substantially contribute to the progress of the Li-S battery technology.

Three-dimensional hierarchical C-Co-N/Se derived from metal-organic framework as superior cathode for Li-Se batteries

NASA Astrophysics Data System (ADS)

He, Jiarui; Lv, Weiqiang; Chen, Yuanfu; Xiong, Jie; Wen, Kechun; Xu, Chen; Zhang, Wanli; Li, Yanrong; Qin, Wu; He, Weidong

2017-09-01

Three-dimensional, porous graphitic carbon co-doped with cobalt and nitrogen (C-Co-N) is prepared with metal-organic framework (MOF) and employed as Lewis base matrix to host selenium. Owing to the unique structure with abundant micro/meso-pores, the highly-conductive C-Co-N matrix provides highly-efficient channels for electron transfer and ionic diffusion, and sufficient surface area for loading of selenium nanoparticles while mitigating dissolution of polyselenides and suppressing volume expansion. The homogenous distribution of cobalt nanoparticles and nitrogen-group in C-Co-N composite immobilize polyselenides through strong chemical interaction in the operation of Li-Se batteries. With a very high Se loading of 76.5 wt%, the C-Co-N/Se cathode delivers superior electrochemical performance with an ultrahigh reversible capacity of 672.3 mAh g-1 (99.6% of the theoretical value) and a capacity of 574.2 mAh g-1 after 200 cycles, giving a capacity fading of only 0.07% per cycle and a nearly 100% Columbic efficiency. In-situ Raman spectroscopy and density functional theory simulations are employed to investigate the Se (de)lithiation mechanism at the electrolyte/cathode interface, and confirm that the structure and composition of C-Co-N scaffold give rise to efficient cathode host for high-performance Se-based cathodes with dramatically reduced capacity fading.

From Metal-Organic Framework to Li2S@C-Co-N Nanoporous Architecture: A High-Capacity Cathode for Lithium-Sulfur Batteries.

PubMed

He, Jiarui; Chen, Yuanfu; Lv, Weiqiang; Wen, Kechun; Xu, Chen; Zhang, Wanli; Li, Yanrong; Qin, Wu; He, Weidong

2016-12-27

Owing to the high theoretical specific capacity (1166 mAh g -1 ), lithium sulfide (Li 2 S) has been considered as a promising cathode material for Li-S batteries. However, the polysulfide dissolution and low electronic conductivity of Li 2 S limit its further application in next-generation Li-S batteries. In this report, a nanoporous Li 2 S@C-Co-N cathode is synthesized by liquid infiltration-evaporation of ultrafine Li 2 S nanoparticles into graphitic carbon co-doped with cobalt and nitrogen (C-Co-N) derived from metal-organic frameworks. The obtained Li 2 S@C-Co-N architecture remarkably immobilizes Li 2 S within the cathode structure through physical and chemical molecular interactions. Owing to the synergistic interactions between C-Co-N and Li 2 S nanoparticles, the Li 2 S@C-Co-N composite delivers a reversible capacity of 1155.3 (99.1% of theoretical value) at the initial cycle and 929.6 mAh g -1 after 300 cycles, with nearly 100% Coulombic efficiency and a capacity fading of 0.06% per cycle. It exhibits excellent rate capacities of 950.6, 898.8, and 604.1 mAh g -1 at 1C, 2C, and 4C, respectively. Such a cathode structure is promising for practical applications in high-performance Li-S batteries.

Moderate temperature rechargeable sodium batteries

NASA Technical Reports Server (NTRS)

Abraham, K. M.; Rupich, M. W.; Pitts, L.; Elliott, J. E.

1983-01-01

Cells utilizing the organic electrolyte, NaI in triglyme, operated at approx. 130 C with Na(+) - intercalating cathodes. However, their rate and stability were inadequate. NaAlCl4 was found to be a highly useful electrolyte for cell operation at 165-190 C. Na(+) intercalating chalcogenides reacted with NaAlCl4 during cycling to form stable phases. Thus, VS2 became essentially VS2Cl, with reversible capacity of approx 2.8 e(-)/V, and a mid-discharge voltage of approx 2.5V and 100 deep discharge cycles were readily achieved. A positive electrode consisting of VCl3 and S plus NaAlCl4 was subjected to deep-discharge cycles 300 times and it demonstrated identity with the in-situ-formed BSxCly cathode. NiS2 and NiS which are not Na(+)-intercalating structures formed highly reversible electrodes in NaAlCl4. The indicated discharge mechanism implies a theoretical capacity 4e(-)/Ni for NiS2 and 2e(-)/Ni for NiS. The mid-discharge potentials are, respectively, 2.4V and 2.1V. A Na/NiS2 cell cycling at a C/5 rate has exceeded 500 deep discharge cycles with 2.5e(-)/Ni average utilization. A 4 A-hr nominal capacity prototype Na/NiS2 cell was tested at 190 C. It was voluntarily terminated after 80 cycles. Further development, particularly of cathode structure and hardware should produce a battery capable of at least 50-W-hr/lb and more than 1000 cycles.

Modelling bio-electrosynthesis in a reverse microbial fuel cell to produce acetate from CO2 and H2O.

PubMed

Kazemi, M; Biria, D; Rismani-Yazdi, H

2015-05-21

Bio-electrosynthesis is one of the significant developments in reverse microbial fuel cell technology which is potentially capable of creating organic compounds by combining CO2 with H2O. Accordingly, the main objective in the current study was to present a model of microbial electrosynthesis for producing organic compounds (acetate) based on direct conduction of electrons in biofilms. The proposed model enjoys a high degree of rigor because it can predict variations in the substrate concentration, electrical potential, current density and the thickness of the biofilm. Additionally, coulombic efficiency was investigated as a function of substrate concentration and cathode potential. For a system containing CO2 as the substrate and Sporomusa ovata as the biofilm forming microorganism, an increase in the substrate concentration at a constant potential can lead to a decrease in coulombic efficiency as well as an increase in current density and biofilm thickness. On the other hand, an increase in the surface cathodic voltage at a constant substrate concentration may result in an increase in the coulombic efficiency and a decrease in the current density. The maximum coulombic efficiency was revealed to be 75% at a substrate concentration of 0.025 mmol cm(-3) and 55% at a surface cathodic voltage of -0.3 V producing a high range of acetate production by creating an optimal state in the concentration and potential intervals. Finally, the validity of the model was verified by comparing the obtained results with related experimental findings.

Prussian Blue Nanocubes with an Open Framework Structure Coated with PEDOT as High-Capacity Cathodes for Lithium-Sulfur Batteries.

PubMed

Su, Dawei; Cortie, Michael; Fan, Hongbo; Wang, Guoxiu

2017-12-01

It is shown that Prussian blue analogues (PBAs) can be a very competitive sulfur host for lithium-sulfur (Li-S) batteries. Sulfur stored in the large interstitial sites of a PBA host can take advantage of reversible and efficient insertion/extraction of both Li + and electrons, due to the well-trapped mobile dielectron redox centers in the well-defined host. It is demonstrated that Na 2 Fe[Fe(CN) 6 ] has a large open framework, and as a cathode, it both stores sulfur and acts as a polysulfide diffusion inhibitor based on the Lewis acid-base bonding effect. The electrochemical testing shows that the S@Na 2 Fe[Fe(CN) 6 ]@poly(3,4-ethylenedioxythiophene) composite achieves excellent reversibility, good stability, and fast kinetics. Its outstanding electrochemical properties should be ascribed to the internal transport of Li +/e- , maximizing the utilization of sulfur. Moreover, the open metal centers serve as the Lewis acid sites with high affinity to the negatively charged polysulfide anions, reducing the diffusion of polysulfides out of the cathode and minimizing the shuttling effect. The fundamental basis of these exceptional performance characteristics is explored through a detailed analysis of the structural and electrochemical behavior of the material. It is believed that the PBAs will have a useful role in ensuring more effective and stable Li-S batteries. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Tape Casting of High-Performance Low-Temperature Solid Oxide Cells with Thin La0.8Sr0.2Ga0.8Mg0.2O3-δ Electrolytes and Impregnated Nano Anodes.

PubMed

Gao, Zhan; Wang, Hongqian; Miller, Elizabeth; Liu, Qinyuan; Senn, Daniel; Barnett, Scott

2017-03-01

Low-temperature solid oxide cells (LT-SOCs), operating at 400 to 650 °C, have great potential for commercialization since they can provide lower cost and improved long-term durability. Low operating temperature can also enable high round-trip efficiency of SOCs as reversible energy storage devices. This paper describes Sr 0.8 La 0.2 TiO 3-α (SLT) anode supported LT-SOC with thin La 0.8 Sr 0.2 Ga 0.8 Mg 0.2 O 3-δ (LSGM) electrolyte made by tape casting, with screen printed La 0.6 Sr 0.4 Fe 0.8 Co 0.2 O 3-δ (LSCF) cathode and impregnated Ni anode. Optimization of the anode functional layers is described; the best anodes had 68 vol % LSGM and 12.3 vol % Ni and yielded maximum power density of 1.6 Wcm -2 with a cell area specific resistance (ASR) of 0.21 Ωcm 2 at 650 °C. Most of the cell ASR was associated with the cathode. Reversible electrolysis and fuel cell operation yielded similar characteristics with both 50% H 2 -50% H 2 O and syngas fuel. Life testing over 500 h showed that the cathode impedance stabilized after an initial break-in period; the ohmic and anode resistances, though relatively small, increased slightly with time.

A Dynamic Analysis of the Medium Tank Battalion. Volume I

DTIC Science & Technology

1978-06-01

best available copy. W. KEY WORDS (Cortinue an reverse oIde If necessary And Identifty block number) CONSTRUCTION; PLANNING; MANAGEMENT; MODELS...unit, with 64K, 8-bit bytes, (2) Dual-disk drive, 2 Discs at 262K, 8-bit bytes, (3) Cathode Ray Tube Console and Keyboard, (4) High- speed printer, (5

High-performance sodium–organic battery by realizing four-sodium storage in disodium rhodizonate

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

Lee, Minah; Hong, Jihyun; Lopez, Jeffrey

Sodium-ion batteries (SIBs) for grid-scale applications need active materials that combine a high energy density with sustainability. Given the high theoretical specific capacity 501 mAh g -1, and Earth abundance of disodium rhodizonate (Na 2C 6O 6), it is one of the most promising cathodes for SIBs. However, substantially lower reversible capacities have been obtained compared with the theoretical value and the understanding of this discrepancy has been limited. In this paper, we reveal that irreversible phase transformation of Na 2C 6O 6 during cycling is the origin of the deteriorating redox activity of Na 2C 6O 6. The active-particlemore » size and electrolyte conditions were identified as key factors to decrease the activation barrier of the phase transformation during desodiation. Finally, on the basis of this understanding, we achieved four-sodium storage in a Na 2C 6O 6 electrode with a reversible capacity of 484 mAh g -1, an energy density of 726 Wh kg -1 cathode, an energy efficiency above 87% and a good cycle retention.« less

Preparation of γ-LiV2O5 from polyoxovanadate cluster Li7[V15O36(CO3)] as a high-performance cathode material and its reaction mechanism revealed by operando XAFS

NASA Astrophysics Data System (ADS)

Wang, Heng; Isobe, Jin; Shimizu, Takeshi; Matsumura, Daiju; Ina, Toshiaki; Yoshikawa, Hirofumi

2017-08-01

γ-phase LiV2O5, which shows superior electrochemical performance as cathode material in Li-ion batteries, was prepared by annealing the polyoxovanadate cluster Li7 [V15O36(CO3)]. The reaction mechanism was studied using operando X-ray absorption fine structure (XAFS), powder X-ray diffraction (PXRD), and X-ray photoelectron spectroscopy (XPS) analyses. The X-ray absorption near edge structure (XANES) and XPS results reveal that γ-LiV2O5 undergoes two-electron redox reaction per V2O5 pyramid unit, resulting in a large reversible capacity of 260 Ah/kg. The extended X-ray absorption fine structure (EXAFS) and PXRD analyses also suggest that the V-V distance slightly increases, due to the reduction of V5+ to V4+ during Li ion intercalation as the material structure is maintained. As a result, γ-LixV2O5 shows highly reversible electrochemical reaction with x = 0.1-1.9.

High-performance sodium–organic battery by realizing four-sodium storage in disodium rhodizonate

DOE PAGES

Lee, Minah; Hong, Jihyun; Lopez, Jeffrey; ...

2017-10-09

Sodium-ion batteries (SIBs) for grid-scale applications need active materials that combine a high energy density with sustainability. Given the high theoretical specific capacity 501 mAh g -1, and Earth abundance of disodium rhodizonate (Na 2C 6O 6), it is one of the most promising cathodes for SIBs. However, substantially lower reversible capacities have been obtained compared with the theoretical value and the understanding of this discrepancy has been limited. In this paper, we reveal that irreversible phase transformation of Na 2C 6O 6 during cycling is the origin of the deteriorating redox activity of Na 2C 6O 6. The active-particlemore » size and electrolyte conditions were identified as key factors to decrease the activation barrier of the phase transformation during desodiation. Finally, on the basis of this understanding, we achieved four-sodium storage in a Na 2C 6O 6 electrode with a reversible capacity of 484 mAh g -1, an energy density of 726 Wh kg -1 cathode, an energy efficiency above 87% and a good cycle retention.« less

High-performance sodium-organic battery by realizing four-sodium storage in disodium rhodizonate

NASA Astrophysics Data System (ADS)

Lee, Minah; Hong, Jihyun; Lopez, Jeffrey; Sun, Yongming; Feng, Dawei; Lim, Kipil; Chueh, William C.; Toney, Michael F.; Cui, Yi; Bao, Zhenan

2017-11-01

Sodium-ion batteries (SIBs) for grid-scale applications need active materials that combine a high energy density with sustainability. Given the high theoretical specific capacity 501 mAh g-1, and Earth abundance of disodium rhodizonate (Na2C6O6), it is one of the most promising cathodes for SIBs. However, substantially lower reversible capacities have been obtained compared with the theoretical value and the understanding of this discrepancy has been limited. Here, we reveal that irreversible phase transformation of Na2C6O6 during cycling is the origin of the deteriorating redox activity of Na2C6O6. The active-particle size and electrolyte conditions were identified as key factors to decrease the activation barrier of the phase transformation during desodiation. On the basis of this understanding, we achieved four-sodium storage in a Na2C6O6 electrode with a reversible capacity of 484 mAh g-1, an energy density of 726 Wh kg-1cathode, an energy efficiency above 87% and a good cycle retention.

Porous nitrogen-doped carbon derived from silk fibroin protein encapsulating sulfur as a superior cathode material for high-performance lithium-sulfur batteries.

PubMed

Zhang, Jiawei; Cai, Yurong; Zhong, Qiwei; Lai, Dongzhi; Yao, Juming

2015-11-14

The features of a carbon substrate are crucial for the electrochemical performance of lithium-sulfur (Li-S) batteries. Nitrogen doping of carbon materials is assumed to play an important role in sulfur immobilisation. In this study, natural silk fibroin protein is used as a precursor of nitrogen-rich carbon to fabricate a novel, porous, nitrogen-doped carbon material through facile carbonisation and activation. Porous carbon, with a reversible capacity of 815 mA h g(-1) at 0.2 C after 60 cycles, serves as the cathode material in Li-S batteries. Porous carbon retains a reversible capacity of 567 mA h g(-1), which corresponds to a capacity retention of 98% at 1 C after 200 cycles. The promising electrochemical performance of porous carbon is attributed to its mesoporous structure, high specific surface area and nitrogen doping into the carbon skeleton. This study provides a general strategy to synthesise nitrogen-doped carbons with a high specific surface area, which is crucial to improve the energy density and electrochemical performance of Li-S batteries.

Non-Faradaic Li + Migration and Chemical Coordination across Solid-State Battery Interfaces

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

Gittleson, Forrest S.; El Gabaly, Farid

Efficient and reversible charge transfer is essential to realizing high-performance solid-state batteries. Efforts to enhance charge transfer at critical electrode–electrolyte interfaces have proven successful, yet interfacial chemistry and its impact on cell function remains poorly understood. Using X-ray photoelectron spectroscopy combined with electrochemical techniques, we elucidate chemical coordination near the LiCoO 2–LIPON interface, providing experimental validation of space-charge separation. Space-charge layers, defined by local enrichment and depletion of charges, have previously been theorized and modeled, but the unique chemistry of solid-state battery interfaces is now revealed. Here we highlight the non-Faradaic migration of Li+ ions from the electrode to themore » electrolyte, which reduces reversible cathodic capacity by ~15%. Inserting a thin, ion-conducting LiNbO 3 interlayer between the electrode and electrolyte, however, can reduce space-charge separation, mitigate the loss of Li+ from LiCoO 2, and return cathodic capacity to its theoretical value. This work illustrates the importance of interfacial chemistry in understanding and improving solid-state batteries.« less

Buried anode lithium thin film battery and process for forming the same

DOEpatents

Lee, Se-Hee; Tracy, C. Edwin; Liu, Ping

2004-10-19

A reverse configuration, lithium thin film battery (300) having a buried lithium anode layer (305) and process for making the same. The present invention is formed from a precursor composite structure (200) made by depositing electrolyte layer (204) onto substrate (201), followed by sequential depositions of cathode layer (203) and current collector (202) on the electrolyte layer. The precursor is subjected to an activation step, wherein a buried lithium anode layer (305) is formed via electroplating a lithium anode layer at the interface of substrate (201) and electrolyte film (204). The electroplating is accomplished by applying a current between anode current collector (201) and cathode current collector (202).

Sulfur cathodes with hydrogen reduced titanium dioxide inverse opal structure.

PubMed

Liang, Zheng; Zheng, Guangyuan; Li, Weiyang; Seh, Zhi Wei; Yao, Hongbin; Yan, Kai; Kong, Desheng; Cui, Yi

2014-05-27

Sulfur is a cathode material for lithium-ion batteries with a high specific capacity of 1675 mAh/g. The rapid capacity fading, however, presents a significant challenge for the practical application of sulfur cathodes. Two major approaches that have been developed to improve the sulfur cathode performance include (a) fabricating nanostructured conductive matrix to physically encapsulate sulfur and (b) engineering chemical modification to enhance binding with polysulfides and, thus, to reduce their dissolution. Here, we report a three-dimensional (3D) electrode structure to achieve both sulfur physical encapsulation and polysulfides binding simultaneously. The electrode is based on hydrogen reduced TiO2 with an inverse opal structure that is highly conductive and robust toward electrochemical cycling. The relatively enclosed 3D structure provides an ideal architecture for sulfur and polysulfides confinement. The openings at the top surface allow sulfur infusion into the inverse opal structure. In addition, chemical tuning of the TiO2 composition through hydrogen reduction was shown to enhance the specific capacity and cyclability of the cathode. With such TiO2 encapsulated sulfur structure, the sulfur cathode could deliver a high specific capacity of ∼1100 mAh/g in the beginning, with a reversible capacity of ∼890 mAh/g after 200 cycles of charge/discharge at a C/5 rate. The Coulombic efficiency was also maintained at around 99.5% during cycling. The results showed that inverse opal structure of hydrogen reduced TiO2 represents an effective strategy in improving lithium sulfur batteries performance.

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

Chung, Sheng-Heng; Chang, Chi-Hao; Manthiram, Arumugam

Sulfur is an appealing cathode material for establishing advanced lithium batteries as it offers a high theoretical capacity of 1675 mA h g -1 at low material and operating costs. However, the lithium–sulfur (Li–S) electrochemical cells face several formidable challenges arising from both the materials chemistry (e.g., low electrochemical utilization of sulfur and severe polysulfide diffusion) and battery chemistry (e.g., dynamic and static instability and low sulfur loadings). Here in this study, we present the design of a core–shell cathode with a pure sulfur core shielded within a conductive shell-shaped electrode. The new electrode configuration allows Li–S cells to loadmore » with a high amount of sulfur (sulfur loadings of up to 30 mg cm -2 and sulfur content approaching 70 wt%). The core–shell cathodes demonstrate a superior dynamic and static electrochemical stability in Li–S cells. The high-loading cathodes exhibit (i) a high sulfur utilization of up to 97% at C/20–C/2 rates and (ii) a low self-discharge during long-term cell storage for a three-month rest period and at different cell-storage conditions. Finally, a polysulfide-trap cell configuration is designed to evidence the eliminations of polysulfide diffusion and to investigate the relationship between the electrode configuration and electrochemical characteristics. Finally, the comprehensive analytical results based on the high-loading cathodes suggest that (i) the core–shell cathode is a promising solution for designing highly reversible Li–S cells and (ii) the polysulfide-trap cell configuration is a viable approach to qualitatively evaluating the presence or absence of polysulfide diffusion.« less

Efficient reversible electrodes for solid oxide electrolyzer cells

DOEpatents

Elangovan, S.; Hartvigsen, Joseph J.; Zhao, Feng

2013-01-15

An electrolyzer cell is disclosed which includes a cathode to reduce an oxygen-containing molecule, such as H2O, CO.sub.2, or a combination thereof, to produce an oxygen ion and a fuel molecule, such as H.sub.2, CO, or a combination thereof. An electrolyte is coupled to the cathode to transport the oxygen ion to an anode. The anode is coupled to the electrolyte to receive the oxygen ion and produce oxygen gas therewith. In one embodiment, the anode may be fabricated to include an electron-conducting phase having a perovskite crystalline structure or structure similar thereto. This perovskite may have a chemical formula of substantially (Pr(.sub.1-x)La.sub.x)(z-y)A'.sub.yBO(3-.differential.), wherein 0

Nanostructured metal carbides for aprotic Li-O 2 batteries. New insights into interfacial reactions and cathode stability

DOE PAGES

Kundu, Dipan; Black, Robert; Adams, Brian; ...

2015-05-01

The development of nonaqueous Li–oxygen batteries, which relies on the reversible reaction of Li + O 2 to give lithium peroxide (Li 2O 2), is challenged by several factors, not the least being the high charging voltage that results when carbon is typically employed as the cathode host. We report here on the remarkably low 3.2 V potential for Li 2O 2 oxidation on a passivated nanostructured metallic carbide (Mo 2C), carbon-free cathode host. Furthermore, online mass spectrometry coupled with X-ray photoelectron spectroscopy unequivocally demonstrates that lithium peroxide is simultaneously oxidized together with the Li xMoO 3-passivated conductive interface formedmore » on the carbide, owing to their close redox potentials. We found that the process rejuvenates the surface on each cycle upon electrochemical charge by releasing Li xMoO 3 into the electrolyte, explaining the low charging potential.« less

In Situ-Formed Hierarchical Metal-Organic Flexible Cathode for High-Energy Sodium-Ion Batteries.

PubMed

Huang, Ying; Fang, Chun; Zeng, Rui; Liu, Yaojun; Zhang, Wang; Wang, Yanjie; Liu, Qingju; Huang, Yunhui

2017-12-08

Metal-organic compounds are a family of electrode materials with structural diversity and excellent thermal stability for rechargeable batteries. Here, we fabricated a hierarchical nanocomposite with metal-organic cuprous tetracyanoquinodimethane (CuTCNQ) in a 3 D conductive carbon nanofibers (CNFs) network by in situ growth, and evaluated it as flexible cathode for sodium-ion batteries (SIBs). CuTCNQ in such flexible composite electrode is able to exhibit a high capacity of 252 mAh g -1 at 0.1 C and highly reversible stability for 1200 cycles within the voltage range of 2.5-4.1 V (vs. Na + /Na). A high specific energy of 762 Wh kg -1 was obtained with high average potential of 3.2 V (vs. Na + /Na). The in situ-formed electroactive metal-organic composites with tailored nanoarchitecture provide a promising alternative choice for high-performance cathode materials in SIBs with high energy. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

High-Performance Aluminum-Ion Battery with CuS@C Microsphere Composite Cathode.

PubMed

Wang, Shuai; Jiao, Shuqiang; Wang, Junxiang; Chen, Hao-Sen; Tian, Donghua; Lei, Haiping; Fang, Dai-Ning

2017-01-24

On the basis of low-cost, rich resources, and safety performance, aluminum-ion batteries have been regarded as a promising candidate for next-generation energy storage batteries in large-scale energy applications. A rechargeable aluminum-ion battery has been fabricated based on a 3D hierarchical copper sulfide (CuS) microsphere composed of nanoflakes as cathode material and room-temperature ionic liquid containing AlCl 3 and 1-ethyl-3-methylimidazolium chloride ([EMIm]Cl) as electrolyte. The aluminum-ion battery with a microsphere electrode exhibits a high average discharge voltage of ∼1.0 V vs Al/AlCl 4 - , reversible specific capacity of about 90 mA h g -1 at 20 mA g -1 , and good cyclability of nearly 100% Coulombic efficiency after 100 cycles. Such remarkable electrochemical performance is attributed to the well-defined nanostructure of the cathode material facilitating the electron and ion transfer, especially for chloroaluminate ions with large size, which is desirable for aluminum-ion battery applications.

Performance study of magnesium-sulfur battery using a graphene based sulfur composite cathode electrode and a non-nucleophilic Mg electrolyte.

PubMed

Vinayan, B P; Zhao-Karger, Zhirong; Diemant, Thomas; Chakravadhanula, Venkata Sai Kiran; Schwarzburger, Nele I; Cambaz, Musa Ali; Behm, R Jürgen; Kübel, Christian; Fichtner, Maximilian

2016-02-14

Here we report for the first time the development of a Mg rechargeable battery using a graphene-sulfur nanocomposite as the cathode, a Mg-carbon composite as the anode and a non-nucleophilic Mg based complex in tetraglyme solvent as the electrolyte. The graphene-sulfur nanocomposites are prepared through a new pathway by the combination of thermal and chemical precipitation methods. The Mg/S cell delivers a higher reversible capacity (448 mA h g(-1)), a longer cyclability (236 mA h g(-1) at the end of the 50(th) cycle) and a better rate capability than previously described cells. The dissolution of Mg polysulfides to the anode side was studied by X-ray photoelectron spectroscopy. The use of a graphene-sulfur composite cathode electrode, with the properties of a high surface area, a porous morphology, a very good electronic conductivity and the presence of oxygen functional groups, along with a non-nucleophilic Mg electrolyte gives an improved battery performance.

Lithium rich cathode/graphite anode combination for lithium ion cells with high tolerance to near zero volt storage

NASA Astrophysics Data System (ADS)

Crompton, K. R.; Staub, J. W.; Hladky, M. P.; Landi, B. J.

2017-03-01

Management of reversible lithium is an advantageous approach to design lithium ion cells that are tolerant to near zero volt (NZV) storage under fixed resistive load towards highly controllable, enhanced user-inactive safety. Presently, the first cycle loss from a high energy density Li-rich HE5050 cathode is used to provide excess reversible lithium when paired with an appropriately capacity matched mesocarbon microbead (MCMB) anode. Cells utilizing 1.2 M LiPF6 3:7 v/v ethylene carbonate:ethyl methyl carbonate electrolyte and a lithium reference were used for 3-electrode testing. After conditioning, a fixed resistive load was applied to 3-electrode cells for 72 or 168-h during which the anode potential and electrode asymptotic potential (EAP) remained less than the copper dissolution potential. After multiple storage cycles (room temperature or 40 °C), the NZV coulombic efficiency (cell reversibility) exceeded 97% and the discharge capacity retention was >98%. Conventional 2-electrode HE5050/MCMB pouch cells stored at NZV or open circuit for 3 days had nearly identical rate capability (up to 5C) and discharge performance stability (for 500 cycles under a 30% depth of discharge low-earth-orbit regime). Thus, lithium ion cells with appropriately capacity matched HE5050/MCMB electrodes have excellent tolerance to prolonged NZV storage, which can lead to enhanced user-inactive safety.

Evolution of strategies for modern rechargeable batteries.

PubMed

Goodenough, John B

2013-05-21

This Account provides perspective on the evolution of the rechargeable battery and summarizes innovations in the development of these devices. Initially, I describe the components of a conventional rechargeable battery along with the engineering parameters that define the figures of merit for a single cell. In 1967, researchers discovered fast Na(+) conduction at 300 K in Na β,β''-alumina. Since then battery technology has evolved from a strongly acidic or alkaline aqueous electrolyte with protons as the working ion to an organic liquid-carbonate electrolyte with Li(+) as the working ion in a Li-ion battery. The invention of the sodium-sulfur and Zebra batteries stimulated consideration of framework structures as crystalline hosts for mobile guest alkali ions, and the jump in oil prices in the early 1970s prompted researchers to consider alternative room-temperature batteries with aprotic liquid electrolytes. With the existence of Li primary cells and ongoing research on the chemistry of reversible Li intercalation into layered chalcogenides, industry invested in the production of a Li/TiS2 rechargeable cell. However, on repeated recharge, dendrites grew across the electrolyte from the anode to the cathode, leading to dangerous short-circuits in the cell in the presence of the flammable organic liquid electrolyte. Because lowering the voltage of the anode would prevent cells with layered-chalcogenide cathodes from competing with cells that had an aqueous electrolyte, researchers quickly abandoned this effort. However, once it was realized that an oxide cathode could offer a larger voltage versus lithium, researchers considered the extraction of Li from the layered LiMO2 oxides with M = Co or Ni. These oxide cathodes were fabricated in a discharged state, and battery manufacturers could not conceive of assembling a cell with a discharged cathode. Meanwhile, exploration of Li intercalation into graphite showed that reversible Li insertion into carbon occurred without dendrite formation. The SONY corporation used the LiCoO2/carbon battery to power their initial cellular telephone and launched the wireless revolution. As researchers developed 3D transition-metal hosts, manufacturers introduced spinel and olivine hosts in the Lix[Mn2]O4 and LiFe(PO4) cathodes. However, current Li-ion batteries fall short of the desired specifications for electric-powered automobiles and the storage of electrical energy generated by wind and solar power. These demands are stimulating new strategies for electrochemical cells that can safely and affordably meet those challenges.

Cold cathode vacuum discharge tube

DOEpatents

Boettcher, Gordon E.

1998-01-01

A cold cathode vacuum discharge tube, and method for making same, with an interior surface of the trigger probe coated with carbon deposited by carbon vapor deposition (CVD) or diamond-like carbon (DLC) deposition. Preferably a solid graphite insert is employed in the probe-cathode structure in place of an aluminum bushing employed in the prior art. The CVD or DLC probe face is laser scribed to allow resistance trimming to match available trigger voltage signals and to reduce electrical aging.

Vanadyl phosphates as high energy density cathode materials for rechargeable sodium battery

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

Zhang, Ruigang; Mizuno, Fuminori; Ling, Chen

A positive electrode comprising .epsilon.-VOPO.sub.4 and/or Na.sub.x(.epsilon.-VOPO.sub.4) wherein x is a value from 0.1 to 1.0 as an active ingredient, wherein the electrode is capable of insertion and release of sodium ions and a reversible sodium battery containing the positive electrode are provided.

Suppression of shunting current in a magnetically insulated coaxial vacuum diode

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

Yalandin, M. I.; Sharypov, K. A.; Shpak, V. G.

2015-06-08

Real-time investigations of the dynamics of explosive electron emission from a high-voltage cathode holder made of nonmagnetic stainless steel in a magnetically insulated coaxial vacuum diode have been performed. It has been shown that aging the cathode with several tens of voltage pulses at a field of 1–2 MV/cm provides a stray emission delay ranging from hundreds of picoseconds to a nanosecond or more. In addition, the magnetic field must be configured so that the magnetic lines would not cross the vacuum gap between the diode case and the cathode holder in the region behind the emitting edge of themore » cathode. These efforts provide conditions for stable emission of the working beam from a graphite cathode with a sharp emitting edge.« less

Disulfide-Bridged (Mo3S11) Cluster Polymer: Molecular Dynamics and Application as Electrode Material for a Rechargeable Magnesium Battery.

PubMed

Truong, Quang Duc; Kempaiah Devaraju, Murukanahally; Nguyen, Duc N; Gambe, Yoshiyuki; Nayuki, Keiichiro; Sasaki, Yoshikazu; Tran, Phong D; Honma, Itaru

2016-09-14

Exploring novel electrode materials is critical for the development of a next-generation rechargeable magnesium battery with high volumetric capacity. Here, we showed that a distinct amorphous molybdenum sulfide, being a coordination polymer of disulfide-bridged (Mo3S11) clusters, has great potential as a rechargeable magnesium battery cathode. This material provided good reversible capacity, attributed to its unique structure with high flexibility and capability of deformation upon Mg insertion. Free-terminal disulfide moiety may act as the active site for reversible insertion and extraction of magnesium.

An electrochemical study of a liquid crystal used in information displays

NASA Technical Reports Server (NTRS)

Oglesby, D. M.; Kern, J. B.; Robertson, J. B.

1974-01-01

The operational lifetime of liquid crystal displays were investigated. Electrochemical reaction at the electrodes of the display can cause failure after 2000 to 3000 hours of operation. Studies using cyclic voltametry of electrochemical reactions of N (p-methoxybenzilidene p-butylaniline (MBBA), a nematic liquid crystal were made. These studies indicate the presence of a reversible reduction of MBBA at the cathode, and that the reduction product undergoes a further reaction leading to products which are not reversibly oxidized. It is concluded that the degradation of the liquid crystal in displays can be reduced with a suitable frequency of alternating voltage.

Development of reverse biased p-n junction electron emission

NASA Technical Reports Server (NTRS)

Fowler, P.; Muly, E. C.

1971-01-01

A cold cathode emitter of hot electrons for use as a source of electrons in vacuum gauges and mass spectrometers was developed using standard Norton electroluminescent silicon carbide p-n diodes operated under reverse bias conditions. Continued development including variations in the geometry of these emitters was carried out such that emitters with an emission efficiency (emitted current/junction current) as high as 3 x 10-0.00001 were obtained. Pulse measurements of the diode characteristics were made and showed that higher efficiency can be attained under pulse conditions probably due to the resulting lower temperatures resulting from such operation.

Surface and bulk modified high capacity layered oxide cathodes with low irreversible capacity loss

NASA Technical Reports Server (NTRS)

Manthiram, Arumugam (Inventor); Wu, Yan (Inventor)

2010-01-01

The present invention includes compositions, surface and bulk modifications, and methods of making of (1-x)Li[Li.sub.1/3Mn.sub.2/3]O.sub.2.xLi[Mn.sub.0.5-yNi.sub.0.5-yCo.sub.2- y]O.sub.2 cathode materials having an O3 crystal structure with a x value between 0 and 1 and y value between 0 and 0.5, reducing the irreversible capacity loss in the first cycle by surface modification with oxides and bulk modification with cationic and anionic substitutions, and increasing the reversible capacity to close to the theoretical value of insertion/extraction of one lithium per transition metal ion (250-300 mAh/g).

O3-type Na(Mn₀.₂₅Fe₀.₂₅Co₀.₂₅Ni₀.₂₅)O₂: a quaternary layered cathode compound for rechargeable Na ion batteries

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

Li, Xi; Zhou, Yong-Ning; Wu, Di

2014-12-01

We report a new layered Na(Mn₀.₂₅Fe₀.₂₅Co₀.₂₅Ni₀.₂₅)O₂ compound with O3 oxygen stacking. It delivers 180 mAh/g initial discharge capacity and 578 Wh/kg specific energy density with good cycling capability at high cutoff voltage. In situ X-ray diffraction (XRD) shows a reversible structure evolution of O3-P3-O3'-O3'' upon Na de-intercalation. The excellent capacity and cycling performance at high cutoff voltage make it an important model system for studying the general issue of capacity fading in layered Na cathode compounds.

Modeling carbonaceous particle formation in an argon graphite cathode dc discharge

NASA Astrophysics Data System (ADS)

Michau, A.; Lombardi, G.; Colina Delacqua, L.; Redolfi, M.; Arnas, C.; Bonnin, X.; Hassouni, K.

2010-12-01

We develop a model for the nucleation, growth and transport of carbonaceous dust particles in a non-reactive gas dc discharge where the carbon source is provided by cathode sputtering. We consider only the initial phase of the discharge when the dust charge density remains small with respect to the electron density. We find that an electric field reversal at the entrance of the negative glow region promotes trapping of negatively charged clusters and dust particles, confining them for long times in the plasma and favoring molecular growth. An essential ingredient for this process is electron attachment, which negatively charges the initially neutral clusters. We perform sensitivity studies on several number parameters: size of the largest molecular edifice, sticking coefficient, etc.

Surface and bulk modified high capacity layered oxide cathodes with low irreversible capacity loss

DOEpatents

Manthiram, Arumugam; Wu, Yan

2010-03-16

The present invention includes compositions, surface and bulk modifications, and methods of making of (1-x)Li[Li.sub.1/3Mn.sub.2/3]O.sub.2.xLi[Mn.sub.0.5-yNi.sub.0.5-yCo.sub.2- y]O.sub.2 cathode materials having an O3 crystal structure with a x value between 0 and 1 and y value between 0 and 0.5, reducing the irreversible capacity loss in the first cycle by surface modification with oxides and bulk modification with cationic and anionic substitutions, and increasing the reversible capacity to close to the theoretical value of insertion/extraction of one lithium per transition metal ion (250-300 mAh/g).

Direct current microhollow cathode discharges on silicon devices operating in argon and helium

NASA Astrophysics Data System (ADS)

Michaud, R.; Felix, V.; Stolz, A.; Aubry, O.; Lefaucheux, P.; Dzikowski, S.; Schulz-von der Gathen, V.; Overzet, L. J.; Dussart, R.

2018-02-01

Microhollow cathode discharges have been produced on silicon platforms using processes usually used for MEMS fabrication. Microreactors consist of 100 or 150 μm-diameter cavities made from Ni and SiO2 film layers deposited on a silicon substrate. They were studied in the direct current operating mode in two different geometries: planar and cavity configuration. Currents in the order of 1 mA could be injected in microdischarges operating in different gases such as argon and helium at a working pressure between 130 and 1000 mbar. When silicon was used as a cathode, the microdischarge operation was very unstable in both geometry configurations. Strong current spikes were produced and the microreactor lifetime was quite short. We evidenced the fast formation of blisters at the silicon surface which are responsible for the production of these high current pulses. EDX analysis showed that these blisters are filled with argon and indicate that an implantation mechanism is at the origin of this surface modification. Reversing the polarity of the microdischarge makes the discharge operate stably without current spikes, but the discharge appearance is quite different from the one obtained in direct polarity with the silicon cathode. By coating the silicon cathode with a 500 nm-thick nickel layer, the microdischarge becomes very stable with a much longer lifetime. No current spikes are observed and the cathode surface remains quite smooth compared to the one obtained without coating. Finally, arrays of 76 and 576 microdischarges were successfully ignited and studied in argon. At a working pressure of 130 mbar, all microdischarges are simultaneously ignited whereas they ignite one by one at higher pressure.

Spinel compounds as multivalent battery cathodes: A systematic evaluation based on ab initio calculations

DOE PAGES

Liu, Miao; Rong, Ziqin; Malik, Rahul; ...

2014-12-16

In this study, batteries that shuttle multivalent ions such as Mg 2+ and Ca 2+ ions are promising candidates for achieving higher energy density than available with current Li-ion technology. Finding electrode materials that reversibly store and release these multivalent cations is considered a major challenge for enabling such multivalent battery technology. In this paper, we use recent advances in high-throughput first-principles calculations to systematically evaluate the performance of compounds with the spinel structure as multivalent intercalation cathode materials, spanning a matrix of five different intercalating ions and seven transition metal redox active cations. We estimate the insertion voltage, capacity,more » thermodynamic stability of charged and discharged states, as well as the intercalating ion mobility and use these properties to evaluate promising directions. Our calculations indicate that the Mn 2O 4 spinel phase based on Mg and Ca are feasible cathode materials. In general, we find that multivalent cathodes exhibit lower voltages compared to Li cathodes; the voltages of Ca spinels are ~0.2 V higher than those of Mg compounds (versus their corresponding metals), and the voltages of Mg compounds are ~1.4 V higher than Zn compounds; consequently, Ca and Mg spinels exhibit the highest energy densities amongst all the multivalent cation species. The activation barrier for the Al³⁺ ion migration in the Mn₂O₄ spinel is very high (~1400 meV for Al 3+ in the dilute limit); thus, the use of an Al based Mn spinel intercalation cathode is unlikely. Amongst the choice of transition metals, Mn-based spinel structures rank highest when balancing all the considered properties.« less

A core–shell electrode for dynamically and statically stable Li–S battery chemistry

DOE PAGES

Chung, Sheng-Heng; Chang, Chi-Hao; Manthiram, Arumugam

2016-08-17

Sulfur is an appealing cathode material for establishing advanced lithium batteries as it offers a high theoretical capacity of 1675 mA h g -1 at low material and operating costs. However, the lithium–sulfur (Li–S) electrochemical cells face several formidable challenges arising from both the materials chemistry (e.g., low electrochemical utilization of sulfur and severe polysulfide diffusion) and battery chemistry (e.g., dynamic and static instability and low sulfur loadings). Here in this study, we present the design of a core–shell cathode with a pure sulfur core shielded within a conductive shell-shaped electrode. The new electrode configuration allows Li–S cells to loadmore » with a high amount of sulfur (sulfur loadings of up to 30 mg cm -2 and sulfur content approaching 70 wt%). The core–shell cathodes demonstrate a superior dynamic and static electrochemical stability in Li–S cells. The high-loading cathodes exhibit (i) a high sulfur utilization of up to 97% at C/20–C/2 rates and (ii) a low self-discharge during long-term cell storage for a three-month rest period and at different cell-storage conditions. Finally, a polysulfide-trap cell configuration is designed to evidence the eliminations of polysulfide diffusion and to investigate the relationship between the electrode configuration and electrochemical characteristics. Finally, the comprehensive analytical results based on the high-loading cathodes suggest that (i) the core–shell cathode is a promising solution for designing highly reversible Li–S cells and (ii) the polysulfide-trap cell configuration is a viable approach to qualitatively evaluating the presence or absence of polysulfide diffusion.« less

Mitigation of the irreversible capacity and electrolyte decomposition in a LiNi 0.5Mn 1.5O 4/nano-TiO 2 Li-ion battery

NASA Astrophysics Data System (ADS)

Brutti, Sergio; Gentili, Valentina; Reale, Priscilla; Carbone, Lorenzo; Panero, Stefania

Nanosized titanium oxides can achieve large reversible specific capacity (above 200 mAh g -1) and good rate capabilities, but suffer irreversible capacity losses in the first cycle. Moreover, due to the intrinsic safe operating potential (1.5 V), the use of titanium oxide requires to couple it with high-potential cathodes, such as lithium nickel manganese spinel (LNMO) in order to increase the energy density of the final cell. However the use of the 4.7 V vs. Li +/Li 0 LNMO cathode material requires to tackle the continuous electrolyte decomposition upon cycling. Coupling these two electrodes to make a lithium ion battery is thus highly appealing but also highly difficult because the cell balancing must account not only for the charge reversibly exchanged by each electrode but also for the irreversible charge losses. In this paper a LNMO-nano TiO 2 Li-ion cell with liquid electrolyte is presented: two innovative approaches on both the cathode and the anode sides were developed in order to mitigate the electrolyte decomposition upon cycling. In particular the LNMO surface was coated with ZnO in order to minimize the surface reactivity, and the TiO 2 nanoparticles where activated by incorporating nano-lithium in the electrode formulation to compensate for the irreversible capacity loss in the first cycle. With these strategies we were able to assemble balanced Li-ion coin cells thus avoiding the use of electrolyte additives and more hazardous and expensive ex-situ SEI preforming chemical or electrochemical procedures.

Free-standing and flexible organic cathode based on aromatic carbonyl compound/carbon nanotube composite for lithium and sodium organic batteries.

PubMed

Yuan, Chenpei; Wu, Qiong; Shao, Qi; Li, Qiang; Gao, Bo; Duan, Qian; Wang, Heng-Guo

2018-05-01

Free-standing and flexible organic cathode based on aromatic carbonyl compound/carbon nanotubes (CNTs) has been successfully synthesized by a simple vacuum filtration strategy. The obtained flexible and free-standing film could be directly used as the binder-, additive- and current collector-free cathode for lithium ion batteries (LIBs) and sodium ion batteries (SIBs). Benefitting from the synergistic effect provided by the aromatic carbonyl compound and CNTs, the flexible organic cathode shows excellent lithium and sodium storage properties, including high reversible capacity (∼150 mAh g -1 at 50 mA g -1 for LIBs and 57.8 mAh g -1 at 25 mA g -1 for SIBs), excellent cycling stability (over 500 cycles for LIBs and 300 cycles for SIBs) and good rate capability (48 mAh g -1 even at 2000 mA g -1 for LIBs and 48 mAh g -1 even at 1000 mA g -1 for SIBs). In view of the simple preparation process and excellent performance, the proposed strategy might open new avenues for the design of high-performance flexible organic electrode for the application in energy storage and conversion. Copyright © 2018 Elsevier Inc. All rights reserved.

Explosion symmetry improvement of polyimide-coated tungsten wire in vacuum on negative discharge facility

NASA Astrophysics Data System (ADS)

Li, Mo; Wu, Jian; Lu, Yihan; Li, Xingwen; Li, Yang; Qiu, Mengtong

2018-01-01

Tungsten wire explosion is very asymmetric when fast current rate and insulated coatings are both applied on negative discharge facility using a 24-mm-diameter cathode geometry, which is commonly used on mega-ampere facilities. It is inferred, based on an analytical treatment of the guiding center drift and COMSOL simulations, that the large negative radial electric field causes early voltage breakdown and terminates energy deposition into the wire core on the anode side of the wire. After the anode side is short circuited, the radial electric field along the wire surface on the cathode side will change its polarity and thus leading to additional energy deposition into the wire core. This change causes ˜10 times larger energy deposition and ˜14 times faster explosion velocity in the cathode side than the anode side. In order to reduce this asymmetry, a hollow cylindrical cathode geometry was used to reverse the polarity of radial electric field and was optimized to use on multi-MA facilities. In this case, fully vaporized polyimide-coated tungsten wire with great symmetry improvement was achieved with energy deposition of ˜8.8 eV/atom. The atomic and electronic density distributions for the two different load geometries were obtained by the double-wavelength measurement.

The High Performance of Crystal Water Containing Manganese Birnessite Cathodes for Magnesium Batteries.

PubMed

Nam, Kwan Woo; Kim, Sangryun; Lee, Soyeon; Salama, Michael; Shterenberg, Ivgeni; Gofer, Yossi; Kim, Joo-Seong; Yang, Eunjeong; Park, Chan Sun; Kim, Ju-Sik; Lee, Seok-Soo; Chang, Won-Seok; Doo, Seok-Gwang; Jo, Yong Nam; Jung, Yousung; Aurbach, Doron; Choi, Jang Wook

2015-06-10

Rechargeable magnesium batteries have lately received great attention for large-scale energy storage systems due to their high volumetric capacities, low materials cost, and safe characteristic. However, the bivalency of Mg(2+) ions has made it challenging to find cathode materials operating at high voltages with decent (de)intercalation kinetics. In an effort to overcome this challenge, we adopt an unconventional approach of engaging crystal water in the layered structure of Birnessite MnO2 because the crystal water can effectively screen electrostatic interactions between Mg(2+) ions and the host anions. The crucial role of the crystal water was revealed by directly visualizing its presence and dynamic rearrangement using scanning transmission electron microscopy (STEM). Moreover, the importance of lowering desolvation energy penalty at the cathode-electrolyte interface was elucidated by working with water containing nonaqueous electrolytes. In aqueous electrolytes, the decreased interfacial energy penalty by hydration of Mg(2+) allows Birnessite MnO2 to achieve a large reversible capacity (231.1 mAh g(-1)) at high operating voltage (2.8 V vs Mg/Mg(2+)) with excellent cycle life (62.5% retention after 10000 cycles), unveiling the importance of effective charge shielding in the host and facile Mg(2+) ions transfer through the cathode's interface.

Mechanism of Zn Insertion into Nanostructured δ-MnO 2 : A Nonaqueous Rechargeable Zn Metal Battery

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

Han, Sang-Don; Kim, Soojeong; Li, Dongguo

2017-05-19

Unlike the more established lithium-ion based energy storage chemistries, the complex intercalation chemistry of multivalent cations in a host lattice is not well understood, especially the relationship between the intercalating species solution chemistry and the prevalence and type of side reactions. Among multivalent metals, a promising model system can be based on nonaqueous Zn2+ ion chemistry. Several examples of these systems support the use of a Zn metal anode, and reversible intercalation cathodes have been reported. This study utilizes a combination of analytical tools to probe the chemistry of a nanostructured delta-MnO2 cathode in association with a nonaqueous acetonitrile-Zn(TFSI)(2) electrolytemore » and a Zn metal anode. As many of the issues related to understanding a multivalent battery relate to the electrolyte electrode interface, the high surface area of a nanostructured cathode provides a significant interface between the electrolyte and cathode host that maximizes the spectroscopic signal of any side reactions or minor mechanistic pathways. Numerous factors affecting capacity fade and issues associated with the second phase formation including Mn dissolution in heavily cycled Zn/delta-MnO2 cells are presented including dramatic mechanistic differences in the storage mechanism of this couple when compared to similar aqueous electrolytes are noted.« less

Tunnel-structured Na 0.66[Mn 0.66Ti 0.34]O 2-xF x(x <0.1) cathode for high performance sodium-ion batteries

DOE PAGES

Wang, Qin-Chao; Qiu, Qi-Qi; Xiao, Na; ...

2018-03-13

Sodium-ion batteries (SIBs) are attracting significant research attentions for large-scale energy storage applications. Cathode material is the vital part of SIBs to determine the capacity and cycle performance. Here, a series of F-doped Na 0.66[Mn 0.66Ti 0.34]O 2-xF x (x < 0.1) cathodes with tunnel structure are designed and synthesized aiming to enlarge the sodium diffusion paths. The lattice parameters of unit cell are tuned successfully by adjusting F doping amount. Na 0.66[Mn 0.66Ti 0.34]O 1.94F 0.06 with the optimized stoichiometry exhibits a reversible capacity of 97 mAh g -1 and promising cycle performance (85 mAh g -1 is maintainedmore » at 2C after 1000 cycles) with extremely low voltage polarization. More significantly, Na 0.66[Mn 0.66Ti 0.34]O 1.94F 0.06 exhibits superior low temperature performance, owing to the much enhanced thermodynamics and kinetics benefited from F doping. In conclusion, this strategy may open new opportunities to design advanced intercalation-type cathode materials for sodium ion batteries, especially for low-temperature applications.« less

Tunnel-structured Na 0.66[Mn 0.66Ti 0.34]O 2-xF x(x <0.1) cathode for high performance sodium-ion batteries

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

Wang, Qin-Chao; Qiu, Qi-Qi; Xiao, Na

Sodium-ion batteries (SIBs) are attracting significant research attentions for large-scale energy storage applications. Cathode material is the vital part of SIBs to determine the capacity and cycle performance. Here, a series of F-doped Na 0.66[Mn 0.66Ti 0.34]O 2-xF x (x < 0.1) cathodes with tunnel structure are designed and synthesized aiming to enlarge the sodium diffusion paths. The lattice parameters of unit cell are tuned successfully by adjusting F doping amount. Na 0.66[Mn 0.66Ti 0.34]O 1.94F 0.06 with the optimized stoichiometry exhibits a reversible capacity of 97 mAh g -1 and promising cycle performance (85 mAh g -1 is maintainedmore » at 2C after 1000 cycles) with extremely low voltage polarization. More significantly, Na 0.66[Mn 0.66Ti 0.34]O 1.94F 0.06 exhibits superior low temperature performance, owing to the much enhanced thermodynamics and kinetics benefited from F doping. In conclusion, this strategy may open new opportunities to design advanced intercalation-type cathode materials for sodium ion batteries, especially for low-temperature applications.« less

Cold cathode vacuum discharge tube

DOEpatents

Boettcher, G.E.

1998-03-10

A cold cathode vacuum discharge tube, and method for making same, are disclosed with an interior surface of the trigger probe coated with carbon deposited by carbon vapor deposition (CVD) or diamond-like carbon (DLC) deposition. Preferably a solid graphite insert is employed in the probe-cathode structure in place of an aluminum bushing employed in the prior art. The CVD or DLC probe face is laser scribed to allow resistance trimming to match available trigger voltage signals and to reduce electrical aging. 15 figs.

Cold cathode vacuum discharge tube

DOEpatents

Boettcher, G.E.

1998-04-14

A cold cathode vacuum discharge tube, and method for making same, with an interior surface of the trigger probe coated with carbon deposited by chemical vapor deposition (CVD) or diamond-like carbon (DLC) deposition are disclosed. Preferably a solid graphite insert is employed in the probe-cathode structure in place of an aluminum bushing employed in the prior art. The CVD or DLC probe face is laser scribed to allow resistance trimming to match available trigger voltage signals and to reduce electrical aging. 14 figs.

Electro-migration of heavy metals in an aged electroplating contaminated soil affected by the coexisting hexavalent chromium.

PubMed

Zhang, Weihua; Zhuang, Luwen; Tong, Lizhi; Lo, Irene M C; Qiu, Rongliang

2012-02-01

Cr(VI) was often reported to oxidize soil organic matter at acidic environments due to its high ORP, probably thus changing cationic metal species bound to soil organic matter, and influencing their electro-migration patterns. However, such an effect on the electro-migration was not confirmed in most previous studies. Therefore, this study applied a fixed voltage direct current field on an aged electroplating contaminated clayed soil, with a special interest in the direct or indirect influence of Cr(VI) on the electro-migration of other coexisting metals. After 353 h electrokinetic process, 81% of Zn, 53% of Ni and 22% of Cu in the original soil were electro-migrated into the electrolyte, and most of the remaining concentrated near the cathode. The Cr(VI) oxidized some soil organic matter along its migration pathway, with a pronounced reaction occurred near the anode at low pHs. The resulting Cr(III) reversed its original movement, and migrated towards the cathode, leading to the occurrence of a second Cr concentration peak in the soil. Metal species analyses showed that the amount of metals bound to soil organic matter significantly decreased, while a substantial increase in the Cr species bound to Fe/Mn (hydro-)oxides was observed, suggesting an enhancement of cationic metal electro-migration by the reduction of Cr(VI) into Cr(III). However, the Cr(VI) may form some stable lead chromate precipitates, and in turn demobilize Pb in the soil, as the results showed a low Pb removal and an increase in its acid-extractable and residual fractions after electrokinetic remediation. Copyright © 2011 Elsevier Ltd. All rights reserved.

Enhancing Near Zero Volt Storage Tolerance of Lithium-ion Batteries

NASA Astrophysics Data System (ADS)

Crompton, Kyle R.

