Design and Demonstration of Three-Electrode Pouch Cells for Lithium-Ion Batteries

DOE PAGES

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

2017-06-14

Simple three-electrode pouch cells which can be used in distinguishing the voltage and resistance in individual electrodes of lithium ion batteries have been designed. Baseline (1 mm-staggered alignment, cathode away from a reference electrode) and aligned electrodes to a reference electrode located outside of the anode and cathode were studied to see alignment effects on resistance analysis. Cells composed of A12 graphite anodes, LiNi 0.5Mn 0.3Co 0.2O 2 (NMC 532 or NCM 523) cathodes, lithium foil references, microporous tri-layer membranes, and electrolytes, were cycled with cathode cutoff voltages between 3.0 V and 4.3 V for formation cycles or 4.6 Vmore » for C-rate performance testing. By applying a hybrid pulse power characterization (HPPC) technique to the cells, resistances of the baseline cells contributed by the anode and cathode were found to be different from those of the aligned cells, although overall resistances were close to ones from aligned cells. As a result, resistances obtained via electrochemical impedance spectroscopy (EIS) and 2D simulation were also compared with those obtained from HPPC.« less

PEMFC catalyst layers: the role of micropores and mesopores on water sorption and fuel cell activity.

PubMed

Soboleva, Tatyana; Malek, Kourosh; Xie, Zhong; Navessin, Titichai; Holdcroft, Steven

2011-06-01

The effects of carbon microstructure and ionomer loading on water vapor sorption and retention in catalyst layers (CLs) of PEM fuel cells are investigated using dynamic vapor sorption. Catalyst layers based on Ketjen Black and Vulcan XC-72 carbon blacks, which possess distinctly different surface areas, pore volumes, and microporosities, are studied. It is found that pores <20 nm diameter facilitate water uptake by capillary condensation in the intermediate range of relative humidities. A broad pore size distribution (PSD) is found to enhance water retention in Ketjen Black-based CLs whereas the narrower mesoporous PSD of Vulcan CLs is shown to have an enhanced water repelling action. Water vapor sorption and retention properties of CLs are correlated to electrochemical properties and fuel cell performance. Water sorption enhances electrochemical properties such as the electrochemically active surface area (ESA), double layer capacitance and proton conductivity, particularly when the ionomer content is very low. The hydrophilic properties of a CL on the anode and the cathode are adjusted by choosing the PSD of carbon and the ionomer content. It is shown that a reduction of ionomer content on either cathode or anode of an MEA does not necessarily have a significant detrimental effect on the MEA performance compared to the standard 30 wt % ionomer MEA. Under operation in air and high relative humidity, a cathode with a narrow pore size distribution and low ionomer content is shown to be beneficial due to its low water retention properties. In dry operating conditions, adequate ionomer content on the cathode is crucial, whereas it can be reduced on the anode without a significant impact on fuel cell performance. © 2011 American Chemical Society

Toward Increasing Micropore Volume between Hybrid Layered Perovskites with Silsesquioxane Interlayers.

PubMed

Kataoka, Sho; Kamimura, Yoshihiro; Endo, Akira

2018-04-10

Hybrid organic-inorganic layered perovskites are typically nonporous solids. However, the incorporation of silsesquioxanes with a cubic cage structure as interlayer materials creates micropores between the perovskite layers. In this study, we increase in the micropore volume in layered perovskites by replacing a portion of the silsesquioxane interlayers with organic amines. In the proposed method, approximately 20% of the silsesquioxane interlayers can be replaced without changing the layer distance owing to the size of the silsesquioxane. When small amines (e.g., ethylamine) are used in this manner, the micropore volume of the obtained hybrid layered perovskites increases by as much as 44%; when large amines (e.g., phenethylamine) are used, their micropore volume decreases by as much as 43%. Through the variation of amine fraction, the micropore volume can be adjusted in the range. Finally, the magnetic moment measurements reveal that the layered perovskites with mixed interlayers exhibit ferromagnetic ordering at temperature below 20 K, thus indicating that the obtained perovskites maintain their functions as layered perovskites.

Bio-electrochemical characterization of air-cathode microbial fuel cells with microporous polyethylene/silica membrane as separator.

PubMed

Kircheva, Nina; Outin, Jonathan; Perrier, Gérard; Ramousse, Julien; Merlin, Gérard; Lyautey, Emilie

2015-12-01

The aim of this work was to study the behavior over time of a separator made of a low-cost and non-selective microporous polyethylene membrane (RhinoHide®) in an air-cathode microbial fuel cell with a reticulated vitreous carbon foam bioanode. Performances of the microporous polyethylene membrane (RhinoHide®) were compared with Nafion®-117 as a cationic exchange membrane. A non-parametric test (Mann-Whitney) done on the different sets of coulombic or energy efficiency data showed no significant difference between the two types of tested membrane (p<0.05). Volumetric power densities were ranging from 30 to 90 W·m(-3) of RVC foam for both membranes. Similar amounts of biomass were observed on both sides of the polyethylene membrane illustrating bacterial permeability of this type of separator. A monospecific denitrifying population on cathodic side of RhinoHide® membrane has been identified. Electrochemical impedance spectroscopy (EIS) was used at OCV conditions to characterize electrochemical behavior of MFCs by equivalent electrical circuit fitted on both Nyquist and Bode plots. Resistances and pseudo-capacitances from EIS analyses do not differ in such a way that the nature of the membrane could be considered as responsible. Copyright © 2015 Elsevier B.V. All rights reserved.

Cathode for molten carbonate fuel cell

DOEpatents

Kaun, Thomas D.; Mrazek, Franklin C.

1990-01-01

A porous sintered cathode for a molten carbonate fuel cell and method of making same, the cathode including a skeletal structure of a first electronically conductive material slightly soluble in the electrolyte present in the molten carbonate fuel cell covered by fine particles of a second material of possibly lesser electronic conductivity insoluble in the electrolyte present in the molten carbonate fuel cell, the cathode having a porosity in the range of from about 60% to about 70% at steady-state cell operating conditions consisting of both macro-pores and micro-pores.

Carbon with hierarchical pores from carbonized metal-organic frameworks for lithium sulphur batteries.

PubMed

Xi, Kai; Cao, Shuai; Peng, Xiaoyu; Ducati, Caterina; Kumar, R Vasant; Cheetham, Anthony K

2013-03-18

This paper presents a novel method and rationale for utilizing carbonized MOFs for sulphur loading to fabricate cathode structures for lithium-sulphur batteries. Unique carbon materials with differing hierarchical pore structures were synthesized from four types of zinc-containing metal-organic frameworks (MOFs). It is found that cathode materials made from MOFs-derived carbons with higher mesopore (2-50 nm) volumes exhibit increased initial discharge capacities, whereas carbons with higher micropore (<2 nm) volumes lead to cathode materials with better cycle stability.

Graphene-based ultrathin microporous carbon with smaller sulfur molecules for excellent rate performance of lithium-sulfur cathode

NASA Astrophysics Data System (ADS)

Peng, Zhenhuan; Fang, Wenying; Zhao, Hongbin; Fang, Jianhui; Cheng, Hongwei; Doan, The Nam Long; Xu, Jiaqiang; Chen, Pu

2015-05-01

Ultrathin microporous carbon (UMPC) for lithium-sulfur (Li-S) cathode with uniform pore width of approximately 0.6 nm and dozens nm in thickness is synthesized with graphene oxide as template by glucose hydrothermal carbonization and surfactant-assisted assembling method. The UMPC supplies desirable S pregnancy space and the intimate contact between UMPC and S, therefore improving the conductivity of S@UMPC composite and dynamic performance. Smaller sulfur molecules limited in UMPC thoroughly prevent the formation of electrolyte-soluble polysulfides, hence excellent cycling performance with 900 mAh g-1 after 150 cycles is kept. Ultrathin three-dimensional carbon nanosheets are significant to fast electron transfer and Li+ diffusion contributing to excellent dynamic performance (710 mAh g-1 at 3 C).

Porous and Microporous Honeycomb Composites as Potential Boundary-Layer Bleed Materials

NASA Technical Reports Server (NTRS)

Davis, D. O.; Willis, B. P.; Schoenenberger, M.

1997-01-01

Results of an experimental investigation are presented in which the use of porous and microporous honeycomb composite materials is evaluated as an alternate to perforated solid plates for boundary-layer bleed in supersonic aircraft inlets. The terms "porous" and "microporous," respectively, refer to bleed orifice diameters roughly equal to and much less than the displacement thickness of the approach boundary-layer. A Baseline porous solid plate, two porous honeycomb, and three microporous honeycomb configurations are evaluated. The performance of the plates is characterized by the flow coefficient and relative change in boundary-layer profile parameters across the bleed region. The tests were conducted at Mach numbers of 1.27 and 1.98. The results show the porous honeycomb is not as efficient at removing mass compared to the baseline. The microporous plates were about equal to the baseline with one plate demonstrating a significantly higher efficiency. The microporous plates produced significantly fuller boundary-layer profiles downstream of the bleed region for a given mass flow removal rate than either the baseline or the porous honeycomb plates.

Cobalt Ferrite Bearing Nitrogen-Doped Reduced Graphene Oxide Layers Spatially Separated with Microporous Carbon as Efficient Oxygen Reduction Electrocatalyst.

PubMed

Kashyap, Varchaswal; Singh, Santosh K; Kurungot, Sreekumar

2016-08-17

The present work discloses how high-quality dispersion of fine particles of cobalt ferrite (CF) could be attained on nitrogen-doped reduced graphene oxide (CF/N-rGO) and how this material in association with a microporous carbon phase could deliver significantly enhanced activity toward electrochemical oxygen reduction reaction (ORR). Our study indicates that the microporous carbon phase plays a critical role in spatially separating the layers of CF/N-rGO and in creating a favorable atmosphere to ensure the seamless distribution of the reactants to the active sites located on CF/N-rGO. In terms of the ORR current density, the heat-treated hybrid catalyst at 150 °C (CF/N-rGO-150) is found to be clearly outperforming (7.4 ± 0.5 mA/cm(2)) the state-of-the-art 20 wt % Pt-supported carbon catalyst (PtC) (5.4 ± 0.5 mA/cm(2)). The mass activity and stability of CF-N-rGO-150 are distinctly superior to PtC even after 5000 electrochemical cycles. As a realistic system level exploration of the catalyst, testing of a primary zinc-air battery could be demonstrated using CF/N-rGO-150 as the cathode catalyst. The battery is giving a galvanostatic discharge time of 15 h at a discharge current density of 20 mA/cm(2) and a specific capacity of ∼630 mAh g(-1) in 6 M KOH by using a Zn foil as the anode. Distinctly, the battery performance of this system is found to be superior to that of PtC in less concentrated KOH solution as the electrolyte.

X-ray and Electrochemical Impedance Spectroscopy Diagnostic Investigations of Liquid Water in Polymer Electrolyte Membrane Fuel Cell Gas Diffusion Layers

NASA Astrophysics Data System (ADS)

Antonacci, Patrick

In this thesis, electrochemical impedance spectroscopy (EIS) and synchrotron x-ray radiography were utilized to characterize the impact of liquid water distributions in polymer electrolyte membrane fuel cell (PEMFC) gas diffusion layers (GDLs) on fuel cell performance. These diagnostic techniques were used to quantify the effects of liquid water visualized on equivalent resistances measured through EIS. The effects of varying the thickness of the microporous layer (MPL) of GDLs were studied using these diagnostic techniques. In a first study on the feasibility of this methodology, two fuel cell cases with a 100 microm-thick and a 150 microm-thick MPL were compared under constant current density operation. In a second study with 10, 30, 50, and 100 microm-thick MPLs, the liquid water in the cathode substrate was demonstrated to affect mass transport resistance, while the liquid water content in the anode (from back diffusion) affected membrane hydration, evidenced through ohmic resistance measurements.