There are inherent safety risks associated with inactive lithium ion batteries leading to greater restrictions and regulations on shipping and storage. Maintaining all cells of a lithium ion battery at near zero voltage with an applied fixed resistive load is one promising approach which can lessen (and potentially eliminate) the risk of a lithium ion battery entering thermal runaway when in an inactive state. However, in a conventional lithium ion cell, a near zero cell voltage can be damaging if the anode electrochemical potential increases to greater than the potential where dissolution of the standard copper current collector occurs (i.e. 3.1 V vs. Li/Li+ at room temperature). Past approaches to yield lithium ion cells that are resilient to a near zero volt state of charge involve use of secondary active materials or alternative current collectors which have anticipated tradeoffs in terms of cell performance and cost. In the the present dissertation work the approach of managing the amount of reversible lithium in a cell during construction to prevent the anode potential from increasing to greater than 3.1 V vs. Li/Li+ during near zero volt storage is introduced. Anode pre-lithiation was used in LiCoO 2/MCMB pouch cells to appropriately manage the amount of reversible lithium so that there is excess reversible lithium compared to the cathodes intercalation capacity (reversible lithium excess cell or RLE cell). RLE LiCoO 2/MCMB cells maintained 99% of their original capacity after three, 3-day and three, 7-day storage periods at near zero volts under fixed load. A LiCoO2/MCMB pouch cell fabricated with a pre-lithiated anode also maintained its original discharge performance after three, 3-day storage periods under fixed load at 45°C. The strong recharge performance after near zero volt storage is attributed to the anode potential remaining below the copper dissolution potential during near zero volt storage as informed by reference electrode measurements. Pulse discharge measurements were performed and show that double layer capacitance likely plays a major role in determining the behavior of electrode potentials during near zero volt storage. To further the viability of the anode pre-lithiation method in LiCoO2/MCMB cells, stabilization coatings on the cathode materials are being investigated to increase the tolerance of the cathode to the low potentials it may experience during near zero volt storage of an RLE lithium ion cell. Results show that an AlPO4 coating prevents cation exhange in the cathode crystal structure and substantially increases the cathode's resilience to low electrochemical potentials. Investigations into applying anode pre-lithiation to cells utilizing LiNiCoAlO2 (NCA) cathodes have also been initiated and found to maintain the anode potential below the copper dissolution potential during near zero volt storage. RLE NCA/MCMB cells showed strong recharge performance and improved rate capability retention over a conventional NCA/MCMB cell after ten, 3-day near zero volt storage periods. Scale up of reversible lithium management to NCA/MCMB x3450 pouch cells was achieved using bath lithium addition and rendered a cell that retained 100% of its discharge performance after a 14 day period at near zero volts under fixed load. The near zero volt storage tolerance of lithium ion cells utilizing an advanced, high energy density lithium rich cathode material (0.49Li2MnO3˙0.51LiNi 0.37Co0.24Mn0.39O2 or HE5050) has also been studied and found to be high at room temperature without the need for anode pre-lithiation. HE5050/MCMB cells maintained 100% of their discharge capacity after five, 3-day and five, 7-day near zero volt storage periods at room temperature. HE5050/MCMB also maintained 99% of their discharge capacity after two, 3-day near zero volt storage periods at 40°C. The high first cycle loss and lower intercalation potential of the HE5050 cathode lead to the anode potential remaining <2.8 V vs. Li/Li+ during near zero volt storage and as such, no copper dissolution is expected to be occurring. Finally, Carbon Nanotube (CNT) papers have been shown to be stable up to high potentials vs. Li/Li+ and thus, using them as an anode current collector in place of standard copper can generate lithium ion cells that can tolerate near zero volt storage. However, CNT papers suffer from significant irreversible loss due to their high surface area. An Al2O3 coating deposited by atomic layer deposition is investigated for its effect in reducing the irreversible losses of a CNT paper. The Al2O3 coating was found to reduce irreversible loss by 55% over 50 cycles and still serve as an effective current collector for a graphitic anode composite.

Thermal abuse performance of high-power 18650 Li-ion cells

NASA Astrophysics Data System (ADS)

Roth, E. P.; Doughty, D. H.

High-power 18650 Li-ion cells have been developed for hybrid electric vehicle applications as part of the DOE Advanced Technology Development (ATD) program. The thermal abuse response of two advanced chemistries (Gen1 and Gen2) were measured and compared with commercial Sony 18650 cells. Gen1 cells consisted of an MCMB graphite based anode and a LiNi 0.85Co 0.15O 2 cathode material while the Gen2 cells consisted of a MAG10 anode graphite and a LiNi 0.80Co 0.15 Al 0.05O 2 cathode. Accelerating rate calorimetry (ARC) and differential scanning calorimetry (DSC) were used to measure the thermal response and properties of the cells and cell materials up to 400 °C. The MCMB graphite was found to result in increased thermal stability of the cells due to more effective solid electrolyte interface (SEI) formation. The Al stabilized cathodes were seen to have higher peak reaction temperatures that also gave improved cell thermal response. The effects of accelerated aging on cell properties were also determined. Aging resulted in improved cell thermal stability with the anodes showing a rapid reduction in exothermic reactions while the cathodes only showed reduced reactions after more extended aging.

ZnFe2O4-C/LiFePO4-CNT: A Novel High-Power Lithium-Ion Battery with Excellent Cycling Performance.

PubMed

Varzi, Alberto; Bresser, Dominic; von Zamory, Jan; Müller, Franziska; Passerini, Stefano

2014-07-15

An innovative and environmentally friendly battery chemistry is proposed for high power applications. A carbon-coated ZnFe 2 O 4 nanoparticle-based anode and a LiFePO 4 -multiwalled carbon nanotube-based cathode, both aqueous processed with Na-carboxymethyl cellulose, are combined, for the first time, in a Li-ion full cell with exceptional electrochemical performance. Such novel battery shows remarkable rate capabilities, delivering 50% of its nominal capacity at currents corresponding to ≈20C (with respect to the limiting cathode). Furthermore, the pre-lithiation of the negative electrode offers the possibility of tuning the cell potential and, therefore, achieving remarkable gravimetric energy and power density values of 202 Wh kg -1 and 3.72 W kg -1 , respectively, in addition to grant a lithium reservoir. The high reversibility of the system enables sustaining more than 10 000 cycles at elevated C-rates (≈10C with respect to the LiFePO 4 cathode), while retaining up to 85% of its initial capacity.

ZnFe2O4-C/LiFePO4-CNT: A Novel High-Power Lithium-Ion Battery with Excellent Cycling Performance

PubMed Central

Varzi, Alberto; Bresser, Dominic; von Zamory, Jan; Müller, Franziska; Passerini, Stefano

2014-01-01

An innovative and environmentally friendly battery chemistry is proposed for high power applications. A carbon-coated ZnFe2O4 nanoparticle-based anode and a LiFePO4-multiwalled carbon nanotube-based cathode, both aqueous processed with Na-carboxymethyl cellulose, are combined, for the first time, in a Li-ion full cell with exceptional electrochemical performance. Such novel battery shows remarkable rate capabilities, delivering 50% of its nominal capacity at currents corresponding to ≈20C (with respect to the limiting cathode). Furthermore, the pre-lithiation of the negative electrode offers the possibility of tuning the cell potential and, therefore, achieving remarkable gravimetric energy and power density values of 202 Wh kg−1 and 3.72 W kg−1, respectively, in addition to grant a lithium reservoir. The high reversibility of the system enables sustaining more than 10 000 cycles at elevated C-rates (≈10C with respect to the LiFePO4 cathode), while retaining up to 85% of its initial capacity. PMID:26190956

Rechargeable magnesium-ion battery based on a TiSe2-cathode with d-p orbital hybridized electronic structure

PubMed Central

Gu, Yunpeng; Katsura, Yukari; Yoshino, Takafumi; Takagi, Hidenori; Taniguchi, Kouji

2015-01-01

Rechargeable ion-batteries, in which ions such as Li+ carry charges between electrodes, have been contributing to the improvement of power-source performance in a wide variety of mobile electronic devices. Among them, Mg-ion batteries are recently attracting attention due to possible low cost and safety, which are realized by abundant natural resources and stability of Mg in the atmosphere. However, only a few materials have been known to work as rechargeable cathodes for Mg-ion batteries, owing to strong electrostatic interaction between Mg2+ and the host lattice. Here we demonstrate rechargeable performance of Mg-ion batteries at ambient temperature by selecting TiSe2 as a model cathode by focusing on electronic structure. Charge delocalization of electrons in a metal-ligand unit through d-p orbital hybridization is suggested as a possible key factor to realize reversible intercalation of Mg2+ into TiSe2. The viewpoint from the electronic structure proposed in this study might pave a new way to design electrode materials for multivalent-ion batteries. PMID:26228263

Structural changes in a commercial lithium-ion battery during electrochemical cycling: An in situ neutron diffraction study

NASA Astrophysics Data System (ADS)

Sharma, Neeraj; Peterson, Vanessa K.; Elcombe, Margaret M.; Avdeev, Maxim; Studer, Andrew J.; Blagojevic, Ned; Yusoff, Rozila; Kamarulzaman, Norlida

The structural response to electrochemical cycling of the components within a commercial Li-ion battery (LiCoO 2 cathode, graphite anode) is shown through in situ neutron diffraction. Lithuim insertion and extraction is observed in both the cathode and anode. In particular, reversible Li incorporation into both layered and spinel-type LiCoO 2 phases that comprise the cathode is shown and each of these components features several phase transitions attributed to Li content and correlated with the state-of-charge of the battery. At the anode, a constant cell voltage correlates with a stable lithiated graphite phase. Transformation to de-lithiated graphite at the discharged state is characterised by a sharp decrease in both structural cell parameters and cell voltage. In the charged state, a two-phase region exists and is composed of the lithiated graphite phase and about 64% LiC 6. It is postulated that trapping Li in the solid|electrolyte interface layer results in minimal structural changes to the lithiated graphite anode across the constant cell voltage regions of the electrochemical cycle.

Multiangular Rod-Shaped Na0.44MnO2 as Cathode Materials with High Rate and Long Life for Sodium-Ion Batteries.

PubMed

Liu, Qiannan; Hu, Zhe; Chen, Mingzhe; Gu, Qinfen; Dou, Yuhai; Sun, Ziqi; Chou, Shulei; Dou, Shi Xue

2017-02-01

The tunnel-structured Na 0.44 MnO 2 is considered as a promising cathode material for sodium-ion batteries because of its unique three-dimensional crystal structure. Multiangular rod-shaped Na 0.44 MnO 2 have been first synthesized via a reverse microemulsion method and investigated as high-rate and long-life cathode materials for Na-ion batteries. The microstructure and composition of prepared Na 0.44 MnO 2 is highly related to the sintering temperature. This structure with suitable size increases the contact area between the material and the electrolyte and guarantees fast sodium-ion diffusion. The rods prepared at 850 °C maintain specific capacity of 72.8 mA h g -1 and capacity retention of 99.6% after 2000 cycles at a high current density of 1000 mA g -1 . The as-designed multiangular Na 0.44 MnO 2 provides new insight into the development of tunnel-type electrode materials and their application in rechargeable sodium-ion batteries.

Li2C2, a High-Capacity Cathode Material for Lithium Ion Batteries.

PubMed

Tian, Na; Gao, Yurui; Li, Yurong; Wang, Zhaoxiang; Song, Xiaoyan; Chen, Liquan

2016-01-11

As a typical alkaline earth metal carbide, lithium carbide (Li2C2) has the highest theoretical specific capacity (1400 mA h g(-1)) among all the reported lithium-containing cathode materials for lithium ion batteries. Herein, the feasibility of using Li2C2 as a cathode material was studied. The results show that at least half of the lithium can be extracted from Li2C2 and the reversible specific capacity reaches 700 mA h g(-1). The C≡C bond tends to rotate to form C4 (C≡C⋅⋅⋅C≡C) chains during lithium extraction, as indicated with the first-principles molecular dynamics (FPMD) simulation. The low electronic and ionic conductivity are believed to be responsible for the potential gap between charge and discharge, as is supported with density functional theory (DFT) calculations and Arrhenius fitting results. These findings illustrate the feasibility to use the alkali and alkaline earth metal carbides as high-capacity electrode materials for secondary batteries. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Bottom-Up Catalytic Approach towards Nitrogen-Enriched Mesoporous Carbons/Sulfur Composites for Superior Li-S Cathodes

PubMed Central

Sun, Fugen; Wang, Jitong; Chen, Huichao; Qiao, Wenming; Ling, Licheng; Long, Donghui

2013-01-01

We demonstrate a sustainable and efficient approach to produce high performance sulfur/carbon composite cathodes via a bottom-up catalytic approach. The selective oxidation of H2S by a nitrogen-enriched mesoporous carbon catalyst can produce elemental sulfur as a by-product which in-situ deposit onto the carbon framework. Due to the metal-free catalytic characteristic and high catalytic selectivity, the resulting sulfur/carbon composites have almost no impurities that thus can be used as cathode materials with compromising battery performance. The layer-by-layer sulfur deposition allows atomic sulfur binding strongly with carbon framework, providing efficient immobilization of sulfur. The nitrogen atoms doped on the carbon framework can increase the surface interactions with polysulfides, leading to the improvement in the trapping of polysulfides. Thus, the composites exhibit a reversible capacity of 939 mAh g−1 after 100 cycles at 0.2 C and an excellent rate capability of 527 mAh g−1 at 5 C after 70 cycles. PMID:24084754

Habit plane-driven P2-type manganese-based layered oxide as long cycling cathode for Na-ion batteries

NASA Astrophysics Data System (ADS)

Luo, Rui; Wu, Feng; Xie, Man; Ying, Yao; Zhou, Jiahui; Huang, Yongxin; Ye, Yusheng; Li, Li; Chen, RenJie

2018-04-01

Layered transition metal oxides are considered to be promising candidates as cathode materials for sodium-ion batteries. Herein, a facile solid-state reaction is developed to synthesize hexagons plate-like Na0.67Ni0.25Mn0.75O2+δ (denoted as P2-NNM) material with habit plane formed. The structure of this layered oxide is characterized by XRD, HR-TEM and SAED. The layered material delivers a high reversible capacity of 91.8 mAh g-1 at 0.2 C with a capacity retention of 94.4 % after 280 cycles, superior rate capability and long cycle life (84.2 % capacity retention after 1000 cycle). Ni2+ is an active ion and Ni doping alleviates the Jahn-Teller distortion, and Mn3+/Mn4+ coexist as Mn4+ is desired from the stability perspective. Particularly, CV and XPS results confirm these results. Moreover, the electrode exhibits a quasi-solid-solution reaction during the sodium extraction and insertion. This contribution demonstrates that P2-NNM is a promising cathode electrode for rechargeable long-life sodium-ion batteries.

Hierarchical Nitrogen-Doped Graphene/Carbon Nanotube Composite Cathode for Lithium-Oxygen Batteries.

PubMed

Shu, Chaozhu; Li, Bo; Zhang, Bingsen; Su, Dangsheng

2015-12-07

The lithium-oxygen (Li-O2 ) battery is a very appealing candidate for advanced high energy applications owing to its exceptionally high specific energy. However, its poor energy efficiency, rate capability, and cyclability remain key barriers to its practical application. In this work, using a rationally designed cathode based on a bimodal mesoporous nitrogen-doped graphene/carbon nanotube (NGC) composite, we have developed a Li-O2 battery demonstrating enhanced round-trip efficiency (ca. 85 %) and excellent cyclability over 400 cycles under a high current rate of 500 mA g(-1) . The excellent cyclability and rate capability are attributed to improved stability of the aggressive LiO2 intermediate on the nitrogen-doped carbon surface in addition to the favorable hierarchical architecture of NGC. These results demonstrate a valuable research direction to achieve highly stable and reversible Li-O2 batteries through tuning the surface chemistry of the cathode in addition to finding a stable electrolyte solvent. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Low temperature safety of lithium-thionyl chloride cells

NASA Technical Reports Server (NTRS)

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

1988-01-01

The use of lithium thionyl chloride cells for low-temperature applications is presently restricted because of their unsafe behavior. An attempt is made in the present investigation to identify the safe/unsafe low temperature operating conditions and to understand the low temperature cell chemistry responsible for the unsafe behavior. Cells subjected to extended reversal at low rate and -40 C were found to explode upon warm-up. Lithium was found to deposit on the carbon cathodes during reversal. Warming up to room temperature may be accelerating the lithium corrosion in the electrolyte. This may be one of the reasons for the cell thermal runaway.

Primary and secondary room temperature molten salt electrochemical cells

NASA Astrophysics Data System (ADS)

Reynolds, G. F.; Dymek, C. J., Jr.

1985-07-01

Three novel primary cells which use room temperature molten salt electrolytes are examined and found to have high open circuit potentials in the 1.75-2.19 V range, by comparison with the Al/AlCl3-MEICl concentration cell; their cathodes were of FeCl3-MEICl, WCl6-MEICl, and Br2/reticulated vitreous carbon together with Pt. Also, secondary electrochemical cell candidates were examined which combined the reversible Al/AlCl3-MEICl electrode with reversible zinc and cadmium molten salt electrodes to yield open circuit potentials of about 0.7 and 1.0 V, respectively. Room temperature molten salts' half-cell reduction potentials are given.

Electrokinetic delivery of persulfate to remediate PCBs polluted soils: effect of injection spot.

PubMed

Fan, Guangping; Cang, Long; Fang, Guodong; Qin, Wenxiu; Ge, Liqiang; Zhou, Dongmei

2014-12-01

Persulfate-based in situ chemical oxidation (ISCO) is a promising technique for the remediation of organic compounds contaminated soils. Electrokinetics (EK) provides an alternative method to deliver oxidants into the target zones especially in low permeable-soil. In this study, the flexibility of delivering persulfate by EK to remediate polychlorinated biphenyls (PCBs) polluted soil was investigated. 20% (w/w) of persulfate was injected at the anode, cathode and both electrodes to examine its transport behaviors under electrical field, and the effect of field inversion process was also evaluated. The results showed that high dosage of persulfate could be delivered into S4 section (near cathode) by electroosmosis when persulfate was injected from anode, 30.8% of PCBs was removed from the soil, and the formed hydroxyl precipitation near the cathode during EK process impeded the transportation of persulfate. In contrast, only 18.9% of PCBs was removed with the injection of persulfate from cathode, although the breakthrough of persulfate into the anode reservoir was observed. These results indicated that the electroosmotic flow is more effective for the transportation of persulfate into soil. The addition of persulfate from both electrodes did not significantly facilitate the PCBs oxidation as well as the treatment of electrical field reversion, the reinforced negative depolarization function occurring in the cathode at high current consumed most of the oxidant. Furthermore, it was found that strong acid condition near the anode favored the oxidation of PCBs by persulfate and the degradation of PCBs was in consistent with the oxidation of Soil TOC in EK/persulfate system. Copyright © 2014 Elsevier Ltd. All rights reserved.

A nickel-foam@carbon-shell with a pie-like architecture as an efficient polysulfide trap for high-energy Li–S batteries

DOE PAGES

Luo, Liu; Chung, Sheng-Heng; Chang, Chi-Hao; ...

2017-07-06

A high-loading sulfur cathode is critical for establishing rechargeable lithium–sulfur (Li–S) batteries with the anticipated high energy density. However, its fabrication as well as realizing high electrochemical utilization and stability with high-loading sulfur cathodes is a daunting challenge. Here, we present a new pie-like electrode that consists of an electrocatalytic nickel-foam as a “filling” to adsorb and store polysulfide catholytes and an outer carbon shell as a “crust” for facilitating high-loading sulfur cathodes with superior electrochemical and structural stabilities. The inner electrocatalytic nickel-foam is configured to adsorb polysulfides and facilitate their redox reactions. The intertwined carbon shell assists to shieldmore » the polysulfides within the cathode region of the cell. Both the nickel-foam and the carbon shell have high conductivity and porous space, which serve simultaneously as interconnected current collectors to enhance the redox kinetics and as polysulfide reservoirs to confine the active material. The effectiveness of such a pie-like structure in improving the electrochemical efficiency enables the cathode to host an ultrahigh sulfur loading of 40 mg cm -2 and attain a high areal capacity of over 40 mA h cm -2 at a low electrolyte/sulfur (E/S) ratio of 7. The enhanced cyclability is reflected in a high reversible areal capacity approaching 30 mA h cm -2 at C/5 rate after 100 cycles and excellent rate capability up to 2C rate.« less

Sulfur Embedded in a Mesoporous Carbon Nanotube Network as a Binder-Free Electrode for High-Performance Lithium-Sulfur Batteries.

PubMed

Sun, Li; Wang, Datao; Luo, Yufeng; Wang, Ke; Kong, Weibang; Wu, Yang; Zhang, Lina; Jiang, Kaili; Li, Qunqing; Zhang, Yihe; Wang, Jiaping; Fan, Shoushan

2016-01-26

Sulfur-porous carbon nanotube (S-PCNT) composites are proposed as cathode materials for advanced lithium-sulfur (Li-S) batteries. Abundant mesopores are introduced to superaligned carbon nanotubes (SACNTs) through controlled oxidation in air to obtain porous carbon nanotubes (PCNTs). Compared to original SACNTs, improved dispersive behavior, enhanced conductivity, and higher mechanical strength are demonstrated in PCNTs. Meanwhile, high flexibility and sufficient intertube interaction are preserved in PCNTs to support binder-free and flexible electrodes. Additionally, several attractive features, including high surface area and abundant adsorption points on tubes, are introduced, which allow high sulfur loading, provide dual protection to sulfur cathode materials, and consequently alleviate the capacity fade especially during slow charge/discharge processes. When used as cathodes for Li-S batteries, a high sulfur loading of 60 wt % is achieved, with excellent reversible capacities of 866 and 526 mAh g(-1) based on the weights of sulfur and electrode, respectively, after 100 cycles at a slow charge/discharge rate of 0.1C, revealing efficient suppression of polysulfide dissolution. Even with a high sulfur loading of 70 wt %, the S-PCNT composite maintains capacities of 760 and 528 mAh g(-1) based on the weights of sulfur and electrode, respectively, after 100 cycles at 0.1C, outperforming the current state-of-the-art sulfur cathodes. Improved high-rate capability is also delivered by the S-PCNT composites, revealing their potentials as high-performance carbon-sulfur composite cathodes for Li-S batteries.

A nickel-foam@carbon-shell with a pie-like architecture as an efficient polysulfide trap for high-energy Li–S batteries

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

Luo, Liu; Chung, Sheng-Heng; Chang, Chi-Hao

A high-loading sulfur cathode is critical for establishing rechargeable lithium–sulfur (Li–S) batteries with the anticipated high energy density. However, its fabrication as well as realizing high electrochemical utilization and stability with high-loading sulfur cathodes is a daunting challenge. Here, we present a new pie-like electrode that consists of an electrocatalytic nickel-foam as a “filling” to adsorb and store polysulfide catholytes and an outer carbon shell as a “crust” for facilitating high-loading sulfur cathodes with superior electrochemical and structural stabilities. The inner electrocatalytic nickel-foam is configured to adsorb polysulfides and facilitate their redox reactions. The intertwined carbon shell assists to shieldmore » the polysulfides within the cathode region of the cell. Both the nickel-foam and the carbon shell have high conductivity and porous space, which serve simultaneously as interconnected current collectors to enhance the redox kinetics and as polysulfide reservoirs to confine the active material. The effectiveness of such a pie-like structure in improving the electrochemical efficiency enables the cathode to host an ultrahigh sulfur loading of 40 mg cm -2 and attain a high areal capacity of over 40 mA h cm -2 at a low electrolyte/sulfur (E/S) ratio of 7. The enhanced cyclability is reflected in a high reversible areal capacity approaching 30 mA h cm -2 at C/5 rate after 100 cycles and excellent rate capability up to 2C rate.« less

M x Mn 8O 16 (M = Ag or K) as promising cathode materials for secondary Mg based batteries: the role of the cation M

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

Huang, Jianping; Poyraz, Altug S.; Takeuchi, Kenneth J.

2016-01-01

2 × 2 tunneled M xMn 8O 16(M = Ag or K) materials delivered high initial capacities in Mg based electrolyte, and K xMn 8O 16 showed high cycle stability with a reversible capacity of >170 mA h g -1after 20 cycles.

Plasma ARC Welding of High-Performance-Ship Materials

DTIC Science & Technology

1979-05-01

19 REFERENCES .................. ............................ 85 iiii -. -’ - -" -. I LIST OF FIGURES Page I - Comparison of PAW and GTAW ...tungsten-arc- welding ( GTAW ) process. Both processes employ an inert-gas-shielded non- consumable tungsten electrode, as shown in Figure 1. In genernl, both...piece acts as the cathode (ground or negative). However, both PAW and GTAW can be and have been, used with direct-current reverse polarity and with

Molten salt method of preparation and cathodic studies on layered-cathode materials Li(Co0.7Ni0.3)O2 and Li(Ni0.7Co0.3)O2 for Li-ion batteries

NASA Astrophysics Data System (ADS)

Reddy, M. V.; Tung, Bui Dang; Yang, Lu; Quang Minh, Nguyen Dang; Loh, K. P.; Chowdari, B. V. R.

2013-03-01

Layered compounds, Li(Co0.7Ni0.3)O2 (I) and Li(Ni0.7Co0.3)O2(II) were prepared by molten salt method in temperature ranging from 650 to 950 °C. The effect of morphology, crystal structure and electrochemical properties of materials were evaluated by X-Ray Diffraction (XRD), Scanning Electron Microscopy and Brunauer-Emmett-Teller surface area, cyclic voltammetry (CV) and galvanostatic cycling. XRD pattern shows a hexagonal type structure with lattice parameters of a˜2.828 Å, c˜14.096 Å for I and a˜2.851 Å, c˜14.121 Å for II prepared in oxygen flow. The surface area of the compounds, I and II are 1.74 and 0.75 m2 g-1 respectively. CV studies show a main anodic peak occur at ˜3.8-3.94 V vs. Li and a cathodic peak occur at ˜3.6-3.7 V vs. Li. Galvanostatic cycling studies are carried out at a current rate of 30 mA g-1 in the voltage range of 2.5-4.3 V, at room temperature. Li(Co0.7Ni0.3)O2 prepared at 750 °C in air show a reversible capacity of 145 mAh g-1 at the 1st discharge cycle and 13% capacity fading between 2 and 56 cycles, whereas Li(Ni0.7Co0.3)O2 reheated in the presence of oxygen deliver a high and stable reversible capacity of 165 mAh g-1 at the end of 60th cycle.

Modulation of risk-taking in marijuana users by transcranial direct current stimulation (tDCS) of the dorsolateral prefrontal cortex (DLPFC).

PubMed

Boggio, Paulo S; Zaghi, Soroush; Villani, Ana Beatriz; Fecteau, Shirley; Pascual-Leone, Alvaro; Fregni, Felipe

2010-12-01

Cognitive deficits that are reported in heavy marijuana users (attention, memory, affect perception, decision-making) appear to be completely reversible after a prolonged abstinence period of about 28 days. However, it remains unclear whether the reversibility of these cognitive deficits indicates that (1) chronic marijuana use is not associated with long-lasting changes in cortical networks or (2) that such changes occur but the brain adapts to and compensates for the drug-induced changes. Therefore, we examined whether chronic marijuana smokers would demonstrate a differential pattern of response in comparison to healthy volunteers on a decision-making paradigm (Risk Task) while undergoing sham or active transcranial direct current stimulation (tDCS) of the dorsolateral prefrontal cortex (DLPFC). Twenty-five chronic marijuana users who were abstinent for at least 24h were randomly assigned to receive left anodal/right cathodal tDCS of DLPFC (n=8), right anodal/left cathodal tDCS of DLPFC (n=9), or sham stimulation (n=8); results on Risk Task during sham/active tDCS were compared to healthy volunteers from a previously published dataset. Chronic marijuana users demonstrated more conservative (i.e. less risky) decision-making during sham stimulation. While right anodal stimulation of the DLPFC enhanced conservative decision-making in healthy volunteers, both right anodal and left anodal DLPFC stimulation increased the propensity for risk-taking in marijuana users. These findings reveal alterations in the decision-making neural networks among chronic marijuana users. Finally, we also assessed the effects of tDCS on marijuana craving and observed that right anodal/left cathodal tDCS of DLPFC is significantly associated with a diminished craving for marijuana. Copyright © 2010 Elsevier Ireland Ltd. All rights reserved.

Ambient Pressure XPS Study of Mixed Conducting Perovskite-Type SOFC Cathode and Anode Materials under Well-Defined Electrochemical Polarization

PubMed Central

2015-01-01

The oxygen exchange activity of mixed conducting oxide surfaces has been widely investigated, but a detailed understanding of the corresponding reaction mechanisms and the rate-limiting steps is largely still missing. Combined in situ investigation of electrochemically polarized model electrode surfaces under realistic temperature and pressure conditions by near-ambient pressure (NAP) XPS and impedance spectroscopy enables very surface-sensitive chemical analysis and may detect species that are involved in the rate-limiting step. In the present study, acceptor-doped perovskite-type La0.6Sr0.4CoO3-δ (LSC), La0.6Sr0.4FeO3-δ (LSF), and SrTi0.7Fe0.3O3-δ (STF) thin film model electrodes were investigated under well-defined electrochemical polarization as cathodes in oxidizing (O2) and as anodes in reducing (H2/H2O) atmospheres. In oxidizing atmosphere all materials exhibit additional surface species of strontium and oxygen. The polaron-type electronic conduction mechanism of LSF and STF and the metal-like mechanism of LSC are reflected by distinct differences in the valence band spectra. Switching between oxidizing and reducing atmosphere as well as electrochemical polarization cause reversible shifts in the measured binding energy. This can be correlated to a Fermi level shift due to variations in the chemical potential of oxygen. Changes of oxidation states were detected on Fe, which appears as FeIII in oxidizing atmosphere and as mixed FeII/III in H2/H2O. Cathodic polarization in reducing atmosphere leads to the reversible formation of a catalytically active Fe0 phase. PMID:26877827

The effect of left frontal transcranial direct-current stimulation on propranolol-induced fear memory acquisition and consolidation deficits.

PubMed

Nasehi, Mohammad; Khani-Abyaneh, Mozhgan; Ebrahimi-Ghiri, Mohaddeseh; Zarrindast, Mohammad-Reza

2017-07-28

Accumulating evidence supports the efficacy of transcranial direct current stimulation (tDCS) in modulating numerous cognitive functions. Despite the fact that tDCS has been used for the enhancement of memory and cognition, very few animal studies have addressed its impact on the modulation of fear memory. This study was designed to determine whether pre/post-training frontal tDCS application would alter fear memory acquisition and/or consolidation deficits induced by propranolol in NMRI mice. Results indicated that administration of β1-adrenoceptor blocker propranolol (0.1mg/kg) impaired fear memory retrieval. Pre/post-training application of anodal tDCS when propranolol was administered prior to training reversed contextual memory retrieval whereas only the anodal application prior to training could induce the same result in the auditory test. Meanwhile, anodal stimulation had no effect on fear memories by itself. Moreover, regardless of when cathode was applied and propranolol administered, their combination restored contextual memory retrieval, while only cathodal stimulation prior to training facilitated the contextual memory retrieval. Also, auditory memory retrieval was restored when cathodal stimulation and propranolol occurred prior to training but it was abolished when stimulation occurred after training and propranolol was administered prior to training. Collectively, our findings show that tDCS applied on the left frontal cortex of mice affects fear memory performance. This alteration seems to be task-dependent and varies depending on the nature and timing of the stimulation. In certain conditions, tDCS reverses the effect of propranolol. These results provide initial evidence to support the timely use of tDCS for the modulation of fear-related memories. Copyright © 2017 Elsevier B.V. All rights reserved.

Battery Relevant Electrochemistry of Ag 7Fe 3(P 2O 7 ) 4 : Contrasting Contributions from the Redox Chemistries of Ag + and Fe 3+

DOE PAGES

Zhang, Yiman; Kirshenbaum, Kevin C.; Marschilok, Amy C.; ...

2016-10-12

Ag 7Fe 3(P 2O 7 ) 4 is an example of an electrochemical displacement material which contains two different electrochemically active metal cations, where one cation (Ag +) forms metallic silver nanoparticles external to the crystals of Ag 7Fe 3(P 2O 7 ) 4 via an electrochemical reduction displacement reaction, while the other cation (Fe +3) is electrochemically reduced with the retention of iron cations within the anion structural framework concomitant with lithium insertion. These contrasting redox chemistries within one pure cathode material enable high rate capability and reversibility when Ag 7Fe 3(P 2O 7 ) 4 is employed asmore » cathode material in a lithium ion battery (LIB). Further, pyrophosphate materials are thermally and electrically stable, desirable attributes for cathode materials in LIBs. In this article, a bimetallic pyrophosphate material Ag 7Fe 3(P 2O 7 ) 4 is synthesized and confirmed to be a single phase by Rietveld refinement. Electrochemistry of Ag 7Fe 3(P 2O 7 ) 4 is reported for the first time in the context of lithium based batteries using cyclic voltammetry and galvanostatic discharge–charge cycling. The reduction displacement reaction and the lithium (de)insertion processes are investigated using ex situ X-ray absorption spectroscopy and X-ray diffraction of electrochemically reduced and oxidized Ag 7Fe 3(P 2O 7 ) 4. Ag 7Fe 3(P 2O 7 ) 4 exhibits good reversibility at the iron centers indicated by ~80% capacity retention over 100 cycles following the initial formation cycle and excellent rate capability exhibited by ~70% capacity retention upon a 4-fold increase in current.« less

Battery Relevant Electrochemistry of Ag 7Fe 3(P 2O 7 ) 4 : Contrasting Contributions from the Redox Chemistries of Ag + and Fe 3+

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

Zhang, Yiman; Kirshenbaum, Kevin C.; Marschilok, Amy C.

Ag 7Fe 3(P 2O 7 ) 4 is an example of an electrochemical displacement material which contains two different electrochemically active metal cations, where one cation (Ag +) forms metallic silver nanoparticles external to the crystals of Ag 7Fe 3(P 2O 7 ) 4 via an electrochemical reduction displacement reaction, while the other cation (Fe +3) is electrochemically reduced with the retention of iron cations within the anion structural framework concomitant with lithium insertion. These contrasting redox chemistries within one pure cathode material enable high rate capability and reversibility when Ag 7Fe 3(P 2O 7 ) 4 is employed asmore » cathode material in a lithium ion battery (LIB). Further, pyrophosphate materials are thermally and electrically stable, desirable attributes for cathode materials in LIBs. In this article, a bimetallic pyrophosphate material Ag 7Fe 3(P 2O 7 ) 4 is synthesized and confirmed to be a single phase by Rietveld refinement. Electrochemistry of Ag 7Fe 3(P 2O 7 ) 4 is reported for the first time in the context of lithium based batteries using cyclic voltammetry and galvanostatic discharge–charge cycling. The reduction displacement reaction and the lithium (de)insertion processes are investigated using ex situ X-ray absorption spectroscopy and X-ray diffraction of electrochemically reduced and oxidized Ag 7Fe 3(P 2O 7 ) 4. Ag 7Fe 3(P 2O 7 ) 4 exhibits good reversibility at the iron centers indicated by ~80% capacity retention over 100 cycles following the initial formation cycle and excellent rate capability exhibited by ~70% capacity retention upon a 4-fold increase in current.« less

High Rate and Stable Li-Ion Insertion in Oxygen-Deficient LiV3O8 Nanosheets as a Cathode Material for Lithium-Ion Battery.

PubMed

Song, Huanqiao; Luo, Mingsheng; Wang, Aimei

2017-01-25

Low performance of cathode materials has become one of the major obstacles to the application of lithium-ion battery (LIB) in advanced portable electronic devices, hybrid electric vehicles, and electric vehicles. The present work reports a versatile oxygen-deficient LiV 3 O 8 (D-LVO) nanosheet that was synthesized successfully via a facile oxygen-deficient hydrothermal reaction followed by thermal annealing in Ar. When used as a cathode material for LIB, the prepared D-LVO nanosheets display remarkable capacity properties at various current densities (a capacity of 335, 317, 278, 246, 209, 167, and 133 mA h g -1 at 50, 100, 200, 500, 1000, 2000, and 4000 mA g -1 , respectively) and excellent lithium-ion storage stability, maintaining more than 88% of the initial reversible capacity after 200 cycles at 1000 mA g -1 . The outstanding electrochemical properties are believed to arise largely from the introduction of tetravalent V (∼15% V 4+ ) and the attendant oxygen vacancies into LiV 3 O 8 nanosheets, leading to intrinsic electrical conductivity more than 1 order of magnitude higher and lithium-ion diffusion coefficient nearly 2 orders of magnitude higher than those of LiV 3 O 8 without detectable V 4+ (N-LVO) and thus contributing to the easy lithium-ion diffusion, rapid phase transition, and the excellent electrochemical reversibility. Furthermore, the more uniform nanostructure, as well as the larger specific surface area of D-LVO than N-LVO nanosheets may also improve the electrolyte penetration and provide more reaction sites for fast lithium-ion diffusion during the discharge/charge processes.

Estimation of electrode location in a rat motor cortex by laminar analysis of electrophysiology and intracortical electrical stimulation

NASA Astrophysics Data System (ADS)

Yazdan-Shahmorad, A.; Lehmkuhle, M. J.; Gage, G. J.; Marzullo, T. C.; Parikh, H.; Miriani, R. M.; Kipke, D. R.

2011-08-01

While the development of microelectrode arrays has enabled access to disparate regions of a cortex for neurorehabilitation, neuroprosthetic and basic neuroscience research, accurate interpretation of the signals and manipulation of the cortical neurons depend upon the anatomical placement of the electrode arrays in a layered cortex. Toward this end, this report compares two in vivo methods for identifying the placement of electrodes in a linear array spaced 100 µm apart based on in situ laminar analysis of (1) ketamine-xylazine-induced field potential oscillations in a rat motor cortex and (2) an intracortical electrical stimulation-induced movement threshold. The first method is based on finding the polarity reversal in laminar oscillations which is reported to appear at the transition between layers IV and V in laminar 'high voltage spindles' of the rat cortical column. Analysis of histological images in our dataset indicates that polarity reversal is detected 150.1 ± 104.2 µm below the start of layer V. The second method compares the intracortical microstimulation currents that elicit a physical movement for anodic versus cathodic stimulation. It is based on the hypothesis that neural elements perpendicular to the electrode surface are preferentially excited by anodic stimulation while cathodic stimulation excites those with a direction component parallel to its surface. With this method, we expect to see a change in the stimulation currents that elicits a movement at the beginning of layer V when comparing anodic versus cathodic stimulation as the upper cortical layers contain neuronal structures that are primarily parallel to the cortical surface and lower layers contain structures that are primarily perpendicular. Using this method, there was a 78.7 ± 68 µm offset in the estimate of the depth of the start of layer V. The polarity reversal method estimates the beginning of layer V within ±90 µm with 95% confidence and the intracortical stimulation method estimates it within ±69.3 µm. We propose that these methods can be used to estimate the in situ location of laminar electrodes implanted in the rat motor cortex.

Insight into the Capacity Fading Mechanism of Amorphous Se 2 S 5 Confined in Micro/Mesoporous Carbon Matrix in Ether-Based Electrolytes

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

Xu, Gui-Liang; Ma, Tianyuan; Sun, Cheng-Jun

2016-04-13

In contrast to the stable cycle performance of space confined Se-based cathodes for lithium batteries in carbonate-based electrolytes, their common capacity fading in ether-based electrolytes has been paid less attention and not yet well-addressed so far. In this work, the lithiation/delithiation of amorphous Se2S5 confined in micro/mesoporous carbon (Se2S5/MPC) cathode was investigated by in situ X-ray near edge absorption spectroscopy (XANES) and theoretical calculations. The Se2S5/MPC composite was synthesized by a modified vaporization-condensation method to ensure a good encapsulation of Se2S5 into the pores of MPC host. In situ XANES results illustrated that the lithiation/delithiation reversibility of Se component wasmore » gradually decreased in ether-based electrolytes, leading to an aggravated formation of long-chain polyselenides during cycling and further capacity decay. Moreover, ab initio calculations revealed that the binding energy of polyselenides (Li2Sen) with carbon host is in an order of Li2Se6 > Li2Se4 > Li2Se. The insights into the failure mechanism of Se-based cathode gain in this work are expected to serve as a guide for future design on high performance Se-based cathodes.« less

Mechanism of Zn Insertion into Nanostructured δ-MnO 2 : A Nonaqueous Rechargeable Zn Metal Battery

DOE PAGES

Han, Sang-Don; Kim, Soojeong; Li, Dongguo; ...

2017-05-08

Unlike the more established lithium-ion based energy storage chemistries, the complex intercalation chemistry of multivalent cations in a host lattice is not well understood, especially the relationship between the intercalating species solution chemistry and the prevalence and type of side reactions. Among multivalent metals, a promising model system can be based on nonaqueous Zn 2+ ion chemistry. There are several examples of these systems support the use of a Zn metal anode, and reversible intercalation cathodes have been reported. Our study utilizes a combination of analytical tools to probe the chemistry of a nanostructured δ-MnO 2 cathode in association withmore » a nonaqueous acetonitrile–Zn(TFSI) 2 electrolyte and a Zn metal anode. As many of the issues related to understanding a multivalent battery relate to the electrolyte–electrode interface, the high surface area of a nanostructured cathode provides a significant interface between the electrolyte and cathode host that maximizes the spectroscopic signal of any side reactions or minor mechanistic pathways. There are numerous factors affecting capacity fade and issues associated with the second phase formation including Mn dissolution in heavily cycled Zn/δ-MnO 2 cells are presented including dramatic mechanistic differences in the storage mechanism of this couple when compared to similar aqueous electrolytes are noted.« less

A High Capacity, Good Safety and Low Cost Na2FeSiO4-Based Cathode for Rechargeable Sodium-Ion Battery.

PubMed

Guan, Wenhao; Pan, Bin; Zhou, Peng; Mi, Jinxiao; Zhang, Dan; Xu, Jiacheng; Jiang, Yinzhu

2017-07-12

Rechargeable sodium-ion batteries (SIBs) are receiving intense interest because the resource abundance of sodium and its lithium-like chemistry make them low cost alternatives to the prevailing lithium-ion batteries in large-scale energy storage devices. Two typical classes of materials including transition metal oxides and polyanion compounds have been under intensive investigation as cathodes for SIBs; however, they are still limited to poor stability or low capacity of the state-of-art. Herein, we report a low cost carbon-coated Na 2 FeSiO 4 with simultaneous high capacity and good stability, owing to the highly pure Na-rich triclinic phase and the carbon-incorporated three-dimensional network morphology. The present carbon-coated Na 2 FeSiO 4 demonstrates the highest reversible capacity of 181.0 mAh g -1 to date with multielectron redox reaction that occurred among various polyanion-based SIBs cathodes, which achieves a close-to-100% initial Coulombic efficiency and a stable cycling with 88% capacity retention up to 100 cycles. In addition, such an electrode shows excellent stability either charged at a high voltage of 4.5 V or heated up to 800 °C. The present work might open up the possibility for developing high capacity, good safety and low cost polyanion-based cathodes for rechargeable SIBs.

Development of a laser ablation-hollow cathode glow discharge emission source and the application to the analysis of steel samples.

PubMed

Naeem, Tariq M; Matsuta, Hideyuki; Wagatsuma, Kazuaki

2004-12-01

A novel atomic emission spectrometry comprising laser ablation as a sampling source and hollow cathode plasma for the excitation of ablated sample atoms is proposed. In this arrangement, a conventional Grimm-type discharge lamp is employed, but the polarity of the power supply is reversed so that the cylindrical hollow tube acts as a cathode and the glow discharge plasma is produced within this tube. A laser is irradiated to introduce sample atoms into the discharge plasma. Ablated atoms are excited by collisions with electrons and gas species, and emit characteristic radiation upon de-excitation. The experiments were conducted only in an atmosphere of helium gas so as to avoid a rapid erosion of the cathode hollow tube. Phase-sensitive detection with a lock-in amplifier was utilized to reject the continuous background emission of the plasma gas and emissions of sputtered atoms from the tube material. The unique feature of this technique is that the sampling and excitation processes can be controlled independently. The proposed technique was employed for the determination of Cr, Mn, and Ni in low-alloyed steel samples. The obtained concentrations are in good agreement with the reported values. The relative standard deviation (RSD), a measure of the analytical precision, was estimated to be 2-9% for Cr, 3-4% for Mn, and 4-11% for Ni determination.

The cataphoretic emitter effect exhibited in high intensity discharge lamp electrodes

NASA Astrophysics Data System (ADS)

Mentel, Juergen

2018-01-01

A mono-layer of atoms, electropositive with respect to the substrate atoms, forms a dipole layer, reducing its work function. Such a layer is generated by diffusion of emitter material from the interior of the substrate, by vapour deposition or by deposition of emitter material onto arc electrodes by cataphoresis. This cataphoretic emitter effect is investigated within metal halide lamps with transparent YAG ceramic burners, and within model lamps. Within the YAG lamps, arcs are operated with switched-dc current between rod shaped tungsten electrodes in high pressure Hg vapour seeded with metal iodides. Within the model lamps, dc arcs are operated between rod-shaped tungsten electrodes—one doped—in atmospheric pressure Ar. Electrode temperatures are determined by 1λ -pyrometry, combined with simulation of the electrode heat balance. Plasma temperatures, atom and ion densities of emitter material are determined by emission and absorption spectroscopy. Phase resolved measurements in YAG lamps seeded with CeI3, CsI, DyI3, TmI3 and LaI3 show, within the cathodic half period, a reduction of the electrode temperature and an enhanced metal ion density in front of the electrode, and an opposite behavior after phase reversal. With increasing operating frequency, the state of the cathode overlaps onto the anodic phase—except for Cs, being low in adsorption energy. Generally, the phase averaged electrode tip temperature is reduced by seeding a lamp with emitter material; its height depends on admixtures. Measurements at tungsten electrodes doped with ThO2, La2O3 and Ce2O3 within the model lamp show that evaporated emitter material is redeposited by an emitter ion current onto the electrode surface. It reduces the work function of tungsten cathodes above the evaporation temperature of the emitter material, too; and also of cold anodes, indicating a field reversal in front of them. The formation of an emitter spot at low cathode temperature and high emitter material density is traced back to a locally reduced work function generated by a locally enhanced emitter ion current density.

Interfacial chemistry of zinc anodes for reinforced concrete structures

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

Covino, B.S. Jr.; Bullard, S.J.; Cramer, S.D.

1997-12-01

Thermally-sprayed zinc anodes are used in both galvanic and impressed current cathodic protection systems for reinforced concrete structures. The Albany Research Center, in collaboration with the Oregon Department of Transportation, has been studying the effect of electrochemical aging on the bond strength of zinc anodes for bridge cathodic protection systems. Changes in anode bond strength and other anode properties can be explained by the chemistry of the zinc-concrete interface. The chemistry of the zinc-concrete interface in laboratory electrochemical aging studies is compared with that of several bridges with thermal-sprayed zinc anodes and which have been in service for 5 tomore » 10 years using both galvanic and impressed current cathodic protection systems. The bridges are the Cape Creek Bridge on the Oregon coast and the East Camino Undercrossing near Placerville, CA. Also reported are interfacial chemistry results for galvanized steel rebar from the 48 year old Longbird Bridge in Bermuda.« less

Pre-Lithiation of Li(Ni1-x-yMnxCoy)O2 Materials Enabling Enhancement of Performance for Li-Ion Battery.

PubMed

Wu, Zhongzhen; Ji, Shunping; Hu, Zongxiang; Zheng, Jiaxin; Xiao, Shu; Lin, Yuan; Xu, Kang; Amine, Khalil; Pan, Feng

2016-06-22

Transition metal oxide materials Li(NixMnyCoz)O2 (NMCxyz) based on layered structure are potential cathode candidates for automotive Li-ion batteries because of their high specific capacities and operating potentials. However, the actual usable capacity, cycling stability, and first-cycle Coulombic efficiency remain far from practical. Previously, we reported a combined strategy consisting of depolarization with embedded carbon nanotube (CNT) and activation through pre-lithiation of the NMC host, which significantly improved the reversible capacity and cycling stability of NMC532-based material. In the present work we attempt to understand how pre-lithiation leads to these improvements on an atomic level with experimental investigation and ab initio calculations. By lithiating a series of NMC materials with varying chemical compositions prepared via a conventional approach, we identified the Ni in the NMC lattice as the component responsible for accommodating a double-layered Li structure. Specifically, much better improvements in the cycling stability and capacity can be achieved with the NMC lattices populated with Ni(3+) than those populated with only Ni(2+). Using the XRD we also found that the emergence of a double-layer Li structure is not only reversible during the pre-lithiation and the following delithiation, but also stable against elevated temperatures up to 320 °C. These new findings regarding the mechanism of pre-lithiation as well as how it affects the reversibility and stability of NMC-based cathode materials prepared by the conventional slurry approach will promote the possibility of their application in the future battery industry.

The influence of pressure and gas flow on size and morphology of titanium oxide nanoparticles synthesized by hollow cathode sputtering

NASA Astrophysics Data System (ADS)

Gunnarsson, Rickard; Pilch, Iris; Boyd, Robert D.; Brenning, Nils; Helmersson, Ulf

2016-07-01

Titanium oxide nanoparticles have been synthesized via sputtering of a hollow cathode in an argon atmosphere. The influence of pressure and gas flow has been studied. Changing the pressure affects the nanoparticle size, increasing approximately proportional to the pressure squared. The influence of gas flow is dependent on the pressure. In the low pressure regime (107 ≤ p ≤ 143 Pa), the nanoparticle size decreases with increasing gas flow; however, at high pressure (p = 215 Pa), the trend is reversed. For low pressures and high gas flows, it was necessary to add oxygen for the particles to nucleate. There is also a morphological transition of the nanoparticle shape that is dependent on the pressure. Shapes such as faceted, cubic, and cauliflower can be obtained.

Correlating Lithium Hydroxyl Accumulation with Capacity Retention in V2O5 Aerogel Cathodes.

PubMed

Wangoh, Linda W; Huang, Yiqing; Jezorek, Ryan L; Kehoe, Aoife B; Watson, Graeme W; Omenya, Fredrick; Quackenbush, Nicholas F; Chernova, Natasha A; Whittingham, M Stanley; Piper, Louis F J

2016-05-11

V2O5 aerogels are capable of reversibly intercalating more than 5 Li(+)/V2O5 but suffer from lifetime issues due to their poor capacity retention upon cycling. We employed a range of material characterization and electrochemical techniques along with atomic pair distribution function, X-ray photoelectron spectroscopy, and density functional theory to determine the origin of the capacity fading in V2O5 aerogel cathodes. In addition to the expected vanadium redox due to intercalation, we observed LiOH species that formed upon discharge and were only partially removed after charging, resulting in an accumulation of electrochemically inactive LiOH over each cycle. Our results indicate that the tightly bound water that is necessary for maintaining the aerogel structure is also inherently responsible for the capacity fade.

Cryptomelane-type manganese oxide (KMn8O16) nanorods cathode materials synthesized by a rheological phase for lithium ion batteries

NASA Astrophysics Data System (ADS)

Zheng, Hao; Wang, Ting; Zhao, Rongfei; Chen, Jinsong; Li, Lin

2018-01-01

Cryotolerance-type manganese oxide (KMn8O16) nanorods were prepared for the first time by a rheological phase reaction method. The KMn8O16 samples were characterized by X-ray diffraction, scanning electron microscopy, the effects of different annealed temperatures on the morphologies and electrochemical properties of the final products were systematically investigated. The result that the annealed samples exhibit the superior electrochemical performances compared to the unannealed sample. The KMn8O16 nanorods annealed at 400 °C show the highest reversible discharge capacity (147.9 mAh/g even after 80 cycles) at current density of 50 mA/g and the best cycling stability. These results indicate that the KMn8O16 nanorods could be a promising cathode material for lithium ion batteries.

Nitrogen, Fluorine, and Boron Ternary Doped Carbon Fibers as Cathode Electrocatalysts for Zinc-Air Batteries.

PubMed

Wang, Lei; Wang, Yueqing; Wu, Mingguang; Wei, Zengxi; Cui, Chunyu; Mao, Minglei; Zhang, Jintao; Han, Xiaopeng; Liu, Quanhui; Ma, Jianmin

2018-05-01

Zinc-air batteries with high-density energy are promising energy storage devices for the next generation of energy storage technologies. However, the battery performance is highly dependent on the efficiency of oxygen electrocatalyst in the air electrode. Herein, the N, F, and B ternary doped carbon fibers (TD-CFs) are prepared and exhibited higher catalytic properties via the efficient 4e - transfer mechanism for oxygen reduction in comparison with the single nitrogen doped CFs. More importantly, the primary and rechargeable Zn-air batteries using TD-CFs as air-cathode catalysts are constructed. When compared to batteries with Pt/C + RuO 2 and Vulcan XC-72 carbon black catalysts, the TD-CFs catalyzed batteries exhibit remarkable battery reversibility and stability over long charging/discharging cycles. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Correlating Lithium Hydroxyl Accumulation with Capacity Retention in V 2 O 5 Aerogel Cathodes

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

Wangoh, Linda W.; Huang, Yiqing; Jezorek, Ryan L.

V 2O 5 aerogels are capable of reversibly intercalating more than 5 Li +/V 2O 5 but suffer from lifetime issues due to their poor capacity retention upon cycling. We employed a range of material characterization and electrochemical techniques along with atomic pair distribution function, X-ray photoelectron spectroscopy, and density functional theory to determine the origin of the capacity fading in V 2O 5 aerogel cathodes. In addition to the expected vanadium redox due to intercalation, we observed LiOH species that formed upon discharge and were only partially removed after charging, resulting in an accumulation of electrochemically inactive LiOH overmore » each cycle. Our results indicate that the tightly bound water that is necessary for maintaining the aerogel structure is also inherently responsible for the capacity fade.« less

Dual redox catalysts for oxygen reduction and evolution reactions: towards a redox flow Li-O2 battery.

PubMed

Zhu, Yun Guang; Jia, Chuankun; Yang, Jing; Pan, Feng; Huang, Qizhao; Wang, Qing

2015-06-11

A redox flow lithium-oxygen battery (RFLOB) by using soluble redox catalysts with good performance was demonstrated for large-scale energy storage. The new device enables the reversible formation and decomposition of Li2O2 via redox targeting reactions in a gas diffusion tank, spatially separated from the electrode, which obviates the passivation and pore clogging of the cathode.

Pattern Visual Evoked Potentials Elicited by Organic Electroluminescence Screen

PubMed Central

Matsumoto, Celso Soiti; Shinoda, Kei; Matsumoto, Harue; Funada, Hideaki; Minoda, Haruka

2014-01-01

Purpose. To determine whether organic electroluminescence (OLED) screens can be used as visual stimulators to elicit pattern-reversal visual evoked potentials (p-VEPs). Method. Checkerboard patterns were generated on a conventional cathode-ray tube (S710, Compaq Computer Co., USA) screen and on an OLED (17 inches, 320 × 230 mm, PVM-1741, Sony, Tokyo, Japan) screen. The time course of the luminance changes of each monitor was measured with a photodiode. The p-VEPs elicited by these two screens were recorded from 15 eyes of 9 healthy volunteers (22.0 ± 0.8 years). Results. The OLED screen had a constant time delay from the onset of the trigger signal to the start of the luminescence change. The delay during the reversal phase from black to white for the pattern was 1.0 msec on the cathode-ray tube (CRT) screen and 0.5 msec on the OLED screen. No significant differences in the amplitudes of P100 and the implicit times of N75 and P100 were observed in the p-VEPs elicited by the CRT and the OLED screens. Conclusion. The OLED screen can be used as a visual stimulator to elicit p-VEPs; however the time delay and the specific properties in the luminance change must be taken into account. PMID:25197652

Pattern visual evoked potentials elicited by organic electroluminescence screen.

PubMed

Matsumoto, Celso Soiti; Shinoda, Kei; Matsumoto, Harue; Funada, Hideaki; Sasaki, Kakeru; Minoda, Haruka; Iwata, Takeshi; Mizota, Atsushi

2014-01-01

To determine whether organic electroluminescence (OLED) screens can be used as visual stimulators to elicit pattern-reversal visual evoked potentials (p-VEPs). Checkerboard patterns were generated on a conventional cathode-ray tube (S710, Compaq Computer Co., USA) screen and on an OLED (17 inches, 320 × 230 mm, PVM-1741, Sony, Tokyo, Japan) screen. The time course of the luminance changes of each monitor was measured with a photodiode. The p-VEPs elicited by these two screens were recorded from 15 eyes of 9 healthy volunteers (22.0 ± 0.8 years). The OLED screen had a constant time delay from the onset of the trigger signal to the start of the luminescence change. The delay during the reversal phase from black to white for the pattern was 1.0 msec on the cathode-ray tube (CRT) screen and 0.5 msec on the OLED screen. No significant differences in the amplitudes of P100 and the implicit times of N75 and P100 were observed in the p-VEPs elicited by the CRT and the OLED screens. The OLED screen can be used as a visual stimulator to elicit p-VEPs; however the time delay and the specific properties in the luminance change must be taken into account.

Electrochemical Oxidation of Lithium Carbonate Generates Singlet Oxygen.

PubMed

Mahne, Nika; Renfrew, Sara E; McCloskey, Bryan D; Freunberger, Stefan A

2018-05-04

Solid alkali metal carbonates are universal passivation layer components of intercalation battery materials and common side products in metal-O 2 batteries, and are believed to form and decompose reversibly in metal-O 2 /CO 2 cells. In these cathodes, Li 2 CO 3 decomposes to CO 2 when exposed to potentials above 3.8 V vs. Li/Li + . However, O 2 evolution, as would be expected according to the decomposition reaction 2 Li 2 CO 3 →4 Li + +4 e - +2 CO 2 +O 2 , is not detected. O atoms are thus unaccounted for, which was previously ascribed to unidentified parasitic reactions. Here, we show that highly reactive singlet oxygen ( 1 O 2 ) forms upon oxidizing Li 2 CO 3 in an aprotic electrolyte and therefore does not evolve as O 2 . These results have substantial implications for the long-term cyclability of batteries: they underpin the importance of avoiding 1 O 2 in metal-O 2 batteries, question the possibility of a reversible metal-O 2 /CO 2 battery based on a carbonate discharge product, and help explain the interfacial reactivity of transition-metal cathodes with residual Li 2 CO 3 . © 2018 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA.

Mechanical Composite of LiNi0.8Co0.15Al0.05O2/Carbon Nanotubes with Enhanced Electrochemical Performance for Lithium-Ion Batteries.

PubMed

Zhang, Liping; Fu, Ju; Zhang, Chuhong

2017-12-01

LiNi 0.8 Co 0.15 Al 0.05 O 2 /carbon nanotube (NCA/CNT) composite cathode materials are prepared by a facile mechanical grinding method, without damage to the crystal structure and morphology of the bulk. The NCA/CNT composite exhibits enhanced cycling and rate performance compared with pristine NCA. After 60 cycles at a current rate of 0.25 C, the reversible capacity of NCA/CNT composite cathode is 181 mAh/g with a discharge retention rate of 96%, considerably higher than the value of pristine NCA (153 mAh/g with a retention rate of 90%). At a high current rate of 5 C, it also can deliver a reversible capacity of 160 mAh/g, while only 140 mAh/g is maintained for the unmodified NCA. Highly electrical conductive CNTs rather than common inert insulating materials are for the first time employed as surface modifiers for NCA, which are dispersed homogenously on the surface of NCA particles, not only improving the electrical conductivity but also providing effective protection to the side reactions with liquid electrolyte of the battery.

Modulating the Activity of the DLPFC and OFC Has Distinct Effects on Risk and Ambiguity Decision-Making: A tDCS Study

PubMed Central

Yang, Xiaolan; Gao, Mei; Shi, Jinchuan; Ye, Hang; Chen, Shu

2017-01-01

Human beings are constantly exposed to two types of uncertainty situations, risk and ambiguity. Neuroscientific studies suggest that the dorsolateral prefrontal cortex (DLPFC) and the orbital frontal cortex (OFC) play significant roles in human decision making under uncertainty. We applied the transcranial direct current stimulation (tDCS) device to modulate the activity of participants’ DLPFC and OFC separately, comparing the causal relationships between people’s behaviors and the activity of the corresponding brain cortex when confronted with situations of risk and ambiguity. Our experiment employed a pre–post design and a risk/ambiguity decision-making task, from which we could calculate the preferences via an estimation model. We found evidences that modulating the activity of the DLPFC using right anodal/left cathodal tDCS significantly enhanced the participants’ preferences for risk, whereas modulating the activity of the OFC with right anodal/left cathodal tDCS significantly decreased the participants’ preferences for ambiguity. The reverse effects were also observed in the reversed tDCS treatments on the two areas. Our results suggest that decision-making processes under risk and ambiguity are complicated and may be encoded in two distinct circuits in our brains as the DLPFC primarily impacts decisions under risk whereas the OFC affects ambiguity. PMID:28878714

Interfacial reaction dependent performance of hollow carbon nanosphere - sulfur composite as a cathode for Li-S battery

DOE PAGES

Zheng, Jianming; Yan, Pengfei; Gu, Meng; ...

2015-05-26

Lithium-sulfur (Li-S) battery is a promising energy storage system due to its high energy density, cost effectiveness and environmental friendliness of sulfur. However, there are still a number of challenges, such as low Coulombic efficiency and poor long-term cycling stability, impeding the commercialization of Li-S battery. The electrochemical performance of Li-S battery is closely related with the interfacial reactions occurring between hosting substrate and active sulfur species which are poorly conducting at fully oxidized and reduced states. Here, we correlate the relationship between the performance and interfacial reactions in the Li-S battery system, using a hollow carbon nanosphere (HCNS) withmore » highly graphitic character as hosting substrate for sulfur. With an appropriate amount of sulfur loading, HCNS/S composite exhibits excellent electrochemical performance because of the fast interfacial reactions between HCNS and the polysulfides. However, further increase of sulfur loading leads to increased formation of highly resistive insoluble reaction products (Li 2S 2/Li 2S) which limits the reversibility of the interfacial reactions and results in poor electrochemical performance. In conclusion, these findings demonstrate the importance of the interfacial reaction reversibility in the whole electrode system on achieving high capacity and long cycle life of sulfur cathode for Li-S batteries.« less

3D dual-confined sulfur encapsulated in porous carbon nanosheets and wrapped with graphene aerogels as a cathode for advanced lithium sulfur batteries

DOE PAGES

Hou, Yang; Li, Jianyang; Gao, Xianfeng; ...

2016-03-15

Although lithium–sulfur (Li–S) batteries have attracted much attention due to their high theoretical specific energy and low cost, their practical applications have been severely hindered by poor cycle life, inadequate sulfur utilization, and the insulating nature of sulfur. Here, we report a rationally designed Li–S cathode with a dual-confined configuration formed by confining sulfur in 2D carbon nanosheets with an abundant porous structure followed by 3D graphene aerogel wrapping. The porous carbon nanosheets act as the sulfur host and suppress the diffusion of polysulfide, while the graphene conductive networks anchor the sulfur-adsorbed carbon nanosheets, providing pathways for rapid electron/ion transportmore » and preventing polysulfide dissolution. As a result, the hybrid electrode exhibits superior electrochemical performance, including a large reversible capacity of 1328 mA h g -1 in the first cycle, excellent cycling stability (maintaining a reversible capacity of 647 mA h g -1 at 0.2 C after 300 cycles) with nearly 100% Coulombic efficiency, and a high rate capability of 512 mA h g -1 at 8 C for 30 cycles, which is among the best reported rate capabilities.« less

“Rocking-Chair”-Type Metal Hybrid Supercapacitors

DOE PAGES

Yoo, Hyun Deog; Han, Sang-Don; Bayliss, Ryan D.; ...

2016-10-24

Hybrid supercapacitors that follow a “rocking-chair”-type mechanism were developed by coupling divalent metal and activated carbon electrodes in nonaqueous electrolytes. Conventional supercapacitors require a large amount of electrolyte to provide a sufficient quantity of ions to the electrodes, due to their Daniell-type mechanism that depletes the ions from the electrolyte while charging. The alternative “rocking-chair”-type mechanism effectively enhances the energy density of supercapacitors by minimizing the necessary amount of electrolyte, because the ion is replenished from the metal anode while it is adsorbed to the cathode. Newly developed nonaqueous electrolytes for Mg and Zn electrochemistry, based on bis(trifluoromethylsulfonyl)imide (TFSI) salts,more » made the metal hybrid supercapacitors possible by enabling reversible deposition on the metal anodes and reversible adsorption on an activated carbon cathode. Factoring in gains through the cell design, the energy density of the metal hybrid supercapacitors is projected to be a factor of 7 higher than conventional devices thanks to both the “rocking-chair”-type mechanism that minimizes total electrolyte volume and the use of metal anodes, which have substantial merits in capacity and voltage. Self-discharge was also substantially alleviated compared to conventional supercapacitors. This concept offers a route to build supercapacitors that meet dual criteria of power and energy densities with a simple cell design.« less

Highly Rechargeable Lithium-CO2 Batteries with a Boron- and Nitrogen-Codoped Holey-Graphene Cathode.

PubMed

Qie, Long; Lin, Yi; Connell, John W; Xu, Jiantie; Dai, Liming

2017-06-06

Metal-air batteries, especially Li-air batteries, have attracted significant research attention in the past decade. However, the electrochemical reactions between CO 2 (0.04 % in ambient air) with Li anode may lead to the irreversible formation of insulating Li 2 CO 3 , making the battery less rechargeable. To make the Li-CO 2 batteries usable under ambient conditions, it is critical to develop highly efficient catalysts for the CO 2 reduction and evolution reactions and investigate the electrochemical behavior of Li-CO 2 batteries. Here, we demonstrate a rechargeable Li-CO 2 battery with a high reversibility by using B,N-codoped holey graphene as a highly efficient catalyst for CO 2 reduction and evolution reactions. Benefiting from the unique porous holey nanostructure and high catalytic activity of the cathode, the as-prepared Li-CO 2 batteries exhibit high reversibility, low polarization, excellent rate performance, and superior long-term cycling stability over 200 cycles at a high current density of 1.0 A g -1 . Our results open up new possibilities for the development of long-term Li-air batteries reusable under ambient conditions, and the utilization and storage of CO 2 . © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Modulating the Activity of the DLPFC and OFC Has Distinct Effects on Risk and Ambiguity Decision-Making: A tDCS Study.

PubMed

Yang, Xiaolan; Gao, Mei; Shi, Jinchuan; Ye, Hang; Chen, Shu

2017-01-01

Human beings are constantly exposed to two types of uncertainty situations, risk and ambiguity. Neuroscientific studies suggest that the dorsolateral prefrontal cortex (DLPFC) and the orbital frontal cortex (OFC) play significant roles in human decision making under uncertainty. We applied the transcranial direct current stimulation (tDCS) device to modulate the activity of participants' DLPFC and OFC separately, comparing the causal relationships between people's behaviors and the activity of the corresponding brain cortex when confronted with situations of risk and ambiguity. Our experiment employed a pre-post design and a risk/ambiguity decision-making task, from which we could calculate the preferences via an estimation model. We found evidences that modulating the activity of the DLPFC using right anodal/left cathodal tDCS significantly enhanced the participants' preferences for risk, whereas modulating the activity of the OFC with right anodal/left cathodal tDCS significantly decreased the participants' preferences for ambiguity. The reverse effects were also observed in the reversed tDCS treatments on the two areas. Our results suggest that decision-making processes under risk and ambiguity are complicated and may be encoded in two distinct circuits in our brains as the DLPFC primarily impacts decisions under risk whereas the OFC affects ambiguity.

"Rocking-Chair"-Type Metal Hybrid Supercapacitors.

PubMed

Yoo, Hyun Deog; Han, Sang-Don; Bayliss, Ryan D; Gewirth, Andrew A; Genorio, Bostjan; Rajput, Nav Nidhi; Persson, Kristin A; Burrell, Anthony K; Cabana, Jordi

2016-11-16

Hybrid supercapacitors that follow a "rocking-chair"-type mechanism were developed by coupling divalent metal and activated carbon electrodes in nonaqueous electrolytes. Conventional supercapacitors require a large amount of electrolyte to provide a sufficient quantity of ions to the electrodes, due to their Daniell-type mechanism that depletes the ions from the electrolyte while charging. The alternative "rocking-chair"-type mechanism effectively enhances the energy density of supercapacitors by minimizing the necessary amount of electrolyte, because the ion is replenished from the metal anode while it is adsorbed to the cathode. Newly developed nonaqueous electrolytes for Mg and Zn electrochemistry, based on bis(trifluoromethylsulfonyl)imide (TFSI) salts, made the metal hybrid supercapacitors possible by enabling reversible deposition on the metal anodes and reversible adsorption on an activated carbon cathode. Factoring in gains through the cell design, the energy density of the metal hybrid supercapacitors is projected to be a factor of 7 higher than conventional devices thanks to both the "rocking-chair"-type mechanism that minimizes total electrolyte volume and the use of metal anodes, which have substantial merits in capacity and voltage. Self-discharge was also substantially alleviated compared to conventional supercapacitors. This concept offers a route to build supercapacitors that meet dual criteria of power and energy densities with a simple cell design.

Interaction of the Left Dorsolateral Prefrontal Cortex (l-DLPFC) and Right Orbitofrontal Cortex (OFC) in Hot and Cold Executive Functions: Evidence from Transcranial Direct Current Stimulation (tDCS).

PubMed

Nejati, Vahid; Salehinejad, Mohammad Ali; Nitsche, Michael A

2018-01-15

An organizing principle which has recently emerged proposes that executive functions (EF) can be divided into cognitive (cold) and affective/reward-related (hot) processes related to the dorsolateral prefrontal cortex (DLPFC) and orbitofrontal cortex (OFC) respectively. A controversial question is whether cold and hot EF are functionally and structurally independent or not. This study investigated how the left DLPFC (l-DLPFC) and right OFC (r-OFC) interact in hot and cold EF using transcranial direct current stimulation (tDCS). Twenty-four healthy male subjects received anodal, cathodal and sham tDCS (20 min, 1.5 mA) over the l-DLPFC (F3) and r-OFC (Fp2) with a 72-h interval between each stimulation condition. After five minutes of stimulation, participants underwent a series of cold and hot EF tasks including the Go/No-Go and Tower of Hanoi (TOH) as measures of cold EF and the BART and temporal discounting tasks as measures of hot EF. Inhibitory control mostly benefited from anodal l-DLPFC/cathodal r-OFC tDCS. Planning and problem solving were more prominently affected by anodal l-DLPFC/cathodal r-OFC stimulation, although the reversed electrode position with the anode positioned over the r-OFC also affected some aspects of task performance. Risk-taking behavior and risky decision-making decreased under both anodal l-DLPFC/cathodal r-OFC and anodal r-OFC/cathodal l-DLPFC tDCS. Cold EF rely on DLPFC activation while hot EF rely on both, DLPFC and OFC activation. Results suggest that EF are placed on continuum with lateral and mesial prefrontal areas contributing to cold and hot aspects respectively. Copyright © 2017 IBRO. Published by Elsevier Ltd. All rights reserved.

Interference effects of transcranial direct current stimulation over the right frontal cortex and adrenergic system on conditioned fear.

PubMed

Nasehi, Mohammad; Soltanpour, Reyhaneh; Ebrahimi-Ghiri, Mohaddeseh; Zarrabian, Shahram; Zarrindast, Mohammad-Reza

2017-11-01

The effects of pharmacological interventions on fear memory have widely been studied, but there are very few studies about the effects of brain electrical stimulation on fear memory function. Therefore, our aim was to determine whether anodal/cathodal transcranial direct current stimulation (tDCS) over the right frontal cortex would modify propranolol-induced contextual and auditory fear memory deficits, before or after training. The adult NMRI male mice were randomly assigned into three groups: the sham group, the anodal tDCS group, and the cathodal tDCS group. Fear memories were evaluated using a classical fear conditioning apparatus. While the anodal stimulation did not affect fear retrieval, post-training cathodal stimulation improved fear memory retrieval. Regardless of when propranolol (0.1 mg/kg) was administered, it impaired fear memory retrieval. However, when anodal stimulation and propranolol were applied prior to the training, contextual fear memory retrieval was increased and auditory fear memory was reversed. An enhanced contextual retrieval was also observed when propranolol was administered prior to the training and stimulation occurred after the training. Only when the stimulation occurred prior to the training and propranolol was administered after the training was there a selective improvement in contextual fear memory retrieval, leaving the auditory fear memory retrieval impaired. Interestingly, cathodal stimulation improved the effects of propranolol on auditory fear memory only when it occurred prior to the training. The results highlight possible improving effects for anodal/cathodal tDCS on propranolol-induced deficits on fear memories. The timing of the interventions related to the specific phases of memory formation is important in modulating fear behaviors.

Formation of Nanosized Defective Lithium Peroxides through Si-Coated Carbon Nanotube Cathodes for High Energy Efficiency Li-O2 Batteries.

PubMed

Lin, Qi; Cui, Zhonghui; Sun, Jiyang; Huo, Hanyu; Chen, Cheng; Guo, Xiangxin

2018-06-06

The formation and decomposition of lithium peroxides (Li 2 O 2 ) during cycling is the key process for the reversible operation of lithium-oxygen batteries. The manipulation of such products from the large toroidal particles about hundreds of nanometers to the ones in the scale of tens of nanometers can improve the energy efficiency and the cycle life of the batteries. In this work, we carry out an in situ morphology tuning of Li 2 O 2 by virtue of the surface properties of the n-type Si-modified aligned carbon nanotube (CNT) cathodes. With the introduction of an n-type Si coating layer on the CNT surface, the morphology of Li 2 O 2 formed by discharge changes from large toroidal particles (∼300 nm) deposited on the pristine CNT cathodes to nanoparticles (10-20 nm) with poor crystallinity and plenty of lithium vacancies. Beneficial from such changes, the charge overpotential dramatically decreases to 0.55 V, with the charge plateau lying at 3.5 V even in the case of a high discharge capacity (3450 mA h g -1 ) being delivered, resulting in the high electrical energy efficiency approaching 80%. Such an improvement is attributed to the fact that the introduction of the n-type Si coating layer changes the surface properties of CNTs and guides the formation of nanosized amorphous-like lithium peroxides with plenty of defects. These results demonstrate that the cathode surface properties play an important role in the formation of products formed during the cycle, providing inspiration to design superior cathodes for the Li-O 2 cells.

Effect of Reverse Bias Stress on Leakage Currents and Breakdown Voltages of Solid Tantalum Capacitors

NASA Technical Reports Server (NTRS)

Teverovsky, Alexander A.

2011-01-01

The majority of solid tantalum capacitors are produced by high-temperature sintering of a fine tantalum powder around a tantalum wire followed by electrolytic anodization that forms a thin amorphous Ta2O5 dielectric layer and pyrolysis of manganese nitrite on the oxide to create a conductive manganese dioxide electrode. A contact to tantalum wire is used as anode terminal and to the manganese layer as a cathode terminal of the device. This process results in formation of an asymmetric Ta -- Ta2O5 -- MnO2 capacitor that has different characteristics at forward (positive bias applied to tantalum) and reverse (positive bias applied to manganese cathode) voltages. Reverse bias currents might be several orders of magnitude larger than forward leakage currents so I-V characteristics of tantalum capacitors resemble characteristics of semiconductor rectifiers. Asymmetric I-V characteristics of Ta -- anodic Ta2O5 systems have been observed at different top electrode materials including metals, electrolytes, conductive polymers, and manganese oxide thus indicating that this phenomenon is likely related to the specifics of the Ta -- Ta2O5 interface. There have been multiple attempts to explain rectifying characteristics of capacitors employing anodic tantalum pentoxide dielectrics. A brief review of works related to reverse bias (RB) behavior of tantalum capacitors shows that the mechanism of conduction in Ta -- Ta2O5 systems is still not clear and more testing and analysis is necessary to understand the processes involved. If tantalum capacitors behave just as rectifiers, then the assessment of the safe reverse bias operating conditions would be a relatively simple task. Unfortunately, these parts can degrade with time under reverse bias significantly, and this further complicates analysis of the I-V characteristics and establishing safe operating areas of the parts. On other hand, time dependence of reverse currents might provide additional information for investigation of the processes under reverse bias conditions. In practice, there were instances when, due to unforeseen events, the system operated at conditions when capacitors experience periodically a relatively small reverse bias for some time followed by normal, forward bias conditions. In such a case an assessment should be made on the degree to which these capacitors are degraded by application of low-voltage reverse bias, and whether this degradation can be reversed by normal operating conditions. In this study, reverse currents in different types of tantalum capacitors were monitored at different reverse voltages below 15%VR and temperatures in the range from room to 145 C for up to 150 hours to get better understanding of the degradation process and determine conditions favorable to the unstable mode of operation. The reversibility of RB degradation has been evaluated after operation of the capacitors at forward bias conditions. The effect of reverse bias stress (RBS) on reliability at normal operating conditions was evaluated using highly accelerated life testing at voltages of 1.5VR and 2 VR and by analysis of changes in distributions of breakdown voltages. Possible mechanisms of RB degradation are discussed.

Towards High Capacity Li-ion Batteries Based on Silicon-Graphene Composite Anodes and Sub-micron V-doped LiFePO4 Cathodes

NASA Astrophysics Data System (ADS)

Loveridge, M. J.; Lain, M. J.; Johnson, I. D.; Roberts, A.; Beattie, S. D.; Dashwood, R.; Darr, J. A.; Bhagat, R.

2016-11-01

Lithium iron phosphate, LiFePO4 (LFP) has demonstrated promising performance as a cathode material in lithium ion batteries (LIBs), by overcoming the rate performance issues from limited electronic conductivity. Nano-sized vanadium-doped LFP (V-LFP) was synthesized using a continuous hydrothermal process using supercritical water as a reagent. The atomic % of dopant determined the particle shape. 5 at. % gave mixed plate and rod-like morphology, showing optimal electrochemical performance and good rate properties vs. Li. Specific capacities of >160 mAh g-1 were achieved. In order to increase the capacity of a full cell, V-LFP was cycled against an inexpensive micron-sized metallurgical grade Si-containing anode. This electrode was capable of reversible capacities of approximately 2000 mAh g-1 for over 150 cycles vs. Li, with improved performance resulting from the incorporation of few layer graphene (FLG) to enhance conductivity, tensile behaviour and thus, the composite stability. The cathode material synthesis and electrode formulation are scalable, inexpensive and are suitable for the fabrication of larger format cells suited to grid and transport applications.

Towards High Capacity Li-ion Batteries Based on Silicon-Graphene Composite Anodes and Sub-micron V-doped LiFePO4 Cathodes

PubMed Central

Loveridge, M. J.; Lain, M. J.; Johnson, I. D.; Roberts, A.; Beattie, S. D.; Dashwood, R.; Darr, J. A.; Bhagat, R.

2016-01-01

Lithium iron phosphate, LiFePO4 (LFP) has demonstrated promising performance as a cathode material in lithium ion batteries (LIBs), by overcoming the rate performance issues from limited electronic conductivity. Nano-sized vanadium-doped LFP (V-LFP) was synthesized using a continuous hydrothermal process using supercritical water as a reagent. The atomic % of dopant determined the particle shape. 5 at. % gave mixed plate and rod-like morphology, showing optimal electrochemical performance and good rate properties vs. Li. Specific capacities of >160 mAh g−1 were achieved. In order to increase the capacity of a full cell, V-LFP was cycled against an inexpensive micron-sized metallurgical grade Si-containing anode. This electrode was capable of reversible capacities of approximately 2000 mAh g−1 for over 150 cycles vs. Li, with improved performance resulting from the incorporation of few layer graphene (FLG) to enhance conductivity, tensile behaviour and thus, the composite stability. The cathode material synthesis and electrode formulation are scalable, inexpensive and are suitable for the fabrication of larger format cells suited to grid and transport applications. PMID:27898104

Towards High Capacity Li-ion Batteries Based on Silicon-Graphene Composite Anodes and Sub-micron V-doped LiFePO4 Cathodes.

PubMed

Loveridge, M J; Lain, M J; Johnson, I D; Roberts, A; Beattie, S D; Dashwood, R; Darr, J A; Bhagat, R

2016-11-29

Lithium iron phosphate, LiFePO 4 (LFP) has demonstrated promising performance as a cathode material in lithium ion batteries (LIBs), by overcoming the rate performance issues from limited electronic conductivity. Nano-sized vanadium-doped LFP (V-LFP) was synthesized using a continuous hydrothermal process using supercritical water as a reagent. The atomic % of dopant determined the particle shape. 5 at. % gave mixed plate and rod-like morphology, showing optimal electrochemical performance and good rate properties vs. Li. Specific capacities of >160 mAh g -1 were achieved. In order to increase the capacity of a full cell, V-LFP was cycled against an inexpensive micron-sized metallurgical grade Si-containing anode. This electrode was capable of reversible capacities of approximately 2000 mAh g -1 for over 1 50 cycles vs. Li, with improved performance resulting from the incorporation of few layer graphene (FLG) to enhance conductivity, tensile behaviour and thus, the composite stability. The cathode material synthesis and electrode formulation are scalable, inexpensive and are suitable for the fabrication of larger format cells suited to grid and transport applications.

A novel lithium/sulfur battery based on sulfur/graphene nanosheet composite cathode and gel polymer electrolyte

NASA Astrophysics Data System (ADS)

Zhang, Yongguang; Zhao, Yan; Bakenov, Zhumabay

2014-03-01

A novel sulfur/graphene nanosheet (S/GNS) composite was prepared via a simple ball milling of sulfur with commercial multi-layer graphene nanosheet, followed by a heat treatment. High-resolution transmission and scanning electronic microscopy observations showed the formation of irregularly interlaced nanosheet-like structure consisting of graphene with uniform sulfur coating on its surface. The electrochemical properties of the resulting composite cathode were investigated in a lithium cell with a gel polymer electrolyte (GPE) prepared by trapping 1 mol dm-3 solution of lithium bistrifluoromethanesulfonamide in tetraethylene glycol dimethyl ether in a polymer matrix composed of poly(vinylidene fluoride-co-hexafluoropropylene)/poly(methylmethacrylate)/silicon dioxide (PVDF-HFP/PMMA/SiO2). The GPE battery delivered reversible discharge capacities of 809 and 413 mAh g-1 at the 1st and 50th cycles at 0.2C, respectively, along with a high coulombic efficiency over 50 cycles. This performance enhancement of the cell was attributed to the suppression of the polysulfide shuttle effect by a collective effect of S/GNS composite cathode and GPE, providing a higher sulfur utilization. PACS: 82.47.Aa; 82.45.Gj; 62.23.Kn

Synthesis and Exploration of Ladder-Structured Large Aromatic Dianhydrides as Organic Cathodes for Rechargeable Lithium-Ion Batteries.

PubMed

Xie, Jian; Chen, Wangqiao; Wang, Zilong; Jie, Kenneth Choo Wei; Liu, Ming; Zhang, Qichun

2017-04-18

Compared to anode materials in Li-ion batteries, the research on cathode materials is far behind, and their capacities are much smaller. Thus, in order to address these issues, we believe that organic conjugated materials could be a solution. In this study, we synthesized two non-polymeric dianhydrides with large aromatic structures: NDA-4N (naphthalenetetracarboxylic dianhydride with four nitrogen atoms) and PDA-4N (perylenetetracarboxylic dianhydride with four nitrogen atoms). Their electrochemical properties have been investigated between 2.0 and 3.9 V (vs. Li + /Li). Benefiting from multi-electron reactions, NDA-4N and PDA-4N could reversibly achieve 79.7 % and 92.3 %, respectively, of their theoretical capacity. Further cycling reveals that the organic compound with a relatively larger aromatic building block could achieve a better stability, as an obvious 36.5 % improvement of the capacity retention was obtained when the backbone was switched from naphthalene to perylene. This study proposes an opportunity to attain promising small-molecule-based cathode materials through tailoring organic structures. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

NiCo2O4 surface coating Li[Ni0.03Mn1.97]O4 micro-/nano- spheres as cathode material for high-performance lithium ion battery

NASA Astrophysics Data System (ADS)

Ye, Pan; Dong, Hui; Xu, Yunlong; Zhao, Chongjun; Liu, Dong

2018-01-01

Here we report a novel transitional metal oxide (NiCo2O4) coated Li[Ni0.03Mn1.97]O4 micro-/nano- spheres as high-performance Li-ion battery cathode material. A thin layer of ∼10 nm NiCo2O4 was formed by simple wet-chemistry approach adjacent to the surface of Li[Ni0.03Mn1.97]O4 micro-/nano- spheres, leading to significantly enhanced battery electrochemical performance. The optimized sample(1 wt%) not only delivers excellent discharge capacity and cycling stability improvement at both room temperature and elevated temperatures, but also effectively prevents Mn dissolution while retaining its coating structure intact according to XRF and TEM results. The CV and EIS break-down analysis indicated a much faster electrochemical reaction kinetics, more reversible electrode process and greatly reduced charge transfer and Warburg resistance, clearly illustrating the dual role of NiCo2O4 coating to boost electron transport and Li+ diffusion, and alleviation of manganese dissolving. This approach may render as an efficient technique to realize high-performance lithium ion battery cathode material.

Cation-Deficient Spinel ZnMn2O4 Cathode in Zn(CF3SO3)2 Electrolyte for Rechargeable Aqueous Zn-Ion Battery.

PubMed

Zhang, Ning; Cheng, Fangyi; Liu, Yongchang; Zhao, Qing; Lei, Kaixiang; Chen, Chengcheng; Liu, Xiaosong; Chen, Jun

2016-10-05

Rechargeable aqueous Zn-ion batteries are attractive cheap, safe and green energy storage technologies but are bottlenecked by limitation in high-capacity cathode and compatible electrolyte to achieve satisfactory cyclability. Here we report the application of nonstoichiometric ZnMn 2 O 4 /carbon composite as a new Zn-insertion cathode material in aqueous Zn(CF 3 SO 3 ) 2 electrolyte. In 3 M Zn(CF 3 SO 3 ) 2 solution that enables ∼100% Zn plating/stripping efficiency with long-term stability and suppresses Mn dissolution, the spinel/carbon hybrid exhibits a reversible capacity of 150 mAh g -1 and a capacity retention of 94% over 500 cycles at a high rate of 500 mA g -1 . The remarkable electrode performance results from the facile charge transfer and Zn insertion in the structurally robust spinel featuring small particle size and abundant cation vacancies, as evidenced by combined electrochemical measurements, XRD, Raman, synchrotron X-ray absorption spectroscopy, FTIR, and NMR analysis. The results would enlighten and promote the use of cation-defective spinel compounds and trifluoromethanesulfonic electrolyte to develop high-performance rechargeable zinc batteries.

Dual Heteroatom-Doped Carbon Nanofoam-Wrapped Iron Monosulfide Nanoparticles: An Efficient Cathode Catalyst for Li-O2 Batteries.

PubMed

Ramakrishnan, Prakash; Shanmugam, Sangaraju; Kim, Jae Hyun

2017-04-10

Cost-effective dual heteroatom-doped 3D carbon nanofoam-wrapped FeS nanoparticles (NPs), FeS-C, act as efficient bifunctional catalysts for Li-O 2 batteries. This cathode exhibits a maximum deep discharge capacity of 14 777.5 mA h g -1 with a 98.1 % columbic efficiency at 0.1 mA cm -2 . The controlled capacity (500 mA h g -1 ) test of this cathode delivers a minimum polarization gap of 0.73 V at 0.1 mA cm -2 and is sustained for 100 cycles with an energy efficiency of approximately 64 % (1st cycle) and 52 % (100th cycle) at 0.3 mA cm -2 , under the potential window of 2.0-4.5 V. X-ray photoelectron spectroscopy reveals the substantial reversible formation and complete decomposition of Li 2 O 2 . The excellent recharging ability, high rate performance, and cycle stability of this catalyst is attributed to the synergistic effect of FeS catalytic behavior and textural properties of heteroatom-doped carbon nanostructures. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Monitoring local redox processes in LiNi0.5Mn1.5O4 battery cathode material by in operando EPR spectroscopy.

PubMed

Niemöller, Arvid; Jakes, Peter; Eurich, Svitlana; Paulus, Anja; Kungl, Hans; Eichel, Rüdiger-A; Granwehr, Josef

2018-01-07

Despite the multitude of analytical methods available to characterize battery cathode materials, identifying the factors responsible for material aging is still challenging. We present the first investigation of transient redox processes in a spinel cathode during electrochemical cycling of a lithium ion battery by in operando electron paramagnetic resonance (EPR). The battery contains a LiNi 0.5 Mn 1.5 O 4 (LNMO) spinel cathode, which is a material whose magnetic interactions are well understood. The evolution of the EPR signal in combination with electrochemical measurements shows the impact of Mn 3+ on the Li + motion inside the spinel. Moreover, state of charge dependent linewidth variations confirm the formation of a solid solution for slow cycling, which is taken over by mixed models of solid solution and two-phase formation for fast cycling due to kinetic restrictions and overpotentials. Long-term measurements for 480 h showed the stability of the investigated LNMO, but also small amounts of cathode degradation products became visible. The results point out how local, exchange mediated magnetic interactions in cathode materials are linked with battery performance and can be used for material characterization.

Monitoring local redox processes in LiNi0.5Mn1.5O4 battery cathode material by in operando EPR spectroscopy

NASA Astrophysics Data System (ADS)

Niemöller, Arvid; Jakes, Peter; Eurich, Svitlana; Paulus, Anja; Kungl, Hans; Eichel, Rüdiger-A.; Granwehr, Josef

2018-01-01

Despite the multitude of analytical methods available to characterize battery cathode materials, identifying the factors responsible for material aging is still challenging. We present the first investigation of transient redox processes in a spinel cathode during electrochemical cycling of a lithium ion battery by in operando electron paramagnetic resonance (EPR). The battery contains a LiNi0.5Mn1.5O4 (LNMO) spinel cathode, which is a material whose magnetic interactions are well understood. The evolution of the EPR signal in combination with electrochemical measurements shows the impact of Mn3+ on the Li+ motion inside the spinel. Moreover, state of charge dependent linewidth variations confirm the formation of a solid solution for slow cycling, which is taken over by mixed models of solid solution and two-phase formation for fast cycling due to kinetic restrictions and overpotentials. Long-term measurements for 480 h showed the stability of the investigated LNMO, but also small amounts of cathode degradation products became visible. The results point out how local, exchange mediated magnetic interactions in cathode materials are linked with battery performance and can be used for material characterization.

Calendar aging of a graphite/LiFePO4 cell

NASA Astrophysics Data System (ADS)

Kassem, M.; Bernard, J.; Revel, R.; Pélissier, S.; Duclaud, F.; Delacourt, C.

2012-06-01

Graphite/LFP commercial cells are stored under 3 different conditions of temperature (30 °C, 45 °C, and 60 °C) and SOC (30%, 65%, and 100%) during up to 8 months. Several non-destructive electrochemical tests are performed at different storage times in order to understand calendar aging phenomena. After storage, all the cells except those stored at 30 °C exhibited capacity fade. The extent of capacity fade strongly increases with storage temperature and to a lesser extent with the state of charge. From in-depth data analysis, cyclable lithium loss was identified as the main source of capacity fade. This loss arises from side reactions taking place at the anode, e.g. solvent decomposition leading to the growth of the solid electrolyte interphase. However, the existence of reversible capacity loss also suggests the presence of side reactions occurring at the cathode, which are less prominent than those at the anode. The analyses do not show any evidence about active-material loss in the electrodes. The cells do not suffer substantial change in internal resistance. According to EIS analysis, the overall impedance increase is 70% or less.

Magnetic dipole discharges. II. Cathode and anode spot discharges and probe diagnostics

NASA Astrophysics Data System (ADS)

Stenzel, R. L.; Urrutia, J. M.; Ionita, C.; Schrittwieser, R.

2013-08-01

The high current regime of a magnetron-type discharge has been investigated. The discharge uses a permanent magnet as a cold cathode which emits secondary electrons while the chamber wall or a grounded electrode serves as the anode. As the discharge voltage is increased, the magnet develops cathode spots, which are short duration arcs that provide copious electrons to increase the discharge current dramatically. Short (1 μs), high current (200 A) and high voltage (750 V) discharge pulses are produced in a relaxation instability between the plasma and a charging capacitor. Spots are also observed on a negatively biased plane Langmuir probe. The probe current pulses are as large as those on the magnet, implying that the high discharge current does not depend on the cathode surface area but on the properties of the spots. The fast current pulses produce large inductive voltages, which can reverse the electrical polarity of the magnet and temporarily operate it as an anode. The discharge current may also oscillate at the frequency determined by the charging capacitor and the discharge circuit inductance. Each half cycle of high-current current pulses exhibits a fast (≃10 ns) current rise when a spot is formed. It induces high frequency (10-100 MHz) transients and ringing oscillations in probes and current circuits. Most probes behave like unmatched antennas for the electromagnetic pulses of spot discharges. Examples are shown to distinguish the source of oscillations and some rf characteristics of Langmuir probes.

Physicochemical effects on uncontaminated kaolinite due to electrokinetic treatment using inert electrodes.

PubMed

Liaki, Christina; Rogers, Christopher D F; Boardman, David I

2008-07-01

To determine the consequences of applying electrokinetics to clay soils, in terms of mechanisms acting and resulting effects on the clay, tests were conducted in which an electrical gradient was applied across controlled specimens of English China Clay (ECC) using 'inert' electrodes and a 'Reverse Osmosis' water feed to the electrodes (i.e., to mimic electrokinetic stabilisation without the stabiliser added or electrokinetic remediation without the contaminant being present). The specimens in which electromigration was induced over time periods of 3, 7, 14 and 28 days were subsequently tested for Atterberg Limits, undrained shear strength using a hand shear vane, water content, pH, conductivity and zeta potential. Water flowed through the system from anode to cathode and directly affected the undrained shear strength of the clay. Acid and alkali fronts were created around the anode and cathode, respectively, causing changes in the pH, conductivity and zeta potential of the soil. Variations in zeta potential were linked to flocculation and dispersion of the soil particles, thus raising or depressing the Liquid Limit and Plastic Limit, and influencing the undrained shear strength. Initial weakening around the anode and cathode was replaced by a regain of strength at the anode once acidic conditions had been created, while highly alkaline conditions at the cathode induced a marked improvement in strength. A novel means of indicating strength improvement by chemical means, i.e., free from water content effects, is presented to assist in interpretation of the results.

Enhanced thermal safety and high power performance of carbon-coated LiFePO4 olivine cathode for Li-ion batteries

NASA Astrophysics Data System (ADS)

Zaghib, K.; Dubé, J.; Dallaire, A.; Galoustov, K.; Guerfi, A.; Ramanathan, M.; Benmayza, A.; Prakash, J.; Mauger, A.; Julien, C. M.

2012-12-01

The carbon-coated LiFePO4 Li-ion oxide cathode was studied for its electrochemical, thermal, and safety performance. This electrode exhibited a reversible capacity corresponding to more than 89% of the theoretical capacity when cycled between 2.5 and 4.0 V. Cylindrical 18,650 cells with carbon-coated LiFePO4 also showed good capacity retention at higher discharge rates up to 5C rate with 99.3% coulombic efficiency, implying that the carbon coating improves the electronic conductivity. Hybrid Pulse Power Characterization (HPPC) test performed on LiFePO4 18,650 cell indicated the suitability of this carbon-coated LiFePO4 for high power HEV applications. The heat generation during charge and discharge at 0.5C rate, studied using an Isothermal Microcalorimeter (IMC), indicated cell temperature is maintained in near ambient conditions in the absence of external cooling. Thermal studies were also investigated by Differential Scanning Calorimeter (DSC) and Accelerating Rate Calorimeter (ARC), which showed that LiFePO4 is safer, upon thermal and electrochemical abuse, than the commonly used lithium metal oxide cathodes with layered and spinel structures. Safety tests, such as nail penetration and crush test, were performed on LiFePO4 and LiCoO2 cathode based cells, to investigate on the safety hazards of the cells upon severe physical abuse and damage.

Fabrication and Performance of High Energy Li-Ion Battery Based on the Spherical Li[Li(0.2)Ni(0.16)Co(0.1)Mn(0.54)]O2 Cathode and Si Anode.

PubMed

Ye, Jing; Li, Yi-xuan; Zhang, Li; Zhang, Xue-ping; Han, Min; He, Ping; Zhou, Hao-shen

2016-01-13

The cathode materials of Li-ion batteries for electric vehicles require not only a large gravimetric capacity but also a high volumetric capacity. A new Li-rich layered oxide cathode with superior capacity, Li[Li0.20Ni0.16Co0.10Mn0.54]O2 (denoted as LNCM), is synthesized from precursor, a coprecipitated spherical metal hydroxide. The preparation technology of precursor such as stirring speed, concentration of metal solution, and reaction time are regulated elaborately. The final product LNCM shows a well-ordered, hexagonal-layer structure, as confirmed by Rietveld refinement of X-ray diffraction pattern. The particle size of the final product has an average diameter of about 10 μm, and the corresponding tap density is about 2.25 g cm(-3). Electrochemical measurements indicate that as-prepared LNCM has great initial columbic efficiency, reversible capacity, and cycling stability, with specific discharge capacities of 278 and 201 mAh g(-1) at 0.03 and 0.5 C rates, respectively. Cycling at 0.1 C, LNCM delivers a discharge capacity of 226 mAh g(-1) with 95% retention capacity after 50 cycles. Si/LNCM cell is fabricated using Si submicroparticle as anode against LNCM. The cell can exhibit a specific energy of 590 Wh kg(-1) based on the total weight of cathode and anode materials.

Production and Engineering Methods for CARB-TEX (Trade Name) Batteries in Fork Lift Trucks

DTIC Science & Technology

1974-12-01

Temperature Batteries Tellurium Tetra Chloride Battery Pilot Line TO ABSTRACT (Contfinue on reverse side !I mvc.esy mid Identify by block number) This...chloride -1- as the electrolyte, and a tellurium tetrachloride additive. The porous carbon cathode is an aggregation of active carbon particles which have...energy storage using the Helmholtz double-layer princi- ple. However, after treating the carbon with the tellurium tetrachloride additve, the carbon

A magnesium–sodium hybrid battery with high operating voltage

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

Dong, Hui; Li, Yifei; Liang, Yanliang

2016-06-10

We report a high performance magnesium-sodium hybrid battery utilizing a magnesium-sodium dual-salt electrolyte, a magnesium anode, and a Berlin green cathode. The cell delivers an average discharge voltage of 2.2 V and a reversible capacity of 143 mAh g -1. We also demonstrate the cell with an energy density of 135 Wh kg -1 and a high power density of up to 1.67 kW kg -1.

Evidence of enzymatic catalysis of oxygen reduction on stainless steels under marine biofilm.

PubMed

Faimali, Marco; Benedetti, Alessandro; Pavanello, Giovanni; Chelossi, Elisabetta; Wrubl, Federico; Mollica, Alfonso

2011-04-01

Cathodic current trends on stainless steel samples with different surface percentages covered by biofilm and potentiostatically polarized in natural seawater were studied under oxygen concentration changes, temperature increases, and additions of enzymic inhibitors to the solution. The results showed that on each surface fraction covered by biofilm the oxygen reduction kinetics resembled a reaction catalyzed by an immobilised enzyme with high oxygen affinity (apparent Michaelis-Menten dissociation constant close to K(O(2))(M)  ≈ 10 μM) and low activation energy (W ≈ 20 KJ mole(-1)). The proposed enzyme rapidly degraded when the temperature was increased above the ambient (half-life time of ∼1 day at 25°C, and of a few minutes at 50°C). Furthermore, when reversible enzymic inhibitors (eg sodium azide and cyanide) were added, the cathodic current induced by biofilm growth was inhibited.

Full open-framework batteries for stationary energy storage

NASA Astrophysics Data System (ADS)

Pasta, Mauro; Wessells, Colin D.; Liu, Nian; Nelson, Johanna; McDowell, Matthew T.; Huggins, Robert A.; Toney, Michael F.; Cui, Yi

2014-01-01

New types of energy storage are needed in conjunction with the deployment of renewable energy sources and their integration with the electrical grid. We have recently introduced a family of cathodes involving the reversible insertion of cations into materials with the Prussian Blue open-framework crystal structure. Here we report a newly developed manganese hexacyanomanganate open-framework anode that has the same crystal structure. By combining it with the previously reported copper hexacyanoferrate cathode we demonstrate a safe, fast, inexpensive, long-cycle life aqueous electrolyte battery, which involves the insertion of sodium ions. This high rate, high efficiency cell shows a 96.7% round trip energy efficiency when cycled at a 5C rate and an 84.2% energy efficiency at a 50C rate. There is no measurable capacity loss after 1,000 deep-discharge cycles. Bulk quantities of the electrode materials can be produced by a room temperature chemical synthesis from earth-abundant precursors.

Advances in lithium-sulfur batteries based on multifunctional cathodes and electrolytes

NASA Astrophysics Data System (ADS)

Pang, Quan; Liang, Xiao; Kwok, Chun Yuen; Nazar, Linda F.

2016-09-01

Amid burgeoning environmental concerns, electrochemical energy storage has rapidly gained momentum. Among the contenders in the ‘beyond lithium’ energy storage arena, the lithium-sulfur (Li-S) battery has emerged as particularly promising, owing to its potential to reversibly store considerable electrical energy at low cost. Whether or not Li-S energy storage will be able to fulfil this potential depends on simultaneously solving many aspects of its underlying conversion chemistry. Here, we review recent developments in tackling the dissolution of polysulfides — a fundamental problem in Li-S batteries — focusing on both experimental and computational approaches to tailor the chemical interactions between the sulfur host materials and polysulfides. We also discuss smart cathode architectures enabled by recent materials engineering, especially for high areal sulfur loading, as well as innovative electrolyte design to control the solubility of polysulfides. Key factors that allow long-life and high-loading Li-S batteries are summarized.

Light-assisted delithiation of lithium iron phosphate nanocrystals towards photo-rechargeable lithium ion batteries

PubMed Central

Paolella, Andrea; Faure, Cyril; Bertoni, Giovanni; Marras, Sergio; Guerfi, Abdelbast; Darwiche, Ali; Hovington, Pierre; Commarieu, Basile; Wang, Zhuoran; Prato, Mirko; Colombo, Massimo; Monaco, Simone; Zhu, Wen; Feng, Zimin; Vijh, Ashok; George, Chandramohan; Demopoulos, George P.; Armand, Michel; Zaghib, Karim

2017-01-01

Recently, intensive efforts are dedicated to convert and store the solar energy in a single device. Herein, dye-synthesized solar cell technology is combined with lithium-ion materials to investigate light-assisted battery charging. In particular we report the direct photo-oxidation of lithium iron phosphate nanocrystals in the presence of a dye as a hybrid photo-cathode in a two-electrode system, with lithium metal as anode and lithium hexafluorophosphate in carbonate-based electrolyte; a configuration corresponding to lithium ion battery charging. Dye-sensitization generates electron–hole pairs with the holes aiding the delithiation of lithium iron phosphate at the cathode and electrons utilized in the formation of a solid electrolyte interface at the anode via oxygen reduction. Lithium iron phosphate acts effectively as a reversible redox agent for the regeneration of the dye. Our findings provide possibilities in advancing the design principles for photo-rechargeable lithium ion batteries. PMID:28393912

The preparation and graphene surface coating NaTi2(PO4)3 as cathode material for lithium ion batteries

NASA Astrophysics Data System (ADS)

Li, Na; Wang, Yanping; Rao, Richuan; Dong, Xiongzi; Zhang, Xianwen; Zhu, Sane

2017-03-01

The graphene coated NaTi2(PO4)3 has been fabricated via a simple sol-gel process followed by calcination. The NaTi2(PO4)3/graphene (NTP/G) composite is used directly as cathode electrode material for lithium-ion battery and the electrochemical properties of the composite in this system is firstly studied in detail. In the charge-discharge process, two Li+ can occupy octahedral M (2) site and be reversibly intercalated into the 3D framework of NTP through the ion conduction channel where almost all of Na+ are immobilized to sustain the framework. At 5C rate, the capacity retention of the NTP/G composite after 800 cycles is still up to 82.7%. The superior electrochemical properties of NTP/G is ascribed to its stable 3-D framework and the enhanced electronic conduction resulting from the graphene sheets surface modification.

Light-assisted delithiation of lithium iron phosphate nanocrystals towards photo-rechargeable lithium ion batteries

NASA Astrophysics Data System (ADS)

Paolella, Andrea; Faure, Cyril; Bertoni, Giovanni; Marras, Sergio; Guerfi, Abdelbast; Darwiche, Ali; Hovington, Pierre; Commarieu, Basile; Wang, Zhuoran; Prato, Mirko; Colombo, Massimo; Monaco, Simone; Zhu, Wen; Feng, Zimin; Vijh, Ashok; George, Chandramohan; Demopoulos, George P.; Armand, Michel; Zaghib, Karim

2017-04-01

Recently, intensive efforts are dedicated to convert and store the solar energy in a single device. Herein, dye-synthesized solar cell technology is combined with lithium-ion materials to investigate light-assisted battery charging. In particular we report the direct photo-oxidation of lithium iron phosphate nanocrystals in the presence of a dye as a hybrid photo-cathode in a two-electrode system, with lithium metal as anode and lithium hexafluorophosphate in carbonate-based electrolyte; a configuration corresponding to lithium ion battery charging. Dye-sensitization generates electron-hole pairs with the holes aiding the delithiation of lithium iron phosphate at the cathode and electrons utilized in the formation of a solid electrolyte interface at the anode via oxygen reduction. Lithium iron phosphate acts effectively as a reversible redox agent for the regeneration of the dye. Our findings provide possibilities in advancing the design principles for photo-rechargeable lithium ion batteries.

Light-assisted delithiation of lithium iron phosphate nanocrystals towards photo-rechargeable lithium ion batteries.

PubMed

Paolella, Andrea; Faure, Cyril; Bertoni, Giovanni; Marras, Sergio; Guerfi, Abdelbast; Darwiche, Ali; Hovington, Pierre; Commarieu, Basile; Wang, Zhuoran; Prato, Mirko; Colombo, Massimo; Monaco, Simone; Zhu, Wen; Feng, Zimin; Vijh, Ashok; George, Chandramohan; Demopoulos, George P; Armand, Michel; Zaghib, Karim

2017-04-10

Recently, intensive efforts are dedicated to convert and store the solar energy in a single device. Herein, dye-synthesized solar cell technology is combined with lithium-ion materials to investigate light-assisted battery charging. In particular we report the direct photo-oxidation of lithium iron phosphate nanocrystals in the presence of a dye as a hybrid photo-cathode in a two-electrode system, with lithium metal as anode and lithium hexafluorophosphate in carbonate-based electrolyte; a configuration corresponding to lithium ion battery charging. Dye-sensitization generates electron-hole pairs with the holes aiding the delithiation of lithium iron phosphate at the cathode and electrons utilized in the formation of a solid electrolyte interface at the anode via oxygen reduction. Lithium iron phosphate acts effectively as a reversible redox agent for the regeneration of the dye. Our findings provide possibilities in advancing the design principles for photo-rechargeable lithium ion batteries.

A three-dimensional cathode matrix with bi-confinement effect of polysulfide for lithium-sulfur battery

NASA Astrophysics Data System (ADS)

Song, Ren-Sheng; Wang, Bo; Ruan, Ting-Ting; Wang, Lei; Luo, Hao; Wang, Fei; Gao, Tian-Tian; Wang, Dian-Long

2018-01-01

Soluble polysulfide shuttling is still the main cause of restricting the development of lithium-sulfur (Li-S) battery. Here, we propose a novel three-dimensional reduced graphene oxide@sulfur/nitrogen-doped porous carbon polyhedron/carbon nanotubes (rGO@S/NCP/CNTs) composite with bi-confinement effect of polysulfide as an effective cathode material. In rGO@S/NCP/CNTs, NCP provides physical confinement for sulfur and soluble polysulfide by its abundant micropores and mesopores, while oxygen functional groups of rGO provide strong chemical confinement to soluble polysulfide. Additionally, CNTs with one-dimensional conductivity enable facile transport of electrons. Therefore, the resulting rGO@S/NCP/CNTs composite shows an obvious enhancement in cycling performance for Li-S battery, and reversible capacities up to 738 mAh g-1 and 660 mAh g-1 over 100 and 200 cycles are remained at 0.2 C rate.

Full open-framework batteries for stationary energy storage.

PubMed

Pasta, Mauro; Wessells, Colin D; Liu, Nian; Nelson, Johanna; McDowell, Matthew T; Huggins, Robert A; Toney, Michael F; Cui, Yi

2014-01-01

New types of energy storage are needed in conjunction with the deployment of renewable energy sources and their integration with the electrical grid. We have recently introduced a family of cathodes involving the reversible insertion of cations into materials with the Prussian Blue open-framework crystal structure. Here we report a newly developed manganese hexacyanomanganate open-framework anode that has the same crystal structure. By combining it with the previously reported copper hexacyanoferrate cathode we demonstrate a safe, fast, inexpensive, long-cycle life aqueous electrolyte battery, which involves the insertion of sodium ions. This high rate, high efficiency cell shows a 96.7% round trip energy efficiency when cycled at a 5C rate and an 84.2% energy efficiency at a 50C rate. There is no measurable capacity loss after 1,000 deep-discharge cycles. Bulk quantities of the electrode materials can be produced by a room temperature chemical synthesis from earth-abundant precursors.

Synthesis and electrochemical property of amorphous carbon nanotubes wrapped sulfur particles as cathode material for lithium-sulfur batteries

NASA Astrophysics Data System (ADS)

Hu, Jingtian; Zhao, Tingkai; Ji, Xianglin; Peng, Xiarong; Jin, Wenbo; Yang, Wenbo; Zhang, Lei; Gao, Junjie; Dang, Alei; Li, Hao; Li, Tiehu

2017-11-01

Amorphous carbon nanotube (ACNT)/sulfur composites were prepared by solution reaction method. The electrochemical results showed that both ACNT/S composite and ACNT/S mixture had a first reversible capacity of 1020 mA h·g-1, and the capacity retention of ACNT/S composite was 77% after 100 cycles while that of ACNT/S mixture was only 35% with the initial capacity being 850 mA h·g-1. The experimental results showed that the reversible lithium insertion capacity of the composite was obviously high and the cycling stability was good, which was mainly due to the solid and uniform dispersion of the sulfur and amorphous carbon nanotube matrix in the composite.

Mixed metal films with switchable optical properties

NASA Astrophysics Data System (ADS)

Richardson, T. J.; Slack, J. L.; Farangis, B.; Rubin, M. D.

2002-02-01

Thin, Pd-capped metallic films containing magnesium and first-row transition metals (Mn, Fe, Co) switch reversibly from their initial reflecting state to visually transparent states when exposed to gaseous hydrogen or following cathodic polarization in an alkaline electrolyte. Reversion to the reflecting state is achieved by exposure to air or by anodic polarization. The films were prepared by cosputtering from one magnesium target and one manganese, iron, or cobalt target. Both the dynamic optical switching range and the speed of the transition depend on the magnesium-transition metal ratio. Infrared spectra of films in the transparent, hydrided (deuterided) states support the presence of the intermetallic hydride phases Mg3MnH7, Mg2FeH6, and Mg2CoH5.

Crystal Chemistry of Electrochemically and Chemically Lithiated Layered α I-LiVOPO 4

DOE PAGES

He, Guang; Bridges, Craig A.; Manthiram, Arumugam

2015-09-14

LiVOPO 4 is an attractive cathode for lithium-ion batteries with a high operating voltage and the potential to achieve the reversible insertion of two lithium ions between VOPO 4 and Li 2VOPO 4. Among the three known forms of LiVOPO 4 (α, β, and αI), the α I-LiVOPO 4 has a layered structure that could promote better ionic mobility and reversibility than others. However, a comprehensive study of its lithiated product is not available as αI-LiVOPO 4 is metastable and difficult to prepare by conventional approaches. We present here a facile synthesis of highly crystalline αI-LiVOPO 4 and α I-LiVOPOmore » 4/rGO nanocomposite by a microwave-assisted solvothermal method and its electrochemical/chemical lithiation. The LiVOPO 4/rGO cathodes exhibit a high reversible capacity of 225 mAh g –1, indicating the insertion of more than one lithium into VOPO 4. Both electrochemical and chemical lithiation imply a solid-solution reaction mechanism on inserting the second lithium into α I-LiVOPO 4, but a two-phase reaction feature could also occur under certain conditions such as insufficient time for equilibration of Li + diffusion in the structure. The fully lithiated new α I-Li 2VOPO 4 phase was characterized by combined Rietveld refinement of neutron diffraction and X-ray diffraction data and by bond-valence sum maps. The results suggest that αI-Li 2VOPO 4 retains the tetragonal P4/nmm symmetry of the parent α I-LiVOPO 4 structure, where the second lithium ions are located in the lithium layers rather than in the VOPO 4 layers« less

Synthesis and characterization of La{sub 0.6}Sr{sub 0.4}Fe{sub 0.8}Cu{sub 0.2}O{sub 3−δ} oxide as cathode for Intermediate Temperature Solid Oxide Fuel Cells

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

Vázquez, Santiago; Davyt, Sebastián; Basbus, Juan F.