Template-directed fabrication of porous gas diffusion layer for magnesium air batteries

NASA Astrophysics Data System (ADS)

Xue, Yejian; Miao, He; Sun, Shanshan; Wang, Qin; Li, Shihua; Liu, Zhaoping

2015-11-01

The uniform micropore distribution in the gas diffusion layers (GDLs) of the air-breathing cathode is very important for the metal air batteries. In this work, the super-hydrophobic GDL with the interconnected regular pores is prepared by a facile silica template method, and then the electrochemical properties of the Mg air batteries containing these GDLs are investigated. The results indicate that the interconnected and uniform pore structure, the available water-breakout pressure and the high gas permeability coefficient of the GDL can be obtained by the application of 30% silica template. The maximum power density of the Mg air battery containing the GDL with 30% regular pores reaches 88.9 mW cm-2 which is about 1.2 times that containing the pristine GDL. Furthermore, the GDL with 30% regular pores exhibits the improved the long term hydrophobic stability.

Separator for electrochemical cells

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

Griffin, R.A.

1988-12-27

An electrochemical cell is described comprising a sealed casing; an anode, a cathode, a separator positioned between the anode and the cathode, and a non-aqueous electrolyte sealed in the casing; a pair of electrical terminals on the casing; means for electrically isolating the electrical terminals from each other; and means for electrically connecting the anode to one terminal and the cathode to the other terminal; wherein the anode is comprised of lithium foil, the cathode is comprised of manganese dioxide, and the separator consists essentially of a microporous polypropylene film having a thickness of about 1.5 mils and internal voidsmore » of about 60% by volume; wherein the anode, cathode, and separator are spirally wound together in a jelly roll configuration.« less

Interaction between antimony atoms and micropores in silicon

NASA Astrophysics Data System (ADS)

Odzhaev, V. B.; Petlitskii, A. N.; Plebanovich, V. I.; Sadovskii, P. K.; Tarasik, M. I.; Chelyadinskii, A. R.

2018-01-01

The interaction between Sb atoms and micropores of a getter layer in silicon is studied. The getter layer was obtained via implantation of Sb+ ions into silicon and subsequent heat treatment processes. The antimony atoms located in the vicinity of micropores are captured by micropores during gettering annealing and lose its electrical activity. The activation energy of capture process to the pores for antimony is lower than that of antimony diffusion in silicon deformation fields around microvoids on the diffusion process.

Numerical and experimental study of the effects of the electrical resistance and diffusivity under clamping pressure on the performance of a metallic gas-diffusion layer in polymer electrolyte fuel cells

NASA Astrophysics Data System (ADS)

Tanaka, Shiro; Bradfield, Warwick W.; Legrand, Cloe; Malan, Arnaud G.

2016-10-01

The performance of a perforated metal-sheet gas-diffusion layer incorporated with a microporous layer in a fuel cell is evaluated with fine-pitch channel/land designs for the gas flow field on a bipolar plate. The combination of metal-sheet gas-diffusion layer and microporous layer exhibits significant performance without a large flooding effect. When comparing the performance with wider and narrower land cases, the land width affects the performance. To investigate the roles of the microporous layer, land width, etc. in the fuel cell with the metal-sheet gas-diffusion layer, a single-phase, isothermal, and multi-physics simulation is developed and coupled with electrical, mechanical, electrochemical and fluid dynamics factors. The simulated current-voltage performance is then compared to the experimentally measure performance. These are shown to be in good agreement apart for very high current-density cases i.e. greater than 1.5 A cm-2. This is due the flooding effect predominantly appearing. It is further demonstrated that the microporous layer serves as the key component in facilitating gas diffusion and for preventing flooding. Furthermore, the pressure is found to have a strong impact on the performance, affecting the gas diffusion and electric resistance around the microporous layer.

Inorganic dual-layer microporous supported membranes

DOEpatents

Brinker, C. Jeffrey; Tsai, Chung-Yi; Lu, Yungfeng

2003-03-25

The present invention provides for a dual-layer inorganic microporous membrane capable of molecular sieving, and methods for production of the membranes. The inorganic microporous supported membrane includes a porous substrate which supports a first inorganic porous membrane having an average pore size of less than about 25 .ANG. and a second inorganic porous membrane coating the first inorganic membrane having an average pore size of less than about 6 .ANG.. The dual-layered membrane is produced by contacting the porous substrate with a surfactant-template polymeric sol, resulting in a surfactant sol coated membrane support. The surfactant sol coated membrane support is dried, producing a surfactant-templated polymer-coated substrate which is calcined to produce an intermediate layer surfactant-templated membrane. The intermediate layer surfactant-templated membrane is then contacted with a second polymeric sol producing a polymeric sol coated substrate which is dried producing an inorganic polymeric coated substrate. The inorganic polymeric coated substrate is then calcined producing an inorganic dual-layered microporous supported membrane in accordance with the present invention.

Nanocasting hierarchical carbide-derived carbons in nanostructured opal assemblies for high-performance cathodes in lithium-sulfur batteries.

PubMed

Hoffmann, Claudia; Thieme, Sören; Brückner, Jan; Oschatz, Martin; Biemelt, Tim; Mondin, Giovanni; Althues, Holger; Kaskel, Stefan

2014-12-23

Silica nanospheres are used as templates for the generation of carbide-derived carbons with monodisperse spherical mesopores (d=20-40 nm) and microporous walls. The nanocasting approach with a polycarbosilane precursor and subsequent pyrolysis, followed by silica template removal and chlorine treatment, results in carbide-derived carbons DUT-86 (DUT=Dresden University of Technology) with remarkable textural characteristics, monodisperse, spherical mesopores tunable in diameter, and very high pore volumes up to 5.0 cm3 g(-1). Morphology replication allows these nanopores to be arranged in a nanostructured inverse opal-like structure. Specific surface areas are very high (2450 m2 g(-1)) due to the simultaneous presence of micropores. Testing DUT-86 samples as cathode materials in Li-S batteries reveals excellent performance, and tailoring of the pore size allows optimization of cell performance, especially the active center accessibility and sulfur utilization. The outstanding pore volumes allow sulfur loadings of 80 wt %, a value seldom achieved in composite cathodes, and initial capacities of 1165 mAh gsulfur(-1) are reached. After 100 cycle capacities of 860 mAh gsulfur(-1) are retained, rendering DUT-86 a high-performance sulfur host material.

Microporous ceramic coated separators with superior wettability for enhancing the electrochemical performance of sodium-ion batteries

NASA Astrophysics Data System (ADS)

Suharto, Yustian; Lee, Yongho; Yu, Ji-Sang; Choi, Wonchang; Kim, Ki Jae

2018-02-01

Finding an alternative to glass fiber (GF) separators is a crucial factor for the fast commercialization of sodium-ion batteries (SIBs), because GF separators are too thick for use in SIBs, thereby decreasing the volumetric and gravimetric energy density. Here we propose a microporous composite separator prepared by introducing a polymeric coating layer of polyvinylidene fluoride-hexafluoropropylene (PVdF-HFP co-polymer) with ZrO2 nanoparticles to a polyethylene (PE) separator. The coated separator efficiently enhances the cell performance of SIBs. The ZrO2 nanoparticles, finely dispersed on the polymeric coating layer, induce the formation of many micropores on the polymeric coating layer, suggesting that micropore formation on the coating layer renders the composite separator more open in structure. An ethylene carbonate/propylene carbonate liquid electrolyte for SIBs is not absorbed by PE separators even after 1 h of electrolyte droplet testing, while the proposed separator with many micropores is completely wetted by the electrolyte. Sodium ion migration across the composite separator is therefore effectively enhanced by the formation of ion transfer pathways, which improve ionic conductivity. As a result, the microporous composite separator affords stable cycle performances and excellent specific capacity retention (95.8%) after 50 cycles, comparable to those offered by a SIB with a GF separator.

Electrodeposition of platinum and silver into chemically modified microporous silicon electrodes

PubMed Central

2012-01-01

Electrodeposition of platinum and silver into hydrophobic and hydrophilic microporous silicon layers was investigated using chemically modified microporous silicon electrodes. Hydrophobic microporous silicon enhanced the electrodeposition of platinum in the porous layer. Meanwhile, hydrophilic one showed that platinum was hardly deposited within the porous layer, and a film of platinum on the top of the porous layer was observed. On the other hand, the electrodeposition of silver showed similar deposition behavior between these two chemically modified electrodes. It was also found that the electrodeposition of silver started at the pore opening and grew toward the pore bottom, while a uniform deposition from the pore bottom was observed in platinum electrodeposition. These electrodeposition behaviors are explained on the basis of the both effects, the difference in overpotential for metal deposition on silicon and on the deposited metal, and displacement deposition rate of metal. PMID:22720690

A Carbon-Cotton Cathode with Ultrahigh-Loading Capability for Statically and Dynamically Stable Lithium–Sulfur Batteries

DOE PAGES

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

2016-10-26

Sulfur exhibits a high theoretical capacity of 1675 mA h g -1 via a distinct conversion reaction, which is different from the insertion reactions in commercial lithium-ion batteries. In consideration of its conversion reaction battery chemistry, a custom design for electrode materials could establish the way for attaining high-loading capability while simultaneously maintaining high electrochemical utilization and stability. In this study, this process is undertaken by introducing carbon cotton as an attractive electrode-containment material for enhancing the dynamic and static stabilities of lithium-sulfur (Li-S) batteries. The carbon cotton possessing a hierarchical macro-/microporous architecture exhibits a high surface area of 805more » m 2 g -1 and high microporosity with a micropore area of 557 m 2 g -1. The macroporous channels allow the carbon cotton to load and stabilize a high amount of active material. The abundant microporous reaction sites spread throughout the carbon cotton facilitate the redox chemistry of the high-loading/content Li-S system. As a result, the high-loading carbon-cotton cathode exhibits (i) enhanced cycle stability with a good dynamic capacity retention of 70% after 100 cycles and (ii) improved cellstorage stability with a high static capacity retention of above 93% and a low time-dependent self-discharge rate of 0.12% per day after storing for a long period of 60 days. In conclusion, these carbon-cotton cathodes with the remarkably highest values reported so far of both sulfur loading (61.4 mg cm -2) and sulfur content (80 wt %) demonstrate enhanced electrochemical utilization with the highest areal, volumetric, and gravimetric capacities simultaneously.« less

A Carbon-Cotton Cathode with Ultrahigh-Loading Capability for Statically and Dynamically Stable Lithium–Sulfur Batteries

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

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

Sulfur exhibits a high theoretical capacity of 1675 mA h g -1 via a distinct conversion reaction, which is different from the insertion reactions in commercial lithium-ion batteries. In consideration of its conversion reaction battery chemistry, a custom design for electrode materials could establish the way for attaining high-loading capability while simultaneously maintaining high electrochemical utilization and stability. In this study, this process is undertaken by introducing carbon cotton as an attractive electrode-containment material for enhancing the dynamic and static stabilities of lithium-sulfur (Li-S) batteries. The carbon cotton possessing a hierarchical macro-/microporous architecture exhibits a high surface area of 805more » m 2 g -1 and high microporosity with a micropore area of 557 m 2 g -1. The macroporous channels allow the carbon cotton to load and stabilize a high amount of active material. The abundant microporous reaction sites spread throughout the carbon cotton facilitate the redox chemistry of the high-loading/content Li-S system. As a result, the high-loading carbon-cotton cathode exhibits (i) enhanced cycle stability with a good dynamic capacity retention of 70% after 100 cycles and (ii) improved cellstorage stability with a high static capacity retention of above 93% and a low time-dependent self-discharge rate of 0.12% per day after storing for a long period of 60 days. In conclusion, these carbon-cotton cathodes with the remarkably highest values reported so far of both sulfur loading (61.4 mg cm -2) and sulfur content (80 wt %) demonstrate enhanced electrochemical utilization with the highest areal, volumetric, and gravimetric capacities simultaneously.« less

Liquid Sulfur Impregnation of Microporous Carbon Accelerated by Nanoscale Interfacial Effects

DOE PAGES

Pascal, Tod A.; Villaluenga, Irune; Wujcik, Kevin H.; ...