2015-08-15

Nanocrystalline La{sub 0.6}Sr{sub 0.4}Fe{sub 0.8}Cu{sub 0.2}O{sub 3−δ} (LSFCu) material was synthetized by combustion method using EDTA as fuel/chelating agent and NH{sub 4}NO{sub 3} as combustion promoter. Structural characterization using thermodiffraction data allowed to determine a reversible phase transition at 425 °C from a low temperature R-3c phase to a high temperature Pm-3m phase and to calculate the thermal expansion coefficient (TEC) of both phases. Important characteristics for cathode application as electronic conductivity and chemical compatibility with Ce{sub 0.9}Gd{sub 0.1}O{sub 2−δ} (CGO) electrolyte were evaluated. LSFCu presented a p-type conductor behavior with maximum conductivity of 135 S cm{sup −1} at 275more » °C and showed a good stability with CGO electrolyte at high temperatures. This work confirmed that as prepared LSFCu has excellent microstructural characteristics and an electrical conductivity between 100 and 60 S cm{sup −1} in the 500–700 °C range which is sufficiently high to work as intermediate temperature Solid Oxide Fuel Cells (IT-SOFCs) cathode. However a change in the thermal expansion coefficient consistent with a small oxygen loss process may affect the electrode-electrolyte interface during fabrication and operation of a SOFC. - Graphical abstract: Nanocrystalline La{sub 0.6}Sr{sub 0.4}Fe{sub 0.8}Cu{sub 0.2}O{sub 3−δ} was prepared by gel combustion and characterized by X-ray thermodiffraction and its conductivity was determined. The phase shows a reversible rhombohedral to cubic structural phase transition at 425 °C and a semiconductor to metallic phase transition at 275 °C. - Highlights: • LSFCu was prepared by gel combustion route using EDTA and NH{sub 4}NO{sub 3}. • LSFCu shows a reversible phase transition at 425 °C from R-3c to Pm-3m phase. • The sample has a maximum conductivity value of 135 S cm{sup −1} at 275 °C. • LSFCu shows a good chemical compatibility with CGO at 900 °C.« less

Real-Time Terahertz Imaging Using a Quantum Cascade Laser and Uncooled Microbolometer Focal Plane Array

DTIC Science & Technology

2008-06-01

reverse magnetron ” design (in which the polarity of the magnetron elements are reversed—such that the cathode constitutes the outer ring; the anode ...included as inset frames within Fig. 20. The dual nature of this figure (reporting both voltage and intensity vs. bias current) is useful in that it...tuned micro- magnetrons [60]-[61]. Conventional magnetrons (such as those used to generate microwaves) have physical dimensions which are excessively

High Energy Density Lithium Primary Cells Using Nitrogen Containing Polymer Positives.

DTIC Science & Technology

1983-12-01

the charges were stabilized on heteroatoms, particularly nitro- gen. A positive charge would be stored in the form of an ammonium ion. in a high...operate reversibly. 2.0 POLYMERIC CATHODES A polymer which might be expected to exemplify charge stabilization by nitrogen is poly-N-methylpyrrole (PMP...This material is electronically conductive and might store one charge per nitrogen atom. ox. PMP;4 N3 red. I N + N+ An additional, seductive attraction

Insights into the Effects of Zinc Doping on Structural Phase Transition of P2-Type Sodium Nickel Manganese Oxide Cathodes for High-Energy Sodium Ion Batteries.

PubMed

Wu, Xuehang; Xu, Gui-Liang; Zhong, Guiming; Gong, Zhengliang; McDonald, Matthew J; Zheng, Shiyao; Fu, Riqiang; Chen, Zonghai; Amine, Khalil; Yang, Yong

2016-08-31

P2-type sodium nickel manganese oxide-based cathode materials with higher energy densities are prime candidates for applications in rechargeable sodium ion batteries. A systematic study combining in situ high energy X-ray diffraction (HEXRD), ex situ X-ray absorption fine spectroscopy (XAFS), transmission electron microscopy (TEM), and solid-state nuclear magnetic resonance (SS-NMR) techniques was carried out to gain a deep insight into the structural evolution of P2-Na0.66Ni0.33-xZnxMn0.67O2 (x = 0, 0.07) during cycling. In situ HEXRD and ex situ TEM measurements indicate that an irreversible phase transition occurs upon sodium insertion-extraction of Na0.66Ni0.33Mn0.67O2. Zinc doping of this system results in a high structural reversibility. XAFS measurements indicate that both materials are almost completely dependent on the Ni(4+)/Ni(3+)/Ni(2+) redox couple to provide charge/discharge capacity. SS-NMR measurements indicate that both reversible and irreversible migration of transition metal ions into the sodium layer occurs in the material at the fully charged state. The irreversible migration of transition metal ions triggers a structural distortion, leading to the observed capacity and voltage fading. Our results allow a new understanding of the importance of improving the stability of transition metal layers.

A new strategy to mitigate the initial capacity loss of lithium ion batteries

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

Su, Xin; Lin, Chikai; Wang, Xiaoping

2016-08-01

Hard carbon (non-graphitizable) and related materials, like tin, tin oxide, silicon, and silicon oxide, have a high theoretical lithium delivery capacity (>550 mAh/g depending on their structural and chemical properties) but unfortunately they also exhibit a large initial capacity loss (ICL) that overrides the true reversible capacity in a full cell. Overcoming the large ICL of hard carbon in a full-cell lithium-ion battery (LIB) necessitates a new strategy wherein a sacrificial lithium source additive, such as, Li5FeO4 (LFO), is inserted on the cathode side. Full batteries using hard carbon coupled with LFO-LiCoO2 (LCO) are currently under development at our laboratory.more » We find that the reversible capacity of a cathode containing LFO can be increased by 14%. Furthermore, the cycle performance of full cells with LFO additive is improved from <90% to >95%. We show that the LFO additive not only can address the irreversible capacity loss of the anode, but can also provide the additional lithium ion source required to mitigate the lithium loss caused by side reactions. In addition, we have explored the possibility to achieve higher capacity with hard carbon, whereby the energy density of full cells can be increased from ca. 300 Wh/kg to >400 Wh/kg.« less

Passivation Layer and Cathodic Redox Reactions in Sodium-Ion Batteries Probed by HAXPES.

PubMed

Doubaji, Siham; Philippe, Bertrand; Saadoune, Ismael; Gorgoi, Mihaela; Gustafsson, Torbjorn; Solhy, Abderrahim; Valvo, Mario; Rensmo, Håkan; Edström, Kristina

2016-01-08

The cathode material P2-Nax Co2/3 Mn2/9 Ni1/9 O2, which could be used in Na-ion batteries, was investigated through synchrotron-based hard X-ray photoelectron spectroscopy (HAXPES). Nondestructive analysis was made through the electrode/electrolyte interface of the first electrochemical cycle to ensure access to information not only on the active material, but also on the passivation layer formed at the electrode surface and referred to as the solid permeable interface (SPI). This investigation clearly shows the role of the SPI and the complexity of the redox reactions. Cobalt, nickel, and manganese are all electrochemically active upon cycling between 4.5 and 2.0 V; all are in the 4+ state at the end of charging. Reduction to Co(3+), Ni(3+), and Mn(3+) occurs upon discharging and, at low potential, there is partial reversible reduction to Co(2+) and Ni(2+). A thin layer of Na2 CO3 and NaF covers the pristine electrode and reversible dissolution/reformation of these compounds is observed during the first cycle. The salt degradation products in the SPI show a dependence on potential. Phosphates mainly form at the end of the charging cycle (4.5 V), whereas fluorophosphates are produced at the end of discharging (2.0 V). © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Clusters of α-LiFeO2 nanoparticles incorporated into multi-walled carbon nanotubes: a lithium-ion battery cathode with enhanced lithium storage properties.

PubMed

Rahman, Md Mokhlesur; Glushenkov, Alexey M; Chen, Zhiqiang; Dai, Xiujuan J; Ramireddy, Thrinathreddy; Chen, Ying

2013-12-14

We report the preparation of a novel nanocomposite architecture of α-LiFeO2-MWCNT based on clusters of α-LiFeO2 nanoparticles incorporated into multiwalled carbon nanotubes (MWCNTs). The composite represents a promising cathode material for lithium-ion batteries. The preparation of the nanocomposite is achieved by combining a molten salt precipitation process and a radio frequency oxygen plasma for the first time. We demonstrate that clusters of α-LiFeO2 nanoparticles incorporated into MWCNTs are capable of delivering a stable and high reversible capacity of 147 mA h g(-1) at 1 C after 100 cycles with the first cycle Coulombic efficiency of ~95%. The rate capability of the composite is significantly improved and its reversible capacity is measured to be 101 mA h g(-1) at a high current rate of 10 C. Both rate capability and cycling stability are not simply a result of introduction of functionalized MWCNTs but most likely originate from the unique composite structure of clusters of α-LiFeO2 nanoparticles integrated into a network of MWCNTs. The excellent electrochemical performance of this new nanocomposite opens up new opportunities in the development of high-performance electrode materials for energy storage application using the radio frequency oxygen plasma technique.

O3-type layered transition metal oxide Na(NiCoFeTi) 1/4O 2 as a high rate and long cycle life cathode material for sodium ion batteries

DOE PAGES

Yue, Ji -Li; Yang, Xiao -Qing; Zhou, Yong -Ning; ...

2015-10-09

High rate capability and long cycle life are challenging goals for the development of room temperature sodium-ion batteries. Here we report a new single phase quaternary O3-type layer-structured transition metal oxide Na(NiCoFeTi) 1/4O 2 synthesized by a simple solid-state reaction as a new cathode material for sodium-ion batteries. It can deliver a reversible capacity of 90.6 mA h g –1 at a rate as high as 20C. At 5C, 75.0% of the initial specific capacity can be retained after 400 cycles with a capacity-decay rate of 0.07% per cycle, demonstrating a superior long-term cyclability at high current density. X-ray diffractionmore » and absorption characterization revealed reversible phase transformations and electronic structural changes during the Na + deintercalation/intercalation process. Ni, Co and Fe ions contribute to charge compensation during charge and discharge. Although Ti ions do not contribute to the charge transfer, they play a very important role in stabilizing the structure during charge and discharge by suppressing the Fe migration. Additionally, Ti substitution can also smooth the charge–discharge plateaus effectively, which provides a potential advantage for the commercialization of this material for room temperature sodium-ion batteries.« less

Investigating the stability of cathode materials for rechargeable lithium ion batteries

NASA Astrophysics Data System (ADS)

Huang, Yiqing

Lithium ion batteries are widely used in portable electronic devices and electric vehicles. However, safety is one of the most important issues for the Li-ion batteries' use. Some cathode materials, such as LiCoO 2, are thermally unstable in the charged state. Upon decomposition these cathode materials release O2, which could react with organic electrolyte, leading to a thermal runaway. Thus understanding the stability of the cathode materials is critical to the safety of lithium ion batteries. Olivine-type LiMnPO4 is a promising cathode material for lithium ion batteries because of its high energy density. We have revealed the critical role of carbon in the stability and thermal behaviour of olivine MnPO 4 obtained by chemical delithiation of LiMnPO4. (Li)MnPO 4 samples with various particle sizes and carbon contents were studied. Carbon-free LiMnPO4 obtained by solid state synthesis in O 2 becomes amorphous upon delithiation. Small amounts of carbon (0.3 wt.%) help to stabilize the olivine structure, so that completely delithiated crystalline olivine MnPO4 can be obtained. Larger amount of carbon (2 wt.%) prevents full delithiation. Heating in air, O2, or N 2 results in structural disorder (< 300 °C), formation of an intermediate sarcopside Mn3(PO4)2 phase (350 -- 450 °C), and complete decomposition to Mn2P2O 7 on extended heating at 400 °C. Carbon protects MnPO4 from reacting with environmental water, which is detrimental to its structural stability. We not only studied the crystalline olivine MnPO4, but also investigated the amorphous products obtained from carbon-free LiMnPO 4. We have revealed the Mn dissolution phenomenon during chemical delithiation of LiMnPO4, which causes the amorphization of olivine MnPO 4. Properties of crystalline-MnPO4 obtained from carbon-coated LiMnPO4 and of amorphous product resulting from the delithiation of pure LiMnPO4 were studied and compared. The P-rich amorphous phases in the latter are considered to be MnHP2O7 and MnH2P2O7 from XAS and XPS analysis. Safety of batteries not only depends on the stability of the active materials, but also the interactions between the active materials and electrolyte. Thus we study the stability between the cathode materials and the electrolyte. The thermal stability of electrochemically delithiated Li0.1N 0.8C0.15Al0.05O2 (NCA), FePO4 (FP), Mn0.8Fe0.2PO4 (MFP), hydrothermally synthesized VOPO4, LiVOPO4 and electrochemically lithiated Li2VOPO4 is investigated by differential scanning calorimetry (DSC) and thermogravimetric analysis, coupled with mass spectrometry (TGA-MS). The thermal stability is found in the order: NCA< VOPO4< MFP< FP=LiVOPO4=Li2VOPO4. Sealed capsule high pressure experiments show a phase transformation of VOPO4 → HVOPO4 → H2VOPO4 when VOPO4 reacts with electrolyte (1 M LiPF6 in EC: DMC=1:1) between 200 and 300 °C. Finally, we characterize the lithium storage and release mechanism of V2O5 aerogels by x-ray photoelectron spectroscopy (XPS). We study the influence of n--butyllithium (n--BuLi) treatments on the electrochemical performance of the aerogel. In addition to fully reversible V reduction and oxidation due to the intercalation reaction, we observe the formation of LiOH species that are only partially reversible. This is attributed to reaction with the interlayer water and is considered responsible for the gradual capacity fade. The n--BuLi treated aerogels display a higher capacity than those without and our XPS analysis reveals an additional reversible formation of Li2O.

Synthesis and characterization of cathode materials for lithium ion-rechargeable batteries

NASA Astrophysics Data System (ADS)

Nieto Ramos, Santander

Lithium intercalation materials are of special interest for cathodes in rechargeable lihium-ion batteries, because they are capable of reversibly intercalating lithium ions without altering the main unit. We developed a novel solution-based route for the synthesis of these lithium intercalates oxides. The first part of this work was devoted to the optimization of chemical solution process parameters in order to correlate their electrochemical properties. It was found that the lattice parameters and the crystallite size increase, whereas the lattice strain decreases with the increase in calcinations temperature. Powders annealed at 700°C for 15 h yielded best electrochemical performance. The electrochemical performance of substituted Li1.2Mn2O 4, Li1.2Mn1.8O4, Li1.2Cr 0.05Mn1.95O4, and Li1.2Cr0.05 Mn1.75O4 spinel electrodes in lithium cell has been studied. The electrochemical data showed that the Li and Cr dopant effect improves the cycleablility of spinel LiMn2O4 electrodes. The second part of this dissertation was devoted to improve the rate capabilities of these cathode materials by growing nano-size cathode particles and also by cation co-doping. Though the discharge capacity of these nano-crystalline cathodes was equivalent to their microcrystalline counterpart, these exhibited capacity fading in the 4V range. Through a combined X-ray diffraction, micro-Raman spectroscopy, and X-ray photoelectron spectroscopy (XPS) analyses, we correlated the observed capacity fading with the onset of Jahn-Teller (J-T) distortion toward the end of the discharge in the cut-off limit between 4.2 and 3.2V. It was postulated that J-T distortion is the dominant fading mechanism of these nano-crystalline cathodes then by increasing the average oxidation state of the Mn ion in a virgin lithium manganate cathode, the onset of such distortion towards the end of the discharge could be delayed, and therefore, the cycleability of these cathodes could be improved. By synthesizing lithium and aluminum ion co-doped lithium manganate particles, we could increase the average oxidation state of Mn ions in the virgin electrodes. Indeed, the cycleability of these co-doped cathodes was dramatically improved which supports our population. The third part of this thesis was devoted to synthesis and electrochemical properties of layered compounds. Lithium nickel oxides derivatives are promising positive materials for the next generation of lithium-ion batteries. Partial substitution of certain cations for nickel in this family of oxides which satisfies the demanding requirements for rechargeable battery applications. In this part the interest is focused on the effect of simultaneous cobalt as well as aluminum doping was studied to understand their effect on the phase formation behavior and electrochemical properties of solution derived lithium nickel oxide cathode materials for rechargeable batteries. (Abstract shortened by UMI.)

Improving thermal and electrochemical performances of LiCoO{sub 2} cathode at high cut-off charge potentials by MF{sub 3} (M=Ce, Al) coating

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

Aboulaich, Abdelmaula, E-mail: a.aboulaich@managemgroup.com; Ouzaouit, Khalid; Faqir, Hakim

2016-01-15

Highlights: • Fluoride metal is successfully coated on the surface of LiCoO{sub 2}. • Easy and scalable method is adopted for the synthesis of coated-LiCoO{sub 2}. • Appropriate amount of AlF{sub 3} or CeF{sub 3} is beneficial to reduce cation disorder. • The electrochemical performances of coated LiCoO{sub 2} is significantly enhanced at higher potential (cycling efficiency and reversible capacity). • The coated cathode exhibits excellent thermal stability highlighted by calorimetric technique. - Abstract: Surface coating of LiCoO{sub 2} remained one of the efficient methods to enhance its electrochemical and thermal performances, especially at high cut-off potential. In this work,more » MF{sub 3} (M = Ce, Al) coated LiCoO{sub 2} was synthesized via co-precipitation method followed by a solid state reaction at 400 °C. The morphology and structure of the modified cathode material were characterized by scanning electron microscopy (SEM), X-ray diffraction (XRD) and transmission electron microscopy (TEM). The results show that the fluoride compound MF{sub 3} is successfully coated on the surface of LiCoO{sub 2} cathode particles with an average layer thickness about 12 nm and 40 nm for AlF{sub 3} and CeF{sub 3}, respectively. The electrochemical tests show that the AlF{sub 3}-coating layer significantly enhances the cycling performance of LiCoO{sub 2} cathode material, even at high cut-off potential. While the bare LiCoO{sub 2} cathode displays fast fading at 4.6 V vs. Li{sup +}/Li cutoff potential, the surface-modified electrode exhibits the great capacity of 160 mAh g{sup −1} with excellent capacity retention on several cycles. We concluded that the electrochemical and the thermal enhancement at high potential are ascribed to the presence of MF{sub 3} coating layer which prevent the side reaction during the charge discharge process, alleviate the attack by the acidic electrolyte and reduce the damage of electrode structure.« less

Chloride-reinforced carbon nanofiber host as effective polysulfide traps in lithium-sulfur batteries

DOE PAGES

Fan, Lei; Zhuang, Houlong; Zhang, Kaihang; ...

2016-01-01

Lithium-sulfur (Li-S) battery is one of the most promising alternatives for the current state-of-art lithium-ion batteries (LIBs) due to its high theoretical energy density and lower production cost from the use of earth abundant element - sulfur. However, the commercialization of Li-S batteries has been so far limited to the cyclability and the retention of active sulfur materials. Using co-electrospinning and physical vapor deposition procedures, we created a class of chloride-carbon nanofiber composites, and studied their effectiveness on polysulfides sequestration. By trapping sulfur reduction products in the modified-cathode through both chemical and physical confinements in a conductive host, these chloride-coatedmore » cathodes are shown to remarkably suppress the polysulfide dissolution and shuttling between lithium and sulfur electrodes. We show that not only the binding energy but also the electronic conductivity of the host plays an important role on the reversibility of sulfur-based cathode upon repeated cycles. Electrochemical analysis of the chloride-modified cathodes over hundreds of cycles indicates that too strong binding of the sulfur species may lead to the decay of Coulombic efficiency. Cells containing indium chloride-modified carbon nanofiber outperform cells with other halogenated salt modifications, delivering an average specific capacity of above 1200mAh g-1 at 0.2C over 200 cycles. Once loaded with high S content, it shows stable capacity retention with only 0.019% decay per cycle from 5th to 650th cycle. It also shows stabilized cyclability and enhanced Coulombic efficiency in the absence of traditional anode stabilizer lithium nitrite.« less

Synthetic Control of Kinetic Reaction Pathway and Cationic Ordering in High-Ni Layered Oxide Cathodes.

PubMed

Wang, Dawei; Kou, Ronghui; Ren, Yang; Sun, Cheng-Jun; Zhao, Hu; Zhang, Ming-Jian; Li, Yan; Huq, Ashifia; Ko, J Y Peter; Pan, Feng; Sun, Yang-Kook; Yang, Yong; Amine, Khalil; Bai, Jianming; Chen, Zonghai; Wang, Feng

2017-10-01

Nickel-rich layered transition metal oxides, LiNi 1- x (MnCo) x O 2 (1-x ≥ 0.5), are appealing candidates for cathodes in next-generation lithium-ion batteries (LIBs) for electric vehicles and other large-scale applications, due to their high capacity and low cost. However, synthetic control of the structural ordering in such a complex quaternary system has been a great challenge, especially in the presence of high Ni content. Herein, synthesis reactions for preparing layered LiNi 0.7 Mn 0.15 Co 0.15 O 2 (NMC71515) by solid-state methods are investigated through a combination of time-resolved in situ high-energy X-ray diffraction and absorption spectroscopy measurements. The real-time observation reveals a strong temperature dependence of the kinetics of cationic ordering in NMC71515 as a result of thermal-driven oxidation of transition metals and lithium/oxygen loss that concomitantly occur during heat treatment. Through synthetic control of the kinetic reaction pathway, a layered NMC71515 with low cationic disordering and a high reversible capacity is prepared in air. The findings may help to pave the way for designing high-Ni layered oxide cathodes for LIBs. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Synthetic Control of Kinetic Reaction Pathway and Cationic Ordering in High-Ni Layered Oxide Cathodes

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

Wang, Dawei; Kou, Ronghui; Ren, Yang

Nickel-rich layered transition metal oxides, LiNi1-x(MnCo)(x)O-2 (1-x >= 0.5), are appealing candidates for cathodes in next-generation lithium-ion batteries (LIBs) for electric vehicles and other large-scale applications, due to their high capacity and low cost. However, synthetic control of the structural ordering in such a complex quaternary system has been a great challenge, especially in the presence of high Ni content. Herein, synthesis reactions for preparing layered LiNi0.7Mn0.15Co0.15O2 (NMC71515) by solid-state methods are investigated through a combination of time-resolved in situ high-energy X-ray diffraction and absorption spectroscopy measurements. The real-time observation reveals a strong temperature dependence of the kinetics of cationicmore » ordering in NMC71515 as a result of thermal-driven oxidation of transition metals and lithium/oxygen loss that concomitantly occur during heat treatment. Through synthetic control of the kinetic reaction pathway, a layered NMC71515 with low cationic disordering and a high reversible capacity is prepared in air. The findings may help to pave the way for designing high-Ni layered oxide cathodes for LIBs.« less

Synthetic Control of Kinetic Reaction Pathway and Cationic Ordering in High-Ni Layered Oxide Cathodes

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

Wang, Dawei; Kou, Ronghui; Ren, Yang

Nickel-rich layered transition metal oxides, LiNi 1-x(MnCo) xO 2 (1-x ≥ 0.5), are appealing candidates for cathodes in next-generation lithium-ion batteries (LIBs) for electric vehicles and other large-scale applications, due to their high capacity and low cost. However, synthetic control of the structural ordering in such a complex quaternary system has been a great challenge, especially in the presence of high Ni content. Herein, synthesis reactions for preparing layered LiNi 0.7Mn 0.15Co 0.15O 2 (NMC71515) by solid-state methods are investigated through a combination of time-resolved in situ high-energy X-ray diffraction and absorption spectroscopy measurements. The real-time observation reveals a strongmore » temperature dependence of the kinetics of cationic ordering in NMC71515 as a result of thermal-driven oxidation of transition metals and lithium/oxygen loss that concomitantly occur during heat treatment. Through synthetic control of the kinetic reaction pathway, a layered NMC71515 with low cationic disordering and a high reversible capacity is prepared in air. The findings may help to pave the way for designing high-Ni layered oxide cathodes for LIBs« less

Simple synthesis of amorphous NiWO4 nanostructure and its application as a novel cathode material for asymmetric supercapacitors.

PubMed

Niu, Lengyuan; Li, Zhangpeng; Xu, Ye; Sun, Jinfeng; Hong, Wei; Liu, Xiaohong; Wang, Jinqing; Yang, Shengrong

2013-08-28

This study reports a simple synthesis of amorphous nickel tungstate (NiWO4) nanostructure and its application as a novel cathode material for supercapacitors. The effect of reaction temperature on the electrochemical properties of the NiWO4 electrode was studied, and results demonstrate that the material synthesized at 70 °C (NiW-70) has shown the highest specific capacitance of 586.2 F g(-1) at 0.5 A g(-1) in a three-electrode system. To achieve a high energy density, a NiW-70//activated carbon asymmetric supercapacitor is successfully assembled by use of NiW-70 and activated carbon as the cathode and anode, respectively, and then, its electrochemical performance is characterized by cyclic voltammetry and galvanostatic charge-discharge measurements. The results show that the assembled asymmetric supercapacitor can be cycled reversibly between 0 and 1.6 V with a high specific capacitance of 71.1 F g(-1) at 0.25 A g(-1), which can deliver a maximum energy density of 25.3 Wh kg(-1) at a power density of 200 W kg(-1). Furthermore, this asymmetric supercapacitor also presented an excellent, long cycle life along with 91.4% specific capacitance being retained after 5000 consecutive times of cycling.

Chloride-Reinforced Carbon Nanofiber Host as Effective Polysulfide Traps in Lithium-Sulfur Batteries.

PubMed

Fan, Lei; Zhuang, Houlong L; Zhang, Kaihang; Cooper, Valentino R; Li, Qi; Lu, Yingying

2016-12-01

Lithium-sulfur (Li-S) battery is one of the most promising alternatives for the current state-of-the-art lithium-ion batteries due to its high theoretical energy density and low production cost from the use of sulfur. However, the commercialization of Li-S batteries has been so far limited to the cyclability and the retention of active sulfur materials. Using co-electrospinning and physical vapor deposition procedures, we created a class of chloride-carbon nanofiber composites, and studied their effectiveness on polysulfides sequestration. By trapping sulfur reduction products in the modified cathode through both chemical and physical confinements, these chloride-coated cathodes are shown to remarkably suppress the polysulfide dissolution and shuttling between lithium and sulfur electrodes. From adsorption experiments and theoretical calculations, it is shown that not only the sulfide-adsorption effect but also the diffusivity in the vicinity of these chlorides materials plays an important role on the reversibility of sulfur-based cathode upon repeated cycles. Balancing the adsorption and diffusion effects of these nonconductive materials could lead to the enhanced cycling performance of an Li-S cell. Electrochemical analyses over hundreds of cycles indicate that cells containing indium chloride-modified carbon nanofiber outperform cells with other halogenated salts, delivering an average specific capacity of above 1200 mAh g -1 at 0.2 C.

Spherical Macroporous Carbon Nanotube Particles with Ultrahigh Sulfur Loading for Lithium-Sulfur Battery Cathodes.

PubMed

Gueon, Donghee; Hwang, Jeong Tae; Yang, Seung Bo; Cho, Eunkyung; Sohn, Kwonnam; Yang, Doo-Kyung; Moon, Jun Hyuk

2018-01-23

A carbon host capable of effective and uniform sulfur loading is the key for lithium-sulfur batteries (LSBs). Despite the application of porous carbon materials of various morphologies, the carbon hosts capable of uniformly impregnating highly active sulfur is still challenging. To address this issue, we demonstrate a hierarchical pore-structured CNT particle host containing spherical macropores of several hundred nanometers. The macropore CNT particles (M-CNTPs) are prepared by drying the aerosol droplets in which CNTs and polymer particles are dispersed. The spherical macropore greatly improves the penetration of sulfur into the carbon host in the melt diffusion of sulfur. In addition, the formation of macropores greatly develops the volume of the micropore between CNT strands. As a result, we uniformly impregnate 70 wt % sulfur without sulfur residue. The S-M-CNTP cathode shows a highly reversible capacity of 1343 mA h g -1 at a current density of 0.2 C even at a high sulfur content of 70 wt %. Upon a 10-fold current density increase, a high capacity retention of 74% is observed. These cathodes have a higher sulfur content than those of conventional CNT hosts but nevertheless exhibit excellent performance. Our CNTPs and pore control technology will advance the commercialization of CNT hosts for LSBs.

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

Bockris, J.O.; Devanathan, M.A.V.

The galvanostatic double charging method was applied to determine the coverage of Ni cathodes with adsorbed atomic H in 2 N NaOH solutions. Anodic current densities were varied from 0.05 to 1.8 amp/sq cm. The plateau indicating absence of readsorption was between 0.6 and 1.8 amp/sq cm, for a constant cathodic c.d. of 1/10,000 amp/sq cm. The variation of the adsorbed H over cathodic c.d.'s ranging from 10 to the -6th power to 1/10 at a constant anodic c.d. of 1 amp/sq cm were calculated and the coverage calculated. The mechanism of the H evolution reaction was elucidated. The ratemore » determining step is discharge from a water molecules followed by rapid Tafel recombination. The rate constants for these processes and the rate constant for the ionisation, calculated with the extrapolated value of coverage for the reversible H electrode, were determined. A modification of the Tafel equation which takes into account both coverage and ionisation is in harmony with the results. A new method for the determination of coverage suitable for corrodible metals is described which involves the measurement of the rate of permeation of H by electrochemical techniques which enhances the sensitivity of the method. (Author)« 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).

High‐Performance Li–O2 Batteries with Controlled Li2O2 Growth in Graphene/Au‐Nanoparticles/Au‐Nanosheets Sandwich

PubMed Central

Wang, Guoqing; Tu, Fangfang; Du, Gaohui; Zhang, Shichao; Cao, Gaoshao; Zhao, Xinbing

2016-01-01

The working of nonaqueous Li–O2 batteries relies on the reversible formation/decomposition of Li2O2 which is electrically insulating and reactive with carbon and electrolyte. Realizing controlled growth of Li2O2 is a prerequisite for high performance of Li–O2 batteries. In this work, a sandwich‐structured catalytic cathode is designed: graphene/Au‐nanoparticles/Au‐nanosheets (G/Au‐NP/Au‐NS) that enables controlled growth of Li2O2 spatially and structurally. It is found that thin‐layer Li2O2 (below 10 nm) can grow conformally on the surface of Au NPs confined in between graphene and Au NSs. This unique crystalline behavior of Li2O2 effectively relieves or defers the electrode deactivation with Li2O2 accumulation and largely reduces the contact of Li2O2 with graphene and electrolyte. As a result, Li–O2 batteries with the G/Au‐NP/Au‐NS cathode exhibit superior electrochemical performance. A stable cycling of battery can last 300 times at 400 mA g−1 when the capacity is limited at 500 mAh g−1. This work provides a practical design of catalytic cathodes capable of controlling Li2O2 growth. PMID:27840792

Synthesis of Cation and Water Free Cryptomelane Type OMS-2 Cathode Materials: The Impact of Tunnel Water on Electrochemistry

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

Poyraz, Altug S.; Huang, Jianping; Zhang, Bingjie

Cryptomelane type manganese dioxides (α-MnO 2, OMS-2) are interesting potential cathode materials due to the ability of their one dimensional (1D) tunnels to reversibly host various cations including Li +and an accessible stable 3+/4+ redox couple. Here, we synthesized metal cation free OMS-2 materials where the tunnels were occupied by only water and hydronium ions. Water was subsequently removed from the tunnels. Cation free OMS-2 and Dry-OMS-2 were used as cathodes in Li based batteries to investigate the role of tunnel water on their electrochemistry. The initial discharge capacity was higher for Dry-OMS-2 (252 mAh/g) compared to OMS-2 (194 mAh/g),more » however, after 100 cycles Dry-OMS-2 and OMS-2 delivered 137 mAh/g and 134 mAh/g, respectively. Li +ion diffusion was more facile for Dry-OMS as evidenced by rate capability, at 400 mA/g. Dry-OMS-2 delivered 135mAh/g whereas OMS-2 delivered ~115 mAh/g. This first report of the impact of tunnel water on the electrochemistry of OMS-2 type materials demonstrates that the presence of tunnel water in OMS-2 type materials negatively impacts the electrochemistry.« less

Chlorobenzene Poisoning and Recovery of Platinum-Based Cathodes in Proton Exchange Membrane Fuel Cells

PubMed Central

Zhai, Yunfeng; Baturina, Olga; Ramaker, David; Farquhar, Erik; St-Pierre, Jean; Swider-Lyons, Karen

2015-01-01

The platinum electrocatalysts found in proton exchange membrane fuel cells are poisoned both reversibly and irreversibly by air pollutants and residual manufacturing contaminants. In this work, the poisoning of a Pt/C PEMFC cathode was probed by a trace of chlorobenzene in the air feed. Chlorobenzene inhibits the oxygen reduction reaction and causes significant cell performance loss. The performance loss is largely restored by neat air operation and potential cycling between 0.08 V and 1.2 V under H2/N2 (anode/cathode). The analysis of emissions, in situ X-ray absorption spectroscopy and electrochemical impedance spectra show the chlorobenzene adsorption/reaction and molecular orientation on Pt surface depend on the electrode potential. At low potentials, chlorobenzene deposits either on top of adsorbed H atoms or on the Pt surface via the benzene ring and is converted to benzene (ca. 0.1 V) or cyclohexane (ca. 0 V) upon Cl removal. At potentials higher than 0.2 V, chlorobenzene binds to Pt via the Cl atom and can be converted to benzene (less than 0.3 V) or desorbed. Cl− is created and remains in the membrane electrode assembly. Cl− binds to the Pt surface much stronger than chlorobenzene, but can slowly be flushed out by liquid water. PMID:26388963

Synthetic Control of Kinetic Reaction Pathway and Cationic Ordering in High-Ni Layered Oxide Cathodes

DOE PAGES

Wang, Dawei; Kou, Ronghui; Ren, Yang; ...

2017-08-25

Nickel-rich layered transition metal oxides, LiNi 1-x(MnCo) xO 2 (1-x ≥ 0.5), are appealing candidates for cathodes in next-generation lithium-ion batteries (LIBs) for electric vehicles and other large-scale applications, due to their high capacity and low cost. However, synthetic control of the structural ordering in such a complex quaternary system has been a great challenge, especially in the presence of high Ni content. Herein, synthesis reactions for preparing layered LiNi 0.7Mn 0.15Co 0.15O 2 (NMC71515) by solid-state methods are investigated through a combination of time-resolved in situ high-energy X-ray diffraction and absorption spectroscopy measurements. The real-time observation reveals a strongmore » temperature dependence of the kinetics of cationic ordering in NMC71515 as a result of thermal-driven oxidation of transition metals and lithium/oxygen loss that concomitantly occur during heat treatment. Through synthetic control of the kinetic reaction pathway, a layered NMC71515 with low cationic disordering and a high reversible capacity is prepared in air. The findings may help to pave the way for designing high-Ni layered oxide cathodes for LIBs« less

Electrochemical Properties of the LiNi0.6Co0.2Mn0.2O2 Cathode Material Modified by Lithium Tungstate under High Voltage.

PubMed

Fu, Jiale; Mu, Daobin; Wu, Borong; Bi, Jiaying; Cui, Hui; Yang, Hao; Wu, Hanfeng; Wu, Feng

2018-05-31

An amount (5 wt %) of lithium tungstate (Li 2 WO 4 ) as an additive significantly improves the cycle and rate performances of the LiNi 0.6 Co 0.2 Mn 0.2 O 2 electrode at the cutoff voltage of 4.6 V. The 5 wt % Li 2 WO 4 -mixed LiNi 0.6 Co 0.2 Mn 0.2 O 2 electrode delivers a reversible capacity of 199.2 mA h g -1 and keeps 73.1% capacity for 200 cycles at 1 C. It retains 67.4% capacity after 200 cycles at 2 C and delivers a discharge capacity of 167.3 mA h g -1 at 10 C, while those of the pristine electrode are only 44.7% and 87.5 mA h g -1 , respectively. It is shown that the structure of the LiNi 0.6 Co 0.2 Mn 0.2 O 2 cathode material is not affected by mixing Li 2 WO 4 . The introduced Li 2 WO 4 effectively restrains the LiPF 6 and carbonate solvent decomposition by consuming PF 5 at high cutoff voltage, forming a stable cathode/electrolyte interface film with low resistance.

Encoding changes in orbitofrontal cortex in reversal-impaired aged rats.

PubMed

Schoenbaum, Geoffrey; Setlow, Barry; Saddoris, Michael P; Gallagher, Michela

2006-03-01

Previous work in rats and primates has shown that normal aging can be associated with a decline in cognitive flexibility mediated by prefrontal circuits. For example, aged rats are impaired in rapid reversal learning, which in young rats depends critically on the orbitofrontal cortex. To assess whether aging-related reversal impairments reflect orbitofrontal dysfunction, we identified aged rats with reversal learning deficits and then recorded single units as these rats, along with unimpaired aged cohorts and young control rats, learned and reversed a series of odor discrimination problems. We found that the flexibility of neural correlates in orbitofrontal cortex was markedly diminished in aged rats characterized as reversal-impaired in initial training. In particular, although many cue-selective neurons in young and aged-unimpaired rats reversed odor preference when the odor-outcome associations were reversed, cue-selective neurons in reversal-impaired aged rats did not. In addition, outcome-expectant neurons in aged-impaired rats failed to become active during cue sampling after learning. These altered features of neural encoding could provide a basis for cognitive inflexibility associated with normal aging.

Enhanced Lifetime of Polymer Solar Cells by Surface Passivation of Metal Oxide Buffer Layers.

PubMed

Venkatesan, Swaminathan; Ngo, Evan; Khatiwada, Devendra; Zhang, Cheng; Qiao, Qiquan

2015-07-29

The role of electron selective interfaces on the performance and lifetime of polymer solar cells were compared and analyzed. Bilayer interfaces consisting of metal oxide films with cationic polymer modification namely poly ethylenimine ethoxylated (PEIE) were found to enhance device lifetime compared to bare metal oxide films when used as an electron selective cathode interface. Devices utilizing surface-modified metal oxide layers showed enhanced lifetimes, retaining up to 85% of their original efficiency when stored in ambient atmosphere for 180 days without any encapsulation. The work function and surface potential of zinc oxide (ZnO) and ZnO/PEIE interlayers were evaluated using Kelvin probe and Kelvin probe force microscopy (KPFM) respectively. Kelvin probe measurements showed a smaller reduction in work function of ZnO/PEIE films compared to bare ZnO films when aged in atmospheric conditions. KPFM measurements showed that the surface potential of the ZnO surface drastically reduces when stored in ambient air for 7 days because of surface oxidation. Surface oxidation of the interface led to a substantial decrease in the performance in aged devices. The enhancement in the lifetime of devices with a bilayer interface was correlated to the suppressed surface oxidation of the metal oxide layers. The PEIE passivated surface retained a lower Fermi level when aged, which led to lower trap-assisted recombination at the polymer-cathode interface. Further photocharge extraction by linearly increasing voltage (Photo-CELIV) measurements were performed on fresh and aged samples to evaluate the field required to extract maximum charges. Fresh devices with a bare ZnO cathode interlayer required a lower field than devices with ZnO/PEIE cathode interface. However, aged devices with ZnO required a much higher field to extract charges while aged devices with ZnO/PEIE showed a minor increase compared to the fresh devices. Results indicate that surface modification can act as a suitable passivation layer to suppress oxidation in metal oxide thin films for enhanced lifetime in inverted organic solar cells.

Insight into Ca-Substitution Effects on O3-Type NaNi1/3 Fe1/3 Mn1/3 O2 Cathode Materials for Sodium-Ion Batteries Application.

PubMed

Sun, Liqi; Xie, Yingying; Liao, Xiao-Zhen; Wang, Hong; Tan, Guoqiang; Chen, Zonghai; Ren, Yang; Gim, Jihyeon; Tang, Wan; He, Yu-Shi; Amine, Khalil; Ma, Zi-Feng

2018-04-18

O3-type NaNi 1/3 Fe 1/3 Mn 1/3 O 2 (NaNFM) is well investigated as a promising cathode material for sodium-ion batteries (SIBs), but the cycling stability of NaNFM still needs to be improved by using novel electrolytes or optimizing their structure with the substitution of different elements sites. To enlarge the alkali-layer distance inside the layer structure of NaNFM may benefit Na + diffusion. Herein, the effect of Ca-substitution is reported in Na sites on the structural and electrochemical properties of Na 1- x Ca x /2 NFM (x = 0, 0.05, 0.1). X-ray diffraction (XRD) patterns of the prepared Na 1- x Ca x /2 NFM samples show single α-NaFeO 2 type phase with slightly increased alkali-layer distance as Ca content increases. The cycling stabilities of Ca-substituted samples are remarkably improved. The Na 0.9 Ca 0.05 Ni 1/3 Fe 1/3 Mn 1/3 O 2 (Na 0.9 Ca 0.05 NFM) cathode delivers a capacity of 116.3 mAh g -1 with capacity retention of 92% after 200 cycles at 1C rate. In operando XRD indicates a reversible structural evolution through an O3-P3-P3-O3 sequence of Na 0.9 Ca 0.05 NFM cathode during cycling. Compared to NaNMF, the Na 0.9 Ca 0.05 NFM cathode shows a wider voltage range in pure P3 phase state during the charge/discharge process and exhibits better structure recoverability after cycling. The superior cycling stability of Na 0.9 Ca 0.05 NFM makes it a promising material for practical applications in sodium-ion batteries. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Nitrogen-doped MOF-derived micropores carbon as immobilizer for small sulfur molecules as a cathode for lithium sulfur batteries with excellent electrochemical performance.

PubMed

Li, Zhaoqiang; Yin, Longwei

2015-02-25

Nitrogen-doped carbon (NDC) spheres with abundant 22 nm mesopores and 0.5 nm micropores are obtained by directly carbonization of nitrogen-contained metal organic framework (MOF) nanocrystals. Large S8 and small S2-4 molecules are successfully infiltrated into 22 nm mesopores and 0.5 nm micropores, respectively. We successfully investigate the effect of sulfur immobilization in mesopores and micropores on the electrochemical performance of lithium-sulfur (Li-S) battery based on NDC-sulfur hybrid cathodes. The large S8 molecules in 22 nm mesopores can be removed by a prolonged heat treatment, with only small molecules of S2-4 immobilized in micropores of NDC matrices. The NDC/S2-4 hybrid exhibits excellent cycling performance, high Coulombic efficiency, and good rate capability as cathode for Li-S batteries. The confinement of smaller S2-4 molecules in the micropores of NDS efficiently avoids the loss of active sulfur and formation of soluble high-order Li polysulfides. The porous carbon can buffer the volume expansion and contraction changes, promising a stable structure for cathode. Furthermore, N doping in MOF-derived carbon not only facilitates the fast charge transfer but also is helpful in building a stronger interaction between carbon and sulfur, strengthening immobilization ability of S2-4 in micropores. The NDS-sulfur hybrid cathode exhibits a reversible capacity of 936.5 mAh g(-1) at 100th cycle with a Coulombic efficiency of 100% under a current density of 335 mA g(-1). It displays a superior rate capability performance, delivering a capacity of 632 mAh g(-1) at a high rate of 5 A g(-1). This uniquely porous NDC derived from MOF nanocrystals could be applied in related high-energy storage devices.

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

Tesfaye, Meron; MacDonald, Andrew N.; Dudenas, Peter J.

Local gas transport limitation attributed to the ionomer thin-film in the catalyst layer is a major deterrent to widespread commercialization of polymer-electrolyte fuel cells. So far functionality and limitations of these thin-films have been assumed identical in the anode and cathode. In this study, Nafion ionomer thin-films on platinum(Pt) support were exposed to H 2 and air as model schemes, mimicking anode and cathode catalyst layers. Findings indicate decreased swelling, increased densification of ionomer matrix, and increased humidity-induced aging rates in reducing environment, compared to oxidizing and inert environments. Observed phenomenon could be related to underlying Pt-gas interaction dictating Pt-ionomermore » behavior. Presented results could have significant implications about the disparate behavior of ionomer thin-film in anode and cathode catalyst layers.« less

Velocity Spread Reduction for Axis-encircling Electron Beam Generated by Single Magnetic Cusp

NASA Astrophysics Data System (ADS)

Jeon, S. G.; Baik, C. W.; Kim, D. H.; Park, G. S.; Sato, N.; Yokoo, K.

2001-10-01

Physical characteristics of an annular Pierce-type electron gun are investigated analytically. An annular electron gun is used in conjunction with a non-adiabatic magnetic reversal and an adiabatic compression to produce an axis-encircling electron beam. Velocity spread close to zero is realized with an initial canonical angular momentum spread at the cathode when the beam trajectory does not coincide with the magnetic flux line. Both the analytical calculation and the EGUN code simulation confirm this phenomenon.

An all-solid-state metal hydride - Sulfur lithium-ion battery

NASA Astrophysics Data System (ADS)

López-Aranguren, Pedro; Berti, Nicola; Dao, Anh Ha; Zhang, Junxian; Cuevas, Fermín; Latroche, Michel; Jordy, Christian

2017-07-01

A metal hydride is used for the first time as anode in a complete all-solid-state battery with sulfur as cathode and LiBH4 as solid electrolyte. The hydride is a nanocomposite made of MgH2 and TiH2 counterparts. The battery exhibits a high reversible capacity of 910 mAh g-1 with discharge plateaus at 1.8 V and 1.4 V. Moreover, the capacity remains to 85% of the initial value over the 25 first charge/discharge cycles.

Polymer Coatings Reduce Electro-osmosis

NASA Technical Reports Server (NTRS)

Herren, Blair J.; Snyder, Robert; Shafer, Steven G.; Harris, J. Milton; Van Alstine, James M.

1989-01-01

Poly(ethylene glycol) film controls electrostatic potential. Electro-osmosis in quartz or glass chambers reduced or reversed by coating inside surface of chambers with monomacromolecular layers of poly(ethylene glycol). Stable over long times. Electrostatic potential across surface of untreated glass or plastic chamber used in electro-phoresis is negative and attracts cations in aqueous electrolyte. Cations solvated, entrains flow of electrolyte migrating toward cathode. Electro-osmotic flow interferes with desired electrophoresis of particles suspended in electrolyte. Polymer coats nontoxic, transparent, and neutral, advantageous for use in electrophoresis.

A magnesium–sodium hybrid battery with high operating voltage

DOE PAGES

Dong, Hui; Li, Yifei; Liang, Yanliang; ...

2016-06-10

Here, we report a high performance magnesium-sodium hybrid battery utilizing a magnesium-sodium dual-salt electrolyte, a magnesium anode, and a Berlin green cathode. The cell delivers an average discharge voltage of 2.2 V and a reversible capacity of 143 mA h g –1. We also demonstrate the cell with an energy density of 135 W h kg –1 and a high power density of up to 1.67 kW kg –1.

The Role of Solvent Reorganization Dynamics in Electron-Transfer Processes. Theory-Experiment Comparisons for Electrochemical and Homogeneous Electron Exchange Involving Metallocene Redox Couples

DTIC Science & Technology

1985-08-01

Kodak) by crystallization from acetone; it was recrystallized twice from ethanol and dried in a vacuum oven. Tetraethylamonium perchlorate (TEAP) (G...the electrooxidation of in(Cp’) 2 , which yielded significantly smaller reverse (cathodic) currents in the most strongly coordinating solvents (DMX...DM50) at slower scan rates (< 0.5 V sec-1). Nevertheless, satisfactory a.c. polarograms were obtained for each of these system=. 5 4 Temperature

Large volume sample stacking of positively chargeable analytes in capillary zone electrophoresis without polarity switching: use of low reversed electroosmotic flow induced by a cationic surfactant at acidic pH.

PubMed

Quirino, J P; Terabe, S

2000-01-01

A simple and effective way to improve detection sensitivity of positively chargeable analytes in capillary zone electrophoresis more than 100-fold is described. Cationic species were made to migrate toward the cathode even under reversed electroosmotic flow caused by a cationic surfactant by using a low pH run buffer. For the first time, with such a configuration, large volume sample stacking of cationic analytes is achieved without a polarity-switching step and loss of efficiency. Samples are prepared in water or aqueous acetonitrile. Aromatic amines and a variety of drugs were concentrated using background solutions containing phosphoric acid and cetyltrimethylammonium bromide. Qualitative and quantitative aspects are also investigated.

Safe and Durable High-Temperature Lithium-Sulfur Batteries via Molecular Layer Deposited Coating.

PubMed

Li, Xia; Lushington, Andrew; Sun, Qian; Xiao, Wei; Liu, Jian; Wang, Biqiong; Ye, Yifan; Nie, Kaiqi; Hu, Yongfeng; Xiao, Qunfeng; Li, Ruying; Guo, Jinghua; Sham, Tsun-Kong; Sun, Xueliang

2016-06-08

Lithium-sulfur (Li-S) battery is a promising high energy storage candidate in electric vehicles. However, the commonly employed ether based electrolyte does not enable to realize safe high-temperature Li-S batteries due to the low boiling and flash temperatures. Traditional carbonate based electrolyte obtains safe physical properties at high temperature but does not complete reversible electrochemical reaction for most Li-S batteries. Here we realize safe high temperature Li-S batteries on universal carbon-sulfur electrodes by molecular layer deposited (MLD) alucone coating. Sulfur cathodes with MLD coating complete the reversible electrochemical process in carbonate electrolyte and exhibit a safe and ultrastable cycle life at high temperature, which promise practicable Li-S batteries for electric vehicles and other large-scale energy storage systems.

Comparison of hydrogen production and electrical power generation for energy capture in closed-loop ammonium bicarbonate reverse electrodialysis systems.

PubMed

Hatzell, Marta C; Ivanov, Ivan; Cusick, Roland D; Zhu, Xiuping; Logan, Bruce E

2014-01-28

Currently, there is an enormous amount of energy available from salinity gradients, which could be used for clean hydrogen production. Through the use of a favorable oxygen reduction reaction (ORR) cathode, the projected electrical energy generated by a single pass ammonium bicarbonate reverse electrodialysis (RED) system approached 78 W h m(-3). However, if RED is operated with the less favorable (higher overpotential) hydrogen evolution electrode and hydrogen gas is harvested, the energy recovered increases by as much ~1.5× to 118 W h m(-3). Indirect hydrogen production through coupling an RED stack with an external electrolysis system was only projected to achieve 35 W h m(-3) or ~1/3 of that produced through direct hydrogen generation.

Electrochemical and Spectroscopic Analysis of Mg2+ Intercalation into Thin Film Electrodes of Layered Oxides: V2O5 and MoO3

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

Gershinsky, G; Yoo, HD; Gofer, Y

Electrochemical, surface, and structural studies related to rechargeable Mg batteries were carried out with monolithic thin-film cathodes comprising layered V2O5 and MoO3. The reversible intercalation reactions of these electrodes with Mg ion in nonaqueous Mg salt solutions were explored using a variety of analytical tools. These included slow-scan rate cyclic voltammetry (SSCV), chrono-potentiometry (galvanostatic cycling), Raman and photoelectron spectroscopies, high-resolution microscopy, and XRD. The V2O5 electrodes exhibited reversible Mg-ion intercalation at capacities around 150-180 mAh g(-1) with 100% efficiency. A capacity of 220 mAh g(-1) at >95% efficiency was obtained with MoO3 electrodes. By applying the electrochemical driving force sufficientlymore » slowly it was possible to measure the electrodes at equilibrium conditions and verify by spectroscopy, microscopy, and diffractometry that these electrodes undergo fully reversible structural changes upon Mg-ion insertion/deinsertion cycling.« less

Revealing mechanism responsible for structural reversibility of single-crystal VO 2 nanorods upon lithiation/delithiation

DOE PAGES

Liu, Qi; Tan, Guoqiang; Wang, Peng; ...

2017-04-17

A pure phase of VO 2(B) nanorods have been synthesized through an energy-efficient microwave hydrothermal reaction and used as cathode materials of lithium ion batteries, which exhibit promising specific capacity (e.g., 130 mA h g -1 even after 100 charge/discharge cycles) and rate capacity (e.g., ~130 mA h g -1 at a high current of 400 mA g -1). The excellent cyclability originates from the structural reversibility of VO 2(B) upon lithiation/delithiation that is confirmed by the in situ high-energy synchrotron X-ray diffraction (HEXRD) and in situ x-ray adsorption near-edge spectroscopy (XANES) of the VO 2 nanorods in operating batterymore » cells. As a result, the real-time results reveal that discharge forces lithium ions to insert firstly into the tunnels with the largest size along b direction followed by the second largest tunnels along c direction, which is completely reversible in the charge process.« less

Batteries for electric and hybrid-electric vehicles.

PubMed

Cairns, Elton J; Albertus, Paul

2010-01-01

Batteries have powered vehicles for more than a century, but recent advances, especially in lithium-ion (Li-ion) batteries, are bringing a new generation of electric-powered vehicles to the market. Key barriers to progress include system cost and lifetime, and derive from the difficulty of making a high-energy, high-power, and reversible electrochemical system. Indeed, although humans produce many mechanical and electrical systems, the number of reversible electrochemical systems is very limited. System costs may be brought down by using cathode materials less expensive than those presently employed (e.g., sulfur or air), but reversibility will remain a key challenge. Continued improvements in the ability to synthesize and characterize materials at desired length scales, as well as to use computations to predict new structures and their properties, are facilitating the development of a better understanding and improved systems. Battery research is a fascinating area for development as well as a key enabler for future technologies, including advanced transportation systems with minimal environmental impact.

Revealing mechanism responsible for structural reversibility of single-crystal VO 2 nanorods upon lithiation/delithiation

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

Liu, Qi; Tan, Guoqiang; Wang, Peng

A pure phase of VO 2(B) nanorods have been synthesized through an energy-efficient microwave hydrothermal reaction and used as cathode materials of lithium ion batteries, which exhibit promising specific capacity (e.g., 130 mA h g -1 even after 100 charge/discharge cycles) and rate capacity (e.g., ~130 mA h g -1 at a high current of 400 mA g -1). The excellent cyclability originates from the structural reversibility of VO 2(B) upon lithiation/delithiation that is confirmed by the in situ high-energy synchrotron X-ray diffraction (HEXRD) and in situ x-ray adsorption near-edge spectroscopy (XANES) of the VO 2 nanorods in operating batterymore » cells. As a result, the real-time results reveal that discharge forces lithium ions to insert firstly into the tunnels with the largest size along b direction followed by the second largest tunnels along c direction, which is completely reversible in the charge process.« less

Effect of Nickel Coated Multi-Walled Carbon Nanotubes on Electrochemical Performance of Lithium-Sulfur Rechargeable Batteries.

PubMed

Wu, Xiao; Yao, Shanshan; Hou, Jinli; Jing, Maoxiang; Qian, Xinye; Shen, Xiangqian; Xiang, Jun; Xi, Xiaoming

2017-04-01

Conventional lithium-sulfur batteries suffer from severe capacity fade, which is induced by low electron conductivity and high dissolution of intermediated polysulfides. Recent studies have shown the metal (Pt, Au, Ni) as electrocatalyst of lithium polysulfides and improved the performance for lithium sulfur batteries. In this work, we present the nickel coated multi-walled carbon nanotubes (Ni-MWNTs) as additive materials for elemental sulfur positive electrodes for lithium-sulfur rechargeable batteries. Compared with MWNTs, the obtained Ni-MWNTs/sulfur composite cathode demonstrate a reversible specific capacity approaching 545 mAh after 200 cycles at a rate of 0.5C as well as improved cycling stability and excellent rate capacity. The improved electrochemical performance can be attributed to the fact the MWNTs shows a vital role on polysulfides adsorption and nickel has a catalytic effect on the redox reactions during charge–discharge process. Meanwhile, the Ni-MWNTs is a good electric conductor for sulfur cathode.

High energy density rechargeable magnesium battery using earth-abundant and non-toxic elements

PubMed Central

Orikasa, Yuki; Masese, Titus; Koyama, Yukinori; Mori, Takuya; Hattori, Masashi; Yamamoto, Kentaro; Okado, Tetsuya; Huang, Zhen-Dong; Minato, Taketoshi; Tassel, Cédric; Kim, Jungeun; Kobayashi, Yoji; Abe, Takeshi; Kageyama, Hiroshi; Uchimoto, Yoshiharu

2014-01-01

Rechargeable magnesium batteries are poised to be viable candidates for large-scale energy storage devices in smart grid communities and electric vehicles. However, the energy density of previously proposed rechargeable magnesium batteries is low, limited mainly by the cathode materials. Here, we present new design approaches for the cathode in order to realize a high-energy-density rechargeable magnesium battery system. Ion-exchanged MgFeSiO4 demonstrates a high reversible capacity exceeding 300 mAh·g−1 at a voltage of approximately 2.4 V vs. Mg. Further, the electronic and crystal structure of ion-exchanged MgFeSiO4 changes during the charging and discharging processes, which demonstrates the (de)insertion of magnesium in the host structure. The combination of ion-exchanged MgFeSiO4 with a magnesium bis(trifluoromethylsulfonyl)imide–triglyme electrolyte system proposed in this work provides a low-cost and practical rechargeable magnesium battery with high energy density, free from corrosion and safety problems. PMID:25011939

Enhanced electrochemical properties of LiFePO4 (LFP) cathode using the carboxymethyl cellulose lithium (CMC-Li) as novel binder in lithium-ion battery.

PubMed

Qiu, Lei; Shao, Ziqiang; Wang, Daxiong; Wang, Wenjun; Wang, Feijun; Wang, Jianquan

2014-10-13

Novel water-based binder CMC-Li is synthesized using cotton as raw material. The mechanism of the CMC-Li as a binder is reported. Electrochemical properties of batteries cathodes based on commercially available lithium iron phosphate (LiFePO4, LFP) and CMC-Li as a water-soluble binder are investigated. CMC-Li is a novel lithium-ion binder. Compare with conventional poly(vinylidene fluoride) (PVDF) binder, and the battery with CMC-Li as the binder retained 97.8% of initial reversible capacity after 200 cycles at 176 mAh g(-1), which is beyond the theoretical specific capacity of LFP. Constant current charge-discharge test results demonstrate that the LFP electrode using CMC-Li as the binder has the highest rate capability, follow closely by that using PVDF binder. The batteries have good electrochemical property, outstanding pollution-free and excellent stability. Copyright © 2014 Elsevier Ltd. All rights reserved.

Gas-solid interfacial modification of oxygen activity in layered oxide cathodes for lithium-ion batteries.

PubMed

Qiu, Bao; Zhang, Minghao; Wu, Lijun; Wang, Jun; Xia, Yonggao; Qian, Danna; Liu, Haodong; Hy, Sunny; Chen, Yan; An, Ke; Zhu, Yimei; Liu, Zhaoping; Meng, Ying Shirley

2016-07-01

Lattice oxygen can play an intriguing role in electrochemical processes, not only maintaining structural stability, but also influencing electron and ion transport properties in high-capacity oxide cathode materials for Li-ion batteries. Here, we report the design of a gas-solid interface reaction to achieve delicate control of oxygen activity through uniformly creating oxygen vacancies without affecting structural integrity of Li-rich layered oxides. Theoretical calculations and experimental characterizations demonstrate that oxygen vacancies provide a favourable ionic diffusion environment in the bulk and significantly suppress gas release from the surface. The target material is achievable in delivering a discharge capacity as high as 301 mAh g(-1) with initial Coulombic efficiency of 93.2%. After 100 cycles, a reversible capacity of 300 mAh g(-1) still remains without any obvious decay in voltage. This study sheds light on the comprehensive design and control of oxygen activity in transition-metal-oxide systems for next-generation Li-ion batteries.

Improved electrochemical property of nanoparticle polyoxovanadate K7NiV13O38 as cathode material for lithium battery

NASA Astrophysics Data System (ADS)

Ni, Erfu; Uematsu, Shinya; Quan, Zhen; Sonoyama, Noriyuki

2013-06-01

Molecular cluster ion compound K7NiV13O38 (KNiV) has been studied as a novel cathode material for lithium ion battery. The nanoparticles are prepared by a simple re-crystallization method adding different volumes of acetone to the water solution containing the dissolved KNiV. The KNiV re-crystallized from water/acetone ratio of 1:5 shows the most uniform particle size distribution and the smallest particles with thickness of 100 nm and width of 150 nm. The nanoparticle KNiV shows significant improvement in initial discharge capacity and capacity retention after 50 cycles compared to the as-prepared micro-sized particles at various current densities. Ex situ XRD patterns demonstrate that the discharge-charge process proceeds with amorphous KNiV, which is independent from the crystal structure. Ex situ FT-IR spectra indicate that [NiV13O38]7- cluster ion is stable and reacts reversibly with lithium ion in the discharge-charge process.

High energy density rechargeable magnesium battery using earth-abundant and non-toxic elements

NASA Astrophysics Data System (ADS)

Orikasa, Yuki; Masese, Titus; Koyama, Yukinori; Mori, Takuya; Hattori, Masashi; Yamamoto, Kentaro; Okado, Tetsuya; Huang, Zhen-Dong; Minato, Taketoshi; Tassel, Cédric; Kim, Jungeun; Kobayashi, Yoji; Abe, Takeshi; Kageyama, Hiroshi; Uchimoto, Yoshiharu

2014-07-01

Rechargeable magnesium batteries are poised to be viable candidates for large-scale energy storage devices in smart grid communities and electric vehicles. However, the energy density of previously proposed rechargeable magnesium batteries is low, limited mainly by the cathode materials. Here, we present new design approaches for the cathode in order to realize a high-energy-density rechargeable magnesium battery system. Ion-exchanged MgFeSiO4 demonstrates a high reversible capacity exceeding 300 mAh.g-1 at a voltage of approximately 2.4 V vs. Mg. Further, the electronic and crystal structure of ion-exchanged MgFeSiO4 changes during the charging and discharging processes, which demonstrates the (de)insertion of magnesium in the host structure. The combination of ion-exchanged MgFeSiO4 with a magnesium bis(trifluoromethylsulfonyl)imide-triglyme electrolyte system proposed in this work provides a low-cost and practical rechargeable magnesium battery with high energy density, free from corrosion and safety problems.

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

Tian, Huajun; Gao, Tao; Li, Xiaogang

Rechargeable magnesium batteries have attracted considerable attention because of their potential high energy density and low cost. However, their development has been severely hindered because of the lack of appropriate cathode materials. Here we report a rechargeable magnesium/iodine battery, in which the soluble iodine reacts with Mg 2+ to form a soluble intermediate and then an insoluble final product magnesium iodide. The liquid–solid two-phase reaction pathway circumvents solid-state Mg 2+ diffusion and ensures a large interfacial reaction area, leading to fast reaction kinetics and high reaction reversibility. As a result, the rechargeable magnesium/iodine battery shows a better rate capability (180more » mAh g –1 at 0.5 C and 140 mAh g –1 at 1 C) and a higher energy density (~400 Wh kg –1) than all other reported rechargeable magnesium batteries using intercalation cathodes. As a result, this study demonstrates that the liquid–solid two-phase reaction mechanism is promising in addressing the kinetic limitation of rechargeable magnesium batteries.« less

Facilitated Oxygen Chemisorption in Heteroatom-Doped Carbon for Improved Oxygen Reaction Activity in All-Solid-State Zinc-Air Batteries.

PubMed

Liu, Sisi; Wang, Mengfan; Sun, Xinyi; Xu, Na; Liu, Jie; Wang, Yuzhou; Qian, Tao; Yan, Chenglin

2018-01-01

Driven by the intensified demand for energy storage systems with high-power density and safety, all-solid-state zinc-air batteries have drawn extensive attention. However, the electrocatalyst active sites and the underlying mechanisms occurring in zinc-air batteries remain confusing due to the lack of in situ analytical techniques. In this work, the in situ observations, including X-ray diffraction and Raman spectroscopy, of a heteroatom-doped carbon air cathode are reported, in which the chemisorption of oxygen molecules and oxygen-containing intermediates on the carbon material can be facilitated by the electron deficiency caused by heteroatom doping, thus improving the oxygen reaction activity for zinc-air batteries. As expected, solid-state zinc-air batteries equipped with such air cathodes exhibit superior reversibility and durability. This work thus provides a profound understanding of the reaction principles of heteroatom-doped carbon materials in zinc-air batteries. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Environmentally-friendly aqueous Li (or Na)-ion battery with fast electrode kinetics and super-long life

PubMed Central

Dong, Xiaoli; Chen, Long; Liu, Jingyuan; Haller, Servane; Wang, Yonggang; Xia, Yongyao

2016-01-01

Current rechargeable batteries generally display limited cycle life and slow electrode kinetics and contain environmentally unfriendly components. Furthermore, their operation depends on the redox reactions of metal elements. We present an original battery system that depends on the redox of I−/I3− couple in liquid cathode and the reversible enolization in polyimide anode, accompanied by Li+ (or Na+) diffusion between cathode and anode through a Li+/Na+ exchange polymer membrane. There are no metal element–based redox reactions in this battery, and Li+ (or Na+) is only used for charge transfer. Moreover, the components (electrolyte/electrode) of this system are environment-friendly. Both electrodes are demonstrated to have very fast kinetics, which gives the battery a supercapacitor-like high power. It can even be cycled 50,000 times when operated within the electrochemical window of 0 to 1.6 V. Such a system might shed light on the design of high-safety and low-cost batteries for grid-scale energy storage. PMID:26844298

One-Dimensional Cu2- xSe Nanorods as the Cathode Material for High-Performance Aluminum-Ion Battery.

PubMed

Jiang, Jiali; Li, He; Fu, Tao; Hwang, Bing-Joe; Li, Xue; Zhao, Jinbao

2018-05-30

In this work, nonstoichiometric Cu 2- x Se fabricated by a facile water evaporation process is used as high-performance Al-ion battery cathode materials. Cu 2- x Se electrodes show high reversible capacity and excellent cycling stability, even at a high current density of 200 mA g -1 , the specific charge capacity in the initial cycle is 241 mA h g -1 and maintains 100 mA h g -1 after 100 cycles with a Coulombic efficiency of 96.1%, showing good capacity retention. The prominent kinetics of Cu 2- x Se electrodes is also revealed by the GITT, which is attributed to the ultrahigh electronic conductivity of the Cu 2- x Se material. Most importantly, an extensive research is dedicated to investigating the detailed intercalation and de-intercalation of relatively large chloroaluminate anions into the cubic Cu 2- x Se, which is conducive to better understand the reaction mechanism of the Al/Cu 2- x Se battery.

Environmentally-friendly aqueous Li (or Na)-ion battery with fast electrode kinetics and super-long life.

PubMed

Dong, Xiaoli; Chen, Long; Liu, Jingyuan; Haller, Servane; Wang, Yonggang; Xia, Yongyao

2016-01-01

Current rechargeable batteries generally display limited cycle life and slow electrode kinetics and contain environmentally unfriendly components. Furthermore, their operation depends on the redox reactions of metal elements. We present an original battery system that depends on the redox of I(-)/I3 (-) couple in liquid cathode and the reversible enolization in polyimide anode, accompanied by Li(+) (or Na(+)) diffusion between cathode and anode through a Li(+)/Na(+) exchange polymer membrane. There are no metal element-based redox reactions in this battery, and Li(+) (or Na(+)) is only used for charge transfer. Moreover, the components (electrolyte/electrode) of this system are environment-friendly. Both electrodes are demonstrated to have very fast kinetics, which gives the battery a supercapacitor-like high power. It can even be cycled 50,000 times when operated within the electrochemical window of 0 to 1.6 V. Such a system might shed light on the design of high-safety and low-cost batteries for grid-scale energy storage.

High power rechargeable magnesium/iodine battery chemistry

DOE PAGES

Tian, Huajun; Gao, Tao; Li, Xiaogang; ...

2017-01-10

Rechargeable magnesium batteries have attracted considerable attention because of their potential high energy density and low cost. However, their development has been severely hindered because of the lack of appropriate cathode materials. Here we report a rechargeable magnesium/iodine battery, in which the soluble iodine reacts with Mg 2+ to form a soluble intermediate and then an insoluble final product magnesium iodide. The liquid–solid two-phase reaction pathway circumvents solid-state Mg 2+ diffusion and ensures a large interfacial reaction area, leading to fast reaction kinetics and high reaction reversibility. As a result, the rechargeable magnesium/iodine battery shows a better rate capability (180more » mAh g –1 at 0.5 C and 140 mAh g –1 at 1 C) and a higher energy density (~400 Wh kg –1) than all other reported rechargeable magnesium batteries using intercalation cathodes. As a result, this study demonstrates that the liquid–solid two-phase reaction mechanism is promising in addressing the kinetic limitation of rechargeable magnesium batteries.« less

Gas–solid interfacial modification of oxygen activity in layered oxide cathodes for lithium-ion batteries

PubMed Central

Qiu, Bao; Zhang, Minghao; Wu, Lijun; Wang, Jun; Xia, Yonggao; Qian, Danna; Liu, Haodong; Hy, Sunny; Chen, Yan; An, Ke; Zhu, Yimei; Liu, Zhaoping; Meng, Ying Shirley

2016-01-01

Lattice oxygen can play an intriguing role in electrochemical processes, not only maintaining structural stability, but also influencing electron and ion transport properties in high-capacity oxide cathode materials for Li-ion batteries. Here, we report the design of a gas–solid interface reaction to achieve delicate control of oxygen activity through uniformly creating oxygen vacancies without affecting structural integrity of Li-rich layered oxides. Theoretical calculations and experimental characterizations demonstrate that oxygen vacancies provide a favourable ionic diffusion environment in the bulk and significantly suppress gas release from the surface. The target material is achievable in delivering a discharge capacity as high as 301 mAh g−1 with initial Coulombic efficiency of 93.2%. After 100 cycles, a reversible capacity of 300 mAh g−1 still remains without any obvious decay in voltage. This study sheds light on the comprehensive design and control of oxygen activity in transition-metal-oxide systems for next-generation Li-ion batteries. PMID:27363944

Study on novel functional materials carboxymethyl cellulose lithium (CMC-Li) improve high-performance lithium-ion battery.

PubMed

Qiu, Lei; Shao, Ziqiang; Xiang, Pan; Wang, Daxiong; Zhou, Zhenwen; Wang, Feijun; Wang, Wenjun; Wang, Jianquan

2014-09-22

Novel cellulose derivative CMC-Li was synthesized by cotton as raw material. The mechanism of the CMC-Li modified electrode materials by electrospinning was reported. CMC-Li/lithium iron phosphate (LiFePO4, LFP) composite fiber coated with LFP and CMC-Li nanofibers was successfully obtained by electrospinning. Then, CMC-Li/LFP nano-composite fiber was carbonized under nitrogen at a high temperature formed CNF/LFP/Li (CLL) composite nanofibers as cathode material. It can increase the contents of Li+, and improving the diffusion efficiency and specific capacity. The battery with CLL as cathode material retained close to 100% of initial reversible capacity after 200 cycles at 168 mAh g(-1), which was nearly the theoretical specific capacity of LFP. The cyclic voltammetry (CV), electrochemical impedance spectroscopy (EIS), X-ray diffraction (XRD) and scanning electron microscope (SEM) were characterizing material performance. The batteries have good electrochemical property, outstanding pollution-free, excellent stability. Copyright © 2014 Elsevier Ltd. All rights reserved.

BiVO4 Fern Architectures: A Competitive Anode for Lithium-Ion Batteries.

PubMed

Dubal, Deepak P; Patil, Deepak R; Patil, Santosh S; Munirathnam, N R; Gomez-Romero, Pedro

2017-09-21

The development of high-performance anode materials for lithium-ion batteries (LIBs) is currently subject to much interest. In this study, BiVO 4 fern architectures are introduced as a new anode material for LIBs. The BiVO 4 fern shows an excellent reversible capacity of 769 mAh g -1 (ultrahigh volumetric capacity of 3984 mAh cm -3 ) at 0.12 A g -1 with large capacity retention. A LIB full cell is then assembled with a BiVO 4 fern anode and LiFePO 4 (LFP, commercial) as cathode material. The device can achieve a capacity of 140 mAh g -1 at 1C rate, that is, 81 % of the capacity of the cathode and maintained to 104 mAh g -1 at a high rate of 8C, which makes BiVO 4 a promising candidate as a high-energy anode material for LIBs. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Gas-solid interfacial modification of oxygen activity in layered oxide cathodes for lithium-ion batteries

DOE PAGES

Qiu, Bao; Zhang, Minghao; Wu, Lijun; ...

2016-07-01

Lattice oxygen can play an intriguing role in electrochemical processes, not only maintaining structural stability, but also influencing electron and ion transport properties in high-capacity oxide cathode materials for Li-ion batteries. Here, we report the design of a gas–solid interface reaction to achieve delicate control of oxygen activity through uniformly creating oxygen vacancies without affecting structural integrity of Li-rich layered oxides. Theoretical calculations and experimental characterizations demonstrate that oxygen vacancies provide a favourable ionic diffusion environment in the bulk and significantly suppress gas release from the surface. The target material is achievable in delivering a discharge capacity as high asmore » 301 mAh g –1 with initial Coulombic efficiency of 93.2%. After 100 cycles, a reversible capacity of 300 mAh g –1 still remains without any obvious decay in voltage. Lastly, this study sheds light on the comprehensive design and control of oxygen activity in transition-metal-oxide systems for next-generation Li-ion batteries.« less

Aerospace applications of sodium batteries using novel cathode materials

NASA Technical Reports Server (NTRS)

Ratnakumar, B. V.; Di Stefano, S.; Bankston, C. P.

1989-01-01

Preliminary fundamental investigations aimed at evaluating sodium metal chloride systems for future aerospace applications are described. Since the sodium metal chloride systems are relatively new, the approach has been to characterize their fundamental properties in order to understand their limitations. To this end, a series of fundamental electrochemical investigations have been carried out, the results of which are reported here. The metal chloride cathodes show high exchange current densities which corroborate their good reversibility in a battery application. The reduction mechanisms appear to be complex and involve multielectron transfer steps and intermediates. Such intermediates in the reaction mechanism have already been identified in the case of FeCl2. Similar mechanisms may be operative in the case of NiCl2. CuCl2, however, exhibits a second relaxation loop in the impedance plot at low frequencies and also a sloping discharge curve, unlike FeCl2 and NiCl2, which may indicate the existence of monovalent copper in the reduction mechanism.

Humidity Effect on Nanoscale Electrochemistry in Solid Silver Ion Conductors and the Dual Nature of Its Locality

DOE PAGES

Yang, Sangmo; Strelcov, Evgheni; Paranthaman, Mariappan Parans; ...

2015-01-07

Scanning probe microscopy (SPM) is a powerful tool to investigate electrochemistry in nanoscale volumes. While most SPM-based studies have focused on reactions at the tip-surface junction, charge and mass conservation requires coupled and intrinsically non-local cathodic and anodic processes that can be significantly affected by ambient humidity. Here, we explore the role of water in both cathodic and anodic processes, associated charge transport, and topographic volume changes depending on the polarity of tip bias. The first-order reversal curve current-voltage technique combined with simultaneous detection of the sample topography, referred to as FORC-IVz, was applied to a silver solid ion conductor.more » We found that the protons generated from water affect silver ionic conduction, silver particle formation and dissolution, and mechanical integrity of the material. This work highlights the dual nature (simultaneously local and non-local) of electrochemical SPM studies, which should be considered for comprehensive understanding of nanoscale electrochemistry.« less

Cathode buffer composed of fullerene-ethylenediamine adduct for an organic solar cell

NASA Astrophysics Data System (ADS)

Kimoto, Yoshinori; Akiyama, Tsuyoshi; Fujita, Katsuhiko

2017-02-01

We developed a fullerene-ethylenediamine adduct (C60P-DC) for a cathode buffer material in organic bulk heterojunction solar cells, which enhance the open-circuit voltage (V oc). The evaporative spray deposition using ultra dilute solution (ESDUS) technique was employed to deposit the buffer layer onto the organic active layer to avoid damage during the deposition. By the insertion of a C60P-DC buffer layer, V oc and power conversion efficiency (PCE) were increased from 0.41 to 0.57 V and from 1.65 to 2.10%, respectively. The electron-only device with the C60P-DC buffer showed a much lower current level than that without the buffer, indicating that the V oc increase is caused not by vacuum level shift but by hole blocking. The curve fitting of current density-voltage (J-V) characteristics to the equivalent circuit with a single diode indicated that the decrease in reversed saturation current by hole blocking increased caused the V oc.

Humidity effect on nanoscale electrochemistry in solid silver ion conductors and the dual nature of its locality.

PubMed

Yang, Sang Mo; Strelcov, Evgheni; Paranthaman, M Parans; Tselev, Alexander; Noh, Tae Won; Kalinin, Sergei V

2015-02-11

Scanning probe microscopy (SPM) is a powerful tool to investigate electrochemistry in nanoscale volumes. While most SPM-based studies have focused on reactions at the tip-surface junction, charge and mass conservation requires coupled and intrinsically nonlocal cathodic and anodic processes that can be significantly affected by ambient humidity. Here, we explore the role of water in both cathodic and anodic processes, associated charge transport, and topographic volume changes depending on the polarity of tip bias. The first-order reversal curve current-voltage technique combined with simultaneous detection of the sample topography, referred to as FORC-IVz, was applied to a silver solid ion conductor. We found that the protons generated from water affect silver ionic conduction, silver particle formation and dissolution, and mechanical integrity of the material. This work highlights the dual nature (simultaneously local and nonlocal) of electrochemical SPM studies, which should be considered for comprehensive understanding of nanoscale electrochemistry.

Controlling interlayer interactions in vanadium pentoxide-poly(ethylene oxide) nanocomposites for enhanced magnesium-ion charge transport and storage

NASA Astrophysics Data System (ADS)

Perera, Sanjaya D.; Archer, Randall B.; Damin, Craig A.; Mendoza-Cruz, Rubén; Rhodes, Christopher P.

2017-03-01

Rechargeable magnesium batteries provide the potential for lower cost and improved safety compared with lithium-ion batteries, however obtaining cathode materials with highly reversible Mg-ion capacities is hindered by the high polarizability of divalent Mg-ions and slow solid-state Mg-ion diffusion. We report that incorporating poly(ethylene oxide) (PEO) between the layers of hydrated vanadium pentoxide (V2O5) xerogels results in significantly improved reversible Mg-ion capacities. X-ray diffraction and high resolution transmission electron microscopy show that the interlayer spacing between V2O5 layers was increased by PEO incorporation. Vibrational spectroscopy supports that the polymer interacts with the V2O5 lattice. The V2O5-PEO nanocomposite exhibited a 5-fold enhancement in Mg-ion capacity, improved stability, and improved rate capabilities compared with V2O5 xerogels. The Mg-ion diffusion coefficient of the nanocomposite was increased compared with that of V2O5 xerogels which is attributed to enhanced Mg-ion mobility due to the shielding interaction of PEO with the V2O5 lattice. This study shows that beyond only interlayer spacing, the nature of interlayer interactions of Mg-ions with V2O5, PEO, and H2O are key factors that affect Mg-ion charge transport and storage in layered materials. The design of layered materials with controlled interlayer interactions provides a new approach to develop improved cathodes for magnesium batteries.

Insights into the Effects of Zinc Doping on Structural Phase Transition of P2-Type Sodium Nickel Manganese Oxide Cathodes for High-Energy Sodium Ion Batteries

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

Wu, Xuehang; Xu, Gui-Liang; Zhong, Guiming

P2-type sodium nickel manganese oxide-based cathode materials with higher energy densities are prime candidates for applications in rechargeable sodium ion batteries. A systematic study combining in situ high energy X-ray diffraction (HEXRD), ex situ Xray absorption fine spectroscopy (XAFS), transmission electron microscopy (TEM), and solid-state nuclear magnetic resonance (SSNMR) techniques was carried out to gain a deep insight into the structural evolution of P2-Na 0.66Ni 0.33-xZn xMn 0.67O 2 (x = 0, 0.07) during cycling. In situ HEXRD and ex situ TEM measurements indicate that an irreversible phase transition occurs upon sodium insertion-extraction of Na 0.66Ni 0.33Mn 0.67O 2. Zincmore » doping of this system results in a high structural reversibility. XAFS measurements indicate that both materials are almost completely dependent on the Ni 4+/Ni 3+/ Ni 2+ redox couple to provide charge/discharge capacity. SS-NMR measurements indicate that both reversible and irreversible migration of transition metal ions into the sodium layer occurs in the material at the fully charged state. The irreversible migration of transition metal ions triggers a structural distortion, leading to the observed capacity and voltage fading. Our results allow a new understanding of the importance of improving the stability of transition metal layers.« less

Suppression of turbulent particle flux during biased rotation in LAPD

NASA Astrophysics Data System (ADS)

Carter, T. A.

2005-10-01

The edge plasma in LAPD is rotated through the application of a bias voltage (typically 100V-200V) between the plasma source cathode and the vacuum vessel wall. Without bias, cross-field turbulent particle transport causes the density profile to extend well past the cathode edge, with a fairly gentle gradient (Ln˜10 cm). As the bias voltage is applied and increased past a threshold value, the measured density profile steepens dramatically (Ln˜2 cm) at a radius near the peak of the flow shear. Turbulent transport flux measurements in this region show that the flux is reduced and then suppressed completely as the threshold is approached. As the bias voltage is increased further, the measured turbulent transport flux reverses direction. The amplitude of the density and azimuthal electric field fluctuations is observed to decrease during biased rotation, the product of the amplitudes decreasing by a factor of 5. However the dominant change appears in the cross-phase, which is altered dramatically, leading to the observed suppression and reversal of the turbulent flux. Detailed two-dimensional turbulent correlation measurements have been performed using the high repetition rate (1 Hz) and high reproducibility of LAPD plasmas. In unbiased plasmas, the correlation is localized to around 5 cm radially and a slightly smaller distance azimuthally (ρs˜0.5-1 cm). During biased rotation, a dramatic increase in the azimuthal correlation is observed, however there is little change in the radial correlation length.

Achieving high capacity and rate capability in layered lithium transition metal oxide cathodes for lithium-ion batteries

NASA Astrophysics Data System (ADS)

Ahn, Juhyeon; Susanto, Dieky; Noh, Jae-Kyo; Ali, Ghulam; Cho, Byung Won; Chung, Kyung Yoon; Kim, Jong Hak; Oh, Si Hyoung

2017-08-01

In this study, we target to find a new composition for a layered mixed metal oxide, which has a high structural stability and a good electrochemical performance. Our strategy is to alter the transition metal composition focusing on the relative amounts of redox active Ni and Co to the inactive Mn, based on highly-stabilized LiNi1/3Co1/3Mn1/3O2. X-ray absorption near-edge structure and X-ray diffraction analyses show that the degree of cation disorder decreases on increasing the ratio of Ni and Co to Mn, by the presence of Ni3+, suggesting that slightly higher Ni and Co contents lead to improved structural stability. Electrochemical studies demonstrate that LiNi0.4Co0.4Mn0.2O2 cathodes exhibit considerable improvements in both the reversible capacity and the rate capabilities at a voltage range of 2.5-4.6 V. In situ XRD measurements reveal that LiNi0.4Co0.4Mn0.2O2 maintains a single-phase and undergoes lesser structural variations compared to controlled compositions during a delithiation process up to 4.6 V, while achieving a high reversible capacity over 200 mAh g-1. As a result, LiNi0.4Co0.4Mn0.2O2 experiences fewer structural degradations during electrochemical cycling, which explains the excellent long-term cycling performance.

Treating autism by targeting the temporal lobes.

PubMed

Chi, Richard P; Snyder, Allan W

2014-11-01

Compelling new findings suggest that an early core signature of autism is a deficient left anterior temporal lobe response to language and an atypical over-activation of the right anterior temporal lobe. Intriguingly, our recent results from an entirely different line of reasoning and experiments also show that applying cathodal stimulation (suppressing) at the left anterior temporal lobe together with anodal stimulation (facilitating) at the right anterior temporal lobe, by transcranial direct current stimulation (tDCS), can induce some autistic-like cognitive abilities in otherwise normal adults. If we could briefly induce autistic like cognitive abilities in healthy individuals, it follows that we might be able to mitigate some autistic traits by reversing the above stimulation protocol, in an attempt to restore the typical dominance of the left anterior temporal lobe. Accordingly, we hypothesize that at least some autistic traits can be mitigated, by applying anodal stimulation (facilitating) at the left anterior temporal lobe together with cathodal stimulation (suppressing) at the right anterior temporal lobe. Our hypothesis is supported by strong convergent evidence that autistic symptoms can emerge and later reverse due to the onset and subsequent recovery of various temporal lobe (predominantly the left) pathologies. It is also consistent with evidence that the temporal lobes (especially the left) are a conceptual hub, critical for extracting meaning from lower level sensory information to form a coherent representation, and that a deficit in the temporal lobes underlies autistic traits. Copyright © 2014 Elsevier Ltd. All rights reserved.

The polarity-dependent effects of the bilateral brain stimulation on working memory.

PubMed

Keshvari, Fatemeh; Pouretemad, Hamid-Reza; Ekhtiari, Hamed

2013-01-01

Working memory plays a critical role in cognitive processes which are central to our daily life. Neuroimaging studies have shown that one of the most important areas corresponding to the working memory is the dorsolateral prefrontal cortex (DLFPC). This study was aimed to assess whether bilateral modulation of the DLPFC using a noninvasive brain stimulation, namely transcranial direct current stimulation (tDCS), modifies the working memory function in healthy adults. In a randomized sham-controlled cross-over study, 60 subjects (30 Males) received sham and active tDCS in two subgroups (anode left/cathode right and anode right/cathode left) of the DLPFC. Subjects were presented working memory n-back task while the reaction time and accuracy were recorded. A repeated measures, mixed design ANOVA indicated a significant difference between the type of stimulation (sham vs. active) in anodal stimulation of the left DLPFC with cathodal stimulation of the right DLPFC [F(1,55)= 5.29, P=0.019], but not the inverse polarity worsened accuracy in the 2-back working memory task. There were also no statistically significant changes in speed of working memory [F(1,55)= 0.458,P=0.502] related to type or order of stimulation. The results would imply to a polarity dependence of bilateral tDCS of working memory. Left anodal/ right cathodal stimulation of DLPFC could impair working memory, while the reverser stimulation had no effect. Meaning that bilateral stimulation of DLFC would not be a useful procedure to improve working memory. Further studies are required to understand subtle effects of different tDCS stimulation/inhibition electrode positioning on the working memory.

A Molecular Electronic Transducer based Low-Frequency Accelerometer with Electrolyte Droplet Sensing Body

NASA Astrophysics Data System (ADS)

Liang, Mengbing

"Sensor Decade" has been labeled on the first decade of the 21st century. Similar to the revolution of micro-computer in 1980s, sensor R&D developed rapidly during the past 20 years. Hard workings were mainly made to minimize the size of devices with optimal the performance. Efforts to develop the small size devices are mainly concentrated around Micro-electro-mechanical-system (MEMS) technology. MEMS accelerometers are widely published and used in consumer electronics, such as smart phones, gaming consoles, anti-shake camera and vibration detectors. This study represents liquid-state low frequency micro-accelerometer based on molecular electronic transducer (MET), in which inertial mass is not the only but also the conversion of mechanical movement to electric current signal is the main utilization of the ionic liquid. With silicon-based planar micro-fabrication, the device uses a sub-micron liter electrolyte droplet sealed in oil as the sensing body and a MET electrode arrangement which is the anode-cathode-cathode-anode (ACCA) in parallel as the read-out sensing part. In order to sensing the movement of ionic liquid, an imposed electric potential was applied between the anode and the cathode. The electrode reaction, I3-- + 2e-- ↔ 3I --, occurs around the cathode which is reverse at the anodes. Obviously, the current magnitude varies with the concentration of ionic liquid, which will be effected by the movement of liquid droplet as the inertial mass. With such structure, the promising performance of the MET device design is to achieve 10.8 V/G (G=9.81 m/s2) sensitivity at 20 Hz with the bandwidth from 1 Hz to 50 Hz, and a low noise floor of 100 microg/sqrt(Hz) at 20 Hz.

1D nanostructured Na7V4(P2O7)4(PO4) as high-potential and superior-performance cathode material for sodium-ion batteries.

PubMed

Deng, Chao; Zhang, Sen

2014-06-25

Tailoring materials into nanostructure offers unprecedented opportunities in the utilization of their functional properties. High-purity Na7V4(P2O7)4(PO4) with 1D nanostructure is prepared as a cathode material for rechargeable Na-ion batteries. An efficient synthetic approach is developed by carefully controlling the crystal growth in the molten sodium phosphate. Based on the XRD, XPS, TG, and morphological characterization, a molten-salt assisted mechanism for nanoarchitecture formation is revealed. The prepared Na7V4(P2O7)4(PO4) nanorod has rectangle sides and preferential [001] growth orientation. GITT evaluation indicates that the sodium de/intercalation of Na7V4(P2O7)4(PO4) nanorod involves V(3+)/V(4+) redox reaction and Na5V(3.5+)4(P2O7)4(PO4) as intermediate phase, which results in two pairs of potential plateaus at the equilibrium potentials of 3.8713 V (V(3+)/V(3.5+)) and 3.8879 V (V(3.5+)/V(4+)), respectively. The unique nanoarchitecture of the phase-pure Na7V4(P2O7)4(PO4) facilitates its reversible sodium de/intercalation, which is beneficial to the high-rate capability and the cycling stability. The Na7V4(P2O7)4(PO4) cathode delivers 80% of the capacity (obtained at C/20) at the 10 C rate and 95% of the initial capacity after 200 cycles. Therefore, it is feasible to design and fabricate an advanced rechargeable sodium-ion battery by employment of 1D nanostructured Na7V4(P2O7)4(PO4) as the cathode material.

Exploring substrate/ionomer interaction under oxidizing and reducing environments

DOE PAGES

Tesfaye, Meron; MacDonald, Andrew N.; Dudenas, Peter J.; ...

2018-02-09

Local gas transport limitation attributed to the ionomer thin-film in the catalyst layer is a major deterrent to widespread commercialization of polymer-electrolyte fuel cells. So far functionality and limitations of these thin-films have been assumed identical in the anode and cathode. In this study, Nafion ionomer thin-films on platinum(Pt) support were exposed to H 2 and air as model schemes, mimicking anode and cathode catalyst layers. Findings indicate decreased swelling, increased densification of ionomer matrix, and increased humidity-induced aging rates in reducing environment, compared to oxidizing and inert environments. Observed phenomenon could be related to underlying Pt-gas interaction dictating Pt-ionomermore » behavior. Presented results could have significant implications about the disparate behavior of ionomer thin-film in anode and cathode catalyst layers.« less

Structural and Electrochemical Characterization of Pure LiFePO 4 and Nanocomposite C- LiFePO 4 Cathodes for Lithium Ion Rechargeable Batteries

DOE PAGES

Kumar, Arun; Thomas, R.; Karan, N. K.; ...

2009-01-01

Pure limore » thium iron phosphate ( LiFePO 4 ) and carbon-coated LiFePO 4 (C- LiFePO 4 ) cathode materials were synthesized for Li-ion batteries. Structural and electrochemical properties of these materials were compared. X-ray diffraction revealed orthorhombic olivine structure. Micro-Raman scattering analysis indicates amorphous carbon, and TEM micrographs show carbon coating on LiFePO 4 particles. Ex situ Raman spectrum of C- LiFePO 4 at various stages of charging and discharging showed reversibility upon electrochemical cycling. The cyclic voltammograms of LiFePO 4 and C- LiFePO 4 showed only a pair of peaks corresponding to the anodic and cathodic reactions. The first discharge capacities were 63, 43, and 13 mAh/g for C/5, C/3, and C/2, respectively for LiFePO 4 where as in case of C- LiFePO 4 that were 163, 144, 118, and 70 mAh/g for C/5, C/3, C/2, and 1C, respectively. The capacity retention of pure LiFePO 4 was 69% after 25 cycles where as that of C- LiFePO 4 was around 97% after 50 cycles. These results indicate that the capacity and the rate capability improved significantly upon carbon coating.« less

Catalysts for ultrahigh current density oxygen cathodes for space fuel cell applications

NASA Technical Reports Server (NTRS)

Tryk, D.; Yeager, E.; Shingler, M.; Aldred, W.; Wang, C.

1990-01-01

The objective of this research was to identify promising electrocatalyst/support systems for the oxygen cathode in alkaline fuel cells operating at relatively high temperatures, O2 pressures and current densities. A number of materials were prepared, including Pb-Ru and Pb-Ir pyrochlores, RuO2 and Pt-doped RuO2, and lithiated NiO. Several of these were prepared using techniques that had not been previously used to prepare them. Particularly interesting is the use of the alkaline solution technique to prepare the Pt-doped Pb-Ru pyrochlore in high area form. Well-crystallized Pb(2)Ru(2)O(7-y) was used to fabricate high performance O2 cathodes with relatively good stability in room temperature KOH. This material was also found to be stable over a useful potential range at approximately 140 C in concentrated KOH. Other pyrochlores were found to be either unstable (amorphous samples) or the fabrication of the gas-fed electrodes could not be fully optimized during this project period. Future work may be directed at this problem. High area platinum supported on conductive metal oxide supports produced mixed results: small improvements in O2 reduction performance for Pb(2)Ru(2)O(7-y) but a large improvement for Li-doped NiO at room temperature. Nearly reversible behavior was observed for the O2/OH couple for Li-doped NiO at approximately 200 C.

Unraveling the Complex Delithiation and Lithiation Mechanisms of the High Capacity Cathode Material V 6O 13

DOE PAGES

Meng, Wei; Pigliapochi, Roberta; Bayley, Paul M.; ...

2017-06-05

V 6O 13 is a promising Li-ion battery cathode material for use in the high temperature oil field environment. The material exhibits a high capacity, and the voltage profile contains several plateaus associated with a series of complex structural transformations, which are not fully understood. The underlying mechanisms are central to understanding and improving the performance of V 6O 13-based rechargeable batteries. In this study, we present in situ X-ray diffraction data that highlight an asymmetric six-step discharge and five step charge process, due to a phase that is only formed on discharge. The LixV 6O 13 unit cell expandsmore » sequentially in c, b, and a directions during discharge and reversibly contracts back during charge. The process is associated with change of Li ion positions as well as charge ordering in LixV 6O 13. Density functional theory calculations give further insight into the electronic structures and preferred Li positions in the different structures formed upon cycling, particularly at high lithium contents, where no prior structural data are available. Lastly, the results shed light into the high specific capacity of V 6O 13 and are likely to aid in the development of this material for use as a cathode for secondary lithium batteries.« less

Advanced Biasing Experiments on the C-2 Field-Reversed Configuration Device

NASA Astrophysics Data System (ADS)

Thompson, Matthew; Korepanov, Sergey; Garate, Eusebio; Yang, Xiaokang; Gota, Hiroshi; Douglass, Jon; Allfrey, Ian; Valentine, Travis; Uchizono, Nolan; TAE Team

2014-10-01

The C-2 experiment seeks to study the evolution, heating and sustainment effects of neutral beam injection on field-reversed configuration (FRC) plasmas. Recently, substantial improvements in plasma performance were achieved through the application of edge biasing with coaxial plasma guns located in the divertors. Edge biasing provides rotation control that reduces instabilities and E × B shear that improves confinement. Typically, the plasma gun arcs are run at ~ 10 MW for the entire shot duration (~ 5 ms), which will become unsustainable as the plasma duration increases. We have conducted several advanced biasing experiments with reduced-average-power plasma gun operating modes and alternative biasing cathodes in an effort to develop an effective biasing scenario applicable to steady state FRC plasmas. Early results show that several techniques can potentially provide effective, long-duration edge biasing.

A Rechargeable Al/S Battery with an Ionic-Liquid Electrolyte.

PubMed

Gao, Tao; Li, Xiaogang; Wang, Xiwen; Hu, Junkai; Han, Fudong; Fan, Xiulin; Suo, Liumin; Pearse, Alex J; Lee, Sang Bok; Rubloff, Gary W; Gaskell, Karen J; Noked, Malachi; Wang, Chunsheng

2016-08-16

Aluminum metal is a promising anode material for next generation rechargeable batteries owing to its abundance, potentially dendrite-free deposition, and high capacity. The rechargeable aluminum/sulfur (Al/S) battery is of great interest owing to its high energy density (1340 Wh kg(-1) ) and low cost. However, Al/S chemistry suffers poor reversibility owing to the difficulty of oxidizing AlSx . Herein, we demonstrate the first reversible Al/S battery in ionic-liquid electrolyte with an activated carbon cloth/sulfur composite cathode. Electrochemical, spectroscopic, and microscopic results suggest that sulfur undergoes a solid-state conversion reaction in the electrolyte. Kinetics analysis identifies that the slow solid-state sulfur conversion reaction causes large voltage hysteresis and limits the energy efficiency of the system. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Measurement of visual contrast sensitivity

NASA Astrophysics Data System (ADS)

Vongierke, H. E.; Marko, A. R.

1985-04-01

This invention involves measurement of the visual contrast sensitivity (modulation transfer) function of a human subject by means of linear or circular spatial frequency pattern on a cathode ray tube whose contrast is automatically decreasing or increasing depending on the subject pressing or releasing a hand-switch button. The threshold of detection of the pattern modulation is found by the subject by adjusting the contrast to values which vary about the subject's threshold thereby determining the threshold and also providing by the magnitude of the contrast fluctuations between reversals some estimate of the variability of the subject's absolute threshold. The invention also involves the slow automatic sweeping of the spatial frequency of the pattern over the spatial frequencies after preset time intervals or after threshold has been defined at each frequency by a selected number of subject-determined threshold crossings; i.e., contrast reversals.

Pyrite (FeS2) nanocrystals as inexpensive high-performance lithium-ion cathode and sodium-ion anode materials

NASA Astrophysics Data System (ADS)

Walter, Marc; Zünd, Tanja; Kovalenko, Maksym V.

2015-05-01

In light of the impeding depletion of fossil fuels and necessity to lower carbon dioxide emissions, economically viable high-performance batteries are urgently needed for numerous applications ranging from electric cars to stationary large-scale electricity storage. Due to its low raw material cost, non-toxicity and potentially high charge-storage capacity pyrite (FeS2) is a highly promising material for such next-generation batteries. In this work we present the electrochemical performance of FeS2 nanocrystals (NCs) as lithium-ion and sodium-ion storage materials. First, we show that nanoscopic FeS2 is a promising lithium-ion cathode material, delivering a capacity of 715 mA h g-1 and average energy density of 1237 Wh kg-1 for 100 cycles, twice higher than for commonly used LiCoO2 cathodes. Then we demonstrate, for the first time, that FeS2 NCs can serve as highly reversible sodium-ion anode material with long cycling life. As sodium-ion anode material, FeS2 NCs provide capacities above 500 mA h g-1 for 400 cycles at a current rate of 1000 mA g-1. In all our tests and control experiments, the performance of chemically synthesized nanoscale FeS2 clearly surpasses bulk FeS2 as well as large number of other nanostructured metal sulfides.In light of the impeding depletion of fossil fuels and necessity to lower carbon dioxide emissions, economically viable high-performance batteries are urgently needed for numerous applications ranging from electric cars to stationary large-scale electricity storage. Due to its low raw material cost, non-toxicity and potentially high charge-storage capacity pyrite (FeS2) is a highly promising material for such next-generation batteries. In this work we present the electrochemical performance of FeS2 nanocrystals (NCs) as lithium-ion and sodium-ion storage materials. First, we show that nanoscopic FeS2 is a promising lithium-ion cathode material, delivering a capacity of 715 mA h g-1 and average energy density of 1237 Wh kg-1 for 100 cycles, twice higher than for commonly used LiCoO2 cathodes. Then we demonstrate, for the first time, that FeS2 NCs can serve as highly reversible sodium-ion anode material with long cycling life. As sodium-ion anode material, FeS2 NCs provide capacities above 500 mA h g-1 for 400 cycles at a current rate of 1000 mA g-1. In all our tests and control experiments, the performance of chemically synthesized nanoscale FeS2 clearly surpasses bulk FeS2 as well as large number of other nanostructured metal sulfides. Electronic supplementary information (ESI) available: Materials and methods, additional structural and electrochemical characterization. See DOI: 10.1039/c5nr00398a

Development of 8-hydroxyquinoline metal based organic light-emitting diodes

NASA Astrophysics Data System (ADS)

Feng, Xiaodong

Because of its potential application for flat panel displays, solid-state lighting and 1.5 mum emitter for fiber optical communications, organic light-emitting diodes (OLEDs) have been intensively researched. One of the major problems with current OLED technology relates to inefficient electron injection at the cathode interface, which causes high driving voltage and poor device stability. Making a low resistance cathode contact for electron injection is critical to device performance. This work mainly focuses on cathode interface design and engineering. The Ohmic contact using a structure of C60/LiF/Al has been developed in electron only devices. It is found that application of the C60/LiF/Al contact to Alq based OLEDs leads to a dramatic reduction in driving voltages, a significant improvement in power efficiency, and a much slower aging process. A new cathode structure based on metal-organic-metal (MOM) tri-layer films has been developed. It is found that MOM cathodes reduce reflection by deconstructive optical interference from two metal films. The absolute reflectance from the MOM tr-ilayer films can be reduced to as low as 7% in the visible light spectrum. In actual working devices, the reflectance can be reduced from ˜80% to ˜20%. MOM cathodes provide a potential low-cost solution for high contrast full-color OLED displays. Low voltage Erq based OLEDs at 1.5 mum emission have been developed. The Erq/Ag cathode interface has been found to be efficient for electron injection. Dramatic improvement in driving voltage and power efficiency has been realized by implementing Bphen and C60 into Erq devices as an electron transport layer. Integration of Erq devices on Si wafers has also been demonstrated.

A mixed iron-manganese based pyrophosphate cathode, Na2Fe0.5Mn0.5P2O7, for rechargeable sodium ion batteries.

PubMed

Shakoor, Rana A; Park, Chan Sun; Raja, Arsalan A; Shin, Jaeho; Kahraman, Ramazan

2016-02-07

The development of secondary batteries based on abundant and cheap elements is vital. Among various alternatives to conventional lithium-ion batteries, sodium-ion batteries (SIBs) are promising due to the abundant resources and low cost of sodium. While there are many challenges associated with the SIB system, cathode is an important factor in determining the electrochemical performance of this battery system. Accordingly, ongoing research in the field of SIBs is inclined towards the development of safe, cost effective cathode materials having improved performance. In particular, pyrophosphate cathodes have recently demonstrated decent electrochemical performance and thermal stability. Herein, we report the synthesis, electrochemical properties, and thermal behavior of a novel Na2Fe0.5Mn0.5P2O7 cathode for SIBs. The material was synthesized through a solid state process. The structural analysis reveals that the mixed substitution of manganese and iron has resulted in a triclinic crystal structure (P1[combining macron] space group). Galvanostatic charge/discharge measurements indicate that Na2Fe0.5Mn0.5P2O7 is electrochemically active with a reversible capacity of ∼80 mA h g(-1) at a C/20 rate with an average redox potential of 3.2 V. (vs. Na/Na(+)). It is noticed that 84% of initial capacity is preserved over 90 cycles showing promising cyclability. It is also noticed that the rate capability of Na2Fe0.5Mn0.5P2O7 is better than Na2MnP2O7. Ex situ and CV analyses indicate that Na2Fe0.5Mn0.5P2O7 undergoes a single phase reaction rather than a biphasic reaction due to different Na coordination environment and different Na site occupancy when compared to other pyrophosphate materials (Na2FeP2O7 and Na2MnP2O7). Thermogravimetric analysis (25-550 °C) confirms good thermal stability of Na2Fe0.5Mn0.5P2O7 with only 2% weight loss. Owing to promising electrochemical properties and decent thermal stability, Na2Fe0.5Mn0.5P2O7, can be an attractive cathode for SIBs.

[Advanced treatment of coking wastewater with a novel heterogeneous electro-Fenton technology].

PubMed

Li, Hai-Tao; Li, Yu-Ping; Zhang, An-Yang; Cao, Hong-Bin; Li, Xin-Gang; Zhang, Yi

2011-01-01

A novel electro-catalytic reactor, with oxygen-reduction cathode (PAQ/GF), dimensionally stable anode (IrO2-RuO2 -TiO2/ Ti) and heterogeneous catalysts, is developed for advanced treatment of coking wastewater after biological process, integrating cathodic and anodic simultaneous oxidation processes. A PAQ/GF electrode was synthesized by the electro-polymerization of 2-ethyl anthraquinone on graphite felt, which was characterized with cyclic voltametry measurements; the results indicated that the PAQ/GF electrode showed high reversibility for oxidation-reduction reaction of anthraquinone and catalytic activity for O2 reduction to H2O2; 13.5 mmol/L H2O2 was obtained after electrolysis for 6 h at -0.7 V (vs. SCE) and pH 6 with a current efficiency of 50% in a membrane reactor. Fe-Cu/Y350 catalysts, prepared by impregnation method, could catalyze the production of hydroxyl radicals (*OH) from H2O2, which was confirmed both by fading reaction of crystal violet and oxidation of *OH-probe compound (p-chlorobenzoic acid); Fe-Cu/Y350 also showed high catalytic-activity for the oxidation of organics by hypochlorous sodium, because COD removal of coking wastewater reached 26% in the catalytic process while only 11% of COD removal was obtained in the absence of Fe-Cu/Y350. COD removal of coking wastewater reached 49.4% (26.0% and 23.4% in cathodic system and anodic system, respectively) in the developed electrolytic-reactor, which was higher than that of conventional cathodic-anodic-oxidation process (29.8%). At optimal reaction condition of initial COD = 192 mg/L, I = 10A x m(-2) and pH 4-5, more than 50% COD were removed after electrolysis for 1 h. The mechanism might be as follows: in cathodic system, H2O2 is generated from reduction of O2 on PAQ/GF cathode, and catalyzed by Fe-Cu/Y350 for production of *OH, which causes mineralization and degradation of organic pollutants; in anodic system, Cl2 and HClO are generated from Cl- oxidation on IrO2-RuO2-TiO2/Ti anode and the organic pollutants are oxidized by Cl2, and HClO with Fe-Cu/Y350 catalysts or by direct anodic oxidation.

Reversion phenomena of Cu-Cr alloys

NASA Technical Reports Server (NTRS)

Nishikawa, S.; Nagata, K.; Kobayashi, S.

1985-01-01

Cu-Cr alloys which were given various aging and reversion treatments were investigated in terms of electrical resistivity and hardness. Transmission electron microscopy was one technique employed. Some results obtained are as follows: the increment of electrical resistivity after the reversion at a constant temperature decreases as the aging temperature rises. In a constant aging condition, the increment of electrical resistivity after the reversion increases, and the time required for a maximum reversion becomes shorter as the reversion temperature rises. The reversion phenomena can be repeated, but its amount decreases rapidly by repetition. At first, the amount of reversion increases with aging time and reaches its maximum, and then tends to decrease again. Hardness changes by the reversion are very small, but the hardness tends to soften slightly. Any changes in transmission electron micrographs by the reversion treatment cannot be detected.

Natural aging and reversion behavior of Al-Cu-Li-Ag-Mg alloy Weldalite (tm) 049

NASA Technical Reports Server (NTRS)

Gayle, Frank W.; Heubaum, Frank H.; Pickens, Joseph R.

1991-01-01

This study was initiated to understand the natural aging and reversion behavior of Weldalite (trademark) 049 in tempers without cold work. Of particular interest are: (1) the microstructural basis for the high strength in the T4 condition; (2) an explanation of the reversion phenomenon; and (3) the effect of re-aging at room temperature after a reversion treatment. Mechanical properties were measured and transmission electron microscopy (TEM) analysis performed at various stages of microstructural development during aging, reversion, and subsequent re-aging.

2017 NEPP Tasks Update for Ceramic and Tantalum Capacitors

NASA Technical Reports Server (NTRS)

Teverovsky, Alexander A.

2017-01-01

This presentation gives an overview of current NEPP tasks on ceramic and tantalum capacitors and plans for the future. It includes tasks on leakage currents, gas generation and case deformation in wet tantalum capacitors; ESR degradation and acceleration factors in MnO2 and polymer cathode capacitors. Preliminary results on the effect of moisture on degradation of reverse currents in MnO2 tantalum capacitors are discussed. Latest results on mechanical characteristics of MLCCs and modeling of degradation of leakage currents in BME capacitors with defects are also presented.

Performance of high power S-band klystrons focused with permanent magnet

NASA Astrophysics Data System (ADS)

Fukuda, S.; Shidara, T.; Saito, Y.; Hanaki, H.; Nakao, K.; Homma, H.; Anami, S.; Tanaka, J.

1987-02-01

Performance of high power S-band klystrons focused with permanent magnet is presented. The axial magnetic field distribution and the transverse magnetic field play an important role in the tube performance. Effects of the reversal field in the collector and the cathode-anode region are discussed precisely. It is also shown that the tube efficiency is strongly affected with the residual transverse magnetic field. The allowable transverse field is less than 0.3 percent of the longitudinal field in the entire RF interaction region of the klystron.

Study of the long-term operation of a vanadium/oxygen fuel cell

NASA Astrophysics Data System (ADS)

Noack, Jens; Cognard, Gwenn; Oral, Meryem; Küttinger, Michael; Roznyatovskaya, Nataliya; Pinkwart, Karsten; Tübke, Jens

2016-09-01

A vanadium/oxygen fuel cell (VOFC) with a geometrically active area of 51 cm2 and two membranes was discontinuously operated over a period of over 676 h with 47 successive tests at room temperature with a current density of 19.6 mA/cm2 in order to investigate signs of ageing. As well as measuring cell voltages, the test setup was also used to measure anode and redox potentials as well as cell and half-cell impedances. The performance data of the VOFC fluctuated widely over the course of the test period, due to different V2+ concentrations and instabilities of the starting solutions on the one hand and complex changes in cathode conditions on the other. The desired behaviour of the anode reactions was achieved primarily through improved methods for producing the V2+ solutions, and remained stable at the end of the experiments. The kinetics of the cathode reactions were temporarily increased by purging with 2 M H2SO4, however their performance decreased over time. The VOFC had symptoms of ageing by complex and overlaid changes in the cathode's triple phase boundary layer and in the special conditions between the two electrodes and membranes.

Structure-Induced Reversible Anionic Redox Activity in Na Layered Oxide Cathode

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

Rong, Xiaohui; Liu, Jue; Hu, Enyuan

Anionic redox reaction (ARR) in lithium- and sodium-ion batteries is under hot discussion, mainly regarding how oxygen anion participates and to what extent oxygen can be reversibly oxidized and reduced. In this paper, a P3-type Na 0.6[Li 0.2Mn 0.8]O 2 with reversible capacity from pure ARR was studied. The interlayer O-O distance (peroxo-like O-O dimer, 2.506(3) Å), associated with oxidization of oxygen anions, was directly detected by using a neutron total scattering technique. Finally, different from Li 2RuO 3 or Li 2IrO 3 with strong metal-oxygen (M-O) bonding, for P3-type Na 0.6[Li 0.2Mn 0.8]O 2 with relatively weak Mn-O covalentmore » bonding, crystal structure factors might play an even more important role in stabilizing the oxidized species, as both Li and Mn ions are immobile in the structure and thus may inhibit the irreversible transformation of the oxidized species to O 2 gas.« less

Controlling Solid–Liquid Conversion Reactions for a Highly Reversible Aqueous Zinc–Iodine Battery

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

Pan, Huilin; Li, Bin; Mei, Donghai

Aqueous rechargeable batteries are desirable for many energy storage applications due to their low cost and high safety. However, low capacity and short cycle life are the significant obstacles to their practical applications. Here, we demonstrate a highly reversible aqueous zinc-iodine battery using encapsulated iodine in microporous active carbon fibers (ACFs) as cathode materials through the rational control of solid-liquid conversion reactions. The experiments and density function theory (DFT) calculations were employed to investigate the effects of solvents and properties of carbon hosts, e.g. pore size, surface chemistries, on the adsorption of iodine species. The rational manipulation of the competitionmore » between the adsorption in carbon and solvation in electrolytes for iodine species is responsible for the high reversibility and cycling stability. The zinc-iodine batteries deliver a high capacity of 180 mAh g-1 at 1C and a stable cycle life over 3000 cycles with ~90% capacity retention as well as negligible self-discharge. We believe the principles for stabilizing the zinc-iodine system could provide new insight into conversion systems such as Li-S systems.« less

Structure-Induced Reversible Anionic Redox Activity in Na Layered Oxide Cathode

DOE PAGES

Rong, Xiaohui; Liu, Jue; Hu, Enyuan; ...