2017-03-14

Impregnation of porous carbon matrices with liquid sulfur has been exploited to fabricate composite cathodes for lithium-sulfur batteries, aimed at confining soluble sulfur species near conducting carbon to prevent both loss of active material into the electrolyte and parasitic reactions at the lithium metal anode. Here, through extensive computer simulations, we uncover the strongly favorable interfacial free energy between liquid sulfur and graphitic surfaces that underlies this phenomenon. Previously unexplored curvature-dependent enhancements are shown to favor the filling of smaller pores first and effect a quasi-liquid sulfur phase in microporous domains (diameters <2 nm) that persists ~30° below the expectedmore » freezing point. Evidence of interfacial sulfur on carbon is shown to be a 0.3 eV red shift in the simulated and measured interfacial X-ray absorption spectra. Our results elucidate the critical morphology and thermodynamic properties necessary for future cathode design and highlight the importance of molecular-scale details in defining emergent properties of functional nanoscale interfaces.« less

Liquid Sulfur Impregnation of Microporous Carbon Accelerated by Nanoscale Interfacial Effects.

PubMed

Pascal, Tod A; Villaluenga, Irune; Wujcik, Kevin H; Devaux, Didier; Jiang, Xi; Wang, Dunyang Rita; Balsara, Nitash; Prendergast, David

2017-04-12

Impregnation of porous carbon matrices with liquid sulfur has been exploited to fabricate composite cathodes for lithium-sulfur batteries, aimed at confining soluble sulfur species near conducting carbon to prevent both loss of active material into the electrolyte and parasitic reactions at the lithium metal anode. Here, through extensive computer simulations, we uncover the strongly favorable interfacial free energy between liquid sulfur and graphitic surfaces that underlies this phenomenon. Previously unexplored curvature-dependent enhancements are shown to favor the filling of smaller pores first and effect a quasi-liquid sulfur phase in microporous domains (diameters <2 nm) that persists ∼30° below the expected freezing point. Evidence of interfacial sulfur on carbon is shown to be a 0.3 eV red shift in the simulated and measured interfacial X-ray absorption spectra. Our results elucidate the critical morphology and thermodynamic properties necessary for future cathode design and highlight the importance of molecular-scale details in defining emergent properties of functional nanoscale interfaces.

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

NASA Astrophysics Data System (ADS)

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

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

Sulfur-infiltrated porous carbon microspheres with controllable multi-modal pore size distribution for high energy lithium-sulfur batteries

NASA Astrophysics Data System (ADS)

Zhao, Cunyu; Liu, Lianjun; Zhao, Huilei; Krall, Andy; Wen, Zhenhai; Chen, Junhong; Hurley, Patrick; Jiang, Junwei; Li, Ying

2013-12-01

Sulfur has received increasing attention as a cathode material for lithium-sulfur (Li-S) batteries due to its high theoretical specific capacity. However, the commercialization of Li-S batteries is limited by the challenges of poor electrical conductivity of sulfur, dissolution of the polysulfide intermediates into the electrolyte, and volume expansion of sulfur during cycling. Herein, we report the fabrication of novel-structured porous carbon microspheres with a controllable multi-modal pore size distribution, i.e., a combination of interconnected micropores, mesopores and macropores. Cathodes made of sulfur infiltrated in such a hierarchical carbon framework provide several advantages: (1) a continuous and high surface area carbon network for enhanced electrical conductivity and high sulfur loading; (2) macropores and large mesopores bridged by small mesopores to provide good electrolyte accessibility and fast Li ion transport and to accommodate volume expansion of sulfur; and (3) small mesopores and micropores to improve carbon/sulfur interaction and to help trap polysulfides. An initial discharge capacity at 1278 mA h g-1 and capacity retention at 70.7% (904 mA h g-1) after 100 cycles at a high rate (1 C) were achieved. The material fabrication process is relatively simple and easily scalable.Sulfur has received increasing attention as a cathode material for lithium-sulfur (Li-S) batteries due to its high theoretical specific capacity. However, the commercialization of Li-S batteries is limited by the challenges of poor electrical conductivity of sulfur, dissolution of the polysulfide intermediates into the electrolyte, and volume expansion of sulfur during cycling. Herein, we report the fabrication of novel-structured porous carbon microspheres with a controllable multi-modal pore size distribution, i.e., a combination of interconnected micropores, mesopores and macropores. Cathodes made of sulfur infiltrated in such a hierarchical carbon framework provide several advantages: (1) a continuous and high surface area carbon network for enhanced electrical conductivity and high sulfur loading; (2) macropores and large mesopores bridged by small mesopores to provide good electrolyte accessibility and fast Li ion transport and to accommodate volume expansion of sulfur; and (3) small mesopores and micropores to improve carbon/sulfur interaction and to help trap polysulfides. An initial discharge capacity at 1278 mA h g-1 and capacity retention at 70.7% (904 mA h g-1) after 100 cycles at a high rate (1 C) were achieved. The material fabrication process is relatively simple and easily scalable. Electronic supplementary information (ESI) available: Preparation process scheme; X-ray mapping images and EDX analysis for the surface of PMC/S-40; X-ray mapping images for the cross-section of PMC/S-40; thermogravimetric analysis (TGA) of PMC/S samples; T-plot results for PMC sample; and electrochemical measurements of lithium-sulfur batteries using PMC/S as cathode materials. See DOI: 10.1039/c3nr04532c

Improved Separators For Rechargeable Lithium Cells

NASA Technical Reports Server (NTRS)

Shen, David; Surampudi, Subbarao; Huang, Chen-Kuo; Halpert, Gerald

1994-01-01

Improved pairs of separators proposed for use in rechargeable lithium cells operating at ambient temperature. Block growth of lithium dendrites and help prevent short circuits. Each cell contains one separator made of microporous polypropylene placed next to anode, and one separator made of microporous polytetrafluoroethylene (PTFE) next to cathode. Separators increase cycle lives of secondary lithium cells. Cells to which concept applicable those of Li/TiS(2), Li/NbSe(3), Li/CoO(2), Li/MoS(2), Li/VO(x), and Li/MnO(2) chemical systems. Advantageous in spacecraft, military, communications, automotive, and other applications in which high energy density and rechargeability needed.

Controlling porosity of porous carbon cathode for lithium oxygen batteries: Influence of micro and meso porosity

NASA Astrophysics Data System (ADS)

Kim, Minjae; Yoo, Eunjoo; Ahn, Wha-Seung; Shim, Sang Eun

2018-06-01

In rechargeable lithium-oxygen (Li-O2) batteries, the porosity of porous carbon materials plays a crucial role in the electrochemical performance serving as oxygen diffusion path and Li ion transfer passage. However, the influence of optimization of porous carbon as an air electrode on cell electrochemical performance remains unclear. To understand the role of carbon porosity in Li-O2 batteries, carbon materials featuring controlled pore sizes and porosity, including C-800 (nearly 96% microporous) and AC-950 (55:45 micro/meso porosity), are designed and synthesized by carbonization using a triazine-based covalent organic polymer (TCOP). We find that the microporous C-800 cathode allows 120 cycles with a limited capacity of 1000 mAh g-1, about 2 and 10 times higher than that of mixed-porosity AC-950 and mesoporous CMK-3, respectively. Meanwhile, the specific discharge capacity of the C-800 electrode at 200 mA g-1 is 6003 mAh g-1, which is lower than that of the 8433 and 9960 mAh g-1 when using AC-950 and CMK-3, respectively. This difference in the electrochemical performance of the porous carbon cathode with different porosity causes to the generation and decomposition of Li2O2 during the charge and discharge cycle, which affects oxygen diffusion and Li ion transfer.

Microporous structure with layered interstitial surface treatment, and method and apparatus for preparation thereof

NASA Technical Reports Server (NTRS)

Koontz, Steven L. (Inventor)

1994-01-01

A microporous structure with layered interstitial surface treatments, and method and apparatus for preparation thereof is presented. The structure is prepared by sequentially subjecting a uniformly surface-treated structure to atomic oxygen treatment to remove an outer layer of surface treatment to a generally uniform depth, and then surface treating the so exposed layer with another surface treating agent. The atomic oxygen/surface treatment steps may optionally be repeated, each successive time to a lesser depth, to produce a microporous structure having multilayered surface treatments. The apparatus employs at least one side arm from a main atomic oxygen-containing chamber. The side arm has characteristic relaxation times such that a uniform atomic oxygen dose rate is delivered to a specimen positioned transversely in the side arm spaced from the main gas chamber.

Microporous structure with layered interstitial surface treatment, and method and apparatus for preparation thereof

NASA Technical Reports Server (NTRS)

Koontz, Steven L. (Inventor)

1992-01-01

A microporous structure with layered interstitial surface treatments, and the method and apparatus for its preparation are disclosed. The structure is prepared by sequentially subjecting a uniformly surface treated structure to atomic oxygen treatment to remove an outer layer of surface treatment to a generally uniform depth, and then surface treating the so exposed layer with another surface treating agent. The atomic oxygen/surface treatment steps may optionally be repeated, each successive time to a lesser depth, to produce a microporous structure having multilayered surface treatments. The apparatus employs at least one side arm from a main oxygen-containing chamber. The side arm has characteristic relaxation times such that a uniform atomic oxygen dose rate is delivered to a specimen positioned transversely in the side arm spaced from the main gas chamber.

Reflective article having a sacrificial cathodic layer

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

Kabagambe, Benjamin; Buchanan, Michael J.; Scott, Matthew S.

The present invention relates to reflective articles, such as solar mirrors, that include a sacrificial cathodic layer. The reflective article, more particularly includes a substrate, such as glass, having a multi-layered coating thereon that includes a lead-free sacrificial cathodic layer. The sacrificial cathodic layer includes at least one transition metal, such as a particulate transition metal, which can be in the form of flakes (e.g., zinc flakes). The sacrificial cathodic layer can include an inorganic matrix formed from one or more organo-titanates. Alternatively, the sacrificial cathodic layer can include an organic polymer matrix (e.g., a crosslinked organic polymer matrix formedmore » from an organic polymer and an aminoplast crosslinking agent). The reflective article also includes an outer organic polymer coating, that can be electrodeposited over the sacrificial cathodic layer.« less

Electrosorption capacitance of nanostructured carbon-based materials.

PubMed

Hou, Chia-Hung; Liang, Chengdu; Yiacoumi, Sotira; Dai, Sheng; Tsouris, Costas

2006-10-01

The fundamental mechanism of electrosorption of ions developing a double layer inside nanopores was studied via a combination of experimental and theoretical studies. A novel graphitized-carbon monolithic material has proven to be a good electrical double-layer capacitor that can be applied in the separation of ions from aqueous solutions. An extended electrical double-layer model indicated that the pore size distribution plays a key role in determining the double-layer capacitance in an electrosorption process. Because of the occurrence of double-layer overlapping in narrow pores, mesopores and micropores make significantly different contributions to the double-layer capacitance. Mesopores show good electrochemical accessibility. Micropores present a slow mass transfer of ions and a considerable loss of double-layer capacitance, associated with a shallow potential distribution inside pores. The formation of the diffuse layer inside the micropores determines the magnitude of the double-layer capacitance at low electrolyte concentrations and at conditions close to the point of zero charge of the material. The effect of the double-layer overlapping on the electrosorption capacitance can be reduced by increasing the pore size, electrolyte concentration, and applied potential. The results are relevant to water deionization.