2017-11-01

Anionic redox reaction (ARR) in lithium- and sodium-ion batteries is under hot discussion, mainly regarding how oxygen anion participates and to what extent oxygen can be reversibly oxidized and reduced. In this paper, a P3-type Na 0.6[Li 0.2Mn 0.8]O 2 with reversible capacity from pure ARR was studied. The interlayer O-O distance (peroxo-like O-O dimer, 2.506(3) Å), associated with oxidization of oxygen anions, was directly detected by using a neutron total scattering technique. Finally, different from Li 2RuO 3 or Li 2IrO 3 with strong metal-oxygen (M-O) bonding, for P3-type Na 0.6[Li 0.2Mn 0.8]O 2 with relatively weak Mn-O covalentmore » bonding, crystal structure factors might play an even more important role in stabilizing the oxidized species, as both Li and Mn ions are immobile in the structure and thus may inhibit the irreversible transformation of the oxidized species to O 2 gas.« less

Insight into the Atomic Structure of High-Voltage Spinel LiNi 0.5Mn 1.5O4 Cathode Material in the First Cycle

DOE PAGES

Huang, Xuejie; Yu, Xiqian; Lin, Mingxiang; ...

2014-12-22

Application of high-voltage spinel LiNi 0.5Mn 1.5O4 cathode material is the closest and the most realistic approach to meeting the midterm goal of lithium-ion batteries for electric vehicles (EVs) and plug-in hybrid electric vehicles (HEVs). However, this application has been hampered by long-standing issues, such as capacity degradation and poor first-cycle Coulombic efficiency of LiNi 0.5Mn 1.5O4 cathode material. Although it is well-known that the structure of LiNi 0.5Mn 1.5O4 into which Li ions are reversibly intercalated plays a critical role in the above issues, performance degradation related to structural changes, particularly in the first cycle, are not fully understood.more » Here, we report detailed investigations of local atomic-level and average structure of LiNi 0.5Mn 1.5O4 during first cycle (3.5–4.9 V) at room temperature. We observed two types of local atomic-level migration of transition metals (TM) ions in the cathode of a well-prepared LiNi 0.5Mn 1.5O4//Li half-cell during first charge via an aberration-corrected scanning transmission electron microscopy (STEM). Surface regions (~2 nm) of the cycled LiNi 0.5Mn 1.5O4 particles show migration of TM ions into tetrahedral Li sites to form a Mn 3O 4-like structure. However, subsurface regions of the cycled particles exhibit migration of TM ions into empty octahedral sites to form a rocksalt-like structure. The migration of these TM ions are closely related to dissolution of Ni/Mn ions and building-up of charge transfer impedance, which contribute significantly to the capacity degradation and the poor first-cycle Coulombic efficiency of spinel LiNi 0.5Mn 1.5O4 cathode material. Accordingly, we provide suggestions of effective stabilization of LiNi 0.5Mn 1.5O4 structure to obtain better electrochemical performance.« less

Graphite felt modified with bismuth nanoparticles as negative electrode in a vanadium redox flow battery.

PubMed

Suárez, David J; González, Zoraida; Blanco, Clara; Granda, Marcos; Menéndez, Rosa; Santamaría, Ricardo

2014-03-01

A graphite felt decorated with bismuth nanoparticles was studied as negative electrode in a vanadium redox flow battery (VRFB). The results confirm the excellent electrochemical performance of the bismuth modified electrode in terms of the reversibility of the V(3+) /V(2+) redox reactions and its long-term cycling performance. Moreover a mechanism that explains the role that Bi nanoparticles play in the redox reactions in this negative half-cell is proposed. Bi nanoparticles favor the formation of BiHx , an intermediate that reduces V(3+) to V(2+) and, therefore, inhibits the competitive irreversible reaction of hydrogen formation (responsible for the commonly observed loss of Coulombic efficiency of VRFBs). Thus, the total charge consumed during the cathodic sweep in this electrode is used to reduce V(3+) to V(2+) , resulting in a highly reversible and efficient process. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Eliminating degradation and uncovering ion-trapping dynamics in electrochromic WO3 thin films

PubMed Central

Wen, Rui-Tao; Granqvist, Claes G.; Niklasson, Gunnar A.

2015-01-01

Amorphous WO3 thin films are of keen interest as cathodic electrodes in transmittance-modulating electrochromic devices. However, these films suffer from ion-trapping-induced degradation of optical modulation and reversibility upon extended Li+-ion exchange. Here, we demonstrate that ion-trapping-induced degradation, which is commonly believed to be irreversible, can be successfully eliminated by constant-current-driven de-trapping, i.e., WO3 films can be rejuvenated and regain their initial highly reversible electrochromic performance. Pronounced ion-trapping occurs when x exceeds ~0.65 in LixWO3 during ion insertion. We find two main kinds of Li+-ion trapping sites (intermediate and deep) in WO3, where the intermediate ones are most prevalent. Li+-ions can be completely removed from intermediate traps but are irreversibly bound in deep traps. Our results provide a general framework for developing and designing superior electrochromic materials and devices. PMID:26259104

Verticality perception during and after galvanic vestibular stimulation.

PubMed

Volkening, Katharina; Bergmann, Jeannine; Keller, Ingo; Wuehr, Max; Müller, Friedemann; Jahn, Klaus

2014-10-03

The human brain constructs verticality perception by integrating vestibular, somatosensory, and visual information. Here we investigated whether galvanic vestibular stimulation (GVS) has an effect on verticality perception both during and after application, by assessing the subjective verticals (visual, haptic and postural) in healthy subjects at those times. During stimulation the subjective visual vertical and the subjective haptic vertical shifted towards the anode, whereas this shift was reversed towards the cathode in all modalities once stimulation was turned off. Overall, the effects were strongest for the haptic modality. Additional investigation of the time course of GVS-induced changes in the haptic vertical revealed that anodal shifts persisted for the entire 20-min stimulation interval in the majority of subjects. Aftereffects exhibited different types of decay, with a preponderance for an exponential decay. The existence of such reverse effects after stimulation could have implications for GVS-based therapy. Copyright © 2014 Elsevier Ireland Ltd. All rights reserved.

Trap-assisted hole injection and quantum efficiency enhancement in poly(9,9' dioctylfluorene-alt-benzothiadiazole) polymer light-emitting diodes

NASA Astrophysics Data System (ADS)

Seeley, Alexander J. A. B.; Friend, Richard H.; Kim, Ji-Seon; Burroughes, Jeremy H.

2004-12-01

We report a reversible many-fold quantum efficiency enhancement during electrical driving of polymer light-emitting diodes (LEDs) containing poly(9,9' dioctylfluorene-alt-benzothiadiazole) (F8BT), developing over several minutes or hours at low applied bias and recovering on similar time scales after driving. This phenomenon is observed only in devices containing F8BT as an emissive layer in pure or blended form, regardless of anode and cathode choices and even in the absence of a poly(styrene-sulphonate)-doped poly(3,4-ethylene-dioxythiophene) (PEDOT:PSS) layer. We report detailed investigations using a standardized device structure containing PEDOT:PSS and a calcium cathode. Direct measurements of trapped charge recovered from the device after driving significantly exceed the unipolar limit, and thermally activated relaxation suggests a maximum trap depth around 0.6eV. Neither photoluminescence nor electroluminescence spectra reveal any change in the bulk optoelectronic properties of the emissive polymer nor any new emissive species. During the quantum efficiency (QE) enhancement process, the bulk conduction of the device increases. Reverse bias treatment of the device significantly reinforces the QE enhancement. Based on these observations, we propose a simple model in which interfacial dipoles are generated by trapped holes near the anode combining with injected electrons, to produce a narrow tunneling barrier for easy hole injection. The new injection pathway leads to a higher hole current density and thus a better charge injection balance. This produces the relatively high quantum efficiency observed in all F8BT LEDs.

Aging behavior of lithium iron phosphate based 18650-type cells studied by in situ neutron diffraction

NASA Astrophysics Data System (ADS)

Paul, Neelima; Wandt, Johannes; Seidlmayer, Stefan; Schebesta, Sebastian; Mühlbauer, Martin J.; Dolotko, Oleksandr; Gasteiger, Hubert A.; Gilles, Ralph

2017-03-01

The aging behavior of commercially produced 18650-type Li-ion cells consisting of a lithium iron phosphate (LFP) based cathode and a graphite anode based on either mesocarbon microbeads (MCMB) or needle coke (NC) is studied by in situ neutron diffraction and standard electrochemical techniques. While the MCMB cells showed an excellent cycle life with only 8% relative capacity loss (i.e., referenced to the capacity after formation) after 4750 cycles and showed no capacity loss on storage for two years, the needle coke cells suffered a 23% relative capacity loss after cycling and a 11% loss after storage. Based on a combination of neutron diffraction and electrochemical characterization, it is shown that the entire capacity loss for both cell types is dominated by the loss of active lithium; no other aging mechanisms like structural degradation of anode or cathode active materials or deactivation of active material could be found, highlighting the high structural stability of the active material and the excellent quality of the investigated cells.

In Situ Probing and Synthetic Control of Cationic Ordering in Ni-Rich Layered Oxide Cathodes

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

Zhao, Jianqing; Zhang, Wei; Huq, Ashfia

Ni-rich layered oxides (LiNi1-xMxO2; M = Co, Mn, ...) are appealing alternatives to conventional LiCoO2 as cathodes in Li-ion batteries for automobile and other large-scale applications due to their high theoretical capacity and low cost. However, preparing stoichiometric LiNi1-xMxO2 with ordered layer structure and high reversible capacity, has proven difficult due to cation mixing in octahedral sites. Herein, in situ studies of synthesis reactions and the associated structural ordering in preparing LiNiO2 and the Co-substituted variant, LiNi0.8Co0.2O2, are made, to gain insights into synthetic control of the structure and electrochemical properties of Ni-rich layered oxides. Results from this study indicatemore » a direct transformation of the intermediate from the rock salt structure into hexagonal phase, and during the process, Co substitution facilities the nucleation of a Co-rich layered phase at low temperatures and subsequent growth and stabilization of solid solution Li(Ni, Co)O-2 upon further heat treatment. Optimal conditions are identified from the in situ studies and utilized to obtain stoichiometric LiNi0.8Co0.2O2 that exhibits high capacity (up to 200 mA h g(-1) ) with excellent retention. The findings shed light on designing high performance Ni-rich layered oxide cathodes through synthetic control of the structural ordering in the materials.« less

Salinity-gradient energy driven microbial electrosynthesis of hydrogen peroxide

NASA Astrophysics Data System (ADS)

Li, Xiaohu; Angelidaki, Irini; Zhang, Yifeng

2017-02-01

Hydrogen peroxide (H2O2) as a strong oxidant, is widely used in various chemical industries and environmental remediation processes. In this study, we developed an innovative method for cost-effective production of H2O2 by using a microbial reverse-electrodialysis electrolysis cell (MREC). In the MREC, electrical potential generated by the exoelectrogens and the salinity-gradient between salt and fresh water were utilized to drive the high-rate H2O2 production. Operational parameters such as air flow rate, pH, cathodic potential, flow rate of salt and fresh water were investigated. The optimal H2O2 production was observed at salt and fresh water flow rate of 0.5 mL min-1, air flow rate of 12-20 mL min-1, cathode potential of -0.485 ± 0.025 V (vs Ag/AgCl). The maximum H2O2 accumulated concentration of 778 ± 11 mg L-1 was obtained at corresponding production rate of 11.5 ± 0.5 mg L-1 h-1. The overall energy input for the synthesis process was 0.45 ± 0.03 kWh kg-1 H2O2. Cathode potential was the key factor for H2O2 production, which was mainly affected by the air flow rate. This work for the first time proved the potential of MREC as an efficient platform technology for simultaneous electrosynthesis of valuable chemicals and utilization of salinity-gradient energy.

Room temperature large-scale synthesis of layered frameworks as low-cost 4 V cathode materials for lithium ion batteries.

PubMed

Hameed, A Shahul; Reddy, M V; Nagarathinam, M; Runčevski, Tomče; Dinnebier, Robert E; Adams, Stefan; Chowdari, B V R; Vittal, Jagadese J

2015-11-23

Li-ion batteries (LIBs) are considered as the best available technology to push forward the production of eco-friendly electric vehicles (EVs) and for the efficient utilization of renewable energy sources. Transformation from conventional vehicles to EVs are hindered by the high upfront price of the EVs and are mainly due to the high cost of LIBs. Hence, cost reduction of LIBs is one of the major strategies to bring forth the EVs to compete in the market with their gasoline counterparts. In our attempt to produce cheaper high-performance cathode materials for LIBs, an rGO/MOPOF (reduced graphene oxide/Metal-Organic Phosphate Open Framework) nanocomposite with ~4 V of operation has been developed by a cost effective room temperature synthesis that eliminates any expensive post-synthetic treatments at high temperature under Ar/Ar-H2. Firstly, an hydrated nanocomposite, rGO/K2[(VO)2(HPO4)2(C2O4)]·4.5H2O has been prepared by simple magnetic stirring at room temperature which releases water to form the anhydrous cathode material while drying at 90 °C during routine electrode fabrication procedure. The pristine MOPOF material undergoes highly reversible lithium storage, however with capacity fading. Enhanced lithium cycling has been witnessed with rGO/MOPOF nanocomposite which exhibits minimal capacity fading thanks to increased electronic conductivity and enhanced Li diffusivity.

Sustainable Sulfur-rich Copolymer/Graphene Composite as Lithium-Sulfur Battery Cathode with Excellent Electrochemical Performance

PubMed Central

Ghosh, Arnab; Shukla, Swapnil; Khosla, Gaganpreet Singh; Lochab, Bimlesh; Mitra, Sagar

2016-01-01

A sulfur-rich copolymer, poly(S-r-C-a) has been synthesized via a sustainable route, showing the utility of two major industrial wastes- elemental sulfur (petroleum waste) and cardanol (agro waste), to explore its potential as cathode material for Li-S batteries. The sulfur-rich copolymer exhibited a reduction in the active material dissolution into the electrolyte and a low self-discharge rate behavior during the rest time compared to an elemental sulfur cathode, indicating the chemical confinement of sulfur units. The presence of organosulfur moieties in copolymer suppress the irreversible deposition of end-discharge products on electrode surfaces and thus improve the electrochemical performances of Li-S batteries. This sulfur copolymer offered a reversible capacity of 892 mA h g−1 at 2nd cycle and maintained the capacity of 528 mA h g−1 after 50 cycles at 200 mA g−1. Reduced graphene oxide (rGO) prepared via a sustainable route was used as a conductive filler to extract the better electrochemical performances from this sulfur copolymer. Such sustainable origin batteries prepared via economically viable showed an improved specific capacity of ~975 mA h g−1 after 100 cycles at 200 mA g−1 current rate with capacity fading of 0.15% per cycle and maintained a stable performance over 500 cycles at 2000 mA g−1. PMID:27121089

Preparation of Al-Si Master Alloy by Electrochemical Reduction of Volcanic Rock in Cryolite Molten Salt

NASA Astrophysics Data System (ADS)

Liu, Aimin; Shi, Zhongning; Xu, Junli; Hu, Xianwei; Gao, Bingliang; Wang, Zhaowen

2016-06-01

Volcanic rock found in the Longgang Volcano Group in Jilin Province of China has properties essentially similar to Apollo lunar soils and previously prepared lunar soil simulants, such as Johnson Space Center Lunar simulant and Minnesota Lunar simulant. In this study, an electrochemical method of preparation of Al-Si master alloy was investigated in 52.7 wt.%NaF-47.3 wt.%AlF3 melt adding 5 wt.% volcanic rock at 1233 K. The cathodic electrochemical process was studied by cyclic voltammetry, and the results showed that the cathodic reduction of Si(IV) is a two-step reversible diffusion-controlled reaction. Si(IV) is reduced to Si(II) by two electron transfers at -1.05 V versus platinum quasi-reference electrode in 52.7 wt.%NaF-47.3 wt.%AlF3 molten salt adding 5 wt.% volcanic rock, while the reduction peak at -1.18 V was the co-deposition of aluminum and silicon. In addition, the cathodic product obtained by galvanostatic electrolysis for 4 h was analyzed by means of x-ray diffraction, x-ray fluorescence, scanning electron microscopy and energy dispersive spectrometry. The results showed that the phase compositions of the products are Al, Si, Al5FeSi, and Al3.21Si0.47, while the components are 90.5 wt.% aluminum, 4.4 wt.% silicon, 1.9 wt.% iron, and 0.2 wt.% titanium.

Ultradispersed Nanoarchitecture of LiV3O8 Nanoparticle/Reduced Graphene Oxide with High-Capacity and Long-Life Lithium-Ion Battery Cathodes

NASA Astrophysics Data System (ADS)

Mo, Runwei; Du, Ying; Rooney, David; Ding, Guqiao; Sun, Kening

2016-01-01

Lack of high-performance cathode materials has become the major barriers to lithium-ion battery applications in advanced communication equipment and electric vehicles. In this paper, we report a versatile interfacial reaction strategy, which is based on the idea of space confinement, for the synthesis of ultradispersed LiV3O8 nanoparticles (~10 nm) on graphene (denoted as LVO NPs-GNs) with an unprecedented degree of control on the separation and manipulation of the nucleation, growth, anchoring, and crystallization of nanoparticles in a water-in-oil emulsion system over free growth in solution. The prepared LVO NPs-GNs composites displayed high performance as an cathode material for lithium-ion battery, including high reversible lithium storage capacity (237 mA h g-1 after 200 cycles), high Coulombic efficiency (about 98%), excellent cycling stability and high rate capability (as high as 176 mA h g-1 at 0.9 A g-1, 128 mA h g-1 at 1.5 A g-1, 91 mA h g-1 at 3 A g-1 and 59 mA h g-1 at 6 A g-1, respectively). Very significantly, the preparation method employed can be easily adapted and may opens the door to complex hybrid materials design and engineering with graphene for advanced energy storage.

Room temperature large-scale synthesis of layered frameworks as low-cost 4 V cathode materials for lithium ion batteries

PubMed Central

Hameed, A. Shahul; Reddy, M. V.; Nagarathinam, M.; Runčevski, Tomče; Dinnebier, Robert E; Adams, Stefan; Chowdari, B. V. R.; Vittal, Jagadese J.

2015-01-01

Li-ion batteries (LIBs) are considered as the best available technology to push forward the production of eco-friendly electric vehicles (EVs) and for the efficient utilization of renewable energy sources. Transformation from conventional vehicles to EVs are hindered by the high upfront price of the EVs and are mainly due to the high cost of LIBs. Hence, cost reduction of LIBs is one of the major strategies to bring forth the EVs to compete in the market with their gasoline counterparts. In our attempt to produce cheaper high-performance cathode materials for LIBs, an rGO/MOPOF (reduced graphene oxide/Metal-Organic Phosphate Open Framework) nanocomposite with ~4 V of operation has been developed by a cost effective room temperature synthesis that eliminates any expensive post-synthetic treatments at high temperature under Ar/Ar-H2. Firstly, an hydrated nanocomposite, rGO/K2[(VO)2(HPO4)2(C2O4)]·4.5H2O has been prepared by simple magnetic stirring at room temperature which releases water to form the anhydrous cathode material while drying at 90 °C during routine electrode fabrication procedure. The pristine MOPOF material undergoes highly reversible lithium storage, however with capacity fading. Enhanced lithium cycling has been witnessed with rGO/MOPOF nanocomposite which exhibits minimal capacity fading thanks to increased electronic conductivity and enhanced Li diffusivity. PMID:26593096

Room temperature large-scale synthesis of layered frameworks as low-cost 4 V cathode materials for lithium ion batteries

NASA Astrophysics Data System (ADS)

Hameed, A. Shahul; Reddy, M. V.; Nagarathinam, M.; Runčevski, Tomče; Dinnebier, Robert E.; Adams, Stefan; Chowdari, B. V. R.; Vittal, Jagadese J.

2015-11-01

Li-ion batteries (LIBs) are considered as the best available technology to push forward the production of eco-friendly electric vehicles (EVs) and for the efficient utilization of renewable energy sources. Transformation from conventional vehicles to EVs are hindered by the high upfront price of the EVs and are mainly due to the high cost of LIBs. Hence, cost reduction of LIBs is one of the major strategies to bring forth the EVs to compete in the market with their gasoline counterparts. In our attempt to produce cheaper high-performance cathode materials for LIBs, an rGO/MOPOF (reduced graphene oxide/Metal-Organic Phosphate Open Framework) nanocomposite with ~4 V of operation has been developed by a cost effective room temperature synthesis that eliminates any expensive post-synthetic treatments at high temperature under Ar/Ar-H2. Firstly, an hydrated nanocomposite, rGO/K2[(VO)2(HPO4)2(C2O4)]·4.5H2O has been prepared by simple magnetic stirring at room temperature which releases water to form the anhydrous cathode material while drying at 90 °C during routine electrode fabrication procedure. The pristine MOPOF material undergoes highly reversible lithium storage, however with capacity fading. Enhanced lithium cycling has been witnessed with rGO/MOPOF nanocomposite which exhibits minimal capacity fading thanks to increased electronic conductivity and enhanced Li diffusivity.

Lithiated Nafion as polymer electrolyte for solid-state lithium sulfur batteries using carbon-sulfur composite cathode

NASA Astrophysics Data System (ADS)

Gao, Jing; Sun, Chunshui; Xu, Lei; Chen, Jian; Wang, Chong; Guo, Decai; Chen, Hao

2018-04-01

Due to flexible property and light weight, the lithiated Nafion membrane swollen with PC (PC-Li-Nafion) has been employed as both solid-state electrolyte and separator to fabricate solid-state Li-S cells. The electrochemical measurements of PC-Li-Nafion membrane show that its Li-ion transference number is 0.928, ionic conductivity of 2.1 × 10-4 S cm-1 can be achieved at 70 °C and its electrochemical window is 0 ∼ +4.1 V vs. Li+/Li. It is observed that the Li dendrites are suppressed by using PC-Li-Nafion membrane due to its single-ion conducting property. The amounts of Li-Nafion resin binder and conductive carbon in the cathode are optimized as 40% and 10% respectively to make a balance of ionic and electronic conductivities. A thin-layer Li-Nafion resin with a thickness of around 2 μm is fabricated between the cathode and PC-Li-Nafion membrane to improve the interfacial contact and further enhance the specific capacity of the cell. When measured at 70 °C, the Li-S cell delivers a reversible specific capacity of 1072.8 mAh g-1 (S) at 0.05 C and 895 mAh g-1 (S) at 1 C. The capacity retention at 1 C is 89% after 100 cycles. These results suggest that high-performance solid-state Li-S cells can be fabricated with the Li-Nafion polymer electrolyte.

Ultra-low cost and highly stable hydrated FePO4 anodes for aqueous sodium-ion battery

NASA Astrophysics Data System (ADS)

Wang, Yuesheng; Feng, Zimin; Laul, Dharminder; Zhu, Wen; Provencher, Manon; Trudeau, Michel L.; Guerfi, Abdelbast; Zaghib, Karim

2018-01-01

The growing demands for large-scale energy storage devices have put a spotlight on aqueous sodium-ion batteries, which possess a number of highly desirable features, such as sodium abundance, low cost and safety over organic electrolytes. While lots of cathode materials were reported, only few candidate materials like active carbon and NaTi2(PO4)3 were proposed as anodes. It is a long-standing common knowledge that the low cost, non-toxicity, and highly reversible FePO4·2H2O is known as an attractive cathode material for non-aqueous lithium- and sodium-ion batteries, but we demonstrate for the first time that nano-size non-carbon coated amorphous FePO4·2H2O can be used as the anode for an aqueous sodium-ion battery. Its optimum operating voltage (∼2.75 V vs. Na+/Na) avoids hydrogen evolution. The capacity is as high as 80 mAh/g at a rate of 0.5 C in a three-electrode system. The full cell, using the Na0.44MnO2 as cathode, maintained 90% of the capacity at 300 cycles at a rate of 3 C. The calculations also show that its volume change during the intercalation of Na ions is below 2%. Its low cost, high safety, along with its outstanding electrochemical performance makes amorphous FePO4·2H2O a promising anode material for aqueous sodium-ion 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.

Surface-enhanced redox chemistry of polysulphides on a metallic and polar host for lithium-sulphur batteries.

PubMed

Pang, Quan; Kundu, Dipan; Cuisinier, Marine; Nazar, L F

2014-08-26

The lithium-sulphur battery relies on the reversible conversion between sulphur and Li2S and is highly appealing for energy storage owing to its low cost and high energy density. Porous carbons are typically used as sulfur hosts, but they do not adsorb the hydrophilic polysulphide intermediates or adhere well to Li2S, resulting in pronounced capacity fading. Here we report a different strategy based on an inherently polar, high surface area metallic oxide cathode host and show that it mitigates polysulphide dissolution by forming an excellent interface with Li2S. Complementary physical and electrochemical probes demonstrate strong polysulphide/Li2S binding with this 'sulphiphilic' host and provide experimental evidence for surface-mediated redox chemistry. In a lithium-sulphur cell, Ti4O7/S cathodes provide a discharge capacity of 1,070 mAh g(-1) at intermediate rates and a doubling in capacity retention with respect to a typical conductive carbon electrode, at practical sulphur mass fractions up to 70 wt%. Stable cycling performance is demonstrated at high rates over 500 cycles.

Primate translational vestibuloocular reflexes. III. Effects of bilateral labyrinthine electrical stimulation

NASA Technical Reports Server (NTRS)

Angelaki, D. E.; McHenry, M. Q.; Dickman, J. D.; Perachio, A. A.

2000-01-01

The effects of functional, reversible ablation and potential recruitment of the most irregular otolith afferents on the dynamics and sensitivity of the translational vestibuloocular reflexes (trVORs) were investigated in rhesus monkeys trained to fixate near and far targets. Translational motion stimuli consisted of either steady-state lateral and fore-aft sinusoidal oscillations or short-lasting transient lateral head displacements. Short-duration (usually <2 s) anodal (inhibitory) and cathodal (excitatory) currents (50-100 microA) were delivered bilaterally during motion. In the presence of anodal labyrinthine stimulation, trVOR sensitivity and its dependence on viewing distance were significantly decreased. In addition, anodal currents significantly increased phase lags. During transient motion, anodal stimulation resulted in significantly lower initial eye acceleration and more sluggish responses. Cathodal currents tended to have opposite effects. The main characteristics of these results were simulated by a simple model where both regularly and irregularly discharging afferents contribute to the trVORs. Anodal labyrinthine currents also were found to decrease eye velocity during long-duration, constant velocity rotations, although results were generally more variable compared with those during translational motion.

Flexible Li-CO2 Batteries with Liquid-Free Electrolyte.

PubMed

Hu, Xiaofei; Li, Zifan; Chen, Jun

2017-05-15

Developing flexible Li-CO 2 batteries is a promising approach to reuse CO 2 and simultaneously supply energy to wearable electronics. However, all reported Li-CO 2 batteries use liquid electrolyte and lack robust electrolyte/electrodes structure, not providing the safety and flexibility required. Herein we demonstrate flexible liquid-free Li-CO 2 batteries based on poly(methacrylate)/poly(ethylene glycol)-LiClO 4 -3 wt %SiO 2 composite polymer electrolyte (CPE) and multiwall carbon nanotubes (CNTs) cathodes. The CPE (7.14×10 -2  mS cm -1 ) incorporates with porous CNTs cathodes, displaying stable structure and small interface resistance. The batteries run for 100 cycles with controlled capacity of 1000 mAh g -1 . Moreover, pouch-type flexible batteries exhibit large reversible capacity of 993.3 mAh, high energy density of 521 Wh kg -1 , and long operation time of 220 h at different degrees of bending (0-360°) at 55 °C. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Carbon-Nanotube-Supported Bio-Inspired Nickel Catalyst and Its Integration in Hybrid Hydrogen/Air Fuel Cells.

PubMed

Gentil, Solène; Lalaoui, Noémie; Dutta, Arnab; Nedellec, Yannig; Cosnier, Serge; Shaw, Wendy J; Artero, Vincent; Le Goff, Alan

2017-02-06

A biomimetic nickel bis-diphosphine complex incorporating the amino acid arginine in the outer coordination sphere was immobilized on modified carbon nanotubes (CNTs) through electrostatic interactions. The functionalized redox nanomaterial exhibits reversible electrocatalytic activity for the H 2 /2 H + interconversion from pH 0 to 9, with catalytic preference for H 2 oxidation at all pH values. The high activity of the complex over a wide pH range allows us to integrate this bio-inspired nanomaterial either in an enzymatic fuel cell together with a multicopper oxidase at the cathode, or in a proton exchange membrane fuel cell (PEMFC) using Pt/C at the cathode. The Ni-based PEMFC reaches 14 mW cm -2 , only six-times-less as compared to full-Pt conventional PEMFC. The Pt-free enzyme-based fuel cell delivers ≈2 mW cm -2 , a new efficiency record for a hydrogen biofuel cell with base metal catalysts. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Enhanced Performance of a Lithium-Sulfur Battery Using a Carbonate-Based Electrolyte.

PubMed

Xu, Zhixin; Wang, Jiulin; Yang, Jun; Miao, Xiaowei; Chen, Renjie; Qian, Ji; Miao, Rongrong

2016-08-22

The lithium-sulfur battery is regarded as one of the most promising candidates for lithium-metal batteries with high energy density. However, dendrite Li formation and low cycle efficiency of the Li anode as well as unstable sulfur based cathode still hinder its practical application. Herein a novel electrolyte (1 m LiODFB/EC-DMC-FEC) is designed not only to address the above problems of Li anode but also to match sulfur cathode perfectly, leading to extraordinary electrochemical performances. Using this electrolyte, lithium|lithium cells can cycle stably for above 2000 hours and the average Coulumbic efficiency reaches 98.8 %. Moreover, the Li-S battery delivers a reversible capacity of about 1400 mAh g(-1) sulfur with retention of 89 % for 1100 cycles at 1 C, and a capacity above 1100 mAh g(-1) sulfur at 10 C. The more advantages of this cell system are its outstanding cycle stability at 60 °C and no self-discharge phenomena. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Experimental and analytical analysis of polarization and water transport behaviors of hydrogen alkaline membrane fuel cell

NASA Astrophysics Data System (ADS)

Huo, Sen; Zhou, Jiaxun; Wang, Tianyou; Chen, Rui; Jiao, Kui

2018-04-01

Experimental test and analytical modeling are conducted to investigate the operating behavior of an alkaline electrolyte membrane (AEM) fuel cell fed by H2/air (or O2) and explore the effect of various operating pressures on the water transfer mechanism. According to the experimental test, the cell performance is greatly improved through increasing the operating pressure gradient from anode to cathode which leads to significant liquid water permeation through the membrane. The high frequency resistance of the A901 alkaline membrane is observed to be relatively stable as the operating pressure varies based on the electrochemical impedance spectroscopy (EIS) method. Correspondingly, based on the modeling prediction, the averaged water content in the membrane electrode assembly (MEA) does not change too much which leads to the weak variation of membrane ohmic resistance. This reveals that the performance enhancement should give the credit to better electro-chemical reaction kinetics for both the anode and cathode, also prone by the EIS results. The reversion of water back diffusion direction across the membrane is also observed through analytical solution.

Synthesis, optical and electrochemical properties of Zn-porphyrin for dye sensitized solar cell applications

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

Kotteswaran, S.; Pandian, M. Senthil; Ramasamy, P., E-mail: ramasamyp@ssn.edu.in

2016-05-23

Zn-Porphyrin dye has been synthesized by the reaction between aldehydes and pyrrole. The dye structure was confirmed by {sup 1}H NMR, {sup 13}C NMR spectrum. The functional group of the dye molecule was confirmed by FTIR spectrum. The UV-Vis-NIR absorption spectrum of Zn-Porphyrin in DMF solution was recorded in spectrophotometer. The UV-Vis NIR spectrum of dye exhibits a strong Soret band and Q-band. Cyclic Voltammograms were obtained with three electrode systems: Pt as counter electrode, saturated calomel used as a reference electrode and glassy carbon as working electrode at a scan rate of 100 mV/s. The curves recorded the oxidation ofmore » 0.5 mM compound Zn-Porphyrin in a dichloromethane solution containing 0.1M TBAP as supporting electrolyte, reveal two successive quasi reversible redox couples with the first anodic and cathodic peak potentials of -0.2 V and -1 V. The second anodic and cathodic peak potentials are 0.82 V and 0.01 V respectively.« less

Electrochemical Migration Behavior of Copper-Clad Laminate and Electroless Nickel/Immersion Gold Printed Circuit Boards under Thin Electrolyte Layers

PubMed Central

Yi, Pan; Xiao, Kui; Ding, Kangkang; Dong, Chaofang; Li, Xiaogang

2017-01-01

The electrochemical migration (ECM) behavior of copper-clad laminate (PCB-Cu) and electroless nickel/immersion gold printed circuit boards (PCB-ENIG) under thin electrolyte layers of different thicknesses containing 0.1 M Na2SO4 was studied. Results showed that, under the bias voltage of 12 V, the reverse migration of ions occurred. For PCB-Cu, both copper dendrites and sulfate precipitates were found on the surface of FR-4 (board material) between two plates. Moreover, the Cu dendrite was produced between the two plates and migrated toward cathode. Compared to PCB-Cu, PCB-ENIG exhibited a higher tendency of ECM failure and suffered from seriously short circuit failure under high relative humidity (RH) environment. SKP results demonstrated that surface potentials of the anode plates were greater than those of the cathode plates, and those potentials of the two plates exhibited a descending trend as the RH increased. At the end of the paper, an electrochemical migration corrosion failure model of PCB was proposed. PMID:28772497

Reduced graphene oxide supported highly porous V2O5 spheres as a high-power cathode material for lithium ion batteries.

PubMed

Rui, Xianhong; Zhu, Jixin; Sim, Daohao; Xu, Chen; Zeng, Yi; Hng, Huey Hoon; Lim, Tuti Mariana; Yan, Qingyu

2011-11-01

Reduced graphene oxide (rGO) supported highly porous polycrystalline V(2)O(5) spheres (V(2)O(5)/rGO) were prepared by using a solvothermal approach followed by an annealing process. Initially, reduced vanadium oxide (rVO) nanoparticles with sizes in the range of 10-50 nm were formed through heterogeneous nucleation on rGO sheets during the solvothermal process. These rVO nanoparticles were oxidized to V(2)O(5) after the annealing process in air at 350 °C and assembled into polycrystalline porous spheres with sizes of 200-800 nm. The weight ratio between the rGO and V(2)O(5) is tunable by changing the weight ratio of the precursors, which in turn affects the morphology of V(2)O(5)/rGO composites. The V(2)O(5)/rGO composites display superior cathode performances with highly reversible specific capacities, good cycling stabilities and excellent rate capabilities (e.g. 102 mA h g(-1) at 19 C).

In situ atomic force microscopy analysis of morphology and particle size changes in lithium iron phosphate cathode during discharge.

PubMed

Demirocak, Dervis Emre; Bhushan, Bharat

2014-06-01

Li-ion batteries offer great promise for future plug-in hybrid electric vehicles (PHEVs) and pure electric vehicles (EVs). One of the challenges is to improve the cycle life of Li-ion batteries which requires detailed understanding of the aging phenomenon. In situ techniques are especially valuable to understand aging since it allows monitoring the physical and chemical changes in real time. In this study, in situ atomic force microscopy (AFM) is utilized to study the changes in morphology and particle size of LiFePO4 cathode during discharge. The guidelines for in situ AFM cell design for accurate and reliable measurements based on different designs are presented. The effect of working electrode to counter electrode surface area ratio on cycling data of an in situ cell is also discussed. Analysis of the surface area change in LiFePO4 particles when the cell was cycled between 100% and 70% state of charge is presented. Among four particles analyzed, surface area increase of particles during Li intercalation of LiFePO4 spanned from 1.8% to 14.3% indicating the inhomogeneous nature of the cathode surface. Copyright © 2014 Elsevier Inc. All rights reserved.

Incorporating Sulfur Inside the Pores of Carbons for Advanced Lithium-Sulfur Batteries: An Electrolysis Approach.

PubMed

He, Bin; Li, Wen-Cui; Yang, Chao; Wang, Si-Qiong; Lu, An-Hui

2016-01-26

We have developed an electrolysis approach that allows effective and uniform incorporation of sulfur inside the micropores of carbon nanosheets for advanced lithium-sulfur batteries. The sulfur-carbon hybrid can be prepared with a 70 wt % sulfur loading, in which no nonconductive sulfur agglomerations are formed. Because the incorporated sulfur is electrically connected to the carbon matrix in nature, the hybrid cathode shows excellent electrochemical performance, including a high reversible capacity, good rate capability, and good cycling stability, as compared to one prepared using the popular melt-diffusion method.

Hierarchically porous carbon derived from banana peel for lithium sulfur battery with high areal and gravimetric sulfur loading

NASA Astrophysics Data System (ADS)

Li, Fanqun; Qin, Furong; Zhang, Kai; Fang, Jing; Lai, Yanqing; Li, Jie

2017-09-01

Facile and sustainable route is developed to convert biomass into hierarchically porous carbon matrix cooperating with highly conductive graphene. By tailoring the porosity of the carbon matrix to promote fast mass transfer and cooperating highly conductive interconnected graphene frameworks to accelerate the electron transport, the carbon sulfur cathodes simultaneously achieve high areal and gravimetric sulfur loading/content (6 mg cm-2/67 wt%) and deliver outstanding electrochemical performance. After 100 cyclic discharge-charge test at the current density of 0.2 C, the reversible capacity maintains at 707 mA h g-1.

Electrochemical methods for generation of a biological proton motive force

DOEpatents

Zeikus, Joseph Gregory [Okemos, MI; Shin, Hyoun S [Lansing, MI; Jain, Mahendra K [Lexington, KY

2008-12-02

Disclosed are methods using neutral red to mediate the interconversion of chemical and electrical energy. Electrically reduced neutral red has been found to promote cell growth and formation of reduced products by reversibly increasing the ratio of the reduced:oxidized forms of NAD(H) or NADP(H). Electrically reduced neutral red is able to serve as the sole source of reducing power for microbial cell growth. Neutral red is also able to promote conversion of chemical energy to electrical energy by facilitating the transfer of electrons from microbial reducing power to a fuel cell cathode.

Electrochemical methods for generation of a biological proton motive force and pyridine nucleotide cofactor regeneration

DOEpatents

Zeikus, Gregory J.; Shin, Hyoun S.; Jain, Mahendra K.

2002-01-01

Disclosed are methods using neutral red to mediate the interconversion of chemical and electrical energy. Electrically reduced neutral red has been found to promote cell growth and formation of reduced products by reversibly increasing the ratio of the reduced:oxidized forms of NAD(H) or NADP(H). Electrically reduced neutral red is able to serve as the sole source of reducing power for microbial, cell growth. Neutral red is also able to promote conversion of chemical energy to electrical energy by facilitating the transfer of electrons from microbial reducing power to a fuel cell cathode.

Electrochemical methods for generation of a biological proton motive force and pyridine nucleotide cofactor regeneration

DOEpatents

Zeikus, Joseph G.; Park, Doo

2001-01-01

Disclosed are methods using neutral red to mediate the interconversion of chemical and electrical energy. Electrically reduced neutral red has been found to promote cell growth and formation of reduced products by reversibly increasing the ratio of the reduced:oxidized forms of NAD(H) or NADP(H). Electrically reduced neutral red is able to serve as the sole source of reducing power for microbial cell growth. Neutral red is also able to promote conversion of chemical energy to electrical energy by facilitating the transfer of electrons from microbial reducing power to a fuel cell cathode.

Thermal diffusivity study of aged Li-ion batteries using flash method

NASA Astrophysics Data System (ADS)

Nagpure, Shrikant C.; Dinwiddie, Ralph; Babu, S. S.; Rizzoni, Giorgio; Bhushan, Bharat; Frech, Tim

Advanced Li-ion batteries with high energy and power density are fast approaching compatibility with automotive demands. While the mechanism of operation of these batteries is well understood, the aging mechanisms are still under investigation. Investigation of aging mechanisms in Li-ion batteries becomes very challenging, as aging does not occur due to a single process, but because of multiple physical processes occurring at the same time in a cascading manner. As the current characterization techniques such as Raman spectroscopy, X-ray diffraction, and atomic force microscopy are used independent of each other they do not provide a comprehensive understanding of material degradation at different length (nm 2 to m 2) scales. Thus to relate the damage mechanisms of the cathode at mm length scale to micro/nanoscale, data at an intermediate length scale is needed. As such, we demonstrate here the use of thermal diffusivity analysis by flash method to bridge the gap between different length scales. In this paper we present the thermal diffusivity analysis of an unaged and aged cell. Thermal diffusivity analysis maps the damage to the cathode samples at millimeter scale lengths. Based on these maps we also propose a mechanism leading to the increase of the thermal diffusivity as the cells are aged.

High-energy lithium-ion hybrid supercapacitors composed of hierarchical urchin-like WO3/C anodes and MOF-derived polyhedral hollow carbon cathodes.

PubMed

Xu, Juan; Li, Yuanyuan; Wang, Lei; Cai, Qifa; Li, Qingwei; Gao, Biao; Zhang, Xuming; Huo, Kaifu; Chu, Paul K

2016-09-22

A lithium-ion hybrid supercapacitor (Li-HSC) comprising a Li-ion battery type anode and an electrochemical double layer capacitance (EDLC) type cathode has attracted much interest because it accomplishes a large energy density without compromising the power density. In this work, hierarchical carbon coated WO 3 (WO 3 /C) with a unique mesoporous structure and metal-organic framework derived nitrogen-doped carbon hollow polyhedra (MOF-NC) are prepared and adopted as the anode and the cathode for Li-HSCs. The hierarchical mesoporous WO 3 /C microspheres assembled by radially oriented WO 3 /C nanorods along the (001) plane enable effective Li + insertion, thus exhibit high capacity, excellent rate performance and a long cycling life due to their high Li + conductivity, electronic conductivity and structural robustness. The WO 3 /C structure shows a reversible specific capacity of 508 mA h g -1 at a 0.1 C rate (1 C = 696 mA h g -1 ) after 160 discharging-charging cycles with excellent rate capability. The MOF-NC achieved the specific capacity of 269.9 F g -1 at a current density of 0.2 A g -1 . At a high current density of 6 A g -1 , 92.4% of the initial capacity could be retained after 2000 discharging-charging cycles, suggesting excellent cycle stability. The Li-HSC comprising a WO 3 /C anode and a MOF-NC cathode boasts a large energy density of 159.97 W h kg -1 at a power density of 173.6 W kg -1 and 88.3% of the capacity is retained at a current density of 5 A g -1 after 3000 charging-discharging cycles, which are better than those previously reported for Li-HSCs. The high energy and power densities of the Li-HSCs of WO 3 /C//MOF-NC render large potential in energy storage.

In-situ Raman spectroscopic investigation of LiMn1.45Ni0.45M0.1O4 (M = Cr, Co) 5 V cathode materials

NASA Astrophysics Data System (ADS)

Zhu, W.; Liu, D.; Trottier, J.; Gagnon, C.; Howe, J.; Mauger, A.; Julien, C. M.; Zaghib, K.

2015-12-01

In-situ Raman spectroscopy is employed to investigate the valence state variations of nickel and manganese, as well as the local structure change of LiMn1.45Ni0.45M0.1O4 (M = Cr, Co) cathodes (LMN) during galvanostatic charge-discharge. Raman spectra are collected between 3.5 and 4.9 V in the wave number range of 100-800 cm-1. The Raman observations showed that the pristine cathodes of Cr- and Co-doped LMN have essentially the same spectra, and they also have similar evolution patterns during cycling showing their reversible behaviour in the de-lithiation and lithiation processes. The Raman spectra of the pristine cathodes have eleven bands, located at 162, 220, 378, 408, 486, 498, 528, 593, 613, 639 and 672 cm-1. The bands with wave number <300 cm-1 are attributed to the translation mode of molecular vibration; the 486, 593 and 639 cm-1 bands are assigned to the stretching mode of Mn-O bond; and the vibration modes at 408, 498, 528 and 613 cm-1 originated from the Ni-O bond; The band at 672 cm-1 is attributed to A1g mode of Cr3+-O/Co3+-O. During cycling, several new bands are detected near the end of charge, among which the T2g(T) band at 170 cm-1 is attributed to the translation mode of lattice vibration in which the lithium concentration is low, and the T2g band at 538 cm-1 is due to the presence of Ni4+-O bond in the crystal structure. The T2g(T) and T2g(Ni4+-O) bands are clearly evident at V ≥ 4.78 (x ∼ 0.32) and V ≥ 4.82 (x ∼ 0.28) for Cr- and Co-doped LMN, respectively.

High pH instability of quaternary ammonium surfactant coatings in capillary electrophoresis.

PubMed

Shulman, Lisa; Pei, Lei; Bahnasy, Mahmoud F; Lucy, Charles A

2017-06-12

The two-tailed cationic surfactant dioctadecyldimethyl ammonium bromide (DODAB) produces semi-permanent coatings that yield strongly reversed electroosmotic flow (EOF), for example -0.31 ± 0.01 cm 2 kV -1 s -1 at pH 3.5. Moreover, these coatings are easy to prepare, regenerable, cost effective, and yield high efficiency (520 000-900 000 plates per m) separations of cationic proteins over many runs under acidic (pH 3.5) conditions. Given the quaternary amine functionality of DODAB, we were surprised to observe that DODAB coatings become unstable at pH > 7. At pH 7.2, the EOF of a DODAB coated capillary drifted from reversed to cathodic over only 5 runs, and protein separations became severely compromised. By pH 12, no EOF reversal was observed. Electrophoretic and mass spectrometric studies demonstrate that the coating decomposition involves a surface conversion of the quaternary amine in DODAB to a variety of products, although the exact mechanism remains elusive. Regardless, the results herein demonstrate that semi-permanent coatings based on cationic two-tailed surfactants such as DODAB are limited to separations using acidic buffers.

Reverse microemulsion synthesis of nickel-cobalt hexacyanoferrate/reduced graphene oxide nanocomposites for high-performance supercapacitors and sodium ion batteries

NASA Astrophysics Data System (ADS)

Qiu, Xiaoming; Liu, Yongchang; Wang, Luning; Fan, Li-Zhen

2018-03-01

Prussian blue analogues with tunable open channels are of fundamental and technological importance for energy storage systems. Herein, a novel facile synthesis of nickel-cobalt hexacyanoferrate/reduced graphene oxide (denoted as Ni-CoHCF/rGO) nanocomposite is realized by a reverse microemulsion method. The very fine Ni-CoHCF nanoparticles (10-20 nm) are homogeneously anchored on the surface of reduced graphene oxide by electrostatic adsorption and reduced graphene oxide is well-separated by Ni-CoHCF particles. Benefiting from the combined advantages of this structure, the Ni-. It CoHCF/rGO nanocomposite can be used as electrodes for both supercapacitors and sodium ion batteries exhibits excellent pseudocapacitve performance in terms of high specific capacitance of 466 F g-1 at 0.2 A g-1 and 350 F g-1 at 10 A g-1, along with high cycling stabilities. As a cathode material for sodium ion batteries, it also demonstrates a high reversible capacity of 118 mAh g-1 at 0.1 A g-1, good rate capability, and superior cycling stability. These results suggest its potential as an efficient electrode for high-performance energy storage and renewable delivery devices.

Porous V2O5/RGO/CNT hierarchical architecture as a cathode material: Emphasis on the contribution of surface lithium storage

PubMed Central

Palanisamy, Kowsalya; Um, Ji Hyun; Jeong, Mihee; Yoon, Won-Sub

2016-01-01

A three dimensional vanadium pentoxide/reduced graphene oxide/carbon nanotube (3D V2O5/RGO/CNT) composite is synthesized by microwave-assisted hydrothermal method. The combination of 2D RGO and 1D CNT establishes continuous 3D conductive network, and most notably, the 1D CNT is designed to form hierarchically porous structure by penetrating into V2O5 microsphere assembly constituted of numerous V2O5 nanoparticles. The highly porous V2O5 microsphere enhances electrolyte contact and shortens Li+ diffusion path as a consequence of its developed surface area and mesoporosity. The successive phase transformations of 3D V2O5/RGO/CNT from α-phase to ε-, δ-, γ-, and ω-phase and its structural reversibility upon Li+ intercalation/de-intercalation are investigated by in situ XRD analysis, and the electronic and local structure reversibility around vanadium atom in 3D V2O5/RGO/CNT is observed by in situ XANES analysis. The 3D V2O5/RGO/CNT achieves a high capacity of 220 mAh g−1 at 1 C after 80 cycles and an excellent rate capability of 100 mAh g−1 even at a considerably high rate of 20 C. The porous 3D V2O5/RGO/CNT structure not only provides facile Li+ diffusion into bulk but contributes to surface Li+ storage as well, which enables the design of 3D V2O5/RGO/CNT composite to become a promising cathode architecture for high performance LIBs. PMID:27511434

Hydrothermal synthesis and characterization of vanadyl phosphate based cathode materials for lithium ion batteries

NASA Astrophysics Data System (ADS)

Chung, Youngmin

Transition metal phosphate materials have been researched as candidates for lithium-ion battery cathodes for about two decades. Among them, vanadium phosphate compounds are attractive due to their higher free energy of reaction than the corresponding iron compounds, and the greater possible change of oxidation state from V5+ to V3+. This thesis work firstly focuses on the chemical and electrochemical lithiation of epsilon--VOPO4 investigating the possibility of multi-electron intercalation. The second focus is on hydrothermal synthesis and characterization of epsilon--LiVOPO4. The hydrothermal synthesis method developed in this work produces pure epsilon-LiVOPO 4 at high temperature hydrothermal reaction and pure LiVOPO4˙2H 2O at low temperature. The first charge capacity of hydrothermal epsilon-LiVOPO 4 is around 308 mAh/g, which is almost 97% of the theoretical capacity. It also shows good reversibility in the first five cycles after which capacity fading occurs. For more detailed structural analysis of hydrothermal epsilon-LiVOPO 4, we used in-situ synchrotron XRD and EXAFS upon heating combined with TGA-MS. These techniques have revealed intercalated protons that are removed at about 350 °C, and a reversible symmetry change from triclinic to monoclinic at high temperature. Furthermore, we have used chemical lithiation with BuLi to produce and characterize epsilon-Li2VOPO 4 phase. Finally, we have modified the hydrothermal method to produce Cr-substituted epsilon--LiVOPO4 by changing the amount LiOH and adding Cr precursor. Cr substitution is found to modify the stoichiometry of the compound and to improve its cyclability at both high and low current densities.

Direct Evidence of Solution-Mediated Superoxide Transport and Organic Radical Formation in Sodium-Oxygen Batteries.

PubMed

Xia, Chun; Fernandes, Russel; Cho, Franklin H; Sudhakar, Niranjan; Buonacorsi, Brandon; Walker, Sean; Xu, Meng; Baugh, Jonathan; Nazar, Linda F

2016-09-07

Advanced large-scale electrochemical energy storage requires cost-effective battery systems with high energy densities. Aprotic sodium-oxygen (Na-O2) batteries offer advantages, being comprised of low-cost elements and possessing much lower charge overpotential and higher reversibility compared to their lithium-oxygen battery cousins. Although such differences have been explained by solution-mediated superoxide transport, the underlying nature of this mechanism is not fully understood. Water has been suggested to solubilize superoxide via formation of hydroperoxyl (HO2), but direct evidence of these HO2 radical species in cells has proven elusive. Here, we use ESR spectroscopy at 210 K to identify and quantify soluble HO2 radicals in the electrolyte-cold-trapped in situ to prolong their lifetime-in a Na-O2 cell. These investigations are coupled to parallel SEM studies that image crystalline sodium superoxide (NaO2) on the carbon cathode. The superoxide radicals were spin-trapped via reaction with 5,5-dimethyl-pyrroline N-oxide at different electrochemical stages, allowing monitoring of their production and consumption during cycling. Our results conclusively demonstrate that transport of superoxide from cathode to electrolyte leads to the nucleation and growth of NaO2, which follows classical mechanisms based on the variation of superoxide content in the electrolyte and its correlation with the crystallization of cubic NaO2. The changes in superoxide content upon charge show that charge proceeds through the reverse solution process. Furthermore, we identify the carbon-centered/oxygen-centered alkyl radicals arising from attack of these solubilized HO2 species on the diglyme solvent. This is the first direct evidence of such species, which are likely responsible for electrolyte degradation.

Improved Cycling Stability and Fast Charge-Discharge Performance of Cobalt-Free Lithium-Rich Oxides by Magnesium-Doping.

PubMed

Yi, Ting-Feng; Li, Yan-Mei; Yang, Shuang-Yuan; Zhu, Yan-Rong; Xie, Ying

2016-11-30

Layered Li-rich, Co-free, and Mn-based cathode material, Li 1.17 Ni 0.25-x Mn 0.58 Mg x O 2 (0 ≤ x ≤ 0.05), was successfully synthesized by a coprecipitation method. All prepared samples have typical Li-rich layered structure, and Mg has been doped in the Li 1.17 Ni 0.25 Mn 0.58 O 2 material successfully and homogeneously. The morphology and the grain size of all material are not changed by Mg doping. All materials have a estimated size of about 200 nm with a narrow particle size distribution. The electrochemical property results show that Li 1.17 Ni 0.25-x Mn 0.58 Mg x O 2 (x = 0.01 and 0.02) electrodes exhibit higher rate capability than that of the pristine one. Li 1.17 Ni 0.25-x Mn 0.58 Mg x O 2 (x = 0.02) indicates the largest reversible capacity of 148.3 mAh g -1 and best cycling stability (capacity retention of 95.1%) after 100 cycles at 2C charge-discharge rate. Li 1.17 Ni 0.25-x Mn 0.58 Mg x O 2 (x = 0.02) also shows the largest discharge capacity of 149.2 mAh g -1 discharged at 1C rate at elevated temperature (55 °C) after 50 cycles. The improved electrochemical performances may be attributed to the decreased polarization, reduced charge transfer resistance, enhanced the reversibility of Li + ion insertion/extraction, and increased lithium ion diffusion coefficient. This promising result gives a new understanding for designing the structure and improving the electrochemical performance of Li-rich cathode materials for the next-generation lithium-ion battery with high rate cycling performance.

ELECTRO-DEPOSITION OF NICKEL ALLOYS FROM THE PYROPHOSPHATE BATH: NICKEL- ZINC AND NICKEL-MOLYBDENUM ALLOYS

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

Panikkar, S.K.; Char, T.L.R.

1958-02-01

Results of studies on the electrodeposition of nickel-zinc and nickel-- molybdenum alloys in a pyrophosphate bath using platinium electrodes are presented. The fects of varying current density and metal contents of the electrolyte on alloy deposit composition, cathode efficiency, and cathode potential are presented in tabular form. (J.R.D.) l2432 A study was made of the effect of homogenization on the mechanical properties of solution-treated and aged aluminum and the quantitative effects of several variables on hardness. The effect of alloying elements on the increase in hardness of aluminum is shown. (J.E.D.)

Electron gun for a multiple beam klystron with magnetic compression of the electron beams

DOEpatents

Ives, R. Lawrence; Tran, Hien T; Bui, Thuc; Attarian, Adam; Tallis, William; David, John; Forstall, Virginia; Andujar, Cynthia; Blach, Noah T; Brown, David B; Gadson, Sean E; Kiley, Erin M; Read, Michael

2013-10-01

A multi-beam electron gun provides a plurality N of cathode assemblies comprising a cathode, anode, and focus electrode, each cathode assembly having a local cathode axis and also a central cathode point defined by the intersection of the local cathode axis with the emitting surface of the cathode. Each cathode is arranged with its central point positioned in a plane orthogonal to a device central axis, with each cathode central point an equal distance from the device axis and with an included angle of 360/N between each cathode central point. The local axis of each cathode has a cathode divergence angle with respect to the central axis which is set such that the diverging magnetic field from a solenoidal coil is less than 5 degrees with respect to the projection of the local cathode axis onto a cathode reference plane formed by the device axis and the central cathode point, and the local axis of each cathode is also set such that the angle formed between the cathode reference plane and the local cathode axis results in minimum spiraling in the path of the electron beams in a homogenous magnetic field region of the solenoidal field generator.

Degradation Mechanisms of Magnesium Metal Anodes in Electrolytes Based on (CF 3SO 2) 2N – at High Current Densities

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

Yoo, Hyun Deog; Han, Sang-Don; Bolotin, Igor L.

The energy density of rechargeable batteries utilizing metals as anodes surpasses that of Li ion batteries, which employ carbon instead. Among possible metals, magnesium represents a potential alternative to the conventional choice, lithium, in terms of storage density, safety,stability, and cost. However, a major obstacle for metal-based batteries is the identification of electrolytes that show reversible deposition/dissolution of the metal anode and support reversible intercalation of ions into a cathode. Traditional Grignard-based Mg electrolytes are excellent with respect to the reversible deposition of Mg, but their limited anodic stability and compatibility with oxide cathodes hinder their applicability in Mg batteriesmore » with higher voltage. Non-Grignard electrolytes, which consist of ethereal solutions of magnesium(II) bis(trifluoromethanesulfonyl)imide (Mg(TFSI) 2), remain fairly stable near the potential of Mg deposition. The slight reactivity of these electrolytes toward Mg metal can be remedied by the addition of surface-protecting agents, such as MgCl 2. Hence, ethereal solutions of Mg(TFSI) 2 salt with MgCl 2 as an additive have been suggested as a representative non-Grignard Mg electrolyte. In this work, the degradation mechanisms of a Mg metal anode in the TFSI-based electrolyte were studied using a current density of 1 mA cm -2 and an areal capacity of ~0.4 mAh cm -2, which is close to those used in practical applications. The degradation mechanisms identified include the corrosion of Mg metal, which causes the loss of electronic pathways and mechanical integrity, the nonuniform deposition of Mg, and the decomposition of TFSI - anions. This study not only represents an assessment of the behavior of Mg metal anodes at practical current density and areal capacity but also details the outcomes of interfacial passivation, which was detected by simple cyclic voltammetry experiments. This study also points out the absolute absence of any passivation at the electrode-electrolyte interface for the premise of developing electrolytes compatible with a metal anode.« less

Degradation Mechanisms of Magnesium Metal Anodes in Electrolytes Based on (CF 3SO 2) 2N – at High Current Densities

DOE PAGES

Yoo, Hyun Deog; Han, Sang-Don; Bolotin, Igor L.; ...

2017-06-21

The energy density of rechargeable batteries utilizing metals as anodes surpasses that of Li ion batteries, which employ carbon instead. Among possible metals, magnesium represents a potential alternative to the conventional choice, lithium, in terms of storage density, safety,stability, and cost. However, a major obstacle for metal-based batteries is the identification of electrolytes that show reversible deposition/dissolution of the metal anode and support reversible intercalation of ions into a cathode. Traditional Grignard-based Mg electrolytes are excellent with respect to the reversible deposition of Mg, but their limited anodic stability and compatibility with oxide cathodes hinder their applicability in Mg batteriesmore » with higher voltage. Non-Grignard electrolytes, which consist of ethereal solutions of magnesium(II) bis(trifluoromethanesulfonyl)imide (Mg(TFSI) 2), remain fairly stable near the potential of Mg deposition. The slight reactivity of these electrolytes toward Mg metal can be remedied by the addition of surface-protecting agents, such as MgCl 2. Hence, ethereal solutions of Mg(TFSI) 2 salt with MgCl 2 as an additive have been suggested as a representative non-Grignard Mg electrolyte. In this work, the degradation mechanisms of a Mg metal anode in the TFSI-based electrolyte were studied using a current density of 1 mA cm -2 and an areal capacity of ~0.4 mAh cm -2, which is close to those used in practical applications. The degradation mechanisms identified include the corrosion of Mg metal, which causes the loss of electronic pathways and mechanical integrity, the nonuniform deposition of Mg, and the decomposition of TFSI - anions. This study not only represents an assessment of the behavior of Mg metal anodes at practical current density and areal capacity but also details the outcomes of interfacial passivation, which was detected by simple cyclic voltammetry experiments. This study also points out the absolute absence of any passivation at the electrode-electrolyte interface for the premise of developing electrolytes compatible with a metal anode.« less

Designer interphases for the lithium-oxygen electrochemical cell

PubMed Central

Choudhury, Snehashis; Wan, Charles Tai-Chieh; Al Sadat, Wajdi I.; Tu, Zhengyuan; Lau, Sampson; Zachman, Michael J.; Kourkoutis, Lena F.; Archer, Lynden A.

2017-01-01

An electrochemical cell based on the reversible oxygen reduction reaction: 2Li+ + 2e− + O2 ↔ Li2O2, provides among the most energy dense platforms for portable electrical energy storage. Such Lithium-Oxygen (Li-O2) cells offer specific energies competitive with fossil fuels and are considered promising for electrified transportation. Multiple, fundamental challenges with the cathode, anode, and electrolyte have limited practical interest in Li-O2 cells because these problems lead to as many practical shortcomings, including poor rechargeability, high overpotentials, and specific energies well below theoretical expectations. We create and study in-situ formation of solid-electrolyte interphases (SEIs) based on bromide ionomers tethered to a Li anode that take advantage of three powerful processes for overcoming the most stubborn of these challenges. The ionomer SEIs are shown to protect the Li anode against parasitic reactions and also stabilize Li electrodeposition during cell recharge. Bromine species liberated during the anchoring reaction also function as redox mediators at the cathode, reducing the charge overpotential. Finally, the ionomer SEI forms a stable interphase with Li, which protects the metal in high Gutmann donor number liquid electrolytes. Such electrolytes have been reported to exhibit rare stability against nucleophilic attack by Li2O2 and other cathode reaction intermediates, but also react spontaneously with Li metal anodes. We conclude that rationally designed SEIs able to regulate transport of matter and ions at the electrolyte/anode interface provide a promising platform for addressing three major technical barriers to practical Li-O2 cells. PMID:28439557

In Situ Probing and Synthetic Control of Cationic Ordering in Ni-Rich Layered Oxide Cathodes

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

Zhao, Jianqing; Zhang, Wei; Huq, Ashfia

Ni-rich layered oxides (LiNi 1-xM xO 2; M=Co, Mn, …) are appealing alternatives to conventional LiCoO 2 as cathodes in Li-ion batteries for automobile and other large-scale applications due to their high theoretical capacity and low cost. However, preparing stoichiometric LiNi 1-xM xO 2 with ordered layer structure and high reversible capacity, has proven difficult due to Ni 2+/Li + cation mixing in octahedral sites. Herein, we report on in-situ studies of synthesis reactions and the associated structural ordering in preparing LiNiO 2 and the Co-substituted variant, LiNi 0.8Co 0.2O 2, thereby gaining insights into synthetic control of the structuremore » and electrochemical properties of Ni-rich layered oxides. Results from this study indicate a direct transformation of the intermediate from the rock salt structure into hexagonal phase, and during the process, Co substitution facilities the nucleation of a Co-rich layered phase at low temperatures and subsequent growth and stabilization of solid solution Li(Ni, Co)O 2 upon heat treatment in a highly oxidation environment. Optimal conditions were identified from the in-situ studies and utilized in obtaining stoichiometric LiNi 0.8Co 0.2O 2 that exhibits high capacity of about 200 mAh/g with excellent retention. The findings shed light on designing Ni-rich layered oxide cathodes with enhanced electrochemical properties through synthetic control of the structural ordering in the materials.« less

Electrical stimulation modulates injury potentials in rats after spinal cord injury

PubMed Central

Zhang, Guanghao; Huo, Xiaolin; Wang, Aihua; Wu, Changzhe; Zhang, Cheng; Bai, Jinzhu

2013-01-01

An injury potential is the direct current potential difference between the site of spinal cord injury and the healthy nerves. Its initial amplitude is a significant indicator of the severity of spinal cord injury, and many cations, such as sodium and calcium, account for the major portion of injury potentials. This injury potential, as well as injury current, can be modulated by direct current field stimulation; however, the appropriate parameters of the electrical field are hard to define. In this paper, injury potential is used as a parameter to adjust the intensity of electrical stimulation. Injury potential could be modulated to slightly above 0 mV (as the anode-centered group) by placing the anodes at the site of the injured spinal cord and the cathodes at the rostral and caudal sections, or around –70 mV, which is resting membrane potential (as the cathode-centered group) by reversing the polarity of electrodes in the anode-centered group. In addition, rats receiving no electrical stimulation were used as the control group. Results showed that the absolute value of the injury potentials acquired after 30 minutes of electrical stimulation was higher than the control group rats and much lower than the initial absolute value, whether the anodes or the cathodes were placed at the site of injury. This phenomenon illustrates that by changing the polarity of the electrical field, electrical stimulation can effectively modulate the injury potentials in rats after spinal cord injury. This is also beneficial for the spontaneous repair of the cell membrane and the reduction of cation influx. PMID:25206563

The posterior parietal cortex (PPC) mediates anticipatory motor control.

PubMed

Krause, Vanessa; Weber, Juliane; Pollok, Bettina

2014-01-01

Flexible and precisely timed motor control is based on functional interaction within a cortico-subcortical network. The left posterior parietal cortex (PPC) is supposed to be crucial for anticipatory motor control by sensorimotor feedback matching. Intention of the present study was to disentangle the specific relevance of the left PPC for anticipatory motor control using transcranial direct current stimulation (tDCS) since a causal link remains to be established. Anodal vs. cathodal tDCS was applied for 10 min over the left PPC in 16 right-handed subjects in separate sessions. Left primary motor cortex (M1) tDCS served as control condition and was applied in additional 15 subjects. Prior to and immediately after tDCS, subjects performed three tasks demanding temporal motor precision with respect to an auditory stimulus: sensorimotor synchronization as measure of anticipatory motor control, interval reproduction and simple reaction. Left PPC tDCS affected right hand synchronization but not simple reaction times. Motor anticipation was deteriorated by anodal tDCS, while cathodal tDCS yielded the reverse effect. The variability of interval reproduction was increased by anodal left M1 tDCS, whereas it was reduced by cathodal tDCS. No significant effects on simple reaction times were found. The present data support the hypothesis that left PPC is causally involved in right hand anticipatory motor control exceeding pure motor implementation as processed by M1 and possibly indicating subjective timing. Since M1 tDCS particularly affects motor implementation, the observed PPC effects are not likely to be explained by alterations of motor-cortical excitability. Copyright © 2014 Elsevier Inc. All rights reserved.

Superposed Redox Chemistry of Fused Carbon Rings in Cyclooctatetraene-Based Organic Molecules for High-Voltage and High-Capacity Cathodes.

PubMed

Zhao, Xiaolin; Qiu, Wujie; Ma, Chao; Zhao, Yingqin; Wang, Kaixue; Zhang, Wenqing; Kang, Litao; Liu, Jianjun

2018-01-24

Even though many organic cathodes have been developed and have made a significant improvement in energy density and reversibility, some organic materials always generate relatively low voltage and limited discharge capacity because their energy storage mechanism is solely based on redox reactions of limited functional groups [N-O, C═X (X = O, N, S)] linking to aromatic rings. Here, a series of cyclooctatetraene-based (C 8 H 8 ) organic molecules were demonstrated to have electrochemical activity of high-capacity and high-voltage from carbon rings by means of first-principles calculations and electronic structure analysis. Fused molecules of C 8 -C 4 -C 8 (C 16 H 12 ) and C 8 -C 4 -C 8 -C 4 -C 8 (C 24 H 16 ) contain, respectively, four and eight electron-deficient carbons, generating high-capacity by their multiple redox reactions. Our sodiation calculations predict that C 16 H 12 and C 24 H 16 exhibit discharge capacities of 525.3 and 357.2 mA h g -1 at the voltage change from 3.5 to 1.0 V and 3.7 to 1.3 V versus Na + /Na, respectively. Electronic structure analysis reveals that the high voltages are attributed to superposed electron stabilization mechanisms, including double-bond reformation and aromatization from carbon rings. High thermodynamic stability of these C 24 H 16 -based systems strongly suggests feasibility of experimental realization. The present work provides evidence that cyclooctatetraene-based organic molecules fused with the C 4 ring are promising in designing high-capacity and high-voltage organic rechargeable cathodes.

Effect of transcranial direct current stimulation (tDCS) during complex whole body motor skill learning.

PubMed

Kaminski, Elisabeth; Hoff, Maike; Sehm, Bernhard; Taubert, Marco; Conde, Virginia; Steele, Christopher J; Villringer, Arno; Ragert, Patrick

2013-09-27

The aim of the study was to investigate tDCS effects on motor skill learning in a complex whole body dynamic balance task (DBT). We hypothesized that tDCS over the supplementary motor area (SMA), a region that is known to be involved in the control of multi-joint whole body movements, will result in polarity specific changes in DBT learning. In a randomized sham-controlled, double-blinded parallel design, we applied 20 min of tDCS over the supplementary motor area (SMA) and prefrontal cortex (PFC) while subjects performed a DBT. Anodal tDCS over SMA with the cathode placed over contralateral PFC impaired motor skill learning of the DBT compared to sham. This effect was still present on the second day of training. Reversing the polarity (cathode over SMA, anode over PFC) did not affect motor skill learning neither on the first nor on the second day of training. To better disentangle whether the impaired motor skill learning was due to a modulation of SMA or PFC, we performed an additional control experiment. Here, we applied anodal tDCS over SMA together with a larger and presumably more ineffective electrode (cathode) over PFC. Interestingly this alternative tDCS electrode setup did not affect the outcome of DBT learning. Our results provide novel evidence that a modulation of the (right) PFC seems to impair complex multi-joint motor skill learning. Hence, future studies should take the positioning of both tDCS electrodes into account when investigating complex motor skill learning. Copyright © 2013 Elsevier Ireland Ltd. All rights reserved.

Study of CO 2 stability and electrochemical oxygen activation of mixed conductors with low thermal expansion coefficient based on the TbBaCo 3ZnO 7+ δ system

NASA Astrophysics Data System (ADS)

Vert, Vicente B.; Serra, José M.

The influence of different application-oriented factors on the electrochemical activity and stability of TbBaCo 3ZnO 7+ δ when used as a solid oxide fuel cell cathode has been studied. Calcination at temperatures above 900 °C (e.g. 1000 °C) leads to a significant increase in the electrode polarization resistance. The effect of the sintering temperature of the TbBaCo 3ZnO 7+ δ cathode seems to be more important than the effect produced by the Tb substitution as observed when compared with 900 °C-sintered YBaCo 3ZnO 7+ δ; and ErBaCo 3ZnO 7+ δ electrode performances. The presence of CO 2 in the air flow leads to an increase of roughly 10% in the polarization resistance for the whole studied temperature range (500-850 °C) while this effect is reversible. Analysis of the impedance spectroscopy measurements shows that the exchange rate constant (k G from Gerischer element) is significantly affected by CO 2 at temperatures below 700 °C, while the diffusion coefficient related parameter is slightly influenced at low temperatures. Electrode degrades with a low constant rate of 1 mΩ cm 2 h -1 after 60 h. This cathode material exhibits high CO 2 tolerance, as shown by temperature programmed treatment under a continuous gas flow of air with 5% CO 2, and a relatively low thermal expansion coefficient.

In Situ Probing and Synthetic Control of Cationic Ordering in Ni-Rich Layered Oxide Cathodes

DOE PAGES

Zhao, Jianqing; Zhang, Wei; Huq, Ashfia; ...

2016-10-17

Ni-rich layered oxides (LiNi 1-xM xO 2; M=Co, Mn, …) are appealing alternatives to conventional LiCoO 2 as cathodes in Li-ion batteries for automobile and other large-scale applications due to their high theoretical capacity and low cost. However, preparing stoichiometric LiNi 1-xM xO 2 with ordered layer structure and high reversible capacity, has proven difficult due to Ni 2+/Li + cation mixing in octahedral sites. Herein, we report on in-situ studies of synthesis reactions and the associated structural ordering in preparing LiNiO 2 and the Co-substituted variant, LiNi 0.8Co 0.2O 2, thereby gaining insights into synthetic control of the structuremore » and electrochemical properties of Ni-rich layered oxides. Results from this study indicate a direct transformation of the intermediate from the rock salt structure into hexagonal phase, and during the process, Co substitution facilities the nucleation of a Co-rich layered phase at low temperatures and subsequent growth and stabilization of solid solution Li(Ni, Co)O 2 upon heat treatment in a highly oxidation environment. Optimal conditions were identified from the in-situ studies and utilized in obtaining stoichiometric LiNi 0.8Co 0.2O 2 that exhibits high capacity of about 200 mAh/g with excellent retention. The findings shed light on designing Ni-rich layered oxide cathodes with enhanced electrochemical properties through synthetic control of the structural ordering in the materials.« less

Fast formation cycling for lithium ion batteries

DOE PAGES

An, Seong Jin; Li, Jianlin; Du, Zhijia; ...

2017-01-09

The formation process for lithium ion batteries typically takes several days or more, and it is necessary for providing a stable solid electrolyte interphase on the anode (at low potentials vs. Li/Li +) for preventing irreversible consumption of electrolyte and lithium ions. An analogous layer known as the cathode electrolyte interphase layer forms at the cathode at high potentials vs. Li/Li +. However, several days, or even up to a week, of these processes result in either lower LIB production rates or a prohibitively large size of charging-discharging equipment and space (i.e. excessive capital cost). In this study, a fastmore » and effective electrolyte interphase formation protocol is proposed and compared with an Oak Ridge National Laboratory baseline protocol. Graphite, NMC 532, and 1.2 M LiPF 6 in ethylene carbonate: diethyl carbonate were used as anodes, cathodes, and electrolytes, respectively. Finally, results from electrochemical impedance spectroscopy show the new protocol reduced surface film (electrolyte interphase) resistances, and 1300 aging cycles show an improvement in capacity retention.« less

Ion and gas chromatography mass spectrometry investigations of organophosphates in lithium ion battery electrolytes by electrochemical aging at elevated cathode potentials

NASA Astrophysics Data System (ADS)

Weber, Waldemar; Wagner, Ralf; Streipert, Benjamin; Kraft, Vadim; Winter, Martin; Nowak, Sascha

2016-02-01

The electrochemical aging of commercial non-aqueous lithium hexafluorophosphate (LiPF6)/organic carbonate solvent based lithium ion battery electrolyte has been investigated in view of the formation of ionic and non-ionic alkylated phosphates. Subject was a solvent mixture of ethylene carbonate/ethyl methyl carbonate EC:EMC (1:1, by wt.) with 1 M LiPF6 (LP50 Selectilyte™, BASF). The analysis was carried out by ion chromatography coupled with electrospray ionization mass spectrometry (ESI-MS) for ionic compounds and (headspace) gas chromatography mass spectrometry ((HS)-GC-MS) for non-ionic compounds. The electrochemical aging was performed by galvanostatic charge/discharge cycling and potentiostatic experiments with LiNi0.5Mn1.5O4 (LMNO) as cathode material at increased cut-off potentials (>4.5 V vs. Li/Li+). A strong dependence of the formation of organophosphates on the applied electrode potential was observed and investigated by quantitative analysis of the formed phosphates. In addition, new possible ;fingerprint; compounds for describing the electrolyte status were investigated and compared to existing compounds.

Lithium ion batteries (NMC/graphite) cycling at 80 °C: Different electrolytes and related degradation mechanism

NASA Astrophysics Data System (ADS)

Genieser, R.; Ferrari, S.; Loveridge, M.; Beattie, S. D.; Beanland, R.; Amari, H.; West, G.; Bhagat, R.

2018-01-01

A comprehensive study on high temperature cycling (80 °C) of industrial manufactured Li-ion pouch cells (NMC-111/Graphite) filled with different electrolytes is introduced. Ageing processes such as capacity fade, resistance increase and gas generation are reduced by the choice of appropriate electrolyte formulations. However, even by using additive formulations designed for elevated temperatures a large resistance increase is observed after 200 cycles and more (which does not happen at 55 °C). Symmetrical EIS (Electrochemical Impedance Spectroscopy) shows that the cathodic charge transfer resistance is the main reason for this behaviour. Nonetheless most of the active Li is still available when cycling with suitable additives. No change of the cathode crystalline structure or a growth of the cathodic surface reconstruction layer is observed post cycling at 80 °C. Therefore a disintegration of NMC secondary particles is believed to be the main reason of the cell failure. A separation of single grains is leading to new decomposition and reconstruction layers between primary particles and an increased charge transfer resistance. Further approaches to improve the high temperature cycle stability of NMC based materials should therefore be aimed at the cathode particles morphology in combination with similar electrolyte formulations as used in this study.

Ageing and spatial reversal learning in humans: findings from a virtual water maze.

PubMed

Schoenfeld, R; Foreman, N; Leplow, B

2014-08-15

Deterioration in spatial memory with normal ageing is well accepted. Animal research has shown spatial reversal learning to be most vulnerable to pathological changes in the brain, but this has never been tested in humans. We studied ninety participants (52% females, 20-80 yrs) in a virtual water maze with a reversal learning procedure. Neuropsychological functioning, mood and personality were assessed to control moderator effects. For data analysis, participants were subdivided post hoc into groups aged 20-24, 25-34, 35-44, 45-64 and 65-80 yrs. Initial spatial learning occurred in all age groups but 65-80-yrs-olds never reached the level of younger participants. When tested for delayed recall of spatial memory, younger people frequented the target area but those over 65 yrs did not. In spatial reversal learning, age groups over 45 yrs were deficient and the 65-80-yrs-olds showed no evidence of reversal. Spatial measures were associated with neuropsychological functioning. Extraversion and measures of depression moderated the age effect on the learning index with older introverted and non-depressed individuals showing better results. Measures of anxiety moderated the age effect on reversal learning with older people having higher anxiety scores showing a preserved reversal learning capability. Results confirmed age to be a major factor in spatial tasks but further showed neuropsychological functioning, psycho-affective determinants and personality traits to be significant predictors of individual differences. Copyright © 2014 Elsevier B.V. All rights reserved.

Singlet oxygen generation as a major cause for parasitic reactions during cycling of aprotic lithium-oxygen batteries

NASA Astrophysics Data System (ADS)

Mahne, Nika; Schafzahl, Bettina; Leypold, Christian; Leypold, Mario; Grumm, Sandra; Leitgeb, Anita; Strohmeier, Gernot A.; Wilkening, Martin; Fontaine, Olivier; Kramer, Denis; Slugovc, Christian; Borisov, Sergey M.; Freunberger, Stefan A.

2017-03-01

Non-aqueous metal-oxygen batteries depend critically on the reversible formation/decomposition of metal oxides on cycling. Irreversible parasitic reactions cause poor rechargeability, efficiency, and cycle life, and have predominantly been ascribed to the reactivity of reduced oxygen species with cell components. These species, however, cannot fully explain the side reactions. Here we show that singlet oxygen forms at the cathode of a lithium-oxygen cell during discharge and from the onset of charge, and accounts for the majority of parasitic reaction products. The amount increases during discharge, early stages of charge, and charging at higher voltages, and is enhanced by the presence of trace water. Superoxide and peroxide appear to be involved in singlet oxygen generation. Singlet oxygen traps and quenchers can reduce parasitic reactions effectively. Awareness of the highly reactive singlet oxygen in non-aqueous metal-oxygen batteries gives a rationale for future research towards achieving highly reversible cell operation.

Ionomycin-Induced Changes in Membrane Potential Alter Electroporation Outcomes in HL-60 Cells.

PubMed

Aiken, Erik J; Kilberg, Brian G; Yu, Siyuan; Hagness, Susan C; Booske, John H

2018-06-19

Previous studies have shown greater fluorophore uptake during electroporation on the anode-facing side of the cell than on the cathode-facing side. Based on these observations, we hypothesized that hyperpolarizing a cell before electroporation would decrease the requisite pulsed electric field intensity for electroporation outcomes, thereby yielding a higher probability of reversible electroporation at lower electric field strengths and a higher probability of irreversible electroporation (IRE) at higher electric field strengths. In this study, we tested this hypothesis by hyperpolarizing HL-60 cells using ionomycin before electroporation. These cells were then electroporated in a solution containing propidium iodide, a membrane integrity indicator. After 20 min, we added trypan blue to identify IRE cells. Our results showed that hyperpolarizing cells before electroporation alters the pulsed electric field intensity thresholds for reversible electroporation and IRE, allowing for greater control and selectivity of electroporation outcomes. Copyright © 2018 Biophysical Society. Published by Elsevier Inc. All rights reserved.

A stable lithium-rich surface structure for lithium-rich layered cathode materials

PubMed Central

Kim, Sangryun; Cho, Woosuk; Zhang, Xiaobin; Oshima, Yoshifumi; Choi, Jang Wook

2016-01-01

Lithium ion batteries are encountering ever-growing demand for further increases in energy density. Li-rich layered oxides are considered a feasible solution to meet this demand because their specific capacities often surpass 200 mAh g−1 due to the additional lithium occupation in the transition metal layers. However, this lithium arrangement, in turn, triggers cation mixing with the transition metals, causing phase transitions during cycling and loss of reversible capacity. Here we report a Li-rich layered surface bearing a consistent framework with the host, in which nickel is regularly arranged between the transition metal layers. This surface structure mitigates unwanted phase transitions, improving the cycling stability. This surface modification enables a reversible capacity of 218.3 mAh g−1 at 1C (250 mA g−1) with improved cycle retention (94.1% after 100 cycles). The present surface design can be applied to various battery electrodes that suffer from structural degradations propagating from the surface. PMID:27886178

Separator Decoration with Cobalt/Nitrogen Codoped Carbon for Highly Efficient Polysulfide Confinement in Lithium-Sulfur Batteries.

PubMed

Hu, Wen; Hirota, Yuichiro; Zhu, Yexin; Yoshida, Nao; Miyamoto, Manabu; Zheng, Tao; Nishiyama, Norikazu

2017-09-22

A macro-/mesoporous Co-N-C-decorated separator is proposed to confine and reutilize migrating polysulfides. Endowed with a desirable structure and synchronous lithio- and sulfiphilic chemistry, the macro-/mesoporous Co-N-C interface manipulates large polysulfide adsorption uptake, enabling good polysulfide adsorption kinetics, reversible electrocatalysis toward redox of anchored polysulfides, and facile charge transport. It significantly boosts the performance of a simple 70 wt % S/MWCNTs (MWCNTs=multi-walled carbon nanotubes) cathode, achieving high initial capacities (e.g., 1406 mAh g -1 at 0.2C, 1203 mAh g -1 at 1C), nearly 100 % Coulombic efficiencies, and high reversible capacities after cycle tests (e.g., 828.4 mAh g -1 at 1C after 100 cycles) at both low and high current rates. These results demonstrate that decorating separator with macro-/mesoporous Co-N-C paves a feasible way for developing advanced Li-S batteries. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Dual Electrolytic Plasma Processing for Steel Surface Cleaning and Passivation

NASA Astrophysics Data System (ADS)

Yang, L.; Zhang, P.; Shi, J.; Liang, J.; Tian, W. B.; Zhang, Y. M.; Sun, Z. M.

2017-10-01

To remove the rust on rebars and passivate the fresh surfaces, electrodes reversing electrolytic plasma processing (EPP) was proposed and conducted in a 10 wt.% Na2CO3 aqueous solution. The morphology and the composition of the surface were investigated by SEM and XPS. Experimental results show that the rust on the surface was removed effectively by cathode EPP, and a passive film containing Cr2O3 was achieved by the succeeding anode EPP treatment, by a simple operation of reversing the bias. The corrosion resistance was evaluated in a 3.5 wt.% NaCl aqueous solution using an electrochemical workstation. In comparison, the corrosion resistance was improved by the succeeding anode EPP treatment, which is evidenced by a positive shift of the open-circuit potential, an increase in the electrochemical impedance representing the inner layer by 76.8% and the decrease in the corrosion current density by 49.6%. This is an effective and environment-friendly technique to clean and passivate rebars and similar steel materials.

Reverse Current Characteristics of InP Gunn Diodes for W-Band Waveguide Applications.

PubMed

Kim, Hyun-Seok; Heo, Jun-Woo; Chol, Seok-Gyu; Ko, Dong-Sik; Rhee, Jin-Koo

2015-07-01

InP is considered as the most promising material for millimeter-wave laser-diode applications owing to its superior noise performance and wide operating frequency range of 75-110 GHz. In this study, we demonstrate the fabrication of InP Gunn diodes with a current-limiting structure using rapid thermal annealing to modulate the potential height formed between an n-type InP active layer and a cathode contact. We also explore the reverse current characteristics of the InP Gunn diodes. Experimental results indicate a maximum anode current and an oscillation frequency of 200 mA and 93.53 GHz, respectively. The current-voltage characteristics are modeled by considering the Schottky and ohmic contacts, work function variations, negative differential resistance (NDR), and tunneling effect. Although no direct indication of the NDR is observed, the simulation results match the measured data well. The modeling results show that the NDR effect is always present but is masked because of electron emission across the shallow Schottky barrier.

Three-dimensionally ordered macroporous Li2FeSiO4/C composite as a high performance cathode for advanced lithium ion batteries

NASA Astrophysics Data System (ADS)

Ding, Zhengping; Liu, Jiatu; Ji, Ran; Zeng, Xiaohui; Yang, Shuanglei; Pan, Anqiang; Ivey, Douglas G.; Wei, Weifeng

2016-10-01

Li2MSiO4 (M = Mn, Fe, Co, Ni, et al.) has received great attention because of the theoretical possibility to reversibly deintercalate two Li+ ions from the structure. However, the silicates still suffer from low electronic conductivity, sluggish lithium ion diffusion and structural instability upon deep cycling. In order to solve these problems, a "hard-soft" templating method has been developed to synthesize three-dimensionally ordered macroporous (3DOM) Li2FeSiO4/C composites. The 3DOM Li2FeSiO4/C composites show a high reversible capacity (239 mAh g-1) with ∼1.50 lithium ion insertion/extraction, a capacity retention of nearly 100% after 420 cycles and excellent rate capability. The enhanced electrochemical performance is ascribed to the interconnected carbon framework that improves the electronic conductivity and the 3DOM structure that offers short Li ion diffusion pathways and restrains volumetric changes.

In-situ preparation and unique electrochemical behavior of pore-embedding CoO/Co3O4 intermixed composite for Li+ rechargeable battery electrodes

NASA Astrophysics Data System (ADS)

Kim, Jin Kyu; Ju, Ji Young; Choi, Seul Ki; Unithrattil, Sanjith; Lee, Sun Sook; Kang, Yongku; Kim, Yongseon; Im, Won Bin; Choi, Sungho

2018-02-01

Electrochemically active CoO/Co3O4 co-existing microspheres with morphology-inherited porous particles is successfully synthesized via a simple solvothermal method. The as-prepared intermixed composite undergoes a monoxide CoO-preferred conversion reaction with an extremely enhanced capacity retention, ∼905 mA h g-1 after 250 cycles for discharge state, which is 1.6 times higher than the conventional CoOx-based anodes. Moreover, stable catalytic behavior of the electrocatalysts in Li-air cathodes of the given composites is also demonstrated. We believe that the extraordinarily enhanced electrode performance might be due to the novel pore-tempered microspheres packed with double electrochemically active centers of the CoO/Co3O4 composite effectively confine the detrimental volume exchange during the reversible cyclic reactions as well as the preserved multiple reactive sites for a reversible Li+ ⇄ LiOx reaction, which is advantageous for advanced Li rechargeable battery.

Soft x-ray pinhole imaging diagnostics for compact toroid plasmas

NASA Astrophysics Data System (ADS)

Crawford, E. A.; Taggart, D. P.; Bailey, A. D., III

1990-10-01

Soft x-ray pinhole imaging has recently become established as a valuable diagnostic for visualization of field reversed configuration (FRC) plasmas in the TRX-2, FRX-C/LSM devices. Gated MCP image converter devices with CsI cathodes and Be filters with a peak response around 11 nm wavelength are used for exposure durations ranging from a few tenths up to several microseconds. Results of experiments with single and Chevron channel plates are discussed along with estimates of linear exposure limitations with both film and CCD cameras as recording media. Plans for multiframe devices on the FRX-C/LSM and the LSX devices are also discussed.

Superior high-rate capability of Na3(VO(0.5))2(PO4)2F2 nanoparticles embedded in porous graphene through the pseudocapacitive effect.

PubMed

Xiang, Xingde; Lu, Qiongqiong; Han, Mo; Chen, Jun

2016-03-04

Na3(VO(0.5))2(PO4)2F2 nanoparticles embedded in porous graphene have been reported as a superior high-rate cathode material for sodium-ion batteries, exhibiting an excellent electrochemical performance with a high reversible capacity of 100 mA h g(-1) at 1 C, 77 mA h g(-1) at 50 C, and a capacity retention of 73% after 1000 cycles at 50 C. In particular, a significant contribution of the pseudocapacitive effect to the Na-storage capacity has been found for the first time.

Binder-free 2D titanium carbide (MXene)/carbon nanotube composites for high-performance lithium-ion capacitors.

PubMed

Yu, Peng; Cao, Gejin; Yi, Sha; Zhang, Xiong; Li, Chen; Sun, Xianzhong; Wang, Kai; Ma, Yanwei

2018-03-29

Two-dimensional (2D) MXenes have a very good application prospect in the field of electrochemical energy storage due to their metallic conductivity, high volumetric capacity, mechanical and thermal stability. Herein, we report the preparation of titanium carbide (Ti3C2Tx)/carbon nanotube (CNT) flexible self-supporting composite films by vacuum filtration. The CNTs can effectively prevent Ti3C2Tx from stacking and improve the electrochemical performance. The as-fabricated Ti3C2Tx/CNT film shows a high reversible capacity of 489 mA h g-1 at a current density of 50 mA g-1 together with good cycling performance. The full-cell lithium-ion capacitor (LIC) is assembled using the Ti3C2Tx/CNT film as the anode and activated carbon as the cathode. The LIC exhibits a high energy density of 67 Wh kg-1 (based on the total weight of the anode and the cathode), and a good capacity retention of 81.3% after 5000 cycles. These results suggest that Ti3C2Tx-CNT films are promising as anode materials for lithium ion capacitors.

Optimization of Microporous Carbon Structures for Lithium-Sulfur Battery Applications in Carbonate-Based Electrolyte.

PubMed

Hu, Lei; Lu, Yue; Li, Xiaona; Liang, Jianwen; Huang, Tao; Zhu, Yongchun; Qian, Yitai

2017-03-01

Developing appropriate sulfur cathode materials in carbonate-based electrolyte is an important research subject for lithium-sulfur batteries. Although several microporous carbon materials as host for sulfur reveal the effect, methods for producing microporous carbon are neither easy nor well controllable. Moreover, due to the complexity and limitation of microporous carbon in their fabrication process, there has been rare investigation of influence on electrochemical behavior in the carbonate-based electrolyte for lithium-sulfur batteries by tuning different micropore size(0-2 nm) of carbon host. Here, we demonstrate an immediate carbonization process, self-activation strategy, which can produce microporous carbon for a sulfur host from alkali-complexes. Besides, by changing different alkali-ion in the previous complex, the obtained microporous carbon exhibits a major portion of ultramicropore (<0.7 nm, from 54.9% to 25.8%) and it is demonstrated that the micropore structure of the host material plays a vital role in confining sulfur molecule. When evaluated as cathode materials in a carbonate-based electrolyte for Li-S batteries, such microporous carbon/sulfur composite can provide high reversible capacity, cycling stability and good rate capability. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

High-Temperature Electrochemical Performance of FeF3/C Nanocomposite as a Cathode Material for Lithium-Ion Batteries

NASA Astrophysics Data System (ADS)

Tang, Mengyun; Zhang, Zhengfu; Wang, Zi; Liu, Jingfeng; Yan, Hongge; Peng, Jinhui

2018-02-01

Iron trifluoride has been studied as a cathode material due to its cost-effectiveness, low toxicity, and high theoretical capacities of 712 mA h g-1. However, FeF3 has serious shortcomings of poor electronic conductivity and a slow diffusion rate of lithium ions, leading to a lower reversible specific capacity. In this work, FeF3/C nanocomposite has been synthesized successfully via a high-energy ball-milling method, and acetylene black is used as the conductive agent to improve the conductivity of FeF3. The FeF3/C nanocomposite shows a high initial discharge capacity of 346.25 and 161.58 mA h g-1 after 40th cycle at 50 mA g-1. It exhibits good cycle performance and rate performance. The high-temperature discharge capacities decreased with increase in the temperature. The initial high-temperature discharge capacities are found to be 254.17, 300.01, 281.25 and 125.16, and 216.875, 156, 141.67, 150, and 64.98 mA h g-1 at 20th cycles at the 40, 50, 60, and 70 °C, respectively.

Faradaic reactions in capacitive deionization (CDI) - problems and possibilities: A review.

PubMed

Zhang, Changyong; He, Di; Ma, Jinxing; Tang, Wangwang; Waite, T David

2018-01-01

Capacitive deionization (CDI) is considered to be one of the most promising technologies for the desalination of brackish water with low to medium salinity. In practical applications, Faradaic redox reactions occurring in CDI may have both negative and positive effects on CDI performance. In this review, we present an overview of the types and mechanisms of Faradaic reactions in CDI systems including anodic oxidation of carbon electrodes, cathodic reduction of oxygen and Faradaic ion storage and identify their apparent negative and positive effects on water desalination. A variety of strategies including development of novel electrode materials and use of alternative configurations and/or operational modes are proposed for the purpose of mitigation or elimination of the deterioration of electrodes and the formation of byproducts caused by undesired side Faradaic reactions. It is also recognized that Faradaic reactions facilitate a variety of exciting new applications including i) the incorporation of intercalation electrodes to enhance water desalination or to selectively separate certain ions through reversible Faradaic reactions and ii) the use of particular anodic oxidation and cathodic reduction reactions to realize functions such as water disinfection and contaminant removal. Copyright © 2017 Elsevier Ltd. All rights reserved.

Modulation of iTBS after-effects via concurrent directional TDCS: A proof of principle study.

PubMed

Tremblay, Sara; Hannah, Ricci; Rawji, Vishal; Rothwell, John C

Polarising currents can modulate membrane potentials in animals, affecting the after-effect of theta burst stimulation (TBS) on synaptic strength. We examined whether a similar phenomenon could also be observed in human motor cortex (M1) using transcranial direct current stimulation (TDCS) during monophasic intermittent TBS (iTBS). TDCS was applied during posterior-anterior iTBS using three different conditions: posterior-anterior TDCS (anode 3.5 cm posterior to M1, cathode 3.5 cm anterior to M1), anterior-posterior TDCS (cathode 3.5 cm posterior to M1, anode 3.5 cm anterior to M1), and sham TDCS. When the direction of TDCS (posterior-anterior) matched the direction of the electrical field induced by iTBS, we found a 19% non-significant increase in excitability changes in comparison with iTBS combined with sham TDCS. When the TDCS was reversed (anterior-posterior), the excitatory effect of iTBS was abolished. Our findings suggest that excitatory after-effects of iTBS can be modulated by directionally-specific TDCS. Copyright © 2017 The Authors. Published by Elsevier Inc. All rights reserved.

Morphology Engineering of Co3O4 Nanoarrays as Free-Standing Catalysts for Lithium-Oxygen Batteries.

PubMed

He, Mu; Zhang, Peng; Xu, Shan; Yan, Xingbin

2016-09-14

The effective shape-controlled synthesis of Co3O4 nanoarrays on nickel foam substrates has been achieved through a simple hydrothermal strategy. When they served as the binder- and conductive-agent-free porous cathodes for nonaqueous Li-O2 batteries, they sufficiently reflect the favorable catalytic characteristic of Co3O4 and alleviate the problems of serious pore blocking and surface passivation caused by insoluble and insulating discharge products. In particular, Co3O4 rectangular nanosheets exhibit superior electrocatalytic performance comparing with Co3O4 nanowires and hexagonal nanosheets, leading to higher specific capacity and better cycling stability over 54 cycles at 100 mA g(-1), which relate to their good pore structure, large specific surface area, and highly active {112} exposed plane, effectively promoting the mass transport and reversible formation and decomposition of discharge products in the cathode. These comparisons further indicate the morphology effect of nanostructured Co3O4 on their performances as free-standing catalysts for Li-O2 batteries, which also have been proved through the further analysis of discharge products on different shapes of Co3O4 nanoarrays electrodes.

In-situ carbon-coated Na2FeP2O7 anchored in three-dimensional reduced graphene oxide framework as a durable and high-rate sodium-ion battery cathode

NASA Astrophysics Data System (ADS)

Chen, Xiaobin; Du, Ke; Lai, Yanqing; Shang, Guozhi; Li, Huangxu; Xiao, Zhiwei; Chen, Yuxiang; Li, Junming; Zhang, Zhian

2017-07-01

Na2FeP2O7, which is considered as a promising cathode for sodium ion batteries (SIBs) on account of its economical efficiency and outstanding thermal stability, has been widely studied for the purpose of enhancing its electronic conductivity and interface ion transportation. In this paper, a double-carbon synergistically modified strategy was firstly introduced to facilitate the electrochemical performance of Na2FeP2O7. Na2FeP2O7 particles are enwrapped in situ by a carbon layer and further anchored in reduced graphene oxide (RGO) framework through a facile urea-nitrate combustion method. Consequently, the excellent rate performance and durable cycle stability of this compound are identified, which exhibits a reversible sodium storage capacity of 65 mAh g-1 at a current density of 10 C and no obvious decay in capacity after circling for 300 cycles at 1 C. What's more, no drastic degradation in capacity is observed when the cycling current density is brought back to high rates after cycling for more than 360 cycles at various rates.

Reversible multi-electron redox chemistry of π-conjugated N-containing heteroaromatic molecule-based organic cathodes

NASA Astrophysics Data System (ADS)

Peng, Chengxin; Ning, Guo-Hong; Su, Jie; Zhong, Guiming; Tang, Wei; Tian, Bingbing; Su, Chenliang; Yu, Dingyi; Zu, Lianhai; Yang, Jinhu; Ng, Man-Fai; Hu, Yong-Sheng; Yang, Yong; Armand, Michel; Loh, Kian Ping

2017-07-01

Even though organic molecules with well-designed functional groups can be programmed to have high electron density per unit mass, their poor electrical conductivity and low cycle stability limit their applications in batteries. Here we report a facile synthesis of π-conjugated quinoxaline-based heteroaromatic molecules (3Q) by condensation of cyclic carbonyl molecules with o-phenylenediamine. 3Q features a number of electron-deficient pyrazine sites, where multiple redox reactions take place. When hybridized with graphene and coupled with an ether-based electrolyte, an organic cathode based on 3Q molecules displays a discharge capacity of 395 mAh g-1 at 400 mA g-1 (1C) in the voltage range of 1.2-3.9 V and a nearly 70% capacity retention after 10,000 cycles at 8 A g-1. It also exhibits a capacity of 222 mAh g-1 at 20C, which corresponds to 60% of the initial specific capacity. Our results offer evidence that heteroaromatic molecules with multiple redox sites are promising in developing high-energy-density, long-cycle-life organic rechargeable batteries.

Attainable high capacity in Li-excess Li-Ni-Ru-O rock-salt cathode for lithium ion battery

NASA Astrophysics Data System (ADS)

Wang, Xingbo; Huang, Weifeng; Tao, Shi; Xie, Hui; Wu, Chuanqiang; Yu, Zhen; Su, Xiaozhi; Qi, Jiaxin; Rehman, Zia ur; Song, Li; Zhang, Guobin; Chu, Wangsheng; Wei, Shiqiang

2017-08-01

Peroxide structure O2n- has proven to appear after electrochemical process in many lithium-excess precious metal oxides, representing extra reversible capacity. We hereby report construction of a Li-excess rock-salt oxide Li1+xNi1/2-3x/2Ru1/2+x/2O2 electrode, with cost effective and eco-friendly 3d transition metal Ni partially substituting precious 4d transition metal Ru. It can be seen that O2n- is formed in pristine Li1.23Ni0.155Ru0.615O2, and stably exists in subsequent cycles, enabling discharge capacities to 295.3 and 198 mAh g-1 at the 1st/50th cycle, respectively. Combing ex-situ X-ray absorption near edge spectroscopy, X-ray photoelectron spectroscopy, X-ray diffraction, high resolution transmission electron microscopy and electrochemical characterization, we demonstrate that the excellent electrochemical performance comes from both percolation network with disordered structure and cation/anion redox couples occurring in charge-discharge process. Li-excess and substitution of common element have been demonstrated to be a breakthrough for designing novel high performance commercial cathodes in rechargeable lithium ion battery field.

Binder-free flexible LiMn2O4/carbon nanotube network as high power cathode for rechargeable hybrid aqueous battery

NASA Astrophysics Data System (ADS)

Zhu, Xiao; Wu, Xianwen; Doan, The Nam Long; Tian, Ye; Zhao, Hongbin; Chen, P.

2016-09-01

Highly flexible LiMn2O4/carbon nanotube (CNT) electrodes are developed and used as a high power cathode for the Rechargeable Hybrid Aqueous Battery (ReHAB). LiMn2O4 particles are entangled into CNT networks, forming a self-supported free-standing hybrid films. Such hybrid films can be used as electrodes of ARLB without using any additional binders. The binder-free LiMn2O4/CNT electrode exhibits good mechanical properties, high conductivity, and effective charge transport. High-rate capability and high cycling stability are obtained. Typically, the LiMn2O4/CNT electrode achieves a discharge capacity of 72 mAh g-1 at the large-current of 20 C (1 C = 120 mAh g-1), and exhibits good cycling performance and high reversibility: Coulombic efficiency of almost 100% over 300 charge-discharge cycles at 4 C. By reducing the weight, and improving the large-current rate capability simultaneously, the LiMn2O4/CNT electrode can highly enhance the energy/power density of ARLB and hold potential to be used in ultrathin, lightweight electronic devices.

Improving the performance of lithium-sulfur batteries by graphene coating

NASA Astrophysics Data System (ADS)

Zhou, Xiangyang; Xie, Jing; Yang, Juan; Zou, Youlan; Tang, Jingjing; Wang, Songcan; Ma, Lulu; Liao, Qunchao

2013-12-01

A graphene coating mesoporous carbon/sulfur (RGO@CMK-3/S) composite, which is characteristic of a hybrid structure by incorporating the merits of CMK-3 matrix and graphene (RGO) skin, is synthesized by a facile and scalable route. The CMK-3/S composite is synthesized via a simple melt-diffusion strategy, and then a thin RGO skin is absorbed on the CMK-3/S composite surface in aqueous solution. When evaluating the electrochemical properties of as-prepared RGO wrapped nanostructures as cathode materials in lithium-sulfur batteries, it exhibits much improved cyclical stability and high rate performance. The RGO@CMK-3/S composite with 53.14 wt.% sulfur presents a reversible discharge capacity of about 734 mA h g-1 after 100 cycles at 0.5 C. The improved performance is attributed to the unique structure of RGO@CMK-3/S composite. CMK-3 with extensively mesopores can offer buffering space for the volume change of sulfur and efficient diffusion channel for lithium ions during the charge/discharge process. Meanwhile, the conductive RGO coating skin physically and chemically prevents the dissolution of polysulfides from the cathode, both of which contribute to the reduced capacity fade and improved electrochemical properties.

Electrochemical treatment of concentrate from reverse osmosis of sanitary landfill leachate.

PubMed

Labiadh, Lazhar; Fernandes, Annabel; Ciríaco, Lurdes; Pacheco, Maria José; Gadri, Abdellatif; Ammar, Salah; Lopes, Ana

2016-10-01

Conventional sanitary landfill leachate treatment has recently been complemented and, in some cases, completely replaced by reverse osmosis technology. Despite the good quality of treated water, the efficiency of the process is low and a large volume of reverse osmosis concentrate has to be either discharged or further treated. In this study, the use of anodic oxidation combined with electro-Fenton processes to treat the concentrate obtained in the reverse osmosis of sanitary landfill leachate was evaluated. The anodic oxidation pretreatment was performed in a pilot plant using an electrochemical cell with boron-doped diamond electrodes. In the electro-Fenton experiments, a boron-doped diamond anode and carbon-felt cathode were used, and the influence of the initial pH and iron concentration were studied. For the experimental conditions, the electro-Fenton assays performed at an initial pH of 3 had higher organic load removal levels, whereas the best nitrogen removal was attained when the electrochemical process was performed at the natural pH of 8.8. The increase in the iron concentration had an adverse impact on treatment under natural pH conditions, but it enhanced the nitrogen removal in the electro-Fenton assays performed at an initial pH of 3. The combined anodic oxidation and electro-Fenton process is useful for treating the reverse osmosis concentrate because it is effective at removing the organic load and nitrogen-containing species. Additionally, this process potentiates the increase in the biodegradability index of the treated effluent. Copyright © 2016 Elsevier Ltd. All rights reserved.

Transcranial direct current stimulation improves seizure control in patients with Rasmussen encephalitis.

PubMed

Tekturk, Pinar; Erdogan, Ezgi Tuna; Kurt, Adnan; Kocagoncu, Ece; Kucuk, Zeynep; Kinay, Demet; Yapici, Zuhal; Aksu, Serkan; Baykan, Betul; Karamursel, Sacit

2016-03-01

Rasmussen encephalitis is associated with severe seizures that are unresponsive to antiepileptic drugs, as well as immunosuppressants. Transcranial direct current stimulation (t-DCS) is a non-invasive and safe method tried mostly for focal epilepsies with different aetiologies. To date, there is only one published study with two case reports describing the effect of t-DCS in Rasmussen encephalitis. Our aim was to investigate the effect of t-DCS on seizures in Rasmussen encephalitis and to clarify its safety. Five patients (mean age: 19; three females), diagnosed with Rasmussen encephalitis were included in this study. Patients received first cathodal, then anodal (2 mA for 30 minutes on three consecutive days for non-sham stimulations), and finally sham stimulation with two-month intervals, respectively. Three patients received classic (DC) cathodal t-DCS whereas two patients received cathodal stimulation with amplitude modulation at 12 Hz. Afterwards, all patients received anodal stimulation with amplitude modulation at 12 Hz. In the last part of the trial, sham stimulation (a 60-second stimulation with gradually decreasing amplitude to zero in the last 15 seconds) was applied to three patients. Maximum current density was 571 mA/m2 using 70 mm x 50 mm wet sponge electrodes with 2-mA maximum, current controlled stimulator, and maximum charge density was 1028 C/m2 for a 30-minute stimulation period. After cathodal stimulation, all but one patient had a greater than 50% decrease in seizure frequency. Two patients who received modulated cathodal t-DCS had better results. The longest positive effect lasted for one month. A second trial with modulated anodal stimulation and a third with sham stimulation were not effective. No adverse effect was reported with all types of stimulations. Both classic and modulated cathodal t-DCS may be suitable alternative methods for improving seizure outcome in Rasmussen encephalitis patients.

Cathode power distribution system and method of using the same for power distribution

DOEpatents

Williamson, Mark A; Wiedmeyer, Stanley G; Koehl, Eugene R; Bailey, James L; Willit, James L; Barnes, Laurel A; Blaskovitz, Robert J

2014-11-11

Embodiments include a cathode power distribution system and/or method of using the same for power distribution. The cathode power distribution system includes a plurality of cathode assemblies. Each cathode assembly of the plurality of cathode assemblies includes a plurality of cathode rods. The system also includes a plurality of bus bars configured to distribute current to each of the plurality of cathode assemblies. The plurality of bus bars include a first bus bar configured to distribute the current to first ends of the plurality of cathode assemblies and a second bus bar configured to distribute the current to second ends of the plurality of cathode assemblies.

Differential voltage analysis as a tool for analyzing inhomogeneous aging: A case study for LiFePO4|Graphite cylindrical cells

NASA Astrophysics Data System (ADS)

Lewerenz, Meinert; Marongiu, Andrea; Warnecke, Alexander; Sauer, Dirk Uwe

2017-11-01

In this work the differential voltage analysis (DVA) is evaluated for LiFePO4|Graphite cylindrical cells aged in calendaric and cyclic tests. The homogeneity of the active lithium distribution and the loss of anode active material (LAAM) are measured by the characteristic shape and peaks of the DVA. The results from this analysis exhibit an increasing homogeneity of the lithium-ion distribution during aging for all cells subjected to calendaric aging. At 60 °C, LAAM is found additionally and can be associated with the deposition of dissolved Fe from the cathode on the anode, where it finally leads to the clogging of pores. For cells aged under cyclic conditions, several phenomena are correlated to degradation, such as loss of active lithium and local LAAM for 100% DOD. Moreover, the deactivation of certain parts of anode and cathode due to a lithium-impermeable covering layer on top of the anode is observed for some cells. While the 100% DOD cycling is featured by a continuous LAAM, the LAAM due to deactivation by a covering layer of both electrodes starts suddenly. The homogeneity of the active lithium distribution within the cycled cells is successively reduced with deposited passivation layers and with LAAM that is lost locally at positions with lower external pressure on the electrode.

Miniaturized cathodic arc plasma source

DOEpatents

Anders, Andre; MacGill, Robert A.

2003-04-15

A cathodic arc plasma source has an anode formed of a plurality of spaced baffles which extend beyond the active cathode surface of the cathode. With the open baffle structure of the anode, most macroparticles pass through the gaps between the baffles and reflect off the baffles out of the plasma stream that enters a filter. Thus the anode not only has an electrical function but serves as a prefilter. The cathode has a small diameter, e.g. a rod of about 1/4 inch (6.25 mm) diameter. Thus the plasma source output is well localized, even with cathode spot movement which is limited in area, so that it effectively couples into a miniaturized filter. With a small area cathode, the material eroded from the cathode needs to be replaced to maintain plasma production. Therefore, the source includes a cathode advancement or feed mechanism coupled to cathode rod. The cathode also requires a cooling mechanism. The movable cathode rod is housed in a cooled metal shield or tube which serves as both a current conductor, thus reducing ohmic heat produced in the cathode, and as the heat sink for heat generated at or near the cathode. Cooling of the cathode housing tube is done by contact with coolant at a place remote from the active cathode surface. The source is operated in pulsed mode at relatively high currents, about 1 kA. The high arc current can also be used to operate the magnetic filter. A cathodic arc plasma deposition system using this source can be used for the deposition of ultrathin amorphous hard carbon (a-C) films for the magnetic storage industry.

DARHT Axis II Cathode 16 (S/N 22) History as Recorded in the Historian and Shot Data Databases

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

Smith, H. Vernon; Barraza, Juan; Harrison, James F.