Ordered microporous layered lanthanide 1,3,5-benzenetriphosphonates pillared with cationic organic molecules.

PubMed

Araki, Takahiro; Kondo, Atsushi; Maeda, Kazuyuki

2015-04-13

Novel isomorphous pillared-layer-type crystalline lanthanide 1,3,5-benzenetriphosphonates were prepared with bpy and dbo as organic pillars (LnBP-bpy and LnBP-dbo; Ln: Ce, Pr, and Nd). Ab initio crystal structure solution using synchrotron X-ray powder diffraction data revealed that the organic pillars do not exist as neutral coordinating ligands but as cationic molecules. Especially the LnBP-dbo phases have ordered interlayer space filled with water molecules between the dbo pillars, and the interlayer water is successfully removed by heating under vacuum with slightly distorted but basically retained pillared layer structures. Microporosity of the materials is confirmed by adsorption of nitrogen, carbon dioxide, and hydrogen gases. Such microporous layered metal phosphonates pillared with cationic molecules should be unprecedented and should offer new strategies to design ordered microporous materials. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Performance and microbial ecology of air-cathode microbial fuel cells with layered electrode assemblies.

PubMed

Butler, Caitlyn S; Nerenberg, Robert

2010-05-01

Microbial fuel cells (MFCs) can be built with layered electrode assemblies, where the anode, proton exchange membrane (PEM), and cathode are pressed into a single unit. We studied the performance and microbial community structure of MFCs with layered assemblies, addressing the effect of materials and oxygen crossover on the community structure. Four MFCs with layered assemblies were constructed using Nafion or Ultrex PEMs and a plain carbon cloth electrode or a cathode with an oxygen-resistant polytetrafluoroethylene diffusion layer. The MFC with Nafion PEM and cathode diffusion layer achieved the highest power density, 381 mW/m(2) (20 W/m(3)). The rates of oxygen diffusion from cathode to anode were three times higher in the MFCs with plain cathodes compared to those with diffusion-layer cathodes. Microsensor studies revealed little accumulation of oxygen within the anode cloth. However, the abundance of bacteria known to use oxygen as an electron acceptor, but not known to have exoelectrogenic activity, was greater in MFCs with plain cathodes. The MFCs with diffusion-layer cathodes had high abundance of exoelectrogenic bacteria within the genus Geobacter. This work suggests that cathode materials can significantly influence oxygen crossover and the relative abundance of exoelectrogenic bacteria on the anode, while PEM materials have little influence on anode community structure. Our results show that oxygen crossover can significantly decrease the performance of air-cathode MFCs with layered assemblies, and therefore limiting crossover may be of particular importance for these types of MFCs.

Cathodes for lithium-air battery cells with acid electrolytes

DOEpatents

Xing, Yangchuan; Huang, Kan; Li, Yunfeng

2016-07-19

In various embodiments, the present disclosure provides a layered metal-air cathode for a metal-air battery. Generally, the layered metal-air cathode comprises an active catalyst layer, a transition layer bonded to the active catalyst layer, and a backing layer bonded to the transition layer such that the transition layer is disposed between the active catalyst layer and the backing layer.

Study of superhydrophobic electrosprayed catalyst layers using a localized reference electrode technique

NASA Astrophysics Data System (ADS)

Chaparro, A. M.; Ferreira-Aparicio, P.; Folgado, M. A.; Brightman, E.; Hinds, G.

2016-09-01

The performance of electrosprayed cathode catalyst layers in a polymer electrolyte membrane fuel cell (PEMFC) is studied using a localized reference electrode technique. Single cells with an electrosprayed cathode catalyst layer show an increase of >20% in maximum power density under standard testing conditions, compared with identical cells assembled with a conventional, state-of-the-art, gas diffusion cathode. When operated at high current density (1.2 A cm-2) the electrosprayed catalyst layers show more homogeneous distribution of the localized cathode potential, with a standard deviation from inlet to outlet of <50 mV, compared with 79 mV for the conventional gas diffusion cathode. Higher performance and homogeneity of cell response is attributed to the superhydrophobic nature of the macroporous electrosprayed catalyst layer structure, which enhances the rate of expulsion of liquid water from the cathode. On the other hand, at low current densities (<0.5 A cm-2), the electrosprayed layers exhibit more heterogeneous distribution of cathode potential than the conventional cathodes; this behavior is attributed to less favorable kinetics for oxygen reduction in very hydrophobic catalyst layers. The optimum performance may be obtained with electrosprayed catalyst layers employing a high Pt/C catalyst ratio.

Effect of phase inversion on microporous structure development of Al 2O 3/poly(vinylidene fluoride-hexafluoropropylene)-based ceramic composite separators for lithium-ion batteries

NASA Astrophysics Data System (ADS)

Jeong, Hyun-Seok; Kim, Dong-Won; Jeong, Yeon Uk; Lee, Sang-Young

To improve the thermal shrinkage of the separators that are essential to securing the electrical isolation between electrodes in lithium-ion batteries, we develop a new separator based on a ceramic composite membrane. Introduction of microporous, ceramic coating layers onto both sides of a polyethylene (PE) separator allows such a progress. The ceramic coating layers consist of nano-sized alumina (Al 2O 3) powders and polymeric binders (PVdF-HFP). The microporous structure of the ceramic coating layers is observed to be crucial to governing the thermal shrinkage as well as the ionic transport of the ceramic composite separators. This microporous structure is determined by controlling the phase inversion, more specifically, nonsolvent (water) contents in the coating solutions. To provide a theoretical basis for this approach, a pre-investigation on the phase diagram for a ternary mixture comprising PVdF-HFP, acetone, and water is conducted. On the basis of this observation, the effect of phase inversion on the morphology and air permeability (i.e. Gurley value) of ceramic coating layers is systematically discussed. In addition, to explore the application of ceramic composite separators to lithium-ion batteries, the influence of the structural change in the coating layers on the thermal shrinkage and electrochemical performance of the separators is quantitatively identified.

Multi-layer coatings for bipolar rechargeable batteries with enhanced terminal voltage

DOEpatents

Farmer, Joseph C.; Kaschmitter, James; Pierce, Steve

2017-06-06

A method for producing a multi-layer bipolar coated cell according to one embodiment includes applying a first active cathode material above a substrate to form a first cathode; applying a first solid-phase ionically-conductive electrolyte material above the first cathode to form a first electrode separation layer; applying a first active anode material above the first electrode separation layer to form a first anode; applying an electrically conductive barrier layer above the first anode; applying a second active cathode material above the anode material to form a second cathode; applying a second solid-phase ionically-conductive electrolyte material above the second cathode to form a second electrode separation layer; applying a second active anode material above the second electrode separation layer to form a second anode; and applying a metal material above the second anode to form a metal coating section. In another embodiment, the anode is formed prior to the cathode. Cells are also disclosed.

Cathodic electrocatalyst layer for electrochemical generation of hydrogen peroxide

NASA Technical Reports Server (NTRS)

Tennakoon, Charles L. K. (Inventor); Singh, Waheguru Pal (Inventor); Rhodes, Christopher P. (Inventor); Anderson, Kelvin C. (Inventor)

2011-01-01

A cathodic gas diffusion electrode for the electrochemical production of aqueous hydrogen peroxide solutions. The cathodic gas diffusion electrode comprises an electrically conductive gas diffusion substrate and a cathodic electrocatalyst layer supported on the gas diffusion substrate. A novel cathodic electrocatalyst layer comprises a cathodic electrocatalyst, a substantially water-insoluble quaternary ammonium compound, a fluorocarbon polymer hydrophobic agent and binder, and a perfluoronated sulphonic acid polymer. An electrochemical cell using the novel cathodic electrocatalyst layer has been shown to produce an aqueous solution having between 8 and 14 weight percent hydrogen peroxide. Furthermore, such electrochemical cells have shown stable production of hydrogen peroxide solutions over 1000 hours of operation including numerous system shutdowns.

Optimizing membrane electrode assembly of direct methanol fuel cells for portable power

NASA Astrophysics Data System (ADS)

Liu, Fuqiang

Direct methanol fuel cells (DMFCs) for portable power applications require high power density, high-energy conversion efficiency and compactness. These requirements translate to fundamental properties of high methanol oxidation and oxygen reduction kinetics, as well as low methanol and water crossover. In this thesis a novel membrane electrode assembly (MEA) for direct methanol fuel cells has been developed, aiming to improve these fundamental properties. Firstly, methanol oxidation kinetics has been enhanced and methanol crossover has been minimized by proper control of ionomer crystallinity and its swelling in the anode catalyst layer through heat-treatment. Heat-treatment has a major impact on anode characteristics. The short-cured anode has low ionomer crystallinity, and thus swells easily when in contact with methanol solution to create a much denser anode structure, giving rise to higher methanol transport resistance than the long-cured anode. Variations in interfacial properties in the anode catalyst layer (CL) during cell conditioning were also characterized, and enhanced kinetics of methanol oxidation and severe limiting current phenomenon were found to be caused by a combination of interfacial property variations and swelling of ionomer over time. Secondly, much effort has been expended to develop a cathode CL suitable for operation under low air stoichiometry. The effects of fabrication procedure, ionomer content, and porosity distribution on the microstructure and cathode performance under low air stoichiometry are investigated using electrochemical and surface morphology characterizations to reveal the correlation between microstructure and electrochemical behavior. At the same time, computational fluid dynamics (CFD) models of DMFC cathodes have been developed to theoretically interpret the experimental results, to investigate two-phase transport, and to elucidate mechanism of cathode mixed potential due to methanol crossover. Thirdly, a MEA with low water crossover has been developed by employing a highly-hydrophobic microporous layer (MPL) to build up hydraulic pressure at the cathode, promoting product water permeation from the cathode to anode to offset water dragged by electro-osmosis. Water crossover through the MEA is further reduced by an anode hydrophobic MPL through facilitating water back diffusion. Under different current densities, the MEA with hydrophobic MPL has consistently low alpha, several times smaller than those with hydrophilic or without MPL. A simulation study of anode water transport by a two-phase model shows that anode MPL wettability strongly determines liquid saturation in the anode, and thus is identified as playing a crucial role in promoting water back diffusion. Finally, direct feed of highly-concentrated methanol using the optimized MEA has been successfully demonstrated by a face-feed anode plate, which minimizes methanol crossover by controlling the fuel delivery rate. Using 10 M methanol, a steady-state power density of ˜67mW/cm2 is reached at 60°C and 175mA/cm2, which is almost identical to that with 2M methanol.

Low cost fuel cell diffusion layer configured for optimized anode water management

DOEpatents

Owejan, Jon P; Nicotera, Paul D; Mench, Matthew M; Evans, Robert E

2013-08-27

A fuel cell comprises a cathode gas diffusion layer, a cathode catalyst layer, an anode gas diffusion layer, an anode catalyst layer and an electrolyte. The diffusion resistance of the anode gas diffusion layer when operated with anode fuel is higher than the diffusion resistance of the cathode gas diffusion layer. The anode gas diffusion layer may comprise filler particles having in-plane platelet geometries and be made of lower cost materials and manufacturing processes than currently available commercial carbon fiber substrates. The diffusion resistance difference between the anode gas diffusion layer and the cathode gas diffusion layer may allow for passive water balance control.