2014-01-10

Long DARHT II injector cathode operating lifetimes are desirable for flash radiography of hydrodynamic tests at the dual-axis radiographic hydrotest facility (DARHT). The specification for cathode operating lifetime given to Spectra-Mat in the purchase orders for the 311X-M cathodes is ≥ 1000 hours at full operating temperature (~1120 oC). Of the five most-recent cathodes operated on DARHT II, only two have met this specification. It is desirable to have cathodes lifetimes considerably longer than the specified 1000 hours. In this report we present the thermal and vacuum history of cathode 16 (serial no. [S/N] 22), a 311X-M cathode, as recordedmore » in the historian database and the shot data database. The hope is that by examining this history we can identify the parameter (or parameters) that are limiting the DARHT II 311X-M cathode lifetimes. This is the fifth in a series of 5 DARHT Tech Notes in which recent cathode thermal and vacuum histories are examined. The other tech notes in this series are DARHT Tech Notes Nos. 501 (cathode 12, S/N 15), 502 (cathode 13, S/N 19), 503 (cathode 14, S/N 20), and 504 (cathode 15, S/N 21). In DARHT Tech Note No. 506 we will compare the recorded thermal and vacuum histories of cathodes 12-16 and attempt to understand the cathode lifetime limitations based on the stored cathode data presented in DARHT Tech Notes 501-505 and other relevant information.« less

Advanced electrorefiner design

DOEpatents

Miller, W.E.; Gay, E.C.; Tomczuk, Z.

1996-07-02

A combination anode and cathode is described for an electrorefiner which includes a hollow cathode and an anode positioned inside the hollow cathode such that a portion of the anode is near the cathode. A retaining member is positioned at the bottom of the cathode. Mechanism is included for providing relative movement between the anode and the cathode during deposition of metal on the inside surface of the cathode during operation of the electrorefiner to refine spent nuclear fuel. A method is also disclosed which includes electrical power means selectively connectable to the anode and the hollow cathode for providing electrical power to the cell components, electrically transferring uranium values and plutonium values from the anode to the electrolyte, and electrolytically depositing substantially pure uranium on the hollow cathode. Uranium and plutonium are deposited at a liquid cathode together after the PuCl{sub 3} to UCl{sub 3} ratio is greater than 2:1. Slots in the hollow cathode provides close anode access for the liquid pool in the liquid cathode. 6 figs.

Advanced electrorefiner design

DOEpatents

Miller, William E.; Gay, Eddie C.; Tomczuk, Zygmunt

1996-01-01

A combination anode and cathode for an electrorefiner which includes a hollow cathode and an anode positioned inside the hollow cathode such that a portion of the anode is near the cathode. A retaining member is positioned at the bottom of the cathode. Mechanism is included for providing relative movement between the anode and the cathode during deposition of metal on the inside surface of the cathode during operation of the electrorefiner to refine spent nuclear fuel. A method is also disclosed which includes electrical power means selectively connectable to the anode and the hollow cathode for providing electrical power to the cell components, electrically transferring uranium values and plutonium values from the anode to the electrolyte, and electrolytically depositing substantially pure uranium on the hollow cathode. Uranium and plutonium are deposited at a liquid cathode together after the PuCl.sub.3 to UCl.sub.3 ratio is greater than 2:1. Slots in the hollow cathode provides close anode access for the liquid pool in the liquid cathode.

Scenario for Hollow Cathode End-Of-Life

NASA Technical Reports Server (NTRS)

Sarver-Verhey, Timothy R.

2000-01-01

Recent successful hollow cathode life tests have demonstrated that lifetimes can meet the requirements of several space applications. However, there are no methods for assessing cathode lifetime short of demonstrating the requirement. Previous attempts to estimate or predict cathode lifetime were based on relatively simple chemical depletion models derived from the dispenser cathode community. To address this lack of predicative capability, a scenario for hollow cathode lifetime under steady-state operating conditions is proposed. This scenario has been derived primarily from the operating behavior and post-test condition of a hollow cathode that was operated for 28,000 hours. In this scenario, the insert chemistry evolves through three relatively distinct phases over the course of the cathode lifetime. These phases are believed to correspond to demonstrable changes in cathode operation. The implications for cathode lifetime limits resulting from this scenario are examined, including methods to assess cathode lifetime without operating to End-of- Life and methods to extend the cathode lifetime.

Effect of the electric field during annealing of organic light emitting diodes for improving its on/off ratio.

PubMed

Sharma, Rahul K; Katiyar, Monica; Rao, I V Kameshwar; Unni, K N Narayanan; Deepak

2016-01-28

If an organic light emitting diode is to be used as part of a matrix addressed array, it should exhibit low reverse leakage current. In this paper we present a method to improve the on/off ratio of such a diode by simultaneous application of heat and electric field post device fabrication. A green OLED with excellent current efficiency was seen to be suffering from a poor on/off ratio of 10(2). After examining several combinations of annealing along with the application of a reverse bias voltage, the on/off ratio of the same device could be increased by three orders of magnitude, specifically when the device was annealed at 80 °C under reverse bias (-15 V) followed by slow cooling also under the same bias. Simultaneously, the forward characteristics of the device were relatively unaffected. The reverse leakage in the OLED is mainly due to the injection of minority carriers in the hole transport layer (HTL) and the electron transport layer (ETL), in this case, of holes in tris-(8-hydroxyquinoline)aluminum(Alq3) and electrons in 4,4',4''-tris(N-3-methylphenyl-N-phenylamino)triphenylamine (m-MTDATA). Hence, to investigate these layers adjacent to the electrodes, we fabricated their single layer devices. The possibility of bulk traps present adjacent to electrodes providing states for injection was ruled out after estimating the trap density both before and after the reverse biased annealing. The temperature independent current in reverse bias ruled out the possibility of thermionic injection. The origin of the reverse bias current is attributed to the availability of interfacial hole levels in Alq3 at the cathode work function level in the as-fabricated device; the suppression of the same being attributed to the fact that these levels in Alq3 are partly removed after annealing under an electric field.

Enhancing the energy density of safer Li-ion batteries by combining high-voltage lithium cobalt fluorophosphate cathodes and nanostructured titania anodes

PubMed Central

Ortiz, Gregorio F.; López, María C.; Li, Yixiao; McDonald, Matthew J.; Cabello, Marta; Tirado, José L.; Yang, Yong

2016-01-01

Recently, Li-ion batteries have been heavily scrutinized because of the apparent incompatibility between safety and high energy density. This work report a high voltage full battery made with TiO2/Li3PO4/Li2CoPO4F. The Li2CoPO4F cathode and TiO2 anode materials are synthesized by a sol–gel and anodization methods, respectively. X-ray diffraction (XRD) analysis confirmed that Li2CoPO4F is well-crystallized in orthorhombic crystal structure with Pnma space group. The Li3PO4-coated anode was successfully deposited as shown by the (011) lattice fringes of anatase TiO2 and (200) of γ-Li3PO4, as detected by HRTEM. The charge profile of Li2CoPO4F versus lithium shows a plateau at 5.0 V, revealing its importance as potentially high-voltage cathode and could perfectly fit with the plateau of anatase anode (1.8–1.9 V). The full cell made with TiO2/Li3PO4/Li2CoPO4F delivered an initial reversible capacity of 150 mA h g−1 at C rate with good cyclic performance at an average potential of 3.1–3.2 V. Thus, the full cell provides an energy density of 472 W h kg−1. This full battery behaves better than TiO2/Li2CoPO4F. The introduction of Li3PO4 as buffer layer is expected to help the cyclability of the electrodes as it allows a rapid Li-ion transport. PMID:26879916

Organic-Acid-Assisted Fabrication of Low-Cost Li-Rich Cathode Material (Li[Li1/6Fe1/6Ni1/6Mn1/2]O-2) for Lithium-Ion Battery

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

Zhao, Taolin; Chen, Shi; Li, Li

2014-12-24

A novel Li-rich cathode Li[Li1/6Fe1/6Ni1/6Mn1/2]O-2 (0.4Li(2)MnO(3-)0.6LiFe(1/3)Ni(1/3)Mn(1/3)O(2)) was synthesized by a solgel method, which uses citric acid (SC), tartaric acid (ST), or adipic acid (SA) as a chelating agent. The structural, morphological, and electrochemical properties of the prepared samples were characterized by various methods. X-ray diffraction showed that single-phase materials are formed mainly with typical alpha-NaFeO2 layered structure (R3 m), and the SC sample has the lowest Li/Ni cation disorder. The morphological study indicated homogeneous primary particles in good distribution size (100 nm) with small aggregates. The Fe, Ni, and Mn valences were determined by X-ray absorption near-edge structure analysis. Inmore » coin cell tests, the initial reversible discharge capacity of an SA electrode was 289.7 mAh g(-1) at the 0.1C rate in the 1.54.8 V voltage range, while an SC electrode showed a better cycling stability with relatively high capacity retention. At the 2C rate, the SC electrode can deliver a discharge capacity of 150 mAh g(-1) after 50 cycles. Differential capacity vs voltage curves were employed to further investigate the electrochemical reactions and the structural change process during cycling. This low-cost, Fe-based compound prepared by the solgel method has the potential to be used as the high capacity cathode material for Liion batteries.« less

Cr{sub 2}O{sub 5} as new cathode for rechargeable sodium ion batteries

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

Feng, Xu-Yong; Chien, Po-Hsiu; Rose, Alyssa M.

2016-10-15

Chromium oxide, Cr{sub 2}O{sub 5}, was synthesized by pyrolyzing CrO{sub 3} at 350 °C and employed as a new cathode in rechargeable sodium ion batteries. Cr{sub 2}O{sub 5}/Na rechargeable batteries delivered high specific capacities up to 310 mAh/g at a current density of C/16 (or 20 mA/g). High-resolution solid-state {sup 23}Na NMR both qualitatively and quantitatively revealed the reversible intercalation of Na ions into the bulk electrode and participation of Na ions in the formation of the solid-electrolyte interphase largely at low potentials. Amorphization of the electrode structure occurred during the first discharge revealed by both NMR and X-ray diffractionmore » data. CrO{sub 3}-catalyzed electrolyte degradation and loss in electronic conductivity led to gradual capacity fading. The specific capacity stabilized at >120 mAh/g after 50 charge-discharge cycles. Further improvement in electrochemical performance is possible via electrode surface modification, polymer binder incorporation, or designs of new morphologies. - Graphical abstract: Electrochemical profile of a Cr{sub 2}O{sub 5}/Na battery cell and high-resolution solid-state {sup 23}Na MAS NMR spectrum of a Cr{sub 2}O{sub 5} electrode discharged to 2 V. - Highlights: • Cr{sub 2}O{sub 5} was synthesized and used as a new cathode in rechargeable Na ion batteries. • A high capacity of 310 mAh/g and an energy density of 564 Wh/kg were achieved. • High-resolution solid-state {sup 23}Na NMR was employed to follow the reaction mechanisms.« less

Structural characterization of layered Na0.5Co0.5Mn0.5O2 material as a promising cathode for sodium-ion batteries

NASA Astrophysics Data System (ADS)

Manikandan, Palanisamy; Heo, Seongwoo; Kim, Hyun Woo; Jeong, Hu Young; Lee, Eungje; Kim, Youngsik

2017-09-01

Layered Na0.5Co0.5Mn0.5O2 material is synthesized through a facile mixed hydroxy-carbonate route using (Co0.5Mn0.5)2(OH)2CO3 precursor and well characterized as a hexagonal layered structure under P63/mmc space group. The lattice parameters and unit cell volume (a = 2.8363 Å, c = 11.3152 Å and V = 78.83 Å3) are calculated by Rietveld refinement analysis. A flaky-bundle morphology is obtained to the layered Na0.5Co0.5Mn0.5O2 material with the hexagonal flake size ∼30 nm. Advanced transmission electron microscopic images are revealed the local structure of the layered Na0.5Co0.5Mn0.5O2 material with contrasting bright dots and faint dark dots corresponding to the Co/Mn and Na atoms. Two oxidation and reduction peaks are occurred in a cyclic voltammetric analysis corresponding to Co3+/Co4+ and Mn3+/Mn4+ redox processes. These reversible processes are attributed to the intercalation/de-intercalation of Na+ ions into the host structure of layered Na0.5Co0.5Mn0.5O2 material. Accordingly, the sodium cell is delivered the initial charge-discharge capacity 53/144 mAh g-1 at 0.5 C, which cycling studies are extended to rate capability test at 1 C, 3 C and 5C. Eventually, the Na-ion full-cell is yielded cathode charge-discharge capacity 55/52 mAh g-1 at 0.212 mA and exhibited as a high voltage cathode for Na-ion batteries.

Organic electrolyte-based rechargeable zinc-ion batteries using potassium nickel hexacyanoferrate as a cathode material

NASA Astrophysics Data System (ADS)

Chae, Munseok S.; Heo, Jongwook W.; Kwak, Hunho H.; Lee, Hochun; Hong, Seung-Tae

2017-01-01

This study demonstrates an organic electrolyte-based rechargeable zinc-ion battery (ZIB) using Prussian blue (PB) analogue potassium nickel hexacyanoferrate K0.86Ni[Fe(CN)6]0.954(H2O)0.766 (KNF-086) as the cathode material. KNF-086 is prepared via electrochemical extraction of potassium ions from K1.51Ni[Fe(CN)6]0.954(H2O)0.766 (KNF-151). The cell is composed of a KNF-086 cathode, a zinc metal anode, and a 0.5 M Zn(ClO4)2 acetonitrile electrolyte. This cell shows a reversible discharge capacity of 55.6 mAh g-1 at 0.2 C rate with the discharge voltage at 1.19 V (vs. Zn2+/Zn). As evidenced by Fourier electron density analysis with powder XRD data, the zinc-inserted phase is confirmed as Zn0.32K0.86Ni[Fe(CN)6]0.954(H2O)0.766 (ZKNF-086), and the position of the zinc ion in ZKNF-086 is revealed as the center of the large interstitial cavities of the cubic PB. Compared to KNF-086, ZKNF-086 exhibits a decreased unit cell parameter (0.9%) and volume (2.8%) while the interatomic distance of d(Fe-C) increased (from 1.84 to 1.98 Å), and the oxidation state of iron decreases from 3 to 2.23. The organic electrolyte system provides higher zinc cycling efficiency (>99.9%) than the aqueous system (ca. 80%). This result demonstrates an organic electrolyte-based ZIB, and offers a crucial basis for understanding the electrochemical intercalation chemistry of zinc ions in organic electrolytes.

Scalable and template-free synthesis of nanostructured Na{sub 1.08}V{sub 6}O{sub 15} as high-performance cathode material for lithium-ion batteries

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

Zheng, Shili, E-mail: slzheng@ipe.ac.cn; Wang, Xinran; Yan, Hong

2016-09-15

Highlights: • Nanostructured Na{sub 1.08}V{sub 6}O{sub 15} was synthesized through additive-free sol-gel process. • Prepared Na{sub 1.08}V{sub 6}O{sub 15} demonstrated high capacity and sufficient cycling stability. • The reaction temperature was optimized to allow scalable Na{sub 1.08}V{sub 6}O{sub 15} fabrication. - Abstract: Developing high-capacity cathode material with feasibility and scalability is still challenging for lithium-ion batteries (LIBs). In this study, a high-capacity ternary sodium vanadate compound, nanostructured NaV{sub 6}O{sub 15}, was template-free synthesized through sol-gel process with high producing efficiency. The as-prepared sample was systematically post-treated at different temperature and the post-annealing temperature was found to determine the cycling stabilitymore » and capacity of NaV{sub 6}O{sub 15}. The well-crystallized one exhibited good electrochemical performance with a high specific capacity of 302 mAh g{sup −1} when cycled at current density of 0.03 mA g{sup −1}. Its relatively long-term cycling stability was characterized by the cell performance under the current density of 1 A g{sup −1}, delivering a reversible capacity of 118 mAh g{sup −1} after 300 cycles with 79% capacity retention and nearly 100% coulombic efficiency: all demonstrating its significant promise of proposed strategy for large-scale synthesis of NaV{sub 6}O{sub 15} as cathode with high-capacity and high energy density for LIBs.« less

GALVANOTAXIS OF SLIME MOLD

PubMed Central

Anderson, John D.

1951-01-01

The plasmodium of Physarum polycephalum reacts to direct current by migration toward the cathode. Cathodal migration was obtained upon a variety of substrata such as baked clay, paper, cellophane, and agar with a current density in the substratum of 1.0 µa./mm.2 Injury was produced by current densities of 8.0 to 12.0 µa./mm.2 The negative galvanotactic response was not due to electrode products. Attempts to demonstrate that the response was due to gradients or orientation in the substratum, pH changes in the mold, cataphoresis, electroosmosis, or endosmosis were not successful. The addition of salts (CaCl2, LiCl, NaCl, Na2SO4, NaHCO3, KCl, MgSO4, sodium citrate, and sea water) to agar indicated that change of cations had more effect than anions upon galvanotaxis and that the effect was upon threshold values. K ion (0.01 M KCl) increased the lower threshold value to 8.0 µa./mm.2 and the upper threshold value to 32.0 µa./mm.2, whereas the Li ion (0.01 M LiCl) increased the lower threshold to only 4.0 µa./mm.2 and the upper threshold to only 16.0 µa./mm.2 The passage of electric current produced no increase in the rate of cathodal migration; neither was there a decrease until injurious current densities were reached. With increase of subthreshold current densities there was a progressive decrease in rate of migration toward the anode until complete anodal inhibition occurred. There was orientation at right angles to the electrodes in alternating current (60 cycle) with current density of 4.0 µa./mm.2 and in direct current of 5.0 µa./mm.2 when polarity of current was reversed every minute. It is concluded that the negative galvanotactic response of P. polycephalum is due to inhibition of migration on the anodal side of the plasmodium and that this inhibition results in the limitation of the normal migration of the mold to a cathodal direction. The mechanism of the anodal inhibition has not been elucidated. PMID:14873916

Hierarchically Designed 3D Holey C2N Aerogels as Bifunctional Oxygen Electrodes for Flexible and Rechargeable Zn-Air Batteries.

PubMed

Shinde, Sambhaji S; Lee, Chi Ho; Yu, Jin-Young; Kim, Dong-Hyung; Lee, Sang Uck; Lee, Jung-Ho

2018-01-23

The future of electrochemical energy storage spotlights on the designed formation of highly efficient and robust bifunctional oxygen electrocatalysts that facilitate advanced rechargeable metal-air batteries. We introduce a scalable facile strategy for the construction of a hierarchical three-dimensional sulfur-modulated holey C 2 N aerogels (S-C 2 NA) as bifunctional catalysts for Zn-air and Li-O 2 batteries. The S-C 2 NA exhibited ultrahigh surface area (∼1943 m 2 g -1 ) and superb electrocatalytic activities with lowest reversible oxygen electrode index ∼0.65 V, outperforms the highly active bifunctional and commercial (Pt/C and RuO 2 ) catalysts. Density functional theory and experimental results reveal that the favorable electronic structure and atomic coordination of holey C-N skeleton enable the reversible oxygen reactions. The resulting Zn-air batteries with liquid electrolytes and the solid-state batteries with S-C 2 NA air cathodes exhibit superb energy densities (958 and 862 Wh kg -1 ), low charge-discharge polarizations, excellent reversibility, and ultralong cycling lives (750 and 460 h) than the commercial Pt/C+RuO 2 catalysts, respectively. Notably, Li-O 2 batteries with S-C 2 NA demonstrated an outstanding specific capacity of ∼648.7 mA h g -1 and reversible charge-discharge potentials over 200 cycles, illustrating great potential for commercial next-generation rechargeable power sources of flexible electronics.

Kinetically inert Cu in coastal waters.

PubMed

Kogut, Megan B; Voelker, Bettina M

2003-02-01

Many studies have shown that Cu and other metals in natural waters are mostly bound by unidentified compounds interpreted to be strong ligands reversibly complexing a given metal. However, commonly applied analytical techniques are not capable of distinguishing strongly but reversibly complexed metal from metal bound in kinetically inert compounds. In this work, we use a modified competitive ligand exchange adsorptive cathodic stripping voltammetry method combined with size fractionation to show that most if not all of the apparently very strongly (log K > or = 13) bound Cu in samples from five New England coastal waters (1-18 nM, 10-60% of total Cu) is actually present as kinetically inert compounds. In three of the five samples examined by ultrafiltration, a significant portion of the 0.2-microm-filtrable inert Cu was retained by a 0.02-microm-pore size filter, suggesting that at least some of the Cu was kinetically inert because it was physically sequestered in colloidal material. The rest of the ambient Cu, and Cu added in titrations, were reversibly bound in complexes that could be modeled as having conditional stability constants of 10(10)-10(13). The Cu-binding ability of these complexes was equivalent to that of seawater containing reasonable concentrations of humic substances from terrestrial sources, approximately 0.15-0.45 mg of C/L. Both the inert compounds and the reversible ligands were important for determining [Cu2+] at ambient Cu levels in our samples.

Improved materials and processes of dispenser cathodes

NASA Astrophysics Data System (ADS)

Longo, R. T.; Sundquist, W. F.; Adler, E. A.

1984-08-01

Several process variables affecting the final electron emission properties of impregnated dispenser cathodes were investigated. In particular, the influence of billet porosity, impregnant composition and purity, and osmium-ruthenium coating were studied. Work function and cathode evaporation data were used to evaluate cathode performance and to formulate a model of cathode activation and emission. Results showed that sorted tungsten powder can be reproducibly fabricated into cathode billets. Billet porosity was observed to have the least effect on cathode performance. Use of the 4:1:1 aluminate mixture resulted in lower work functions than did use of the 5:3:2 mixture. Under similar drawout conditions, the coated cathodes showed superior emission relative to uncoated cathodes. In actual Pierce gun structures under accelerated life test, the influence of impregnated sulfur is clearly shown to reduce cathode performance.

Remote control for anode-cathode adjustment

DOEpatents

Roose, Lars D.

1991-01-01

An apparatus for remotely adjusting the anode-cathode gap in a pulse power machine has an electric motor located within a hollow cathode inside the vacuum chamber of the pulse power machine. Input information for controlling the motor for adjusting the anode-cathode gap is fed into the apparatus using optical waveguides. The motor, controlled by the input information, drives a worm gear that moves a cathode tip. When the motor drives in one rotational direction, the cathode is moved toward the anode and the size of the anode-cathode gap is diminished. When the motor drives in the other direction, the cathode is moved away from the anode and the size of the anode-cathode gap is increased. The motor is powered by batteries housed in the hollow cathode. The batteries may be rechargeable, and they may be recharged by a photovoltaic cell in combination with an optical waveguide that receives recharging energy from outside the hollow cathode. Alternatively, the anode-cathode gap can be remotely adjusted by a manually-turned handle connected to mechanical linkage which is connected to a jack assembly. The jack assembly converts rotational motion of the handle and mechanical linkage to linear motion of the cathode moving toward or away from the anode.

Methods and apparatus for using gas and liquid phase cathodic depolarizers

NASA Technical Reports Server (NTRS)

Murphy, Oliver J. (Inventor); Hitchens, G. Duncan (Inventor)

1998-01-01

The invention provides methods for using gas and liquid phase cathodic depolarizers in an electrochemical cell having a cation exchange membrane in intimate contact with the anode and cathode. The electrochemical conversion of cathodic depolarizers at the cathode lowers the cell potential necessary to achieve a desired electrochemical conversion, such as ozone evolution, at the anode. When gaseous cathodic depolarizers, such as oxygen, are used, a gas diffusion cathode having the cation exchange membrane bonded thereto is preferred. When liquid phase cathodic depolarizers are used, the cathode may be a flow-by electrode, flow-through electrode, packed-bed electrode or a fluidized-bed electrode in intimate contact with the cation exchange membrane.

Lithium ion rechargeable systems studies

NASA Astrophysics Data System (ADS)

Levy, Samuel C.; Lasasse, Robert R.; Cygan, Randall T.; Voigt, James A.

Lithium ion systems, although relatively new, have attracted much interest worldwide. Their high energy density, long cycle life and relative safety, compared with metallic lithium rechargeable systems, make them prime candidates for powering portable electronic equipment. Although lithium ion cells are presently used in a few consumer devices, e.g., portable phones, camcorders, and laptop computers, there is room for considerable improvement in their performance. Specific areas that need to be addressed include: (1) carbon anode-increase reversible capacity, and minimize passivation; (2) cathode-extend cycle life, improve rate capability, and increase capacity. There are several programs ongoing at Sandia National Laboratories which are investigating means of achieving the stated objectives in these specific areas. This paper will review these programs.

Aerosol-assisted chemical vapor deposition of V2O5 cathodes with high rate capabilities for magnesium-ion batteries

NASA Astrophysics Data System (ADS)

Drosos, Charalampos; Jia, Chenglin; Mathew, Shiny; Palgrave, Robert G.; Moss, Benjamin; Kafizas, Andreas; Vernardou, Dimitra

2018-04-01

The growth of orthorhombic vanadium pentoxide nanostructures was accomplished using an aerosol-assisted chemical vapor deposition process. These materials showed excellent electrochemical performance for magnesium-ion storage in an aqueous electrolyte; showing specific discharge capacities of up to 427 mAh g-1 with a capacity retention of 82% after 2000 scans under a high specific current of 5.9 A g-1. The high rate capability suggested good structural stability and high reversibility. We believe the development of low-cost and large-area coating methods, such as the technique used herein, will be essential for the upscalable fabrication of next-generation rechargeable battery technologies.

Anode property of carbon coated LiFePO4 nanocrystals

NASA Astrophysics Data System (ADS)

Ni, Jiangfeng; Jiang, Jiaxing; Savilov, S. V.; Aldoshin, S. M.

2016-10-01

Nanostructured LiFePO4 is appealing cathode material for rechargeable lithium batteries. Herein, however, we report the intriguing anode properties of carbon coated LiFePO4 nanocrystals. In the potential range of 0-3.0 V, the LiFePO4 nanocrystal electrodes afford high reversible capacity of 373 mAhg-1 at a current rate of 0.05 Ag-1 and retains 239 mAhg-1 at a much higher rate of 1.25 Ag-1. In addition, it is capable of sustaining 1000 cycles at 1.25 Ag-1 without any capacity fading. Such superior properties indicate that nanostructured LiFePO4 could also be promising anode for rechargeable battery applications.

Graphene oxide as a sulfur immobilizer in high performance lithium/sulfur cells

DOEpatents

Zhang, Yuegang; Cairns, Elton J.; Ji, Liwen; Rao, Mumin

2017-06-06

The loss of sulfur cathode material as a result of polysulfide dissolution causes significant capacity fading in rechargeable lithium/sulfur cells. Embodiments of the invention use a chemical approach to immobilize sulfur and lithium polysulfides via the reactive functional groups on graphene oxide. This approach obtains a uniform and thin (.about.tens of nanometers) sulfur coating on graphene oxide sheets by a chemical reaction-deposition strategy and a subsequent low temperature thermal treatment process. Strong interaction between graphene oxide and sulfur or polysulfides demonstrate lithium/sulfur cells with a high reversible capacity of 950-1400 mAh g.sup.-1, and stable cycling for more than 50 deep cycles at 0.1 C.

1.9 kV AlGaN/GaN Lateral Schottky Barrier Diodes on Silicon

DOE PAGES

Zhu, Mingda; Song, Bo; Qi, Meng; ...

2015-02-16

In this letter, we present AlGaN/GaN lateral Schottky barrier diodes on silicon with recessed anodes and dual field plates. A low specific on-resistance R ON,SP (5.12 mΩ · cm 2), a low turn-on voltage (<0.7 V) and a high reverse breakdown voltage BV (>1.9 kV), were simultaneously achieved in devices with a 25 μm anode/cathode separation, resulting in a power figure-of-merit (FOM) BV2/R ON,SP of 727 MW·cm 2. The record high breakdown voltage of 1.9 kV is attributed to the dual field plate structure.

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.

Rechargeable thin film battery and method for making the same

DOEpatents

Goldner, Ronald B.; Liu, Te-Yang; Goldner, Mark A.; Gerouki, Alexandra; Haas, Terry E.

2006-01-03

A rechargeable, stackable, thin film, solid-state lithium electrochemical cell, thin film lithium battery and method for making the same is disclosed. The cell and battery provide for a variety configurations, voltage and current capacities. An innovative low temperature ion beam assisted deposition method for fabricating thin film, solid-state anodes, cathodes and electrolytes is disclosed wherein a source of energetic ions and evaporants combine to form thin film cell components having preferred crystallinity, structure and orientation. The disclosed batteries are particularly useful as power sources for portable electronic devices and electric vehicle applications where high energy density, high reversible charge capacity, high discharge current and long battery lifetimes are required.

An Archean Geomagnetic Reversal in the Kaap Valley Pluton, South Africa

PubMed

Layer; Kroner; McWilliams

1996-08-16

The Kaap Valley pluton in South Africa is a tonalite intrusion associated with the Archean Barberton Greenstone Belt. Antipodal paleomagnetic directions determined from the central and marginal parts of the pluton record a geomagnetic reversal that occurred as the pluton cooled. The age of the reversal is constrained by an 40Ar/39Ar plateau age from hornblende at 3214 +/- 4 million years, making it the oldest known reversal. The data presented here suggest that Earth has had a reversing, perhaps dipolar, magnetic field since at least 3.2 billion years ago.

Sintered wire cathode

DOEpatents

Falce, Louis R [San Jose, CA; Ives, R Lawrence [Saratoga, CA

2009-06-09

A porous cathode structure is fabricated from a plurality of wires which are placed in proximity to each other in elevated temperature and pressure for a sintering time. The sintering process produces the porous cathode structure which may be divided into a plurality of individual porous cathodes, one of which may be placed into a dispenser cathode support which includes a cavity for containing a work function reduction material such as BaO, CaO, and Al.sub.2O.sub.3. The work function reduction material migrates through the pores of the porous cathode from a work replenishment surface adjacent to the cavity of the dispenser cathode support to an emitting cathode surface, thereby providing a dispenser cathode which has a uniform work function and therefore a uniform electron emission.

Development program on a cold cathode electron gun

NASA Technical Reports Server (NTRS)

Spindt, C. A.; Holland, C. E.

1985-01-01

During this phase of the cathode development program, SRI improved the multiple electron beam exposure system used to print hole patterns for the cathode arrays, studied anisotropic etch processes, conducted cathode investigations using an emission microscope, reviewed possible alternate materials for cathode fabrication, studied cathode storage techniques, conducted high power operation experiments, and demonstrated high-current-density operation with small arrays of tips.

Modeling and validation of single-chamber microbial fuel cell cathode biofilm growth and response to oxidant gas composition

NASA Astrophysics Data System (ADS)

Ou, Shiqi; Zhao, Yi; Aaron, Douglas S.; Regan, John M.; Mench, Matthew M.

2016-10-01

This work describes experiments and computational simulations to analyze single-chamber, air-cathode microbial fuel cell (MFC) performance and cathodic limitations in terms of current generation, power output, mass transport, biomass competition, and biofilm growth. Steady-state and transient cathode models were developed and experimentally validated. Two cathode gas mixtures were used to explore oxygen transport in the cathode: the MFCs exposed to a helium-oxygen mixture (heliox) produced higher current and power output than the group of MFCs exposed to air or a nitrogen-oxygen mixture (nitrox), indicating a dependence on gas-phase transport in the cathode. Multi-substance transport, biological reactions, and electrochemical reactions in a multi-layer and multi-biomass cathode biofilm were also simulated in a transient model. The transient model described biofilm growth over 15 days while providing insight into mass transport and cathodic dissolved species concentration profiles during biofilm growth. Simulation results predict that the dissolved oxygen content and diffusion in the cathode are key parameters affecting the power output of the air-cathode MFC system, with greater oxygen content in the cathode resulting in increased power output and fully-matured biomass.

Modeling and validation of single-chamber microbial fuel cell cathode biofilm growth and response to oxidant gas composition

DOE PAGES

Ou, Shiqi; Zhao, Yi; Aaron, Douglas S.; ...

2016-08-15

This work describes experiments and computational simulations to analyze single-chamber, air-cathode microbial fuel cell (MFC) performance and cathodic limitations in terms of current generation, power output, mass transport, biomass competition, and biofilm growth. Steady-state and transient cathode models were developed and experimentally validated. Two cathode gas mixtures were used to explore oxygen transport in the cathode: the MFCs exposed to a helium-oxygen mixture (heliox) produced higher current and power output than the group of MFCs exposed to air or a nitrogen-oxygen mixture (nitrox), indicating a dependence on gas-phase transport in the cathode. Multi-substance transport, biological reactions, and electrochemical reactions inmore » a multi-layer and multi-biomass cathode biofilm were also simulated in a transient model. The transient model described biofilm growth over 15 days while providing insight into mass transport and cathodic dissolved species concentration profiles during biofilm growth. Lastly, simulation results predict that the dissolved oxygen content and diffusion in the cathode are key parameters affecting the power output of the air-cathode MFC system, with greater oxygen content in the cathode resulting in increased power output and fully-matured biomass.« less

Extended test of a xenon hollow cathode for a space plasma contactor

NASA Technical Reports Server (NTRS)

Sarver-Verhey, Timothy R.

1994-01-01

Implementation of a hollow cathode plasma contactor for charge control on the Space Station has required validation of long-life hollow cathodes. A test series of hollow cathodes and hollow cathode plasma contactors was initiated as part of the plasma contactor development program. An on-going wear-test of a hollow cathode has demonstrated cathode operation in excess of 4700 hours with small changes in operating parameters. The discharge experienced 4 shutdowns during the test, all of which were due to test facility failures or expellant replenishment. In all cases, the cathode was reignited at approximately 42 volts and resumed typical operation. This test represents the longest demonstrated stable operation of a high current (greater than 1A) xenon hollow cathode reported to date.

Continuing life test of a xenon hollow cathode for a space plasma contactor

NASA Technical Reports Server (NTRS)

Sarver-Verhey, Timothy R.

1994-01-01

Implementation of a hollow cathode plasma contactor for charge control on the Space Station has required validation of long-life hollow cathodes. A test series of hollow cathodes and hollow cathode plasma contactors was initiated as part of the plasma contactor development program. An on-going wear-test of a hollow cathode has demonstrated cathode operation in excess of 10,000 hours with small changes in operating parameters. The discharge has experienced 10 shutdowns during the test, all of which were due to test facility failures or expellant replenishment. In all cases, the cathode was re-ignited at approximately 42 volts and resumed typical operation. This test represents the longest demonstrated stable operation of a high current (greater than 1 A) xenon hollow cathode reported to date.

A multi-layered Fe2O3/graphene composite with mesopores as a catalyst for rechargeable aprotic lithium-oxygen batteries.

PubMed

Feng, Ningning; Mu, Xiaowei; Zheng, Mingbo; Wang, Chaoqiang; Lin, Zixia; Zhang, Xueping; Shi, Yi; He, Ping; Zhou, Haoshen

2016-09-09

Aprotic Li-O2 batteries have attracted a huge amount of interest in the past decade owing to their extremely high energy density. However, identifying a desirable cathodic catalyst for this promising battery system is one of the biggest challenges at present. In this work, a multi-layered Fe2O3/graphene nanosheets (Fe2O3/GNS) composite with sandwich structure was synthesized using an easy thermal casting method, and served as a cathodic catalyst for aprotic Li-O2 batteries. The aprotic Li-O2 cell with the Fe2O3/GNS catalyst demonstrated a better reversibility, lower overpotential for oxygen evolution, and a higher Coulombic efficiency (close to 100%) than those of pure GNS. An excellent rate performance and good cycle stability were also confirmed. The results, characterized by ex and in situ methods, revealed that the dominant discharge product Li2O2 was decomposed below 4.35 V. This superior electrochemical performance is mainly attributed to the unique sandwich structure of the Fe2O3/GNS catalyst with mesopores, which can provide substantially more catalytic sites and prevent direct contact between carbon and Li2O2.

Electronic structure ‘engineering’ in the development of materials for Li-ion and Na-ion batteries

NASA Astrophysics Data System (ADS)

Molenda, Janina

2017-03-01

Transition metal oxides with a general formula A x M a O b (A  =  Li, Na, M  =  transition metal) constitute a group of potential electrode materials for a new generation of alkaline batteries. This application is related to the fact that these compounds can reversibly intercalate high amounts of alkaline ions (1 or more moles per mole of M a O b ) already at room temperature, without significant changes in their crystallographic structure. The author of this work basing on her own investigations of A x M a O b (A  =  Li, Na; M  =  3d, 4d, 5d) has demonstrated that the electronic structure of these materials plays an important role in the intercalation process. Electronic model of intercalation process is presented. Author’s studies show that electronic structure ‘engineering’ is an excellent method of controlling properties of the cathode materials for Li-ion and Na-ion batteries, changing their unfavorable character of the discharge curve, from step-like to monotonic, through modification and control density of states function of a cathode material. Keynote talk at 8th International Workshop on Advanced Materials Science and Nanotechnology (IWAMSN2016), 8-12 November 2016, Ha Long City, Vietnam.

Core–shell-structured Li 3V 2(PO 4) 3 –LiVOPO 4 nanocomposites cathode for high-rate and long-life lithium-ion batteries

DOE PAGES

Sun, Pingping; Wang, Xiuzhen; Zhu, Kai; ...

2017-01-13

A facile strategy has been developed to construct unique core–shell-structured Li 2.7V 2.1(PO 4) 3 nanocomposites with a Li 3V 2(PO 4) 3 core and LiVOPO 4 shell by using nonstoichiometric design and high-energy ball milling (HEBM) treatment. The HEBM treatment supplies enough energy to drive the excess V atoms to the surface to form a V-enriched shell. Such kind of cathode can deliver a high reversible capacity of 131.5 mAhg $-$1 at 0.5 C, which is close to the theoretical capacity (133 mAhg $-$1 in 3.0–4.3 V). Even at 20 C, it still delivers an excellent discharge capacity ofmore » 116.3 mAhg $-$1, and a remarkable capacity of 111.0 mAhg $-$1 after 1000 cycles, corresponding to an ultra-small capacity-loss of 0.0046% per cycle. Finally, the significantly improved high-rate electrochemical performance can be attributed to the active shell of LiVOPO 4, which not only efficiently facilitates the electron and Li + ion transport during cycling processes, but also accommodates more Li+ ions to effectively compensate the capacity loss of the core.« less

Neutral beam dump with cathodic arc titanium gettering

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

Smirnov, A.; Korepanov, S. A.; Putvinski, S.

An incomplete neutral beam capture can degrade the plasma performance in neutral beam driven plasma machines. The beam dumps mitigating the shine-through beam recycling must entrap and retain large particle loads while maintaining the beam-exposed surfaces clean of the residual impurities. The cathodic arc gettering, which provides high evaporation rate coupled with a fast time response, is a powerful and versatile technique for depositing clean getter films in vacuum. A compact neutral beam dump utilizing the titanium arc gettering was developed for a field-reversed configuration plasma sustained by 1 MW, 20-40 keV neutral hydrogen beams. The titanium evaporator features amore » new improved design. The beam dump is capable of handling large pulsed gas loads, has a high sorption capacity, and is robust and reliable. With the beam particle flux density of 5 x 10{sup 17} H/(cm{sup 2}s) sustained for 3-10 ms, the beam recycling coefficient, defined as twice the ratio of the hydrogen molecular flux leaving the beam dump to the incident flux of high-energy neutral atoms, is {approx}0.7. The use of the beam dump allows us to significantly reduce the recycling of the shine-through neutral beam as well as to improve the vacuum conditions in the machine.« less

Open-Structured V 2 O 5 · n H 2 O Nanoflakes as Highly Reversible Cathode Material for Monovalent and Multivalent Intercalation Batteries

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

Wang, Huali; Bi, Xuanxuan; Bai, Ying

The high-capacity cathode material V2O5·nH2O has attracted considerable attention for metal ion batteries due to the multielectron redox reaction during electrochemical processes. It has an expanded layer structure, which can host large ions or multivalent ions. However, structural instability and poor electronic and ionic conductivities greatly handicap its application. Here, in cell tests, self-assembly V2O5·nH2O nanoflakes shows excellent electrochemical performance with either monovalent or multivalent cation intercalation. They are directly grown on a 3D conductive stainless steel mesh substrate via a simple and green hydrothermal method. Well-layered nanoflakes are obtained after heat treatment at 300 °C (V2O5·0.3H2O). Nanoflakes with ultrathinmore » flower petals deliver a stable capacity of 250 mA h g-1 in a Li-ion cell, 110 mA h g-1 in a Na-ion cell, and 80 mA h g-1 in an Al-ion cell in their respective potential ranges (2.0–4.0 V for Li and Na-ion batteries and 0.1–2.5 V for Al-ion battery) after 100 cycles.« less

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

Twu, Nancy; Metzger, Michael; Balasubramanian, Mahalingam

Here, the lithium-excess Li xNi 2-4x/3Sb x/3O 2 (LNSO) materials were previously shown to demonstrate higher capacities and improved cyclability with increasing lithium content. While the performance trend is promising, observed capacities are much lower than theoretical capacities, pointing to a need for further understanding of active redox processes in these materials. In this work, we study the electrochemical behavior of the LNSO materials as a function of lithium content and at slow and fast rates. Surprisingly, Li 1.15Ni 0.47Sb 0.38O 2 (LNSO-15) exhibits higher discharge capacities at faster rates and traverses distinct voltage curves at slow and fast rates.more » To understand these two peculiarities, we characterize the redox activity of nickel, antimony, and oxygen at different rates. While experiments confirm some nickel redox activity and oxygen loss, these two mechanisms cannot account for all observed capacity. We propose that the balance of the observed capacity may be due reversible oxygen redox and that the rate-dependent voltage curve features may derive from irreversible nickel migration occurring on slow charge. As future high energy density cathodes are likely to contain both lithium excess and high nickel content, both of these findings have important implications for the development of novel high capacity cathode materials.« less

First-Principles evaluation of the Chevrel phase intercalated with Be, Mg, Ca, Sr, and Ba

NASA Astrophysics Data System (ADS)

Juran, Taylor; Smeu, Manuel

Li ion batteries are extremely useful when an item requires portability and compactness, such as laptops and cell phones; due to the lightweight/compact nature of Li ion batteries. The lightweight and compact nature of Li ion batteries comes at a high cost. It is sensible to consider Li ion battery alternatives, which are more cost effective and useable when portability is not a priority. An option for a less expensive battery source is the Ca ion battery. The Ca ion battery is interesting as many researchers overlook the potential battery source due to the perplexity of finding suitable anode materials and electrolytes. In order for this technology to work, cathodes that allow for the reversible intercalation of Ca2+ ions and also provide a preferred voltage must be identified. We investigate the Chevrel phase compounds of Mo6X8 (X = S, Se, Te) which can intercalate various ions. The concentration of the ion intercalated with the Chevrel cathode is studied. We consider doped versions of the Chevrel phase, using various dopants to substitute Mo. We use density functional theory to calculate the voltage of several intercalation ions with the Chevrel material. The resulting electronic properties of the aforementioned materials will be investigated.

Biomass derived Ni(OH)2@porous carbon/sulfur composites synthesized by a novel sulfur impregnation strategy based on supercritical CO2 technology for advanced Li-S batteries

NASA Astrophysics Data System (ADS)

Xia, Yang; Zhong, Haoyue; Fang, Ruyi; Liang, Chu; Xiao, Zhen; Huang, Hui; Gan, Yongping; Zhang, Jun; Tao, Xinyong; Zhang, Wenkui

2018-02-01

The rational design and controllable synthesis of sulfur cathode with high sulfur content, superior structural stability and fascinating electrochemical properties is a vital step to realize the large-scale application of rechargeable lithium-sulfur (Li-S) batteries. However, the electric insulation of elemental sulfur and the high solubility of lithium polysulfides are two intractable obstacles to hinder the success of Li-S batteries. In order to overcome aforementioned issues, a novel strategy combined supercritical CO2 fluid technology and biotemplating method is developed to fabricate Ni(OH)2 modified porous carbon microspheres as sulfur hosts to ameliorate the electronic conductive of sulfur and enhance simultaneously the physical and chemical absorptions of polysulfides. This elaborately designed Ni(OH)2@PYC/S composite cathode exhibits high reversible discharge capacity (1335 mAh g-1 at 0.1 C), remarkable cyclic stability (602 mAh g-1 after 200 cycles at 0.2 C) and superior rate capability, which is much better than its PYC/S counterpart. These results clearly demonstrate that the advanced porous carbon with good conductivity and the polar Ni(OH)2 coating layer with strong trapping ability of polysulfides are responsible for the enhanced electrochemical performance.

Influence of cell temperature on sulfur dioxide contamination in proton exchange membrane fuel cells

NASA Astrophysics Data System (ADS)

Zhai, Y.; Bender, G.; Bethune, K.; Rocheleau, R.

2014-02-01

The effects of temperature on sulfur dioxide (SO2) contamination in PEMFCs are investigated by operating single cells with 2 ppm SO2 in the cathode at different temperatures. Cell performance response shows that voltage degradation was delayed and appears a transition of multiple processes at low temperatures; a similar performance loss is observed when performances reached steady state. The restored performance from the reversible and the irreversible degradations highly depends on temperature. At low temperature, the performance recovery is only negligible with neat air operation (self-recovery), while full recovery is observed after cyclic voltammetry (CV) scanning. As temperature increased, so did the self-recovery performance. However, the total recovery performance decreased. Electrochemical impedance spectroscopy analysis indicates that the potential-dependent poisoning process was delayed at low temperature, and the removal of the sulfur species from Pt/C was inhibited during the self-recovery. Water balance analysis implies that the delay could be attributed to the effect of liquid water scavenging and the mass transport of SO2 in the membrane electrode assemblies. The CV analysis confirms that the decomposition/desorption of the sulfur adsorbates was inhibited and indicates that the SO2 crossover from the cathode to the anode side was also mitigated at low temperature.

Pre-sodiated nickel cobaltite for high-performance sodium-ion capacitors

NASA Astrophysics Data System (ADS)

Yang, Dongfang; Sun, Xiaoming; Lim, Kyungmi; Ranganathan Gaddam, Rohit; Ashok Kumar, Nanjundan; Kang, Kisuk; Zhao, Xiu Song

2017-09-01

Sodium-ion capacitors (NICs) are a hybrid energy storage system that store energy via both charge adsorption at the cathode/electrolyte interface and charge intercalation in the bulk of the anode, thereby possessing a higher energy density than supercapacitors and a higher power density than batteries. In this work, nickel cobaltite (NiCo2O4) hollow spheres with a chestnut shell morphology have been solvothermally synthesized and tested in a sodium half-cell. The NiCo2O4 material exhibits a reversible capacity of 313 mAh g-1 at 1 A g-1. Pre-sodiation of NiCo2O4 is found to significantly improve its energy density. A NIC fabricated with pre-sodiated NiCo2O4 as the anode and an activated carbon (AC) as the cathode delivers an energy density of 60 Wh kg-1 at the power density of 10,000 W kg-1. Ex-situ X-ray diffraction (XRD) and transmission electron microscopy (TEM) results reveal that NiCo2O4 is converted to metallic nickel and cobalt and Na2O phases during the pre-sodiation. The metallic nickel and cobalt phases are kinetically favourable for the electrolyte diffusion and electrochemical reactions, thus significantly improving the performance of the pre-sodiated NiCo2O4 electrode.

A Semi-Empirical Two Step Carbon Corrosion Reaction Model in PEM Fuel Cells

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

Young, Alan; Colbow, Vesna; Harvey, David

2013-01-01

The cathode CL of a polymer electrolyte membrane fuel cell (PEMFC) was exposed to high potentials, 1.0 to 1.4 V versus a reversible hydrogen electrode (RHE), that are typically encountered during start up/shut down operation. While both platinum dissolution and carbon corrosion occurred, the carbon corrosion effects were isolated and modeled. The presented model separates the carbon corrosion process into two reaction steps; (1) oxidation of the carbon surface to carbon-oxygen groups, and (2) further corrosion of the oxidized surface to carbon dioxide/monoxide. To oxidize and corrode the cathode catalyst carbon support, the CL was subjected to an accelerated stressmore » test cycled the potential from 0.6 VRHE to an upper potential limit (UPL) ranging from 0.9 to 1.4 VRHE at varying dwell times. The reaction rate constants and specific capacitances of carbon and platinum were fitted by evaluating the double layer capacitance (Cdl) trends. Carbon surface oxidation increased the Cdl due to increased specific capacitance for carbon surfaces with carbon-oxygen groups, while the second corrosion reaction decreased the Cdl due to loss of the overall carbon surface area. The first oxidation step differed between carbon types, while both reaction rate constants were found to have a dependency on UPL, temperature, and gas relative humidity.« less

Electrochemical and ab initio investigations to design a new phenothiazine based organic redox polymeric material for metal-ion battery cathodes.

PubMed

Godet-Bar, T; Leprêtre, J-C; Le Bacq, O; Sanchez, J-Y; Deronzier, A; Pasturel, A

2015-10-14

Different N-substituted phenothiazines have been synthesized and their electrochemical behavior has been investigated in CH3CN in order to design the best polyphenothiazine based cathodic material candidate for lithium batteries. These compounds exhibit two successive reversible one-electron oxidation processes. Ab initio calculations demonstrate that the potential of the first process is a result of both the hybridization effects between the substituent and the phenothiazine unit as well as the change of conformation of the phenothiazine heterocycle during the oxidation process. More specifically, we show that an asymmetric molecular orbital spreading throughout an external cycle of the phenothiazine unit and the alkyl fragment is formed only if the alkyl fragment is long enough (from the methyl moiety onwards) and is at the origin of the bent conformation for N-substituted phenothiazines during oxidation. Electrochemical investigations supported by ab initio calculations allow the selection of a phenothiazinyl unit which is then polymerized by a Suzuki coupling strategy to avoid the common solubilization issue in carbonate-based liquid electrolytes of lithium cells. The first electrochemical measurements performed show that phenothiazine derivatives pave the way for a promising family of redox polymers intended to be used as organic positives for lithium batteries.

Anodal tDCS to V1 blocks visual perceptual learning consolidation.

PubMed

Peters, Megan A K; Thompson, Benjamin; Merabet, Lotfi B; Wu, Allan D; Shams, Ladan

2013-06-01

This study examined the effects of visual cortex transcranial direct current stimulation (tDCS) on visual processing and learning. Participants performed a contrast detection task on two consecutive days. Each session consisted of a baseline measurement followed by measurements made during active or sham stimulation. On the first day, one group received anodal stimulation to primary visual cortex (V1), while another received cathodal stimulation. Stimulation polarity was reversed for these groups on the second day. The third (control) group of subjects received sham stimulation on both days. No improvements or decrements in contrast sensitivity relative to the same-day baseline were observed during real tDCS, nor was any within-session learning trend observed. However, task performance improved significantly from Day 1 to Day 2 for the participants who received cathodal tDCS on Day 1 and for the sham group. No such improvement was found for the participants who received anodal stimulation on Day 1, indicating that anodal tDCS blocked overnight consolidation of visual learning, perhaps through engagement of inhibitory homeostatic plasticity mechanisms or alteration of the signal-to-noise ratio within stimulated cortex. These results show that applying tDCS to the visual cortex can modify consolidation of visual learning. Copyright © 2013 Elsevier Ltd. All rights reserved.

Hierarchical Li1.2Mn0.54Ni0.13Co0.13O2 hollow spherical as cathode material for Li-ion battery

NASA Astrophysics Data System (ADS)

Zhang, Yu; Zhu, Tianjiao; Lin, Liu; Yuan, Mengwei; Li, Huifeng; Sun, Genban; Ma, Shulan

2017-11-01

Lithium-rich manganese-based layered materials have been considered as the most promising cathode materials for future high-energy-density lithium-ion batteries. However, a great loss of irreversible capacity at the initial cycle, poor cycle stability, and rate performance severely restrict its application. Herein, we develop a new strategy to synthesize hierarchical hollow Li1.2Mn0.54Ni0.13Co0.13O2 microspheres using sucrose and cetyltrimethylammonium bromide as a soft template combined with hydrothermal assisted homogeneous precipitation method. The hollow microspheres are assembled by the primary particles with the size of 50 nm. As a result, the as-prepared material exhibits high reversible capacity, good cycling stability, and excellent rate property. It delivers a high initial discharge capacity of 305.9 mAh g-1 at 28 mA g-1 with coulombic efficiency of 80%. Even at high current density of 560 mA g-1, the sample also shows a stable discharge capacity of 215 mAh g-1. The enhanced electrochemical properties are attributed to the stable hierarchical hollow sphere structure and the appropriate contact area between electrode and electrolyte, thus effectively improve the lithium-ion intercalation and deintercalation kinetics. [Figure not available: see fulltext.

Hemoglobin-carbon nanotube derived noble-metal-free Fe5C2-based catalyst for highly efficient oxygen reduction reaction

NASA Astrophysics Data System (ADS)

Vij, Varun; Tiwari, Jitendra N.; Lee, Wang-Geun; Yoon, Taeseung; Kim, Kwang S.

2016-02-01

High performance non-precious cathodic catalysts for oxygen reduction reaction (ORR) are vital for the development of energy materials and devices. Here, we report an noble metal free, Fe5C2 nanoparticles-studded sp2 carbon supported mesoporous material (CNTHb-700) as cathodic catalyst for ORR, which was prepared by pyrolizing the hybrid adduct of single walled carbon nanotubes (CNT) and lyophilized hemoglobin (Hb) at 700 °C. The catalyst shows onset potentials of 0.92 V in 0.1 M HClO4 and in 0.1 M KOH which are as good as commercial Pt/C catalyst, giving very high current density of 6.34 and 6.69 mA cm-2 at 0.55 V vs. reversible hydrogen electrode (RHE), respectively. This catalyst has been confirmed to follow 4-electron mechanism for ORR and shows high electrochemical stability in both acidic and basic media. Catalyst CNTHb-700 possesses much higher tolerance towards methanol than the commercial Pt/C catalyst. Highly efficient catalytic properties of CNTHb-700 could lead to fundamental understanding of utilization of biomolecules in ORR and materialization of proton exchange membrane fuel cells for clean energy production.

Preparation and surface characteristics of Re3W matrix scandate cathode: An experimental and theoretical study

NASA Astrophysics Data System (ADS)

Lai, Chen; Wang, Jinshu; Zhou, Fan; Liu, Wei; Hu, Peng; Wang, Changhao; Wang, Ruzhi; Miao, Naihua

2018-05-01

The Scandia doped thermionic cathodes have received great attention owing to their high electron emission density in past two decades. Here, Scandia doped Re3W matrix scandate (RS) cathodes are fabricated by using Sc2O3 doped Re3W powders that prepared by spray drying method. The micromorphology, surface composition and chemical states of RS cathode are investigated with various modern technologies. It reveals that the reduction temperature of RS powders is dramatically increased by Sc2O3. On the surface of RS cathode, a certain amount of Sc2O3 nanoparticles and barium salt submicron particles are observed. According to the in situ Auger electron spectroscopy analysis, the concentration ratio of Ba:Sc:O is determined to be 2.9:1.1:2.7. The X-ray photoelectron spectroscopy data indicates that low oxidation state of Sc is clearly observed in scandate cathodes. The high atomic ratio of Ba on RS cathode surface is suggested due to the high adsorption of Re3W to Ba. Moreover, RS cathode shows better adsorption to Sc by comparison with conventional tungsten matrix scandate cathode. For RS cathode, the main depletion of Sc is suggested to -OSc desorbing from RS cathode surface. RS cathode is expected to be an impressive thermionic cathode with good emission properties and ion anti-bombarding insensitivity.

Reversible Age-Related Phenotypes Induced during Larval Quiescence in C. elegans

PubMed Central

Roux, Antoine E.; Langhans, Kelley; Huynh, Walter; Kenyon, Cynthia

2017-01-01

Summary Cells can enter quiescent states in which cell cycling and growth are suspended. We find that during a long developmental arrest (quiescence) induced by starvation, newly-hatched C. elegans acquire features associated with impaired proteostasis and aging: mitochondrial fission, ROS production, protein aggregation, decreased proteotoxic-stress resistance, and at the organismal level, decline of mobility and high mortality. All signs of aging but one, the presence of protein aggregates, were reversed upon return to development induced by feeding. The endoplasmic reticulum receptor IRE-1 is completely required for recovery, and the downstream transcription factor XBP-1, as well as a protein kinase, KGB-1, are partially required. Interestingly, kgb-1(−) mutants that do recover fail to reverse aging-like mitochondrial phenotypes and have a short adult lifespan. Our study describes the first pathway that reverses phenotypes of aging at the exit of prolonged quiescence. PMID:27304510