Pool boiling characteristics and critical heat flux mechanisms of microporous surfaces and enhancement through structural modification

NASA Astrophysics Data System (ADS)

Ha, Minseok; Graham, Samuel

2017-08-01

Experimental studies have shown that microporous surfaces induce one of the highest enhancements in critical heat flux (CHF) during pool boiling. However, microporous surfaces may also induce a very large surface superheat (>100 °C) which is not desirable for applications such as microelectronics cooling. While the understanding of the CHF mechanism is the key to enhancing boiling heat transfer, a comprehensive understanding is not yet available. So far, three different theories for the CHF of microporous surfaces have been suggested: viscous-capillary model, hydrodynamic instability model, and dryout of the porous coatings. In general, all three theories account for some aspects of boiling phenomena. In this study, the theories are examined through their correlations with experimental data on microporous surfaces during pool boiling using deionized (DI) water. It was found that the modulation of the vapor-jet through the pore network enables a higher CHF than that of a flat surface based on the hydrodynamic instability theory. In addition, it was found that as the heat flux increases, a vapor layer grows in the porous coatings described by a simple thermal resistance model which is responsible for the large surface superheat. Once the vapor layer grows to fill the microporous structure, transition to film boiling occurs and CHF is reached. By disrupting the formation of this vapor layer through the fabrication of channels to allow vapor escape, an enhancement in the CHF and heat transfer coefficient was observed, allowing CHF greater than 3500 kW/m2 at a superheat less than 50 °C.

Interfacial micropore defect formation in PEDOT:PSS-Si hybrid solar cells probed by TOF-SIMS 3D chemical imaging.

PubMed

Thomas, Joseph P; Zhao, Liyan; Abd-Ellah, Marwa; Heinig, Nina F; Leung, K T

2013-07-16

Conducting p-type polymer layers on n-type Si have been widely studied for the fabrication of cost-effective hybrid solar cells. In this work, time-of-flight secondary ion mass spectrometry (TOF-SIMS) is used to provide three-dimensional chemical imaging of the interface between poly(3,4-ethylene-dioxythiophene):polystyrenesulfonate (PEDOT:PSS) and SiOx/Si in a hybrid solar cell. To minimize structural damage to the polymer layer, an Ar cluster sputtering source is used for depth profiling. The present result shows the formation of micropore defects in the interface region of the PEDOT:PSS layer on the SiOx/Si substrate. This interfacial micropore defect formation becomes more prominent with increasing thickness of the native oxide layer, which is a key device parameter that greatly affects the hybrid solar cell performance. Three-dimensional chemical imaging coupled with Ar cluster ion sputtering has therefore been demonstrated as an emerging technique for probing the interface of this and other polymer-inorganic systems.

Bond layer for a solid oxide fuel cell, and related processes and devices

DOEpatents

Wu, Jian; Striker, Todd-Michael; Renou, Stephane; Gaunt, Simon William

2017-03-21

An electrically-conductive layer of material having a composition comprising lanthanum and strontium is described. The material is characterized by a microstructure having bimodal porosity. Another concept in this disclosure relates to a solid oxide fuel cell attached to at least one cathode interconnect by a cathode bond layer. The bond layer includes a microstructure having bimodal porosity. A fuel cell stack which incorporates at least one of the cathode bond layers is also described herein, along with related processes for forming the cathode bond layer.

Laser pumping of thyristors for fast high current rise-times

DOEpatents

Glidden, Steven C.; Sanders, Howard D.

2013-06-11

An optically triggered semiconductor switch includes an anode metallization layer; a cathode metallization layer; a semiconductor between the anode metallization layer and the cathode metallization layer and a photon source. The semiconductor includes at least four layers of alternating doping in the form P-N-P-N, in which an outer layer adjacent to the anode metallization layer forms an anode and an outer layer adjacent the cathode metallization layer forms a cathode and in which the anode metallization layer has a window pattern of optically transparent material exposing the anode layer to light. The photon source emits light having a wavelength, with the light from the photon source being configured to match the window pattern of the anode metallization layer.

Architectures and criteria for the design of high efficiency organic photovoltaic cells

DOEpatents

Rand, Barry; Forrest, Stephen R; Burk, Diana Pendergrast

2015-03-24

An organic photovoltaic cell includes an anode and a cathode, and a plurality of organic semiconductor layers between the anode and the cathode. At least one of the anode and the cathode is transparent. Each two adjacent layers of the plurality of organic semiconductor layers are in direct contact. The plurality of organic semiconductor layers includes an intermediate layer consisting essentially of a photoconductive material, and two sets of at least three layers. A first set of at least three layers is between the intermediate layer and the anode. Each layer of the first set consists essentially of a different organic semiconductor material having a higher LUMO and a higher HOMO, relative to the material of an adjacent layer of the plurality of organic semiconductor layers closer to the cathode. A second set of at least three layers is between the intermediate layer and the cathode. Each layer of the second set consists essentially of a different organic semiconductor material having a lower LUMO and a lower HOMO, relative to the material of an adjacent layer of the plurality of organic semiconductor layers closer to the anode.

Microscale measurements of oxygen concentration across the thickness of diffusion media in operating polymer electrolyte fuel cells

NASA Astrophysics Data System (ADS)

Epting, William K.; Litster, Shawn

2016-02-01

Although polymer electrolyte fuel cells (PEFCs) offer promise as efficient, low emission power sources, the large amount of platinum catalyst used for the cathode's oxygen reduction (ORR) results in high costs. One approach to using less Pt is to increase the oxygen concentration at the catalyst by reducing the oxygen transport resistances. An important resistance is that of the diffusion media (DM). The DM are highly heterogeneous porous carbon fiber substrates with a graded composition of additives across their thickness. In this work we use an oxygen microsensor with a micro-positioning system to measure the oxygen concentration and presence of liquid water in the pores at discrete points across the thickness of a commercial carbon felt DM in operating PEFCs. Under conditions with no liquid water, the DM accounts for 60% of the oxygen depletion, with 60-70% of that depletion being due to the thin microporous layer (MPL) on the catalyst layer (CL) side. Using concentration gradient data, we quantify the non-uniform local transport resistance across the DM and relate it to high resolution 3D X-ray computed tomography of the same DM.

Note: Measurement of the cathode layer thickness in glow discharges with a Langmuir probe

NASA Astrophysics Data System (ADS)

Wang, Hao; Hou, Xinyu; Zou, Xiaobing; Luo, Haiyun; Wang, Xinxin

2018-06-01

A method using a Langmuir probe to determine the thickness of the cathode layer for a glow discharge is developed. The method is based on the phenomenon that the curve of the voltage-current characteristics changes in shape as the Langmuir probe moves from the positive column into the cathode layer. The method was used to measure the thicknesses of the cathode layer in the normal glow discharges of argon and air with the cathodes made from stainless steel and aluminum. The results are in good agreement with those given in a book of gas discharge.

Three dimensional electrode for the electrolytic removal of contaminants from aqueous waste streams

DOEpatents

Spiegel, Ella F.; Sammells, Anthony F.

2001-01-01

Efficient and cost-effective electrochemical devices and processes for the remediation of aqueous waste streams. The invention provides electrolytic cells having a high surface area spouted electrode for removal of heavy metals and oxidation of organics from aqueous environments. Heavy metal ions are reduced, deposited on cathode particles of a spouted bed cathode and removed from solution. Organics are efficiently oxidized at anode particles of a spouted bed anode and removed from solution. The method of this inventions employs an electrochemical cell having an anolyte compartment and a catholyte compartment, separated by a microporous membrane, in and through which compartments anolyte and catholyte, respectively, are circulated. A spouted-bed electrode is employed as the cathode for metal deposition from contaminated aqueous media introduced as catholyte and as the anode for oxidation of organics from contaminated aqueous media introduced as anolyte.

Amylose-Derived Macrohollow Core and Microporous Shell Carbon Spheres as Sulfur Host for Superior Lithium-Sulfur Battery Cathodes.

PubMed

Li, Xiang; Cheng, Xuanbing; Gao, Mingxia; Ren, Dawei; Liu, Yongfeng; Guo, Zhengxiao; Shang, Congxiao; Sun, Lixian; Pan, Hongge

2017-03-29

Porous carbon can be tailored to great effect for electrochemical energy storage. In this study, we propose a novel structured spherical carbon with a macrohollow core and a microporous shell derived from a sustainable biomass, amylose, by a multistep pyrolysis route without chemical etching. This hierarchically porous carbon shows a particle distribution of 2-10 μm and a surface area of 672 m 2 g -1 . The structure is an effective host of sulfur for lithium-sulfur battery cathodes, which reduces the dissolution of polysulfides in the electrolyte and offers high electrical conductivity during discharge/charge cycling. The hierarchically porous carbon can hold 48 wt % sulfur in its porous structure. The S@C hybrid shows an initial capacity of 1490 mAh g -1 and retains a capacity of 798 mAh g -1 after 200 cycles at a discharge/charge rate of 0.1 C. A capacity of 487 mAh g -1 is obtained at a rate of 3 C. Both a one-step pyrolysis and a chemical-reagent-assisted pyrolysis are also assessed to obtain porous carbon from amylose, but the obtained carbon shows structures inferior for sulfur cathodes. The multistep pyrolysis and the resulting hierarchically porous carbon offer an effective approach to the engineering of biomass for energy storage. The micrometer-sized spherical S@C hybrid with different sizes is also favorable for high-tap density and hence the volumetric density of the batteries, opening up a wide scope for practical applications.

Formation, Structure and Electrochemical Impedance Analysis of Microporous Polyelectrolyte Multilayers

NASA Astrophysics Data System (ADS)

Lutkenhaus, Jodie; McEnnis, Kathleen; Hammond, Paula

2007-03-01

Microporous networks are of interest as electrolyte materials, gas separation membranes and catalytic nanoparticle templates. Here, we create microporous polyelectrolyte networks of tunable pore size and connectivity using the layer-by-layer (LBL) technique. In this method, a film is formed from the alternate adsorption of oppositely charged polyelectrolytes from aqueous solution to create a cohesive thin film. Using poly(ethylene imine) (PEI) and poly(acrylic acid) (PAA), LBL thin films of variable composition and charge density were assembled; then, the films were treated in an acidic bath, which ionizes PEI and de-ionizes PAA. This shift in charge density induces morphological rearrangement realized by a microporous network. Depending on the assembly pH and acidic bath pH, we are able to precisely tune the morphology, which is characterized by atomic force microscopy and scanning electron microscopy. To demonstrate the porous nature of the polyelectrolyte multilayer, the pores were filled with non-aqueous electrolyte (i.e. ethylene carbonate, dimethyl carbonate and lithium hexafluorophosphate) and probed with electrochemical impedance spectroscopy. These microporous networks exhibited two time constants, indicative of ions traveling through the liquid-filled pores and ions traveling through the polyelectrolyte matrix.

Impact of ultra-low Pt loadings on the performance of anode/cathode in a proton-exchange membrane fuel cell

NASA Astrophysics Data System (ADS)

Billy, E.; Maillard, F.; Morin, A.; Guetaz, L.; Emieux, F.; Thurier, C.; Doppelt, P.; Donet, S.; Mailley, S.

This study focuses on the elaboration of PEMFC electrodes containing ultra-low platinum (Pt) loadings by direct liquid injection metal organic chemical vapor deposition (DLI-MOCVD). DLI-MOCVD offers a large number of advantages for the elaboration of model PEMFC electrodes. First, by using different metal precursors or elaboration temperature, the size of the Pt nanoparticles and thus the intrinsic catalytic activity can easily be tailored in the nanometer range. In this work, Pt nanoparticles (1-5 nm) with remarkable low degree of agglomeration and uniform distribution were deposited onto the microporous side of a commercial gas-diffusion layer (GDL). Second, reduction of the Pt loading is made possible by varying the Pt deposition time and its influence of the cell performance can be extracted without variation of the thickness of the catalytic layer (in previous studies, a decrease of the catalyst utilization was observed when increasing the Pt loading, i.e. the thickness of the catalytic layer (CL)). The electrocatalytic activity of home-made Pt nanoparticles elaborated by DLI-MOCVD was measured in liquid electrolyte or in complete fuel cell operating on H 2/O 2 or H 2/air and compared vs. that of a commercially available electrode containing 500 μg Pt cm -2 (Pt Ref500). At the cathode, the performance of the electrodes containing 104-226 μg of Pt per cm 2 of electrode compares favorably with that of the Pt Ref500 in H 2/O 2 conditions. In H 2/air conditions, additional mass-transport losses are detected in the low-current density region but the high effectiveness of our electrodes improves the performance in the high-current density region. At the anode, the Pt loading can be reduced to 35 μg Pt cm -2 without any voltage loss in agreement with previous observations.

Atomic to Nanoscale Investigation of Functionalities of Al2O3 Coating Layer on Cathode for Enhanced Battery Performance

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

Yan, Pengfei; Zheng, Jianming; Zhang, Xiaofeng

2016-01-06

Surface coating of cathode has been identified as an effective approach for enhancing the capacity retention of layered structure cathode. However, the underlying operating mechanism of such a thin layer of coating, in terms of surface chemical functionality and capacity retention, remains unclear. In this work, we use aberration corrected scanning transmission electron microscopy and high efficient spectroscopy to probe the delicate functioning mechanism of Al2O3 coating layer on Li1.2Ni0.2Mn0.6O2 cathode. We discovered that in terms of surface chemical function, the Al2O3 coating suppresses the side reaction between cathode and the electrolyte upon the battery cycling. At the same time,more » the Al2O3 coating layer also eliminates the chemical reduction of Mn from the cathode particle surface, therefore avoiding the dissolution of the reduced Mn into the electrolyte. In terms of structural stability, we found that the Al2O3 coating layer can mitigate the layer to spinel phase transformation, which otherwise will initiate from the particle surface and propagate towards the interior of the particle with the progression of the battery cycling. The atomic to nanoscale effects of the coating layer observed here provide insight for optimized design of coating layer on cathode to enhance the battery properties.« less

Sulfur-infiltrated porous carbon microspheres with controllable multi-modal pore size distribution for high energy lithium-sulfur batteries.

PubMed

Zhao, Cunyu; Liu, Lianjun; Zhao, Huilei; Krall, Andy; Wen, Zhenhai; Chen, Junhong; Hurley, Patrick; Jiang, Junwei; Li, Ying

2014-01-21

Sulfur has received increasing attention as a cathode material for lithium-sulfur (Li-S) batteries due to its high theoretical specific capacity. However, the commercialization of Li-S batteries is limited by the challenges of poor electrical conductivity of sulfur, dissolution of the polysulfide intermediates into the electrolyte, and volume expansion of sulfur during cycling. Herein, we report the fabrication of novel-structured porous carbon microspheres with a controllable multi-modal pore size distribution, i.e., a combination of interconnected micropores, mesopores and macropores. Cathodes made of sulfur infiltrated in such a hierarchical carbon framework provide several advantages: (1) a continuous and high surface area carbon network for enhanced electrical conductivity and high sulfur loading; (2) macropores and large mesopores bridged by small mesopores to provide good electrolyte accessibility and fast Li ion transport and to accommodate volume expansion of sulfur; and (3) small mesopores and micropores to improve carbon/sulfur interaction and to help trap polysulfides. An initial discharge capacity at 1278 mA h g(-1) and capacity retention at 70.7% (904 mA h g(-1)) after 100 cycles at a high rate (1 C) were achieved. The material fabrication process is relatively simple and easily scalable.

Effects of exchanged cation on the microporosity of montmorillonite

USGS Publications Warehouse

Rutherford, David W.; Chiou, Cary T.; Eberl, Dennis D.

1997-01-01

The micropore volumes of 2 montmorillonites (SAz-1 and SWy-1), each exchanged with Ca, Na, K, Cs and tetramethylammonium (TMA) ions, were calculated from the measured vapor adsorption data of N2 and neo-hexane by use of t- and αs-plots. The corresponding surface areas of the exchanged clays were determined from Brunauer-Emmett-Teller (BET) plots of N2 adsorption data. Micropore volumes and surface areas of the samples increased with the size of exchanged cation: TMA > Cs > K > Ca > Na. The SAz-1 exchanged clays showed generally greater micropore volumes and surface areas than the corresponding SWy-1 clays. The vapor adsorption data and d(001) measurements for dry clay samples were used together to evaluate the likely locations and accessibility of clay micropores, especially the relative accessibility of their interlayer spacing. For both source clays exchanged with Na, Ca and K ions, the interlayer spacing appeared to be too small to admit nonpolar gases and the accessible micropores appeared to have dimensions greater than 5.0 Å, the limiting molecular dimension of neo-hexane. In these systems, there was a good consistency of micropore volumes detected by N2 and neo-hexane. When the clays were intercalated with relatively large cations (TMA and possibly Cs), the large layer expansion created additional microporosity, which was more readily accessible to small N2 than to relatively large neo-hexane. Hence, the micropore volume as detected by N2 was greater than that detected by neo-hexane. The micropore volumes with pore dimensions greater than 5 Å determined for clays exchanged with Na, Ca and K likely resulted from the pores on particle edges and void created by overlap regions of layers. The increase in micropore volumes with pore dimensions less than 5 Å determined for clays exchanged with TMA and possibly Cs could be caused by opening of the interlayer region by the intercalation of these large cations.

Manganese oxide nanowires, films, and membranes and methods of making

DOEpatents

Suib, Steven Lawrence [Storrs, CT; Yuan, Jikang [Storrs, CT

2008-10-21

Nanowires, films, and membranes comprising ordered porous manganese oxide-based octahedral molecular sieves, and methods of making, are disclosed. A single crystal ultra-long nanowire includes an ordered porous manganese oxide-based octahedral molecular sieve, and has an average length greater than about 10 micrometers and an average diameter of about 5 nanometers to about 100 nanometers. A film comprises a microporous network comprising a plurality of single crystal nanowires in the form of a layer, wherein a plurality of layers is stacked on a surface of a substrate, wherein the nanowires of each layer are substantially axially aligned. A free standing membrane comprises a microporous network comprising a plurality of single crystal nanowires in the form of a layer, wherein a plurality of layers is aggregately stacked, and wherein the nanowires of each layer are substantially axially aligned.

Improvement of Energy Capacity with Vitamin C Treated Dual-Layered Graphene-Sulfur Cathodes in Lithium-Sulfur Batteries.

PubMed

Kim, Jin Won; Ocon, Joey D; Kim, Ho-Sung; Lee, Jaeyoung

2015-09-07

A graphene-based cathode design for lithium-sulfur batteries (LSB) that shows excellent electrochemical performance is proposed. The dual-layered cathode is composed of a sulfur active layer and a polysulfide absorption layer, and both layers are based on vitamin C treated graphene oxide at various degrees of reduction. By controlling the degree of reduction of graphene, the dual-layered cathode can increase sulfur utilization dramatically owing to the uniform formation of nanosized sulfur particles, the chemical bonding of dissolved polysulfides on the oxygen-rich sulfur active layer, and the physisorption of free polysulfides on the absorption layer. This approach enables a LSB with a high specific capacity of over 600 mAh gsulfur (-1) after 100 cycles even under a high current rate of 1C (1675 mA gsulfur (-1) ). An intriguing aspect of our work is the synthesis of a high-performance dual-layered cathode by a green chemistry method, which could be a promising approach to LSBs with high energy and power densities. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Cathode for a hall-heroult type electrolytic cell for producing aluminum

DOEpatents

Brown, Craig W.

2004-04-13

A method of producing aluminum from alumina in an electrolytic cell including using a cathode comprised of a base material having low electrical conductivity and wettable with molten aluminum to form a reaction layer having a high electrical conductivity on said base layer and a cathode bar extending from said reaction layer through said base material to conduct electrical current from said reaction layer.

Ultrathin spinel membrane-encapsulated layered lithium-rich cathode material for advanced Li-ion batteries.

PubMed

Wu, Feng; Li, Ning; Su, Yuefeng; Zhang, Linjing; Bao, Liying; Wang, Jing; Chen, Lai; Zheng, Yu; Dai, Liqin; Peng, Jingyuan; Chen, Shi

2014-06-11

Lack of high-performance cathode materials has become a technological bottleneck for the commercial development of advanced Li-ion batteries. We have proposed a biomimetic design and versatile synthesis of ultrathin spinel membrane-encapsulated layered lithium-rich cathode, a modification by nanocoating. The ultrathin spinel membrane is attributed to the superior high reversible capacity (over 290 mAh g(-1)), outstanding rate capability, and excellent cycling ability of this cathode, and even the stubborn illnesses of the layered lithium-rich cathode, such as voltage decay and thermal instability, are found to be relieved as well. This cathode is feasible to construct high-energy and high-power Li-ion batteries.

High performance polymer solar cells with as-prepared zirconium acetylacetonate film as cathode buffer layer

PubMed Central

Tan, Zhan'ao; Li, Shusheng; Wang, Fuzhi; Qian, Deping; Lin, Jun; Hou, Jianhui; Li, Yongfang

2014-01-01

Low-work-function active metals are commonly used as cathode in polymer solar cells (PSCs), but sensitivity of the active metals towards moisture and oxygen results in poor stability of the devices. Therefore, solution-proceessable and stable cathode buffer layer is of great importance for the application of PSCs. Here we demonstrate high performance PSCs by employing as-prepared zirconium acetylacetonate (a-ZrAcac) film spin-cast from its ethanol solution as cathode buffer layer. The PSCs based on a low bandgap polymer PBDTBDD as donor and PC60BM as acceptor with a-ZrAcac/Al cathode demonstrated an average power conversion efficiency (PCE) of 8.75% which is significantly improved than that of the devices with traditional Ca/Al cathode. The improved photovoltaic performance is benefitted from the decreased series resistance and enhanced light harvest of the PSCs with the a-ZrAcac/Al cathode. The results indicate that a-ZrAcac is a promising high performance cathode buffer layer for fabricating large area flexible PSCs. PMID:24732976

Micropore and nanopore fabrication in hollow antiresonant reflecting optical waveguides

PubMed Central

Holmes, Matthew R.; Shang, Tao; Hawkins, Aaron R.; Rudenko, Mikhail; Measor, Philip; Schmidt, Holger

2011-01-01

We demonstrate the fabrication of micropore and nanopore features in hollow antiresonant reflecting optical waveguides to create an electrical and optical analysis platform that can size select and detect a single nanoparticle. Micropores (4 μm diameter) are reactive-ion etched through the top SiO2 and SiN layers of the waveguides, leaving a thin SiN membrane above the hollow core. Nanopores are formed in the SiN membranes using a focused ion-beam etch process that provides control over the pore size. Openings as small as 20 nm in diameter are created. Optical loss measurements indicate that micropores did not significantly alter the loss along the waveguide. PMID:21922035

Micropore and nanopore fabrication in hollow antiresonant reflecting optical waveguides.

PubMed

Holmes, Matthew R; Shang, Tao; Hawkins, Aaron R; Rudenko, Mikhail; Measor, Philip; Schmidt, Holger

2010-01-01

We demonstrate the fabrication of micropore and nanopore features in hollow antiresonant reflecting optical waveguides to create an electrical and optical analysis platform that can size select and detect a single nanoparticle. Micropores (4 μm diameter) are reactive-ion etched through the top SiO(2) and SiN layers of the waveguides, leaving a thin SiN membrane above the hollow core. Nanopores are formed in the SiN membranes using a focused ion-beam etch process that provides control over the pore size. Openings as small as 20 nm in diameter are created. Optical loss measurements indicate that micropores did not significantly alter the loss along the waveguide.

Lipon coatings for high voltage and high temperature Li-ion battery cathodes

DOEpatents

Dudney, Nancy J.; Liang, Chengdu; Nanda, Jagjit; Veith, Gabriel M.; Kim, Yoongu; Martha, Surendra Kumar

2017-02-14

A lithium ion battery includes an anode and a cathode. The cathode includes a lithium, manganese, nickel, and oxygen containing compound. An electrolyte is disposed between the anode and the cathode. A protective layer is deposited between the cathode and the electrolyte. The protective layer includes pure lithium phosphorus oxynitride and variations that include metal dopants such as Fe, Ti, Ni, V, Cr, Cu, and Co. A method for making a cathode and a method for operating a battery are also disclosed.

Lipon coatings for high voltage and high temperature Li-ion battery cathodes

DOEpatents

Dudney, Nancy J.; Liang, Chengdu; Nanda, Jagjit; Veith, Gabriel M.; Kim, Yoongu; Martha, Surendra Kumar

2017-12-05

A lithium ion battery includes an anode and a cathode. The cathode includes a lithium, manganese, nickel, and oxygen containing compound. An electrolyte is disposed between the anode and the cathode. A protective layer is deposited between the cathode and the electrolyte. The protective layer includes pure lithium phosphorus oxynitride and variations that include metal dopants such as Fe, Ti, Ni, V, Cr, Cu, and Co. A method for making a cathode and a method for operating a battery are also disclosed.

Exploring Lithium Deficiency in Layered Oxide Cathode for Li-Ion Battery

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

Cho, Sung-Jin; Uddin, Md-Jamal; Alaboina, Pankaj K.

Abstract or short description: The ever-growing demand for high capacity cathode materials is on the rise since the futuristic applications are knocking on the door. Conventional approach to developing such cathode relies on the lithium-excess materials to operate the cathode at high voltage and extract more lithium-ion. Yet, they fail to satiate the needs because of their unresolved issues upon cycling such as, for lithium manganese-rich layered oxides – their voltage fading, and for as nickel-based layered oxides – the structural transition. Here, in contrast, lithium-deficient ratio is demonstrated as a new approach to attain high capacity at high voltagemore » for layered oxide cathodes. Rapid and cost effective lithiation of a porous hydroxide precursor with lithium deficient ratio acted as a driving force to partially convert the layered material to spinel phase yielding in a multiphase structure (MPS) cathode material. Upon cycling, MPS revealed structural stability at high voltage and high temperature and resulted in fast lithium-ion diffusion by providing a distinctive SEI chemistry – MPS displayed minimum lithium loss in SEI and formed a thinner SEI. MPS thus offer high energy and high power applications and provides a new perspective compared to the conventional layered cathode materials denying the focus for lithium excess material.« less

Cathodes for secondary electrochemical power-producing cells. [layers of porous substrates impregnated with S alternate with layers containing electrolyte

DOEpatents

Cairns, E.J.; Kyle, M.; Shimotake, H.

1973-02-13

A secondary electrochemical power-producing cell includes an anode containing lithium, an electrolyte containing lithium ions, and a cathode containing sulfur. The cathode comprises plates of a porous substrate material impregnated with sulfur alternating with layers (which may also comprise porous substrate plates) containing electrolyte.

Extended OLED operational lifetime through phosphorescent dopant profile management

DOEpatents

Forrest, Stephen R.; Zhang, Yifan

2017-05-30

This disclosure relates, at least in part, an organic light emitting device, which in some embodiments comprises an anode; a cathode; a first emissive layer disposed between the anode and the cathode, the first emissive layer comprising an electron transporting compound and a phosphorescent emissive dopant compound; and wherein the phosphorescent emissive dopant compound has a concentration gradient, in the emissive layer, which varies from the cathode side of the first emissive layer to the anode side of the emissive layer.

Atomic to Nanoscale Investigation of Functionalities of an Al2O3 Coating Layer on a Cathode for Enhanced Battery Performance

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

Yan, Pengfei; Zheng, Jianming; Zhang, Xiaofeng

2016-02-09

Surface coating has been identified as an effective approach for enhancing the capacity retention of layered structure cathode. However, the underlying operating mechanism of such a thin coating layer, in terms of surface chemical functionality and capacity retention, remains unclear. In this work, we use aberration-corrected scanning transmission electron microscopy and high-efficiency spectroscopy to probe the delicate functioning mechanism of an Al2O3 coating layer on a Li1.2Ni0.2Mn0.6O2 cathode. We discovered that in terms of surface chemical function, the Al2O3 coating suppresses the side reaction between the cathode and the electrolyte during battery cycling. At the same time, the Al2O3 coatingmore » layer also eliminates the chemical reduction of Mn from the cathode particle surface, therefore preventing the dissolution of the reduced Mn into the electrolyte. In terms of structural stability, we found that the Al2O3 coating layer can mitigate the layer to spinel phase transformation, which otherwise will be initiated from the particle surface and propagate toward the interior of the particle with the progression of battery cycling. The atomic to nanoscale effects of the coating layer observed here provide insight into the optimized design of a coating layer on a cathode to enhance the battery properties.« less

Microporous novolac-derived carbon beads/sulfur hybrid cathode for lithium-sulfur batteries

NASA Astrophysics Data System (ADS)

Choudhury, Soumyadip; Krüner, Benjamin; Massuti-Ballester, Pau; Tolosa, Aura; Prehal, Christian; Grobelsek, Ingrid; Paris, Oskar; Borchardt, Lars; Presser, Volker

2017-07-01

Novolac-derived nanoporous carbon beads were used as conductive matrix for lithium-sulfur battery cathodes. We employed a facile self-emulsifying synthesis to obtain sub-micrometer novolac-derived carbon beads with nanopores. After pyrolysis, the carbon beads showed already a specific surface area of 640 m2 g-1 which was increased to 2080 m2 g-1 after physical activation. The non-activated and the activated carbon beads represent nanoporous carbon with a medium and a high surface area, respectively. This allows us to assess the influence of the porosity on the electrochemical performance of lithium-sulfur battery cathodes. The carbon/sulfur hybrids were obtained from two different approaches of sulfur infiltration: melt-infusion of sulfur (annealing) and in situ formation of sulfur from sodium thiosulfate. The best performance (∼880 mAh gsulfur-1 at low charge rate; 5th cycle) and high performance stability (>600 mAh gsulfur-1 after 100 cycles) were found for the activated carbon beads when using melt infusion of sulfur.

Electrophoretic deposition of bi-layered LSM/LSM-YSZ cathodes for solid oxide fuel cell

NASA Astrophysics Data System (ADS)

Itagaki, Yoshiteru; Watanabe, Shinji; Yamaji, Tsuyoshi; Asamoto, Makiko; Yahiro, Hidenori; Sadaoka, Yoshihiko

2012-09-01

Bi-layered cathodes with the LSM/LSM-YSZ structure for solid oxide fuel cells were successfully formed on the carbon-sputtered surface of a YSZ sheet by electrophoretic deposition (EPD). The thicknesses of the first layer of LSM-YSZ (LY) and the second layer of La0.8Sr0.2MnO3 (LSM) could be controlled by adjusting the deposition time in the EPD process. The cathodic properties of the bi-layered structures were superior to those of the mono-layered structures, and were dependent on the thickness of each layer. Decreasing the thickness of the first layer and increasing that of the second layer tended to reduce both polarization and ohmic resistances. The optimal thickness of the first layer at the operating temperature of 600 °C was 4 μm, suggesting that an effective three-phase boundary was extended from the interface between the electrolyte and cathode film to around 4 μm thickness.

Progress of air-breathing cathode in microbial fuel cells

NASA Astrophysics Data System (ADS)

Wang, Zejie; Mahadevan, Gurumurthy Dummi; Wu, Yicheng; Zhao, Feng

2017-07-01

Microbial fuel cell (MFC) is an emerging technology to produce green energy and vanquish the effects of environmental contaminants. Cathodic reactions are vital for high electrical power density generated from MFCs. Recently tremendous attentions were paid towards developing high performance air-breathing cathodes. A typical air-breathing cathode comprises of electrode substrate, catalyst layer, and air-diffusion layer. Prior researches demonstrated that each component influenced the performance of air-breathing cathode MFCs. This review summarized the progress in development of the individual component and elaborated main factors to the performance of air-breathing cathode.

Arc initiation in cathodic arc plasma sources

DOEpatents

Anders, Andre

2002-01-01

A "triggerless" arc initiation method and apparatus is based on simply switching the arc supply voltage to the electrodes (anode and cathode). Neither a mechanical trigger electrode nor a high voltage flashover from a trigger electrode is required. A conducting path between the anode and cathode is provided, which allows a hot spot to form at a location where the path connects to the cathode. While the conductive path is eroded by the cathode spot action, plasma deposition ensures the ongoing repair of the conducting path. Arc initiation is achieved by simply applying the relatively low voltage of the arc power supply, e.g. 500 V-1 kV, with the insulator between the anode and cathode coated with a conducting layer and the current at the layer-cathode interface concentrated at one or a few contact points. The local power density at these contact points is sufficient for plasma production and thus arc initiation. A conductive surface layer, such as graphite or the material being deposited, is formed on the surface of the insulator which separates the cathode from the anode. The mechanism of plasma production (and arc initiation) is based on explosive destruction of the layer-cathode interface caused by joule heating. The current flow between the thin insulator coating and cathode occurs at only a few contact points so the current density is high.

Fabrication and Characterization of Functionally Graded Cathodes for Solid Oxide Fuel Cells

NASA Astrophysics Data System (ADS)

Simonet, J.; Kapelski, G.; Bouvard, D.

2008-02-01

Solid oxide fuel cells are multi-layered designed. The most prevalent structure is an anode supported cell with a thick porous layer of nickel oxide NiO and yttrium stabilized zirconia (YSZ) composite acting as an anode, a thin dense layer of YSZ as an electrolyte, a composite thin porous layer of lanthanum strontium manganate LSM and YSZ and a current collector layer of porous LSM. Regular operating temperature is 1000 °C. The industrial development requires designing cathodes with acceptable electrochemical and mechanical properties at a lower temperature, typically between 700 and 800 °C. A solution consists in designing composite bulk cathodes with more numerous electro-chemical reaction sites. This requirement could be met by grading the composition of the cathode in increasing the YSZ volume fraction near the electrolyte and the LSM volume fraction near the current collector layer so that the repartition of reaction sites and the interfacial adhesion between the cathode and electrolyte layers are optimal. The fabrication of graded composite cathode has been investigated using a sedimentation process that consists of preparing a suspension containing the powder mixture and allowing the particles to fall by gravity upon a substrate. Different composite cathodes with continuous composition gradient have been obtained by sedimentation of LSM and YSZ powder mixture upon a dense YSZ substrate and subsequent firing. Their compositions and microstructures have been analysed with Scanning Electron Microscope (SEM) and Electron Dispersive Spectrometry (EDS).

Surface studies on scandate cathodes and synthesized scandates

NASA Technical Reports Server (NTRS)

Lesny, Gary; Forman, Ralph

1990-01-01

Auger, ESCA, electron emission, evaporation, and desorption measurements were made on three different types of scandate surfaces. They are: (1) an impregnated top layer scandate cathode, (2) an unimpregnated top layer scandate cathode with a deposited barium or barium oxide adsorbate surface layer, and (3) a synthesized scandate surface, which replicates a scandate cathode surface. The purpose of these experiments was to determine the role that Sc2O3 plays in making the scandate cathode a more copious electron emitter than the conventional impregnated-type cathode. The synthesized scandate surface experiments consisted of depositing multilayer scandium on a tungsten surface, oxidizing the scandium, and then depositing either Ba or BaO on the scandium oxide surface. The results of these measurements showed that the low work function portions of the thin-film scandate cathode are where the Sc2O3 is the substrate and BaO is the adsorbate.

Iridium-coated micropore x-ray optics using dry etching of a silicon wafer and atomic layer deposition.

PubMed

Ogawa, Tomohiro; Ezoe, Yuichiro; Moriyama, Teppei; Mitsuishi, Ikuyuki; Kakiuchi, Takuya; Ohashi, Takaya; Mitsuda, Kazuhisa; Putkonen, Matti

2013-08-20

To enhance x-ray reflectivity of silicon micropore optics using dry etching of silicon (111) wafers, iridium coating is tested by use of atomic layer deposition. An iridium layer is successfully formed on sidewalls of tiny micropores with a pore width of 20 μm and depth of 300 μm. The film thickness is ∼20  nm. An enhanced x-ray reflectivity compared to that of silicon is confirmed at Ti K_α 4.51 keV, for what we believe to be the first time, with this type of optics. Some discrepancies from a theoretical reflectivity curve of iridium-coated silicon are noticed at small incident angles <1.3°. When a geometrical shadowing effect due to occultation by a ridge existing on the sidewalls is taken into account, the observed reflectivity becomes well represented by the modified theoretical curve. An estimated surface micro roughness of ∼1  nm rms is consistent with atomic force microscope measurements of the sidewalls.

Electronic structure of the polymer-cathode interface of an organic electroluminescent device investigated using operando hard x-ray photoelectron spectroscopy

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

Ikeuchi, J.; Hamamatsu, H.; Miyamoto, T.

2015-08-28

The electronic structure of a polymer-cathode interface of an operating organic light-emitting diode (OLED) was directly investigated using hard X-ray photoelectron spectroscopy (HAXPES). The potential distribution profile of the light-emitting copolymer layer as a function of the depth under the Al/Ba cathode layer in the OLED depended on the bias voltage. We found that band bending occurred in the copolymer of 9,9-dioctylfluorene (50%) and N-(4-(2-butyl)-phenyl)diphenylamine (F8-PFB) layer near the cathode at 0 V bias, while a linear potential distribution formed in the F8-PFB when a bias voltage was applied to the OLED. Direct observation of the built-in potential and that bandmore » bending formed in the F8-PFB layer in the operating OLED suggested that charges moved in the F8-PFB layer before electron injection from the cathode.« less

An Ideal Electrode Material, 3D Surface-Microporous Graphene for Supercapacitors with Ultrahigh Areal Capacitance

DOE PAGES

Chang, Liang; Stacchiola, Dario J.; Hu, Yun Hang

2017-07-03

The efficient charge accumulation of an ideal supercapacitor electrode requires abundant micropores and its fast electrolyte-ions transport prefers meso/macropores. But, current electrode materials cannot meet both requirements, resulting in poor performance. We creatively constructed three-dimensional cabbage-coral-like graphene as an ideal electrode material, in which meso/macro channels are formed by graphene walls and rich micropores are incorporated in the surface layer of the graphene walls. The unique 3D graphene material can achieve a high gravimetric capacitance of 200 F/g with aqueous electrolyte, 3 times larger than that of commercially used activated carbon (70.8 F/g). Furthermore, it can reach an ultrahigh arealmore » capacitance of 1.28 F/cm 2 and excellent rate capability (83.5% from 0.5 to 10 A/g) as well as high cycling stability (86.2% retention after 5000 cycles). The excellent electric double-layer performance of the 3D graphene electrode can be attributed to the fast electrolyte ion transport in the meso/macro channels and the rapid and reversible charge adsorption with negligible transport distance in the surface micropores.« less

Pt thermal atomic layer deposition for silicon x-ray micropore optics.

PubMed

Takeuchi, Kazuma; Ezoe, Yuichiro; Ishikawa, Kumi; Numazawa, Masaki; Terada, Masaru; Ishi, Daiki; Fujitani, Maiko; Sowa, Mark J; Ohashi, Takaya; Mitsuda, Kazuhisa

2018-04-20

We fabricated a silicon micropore optic using deep reactive ion etching and coated by Pt with atomic layer deposition (ALD). We confirmed that a metal/metal oxide bilayer of Al 2 O 3 ∼10  nm and Pt ∼20  nm was successfully deposited on the micropores whose width and depth are 20 μm and 300 μm, respectively. An increase of surface roughness of sidewalls of the micropores was observed with a transmission electron microscope and an atomic force microscope. X-ray reflectivity with an Al Kα line at 1.49 keV before and after the deposition was measured and compared to ray-tracing simulations. The surface roughness of the sidewalls was estimated to increase from 1.6±0.2  nm rms to 2.2±0.2  nm rms. This result is consistent with the microscope measurements. Post annealing of the Pt-coated optic at 1000°C for 2 h showed a sign of reduced surface roughness and better angular resolution. To reduce the surface roughness, possible methods such as the annealing after deposition and a plasma-enhanced ALD are discussed.

An Ideal Electrode Material, 3D Surface-Microporous Graphene for Supercapacitors with Ultrahigh Areal Capacitance

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

Chang, Liang; Stacchiola, Dario J.; Hu, Yun Hang

The efficient charge accumulation of an ideal supercapacitor electrode requires abundant micropores and its fast electrolyte-ions transport prefers meso/macropores. But, current electrode materials cannot meet both requirements, resulting in poor performance. We creatively constructed three-dimensional cabbage-coral-like graphene as an ideal electrode material, in which meso/macro channels are formed by graphene walls and rich micropores are incorporated in the surface layer of the graphene walls. The unique 3D graphene material can achieve a high gravimetric capacitance of 200 F/g with aqueous electrolyte, 3 times larger than that of commercially used activated carbon (70.8 F/g). Furthermore, it can reach an ultrahigh arealmore » capacitance of 1.28 F/cm 2 and excellent rate capability (83.5% from 0.5 to 10 A/g) as well as high cycling stability (86.2% retention after 5000 cycles). The excellent electric double-layer performance of the 3D graphene electrode can be attributed to the fast electrolyte ion transport in the meso/macro channels and the rapid and reversible charge adsorption with negligible transport distance in the surface micropores.« less

Multi-layer electrode for high contrast electrochromic devices

DOEpatents

Schwendeman, Irina G [Wexford, PA; Finley, James J [Pittsburgh, PA; Polcyn, Adam D [Pittsburgh, PA; Boykin, Cheri M [Wexford, PA

2011-11-01

An electrochromic device includes a first substrate spaced from a second substrate. A first transparent conductive electrode is formed over at least a portion of the first substrate. A polymeric anode is formed over at least a portion of the first conductive electrode. A second transparent conductive electrode is formed over at least a portion of the second substrate. In one aspect of the invention, a multi-layer polymeric cathode is formed over at least a portion of the second conductive electrode. In one non-limiting embodiment, the multi-layer cathode includes a first cathodically coloring polymer formed over at least a portion of the second conductive electrode and a second cathodically coloring polymer formed over at least a portion of the first cathodically coloring polymer. An ionic liquid is positioned between the anode and the cathode.

Performance of a Cross-Flow Humidifier with a High Flux Water Vapor Transport Membrane

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

Ahluwalia, R. K.; Wang, X.; Johnson, W. B.

Water vapor transport (WVT) flux across a composite membrane that consists of a very thin perfluorosulfonic acid (PFSA) ionomer layer sandwiched between two expanded polytetrafluoroethylene (PTFE) microporous layers is investigated. Static and dynamic tests are conducted to measure WVT flux for different composite structures; a transport model shows that the underlying individual resistances for water diffusion in the gas phase and microporous and ionomer layers and for interfacial kinetics of water uptake at the ionomer surface are equally important under different conditions. A finite-difference model is formulated to determine water transport in a full-scale (2-m2 active membrane area) planar cross-flowmore » humidifier module assembled using pleats of the optimized composite membrane. In agreement with the experimental data, the modeled WVT flux in the module increases at higher inlet relative humidity (RH) of the wet stream and at lower pressures, but the mass transfer effectiveness is higher at higher pressures. The model indicates that the WVT flux is highest under conditions that maintain the wet stream at close to 100% RH while preventing the dry stream from becoming saturated. The overall water transport is determined by the gradient in RH of the wet and dry streams but is also affected by vapor diffusion in the gas layer and the microporous layer.« less

Understanding the effect of an in situ generated and integrated spinel phase on a layered Li-rich cathode material using a non-stoichiometric strategy.

PubMed

Zhang, Jicheng; Gao, Rui; Sun, Limei; Li, Zhengyao; Zhang, Heng; Hu, Zhongbo; Liu, Xiangfeng

2016-09-14

Recently, spinel-layered integrated Li-rich cathode materials have attracted great interest due to the large enhancement of their electrochemical performances. However, the modification mechanism and the effect of the integrated spinel phase on Li-rich layered cathode materials are still not very clear. Herein, we have successfully synthesized the spinel-layered integrated Li-rich cathode material using a facile non-stoichiometric strategy (NS-LNCMO). The rate capability (84 mA h g -1 vs. 28 mA h g -1 , 10 C), cycling stability (92.4% vs. 80.5%, 0.2 C), low temperature electrochemical capability (96.5 mA h g -1 vs. 59 mA h g -1 , -20 °C), initial coulomb efficiency (92% vs. 79%) and voltage fading (2.77 V vs. 3.02 V, 200 cycles@1 C) of spinel-layered integrated Li-rich cathode materials have been significantly improved compared with a pure Li-rich phase cathode. Some new insights into the effect of the integrated spinel phase on a layered Li-rich cathode have been proposed through a comparison of the structure evolution of the integrated and Li-rich only materials before and after cycling. The Li-ion diffusion coefficient of NS-LNCMO has been enlarged by about 3 times and almost does not change even after 100 cycles indicating an enhanced structure stability. The integration of the spinel phase not only enhances the structure stability of the layered Li-rich phase during charging-discharging but also expands the interslab spacing of the Li-ion diffusion layer, and elongates TM-O covalent bond lengths, which lowers the activation barrier of Li + -transportation, and alleviates the structure strain during the cycling procedure.

Polyethylenimine Interfacial Layers in Inverted Organic Photovoltaic Devices: Effects of Ethoxylation and Molecular Weight on Efficiency and Temporal Stability.

PubMed

Courtright, Brett A E; Jenekhe, Samson A

2015-12-02

We report a comparative study of polyethylenimine (PEI) and ethoxylated-polyethylenimine (PEIE) cathode buffer layers in high performance inverted organic photovoltaic devices. The work function of the indium-tin oxide (ITO)/zinc oxide (ZnO) cathode was reduced substantially (Δφ = 0.73-1.09 eV) as the molecular weight of PEI was varied from 800 g mol(-1) to 750 000 g mol(-1) compared with the observed much smaller reduction when using a PEIE thin film (Δφ = 0.56 eV). The reference inverted polymer solar cells based on the small band gap polymer PBDTT-FTTE (ITO/ZnO/PBDTT-FTTE:PC70BM/MoO3/Ag), without a cathode buffer layer, had an average power conversion efficiency (PCE) of 6.06 ± 0.22%. Incorporation of a PEIE cathode buffer layer in the same PBDTT-FTTE:PC70BM blend devices gave an enhanced performance with a PCE of 7.37 ± 0.53%. In contrast, an even greater photovoltaic efficiency with a PCE of 8.22 ± 0.10% was obtained in similar PBDTT-FTTE:PC70BM blend solar cells containing a PEI cathode buffer layer. The temporal stability of the inverted polymer solar cells was found to increase with increasing molecular weight of the cathode buffer layer. The results show that PEI is superior to PEIE as a cathode buffer layer in high performance organic photovoltaic devices and that the highest molecular weight PEI interlayer provides the highest temporal stability.

Thin films of aluminum nitride and aluminum gallium nitride for cold cathode applications

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

Sowers, A.T.; Christman, J.A.; Bremser, M.D.

1997-10-01

Cold cathode structures have been fabricated using AlN and graded AlGaN structures (deposited on n-type 6H-SiC) as the thin film emitting layer. The cathodes consist of an aluminum grid layer separated from the nitride layer by a SiO{sub 2} layer and etched to form arrays of either 1, 3, or 5 {mu}m holes through which the emitting nitride surface is exposed. After fabrication, a hydrogen plasma exposure was employed to activate the cathodes. Cathode devices with 5 {mu}m holes displayed emission for up to 30 min before failing. Maximum emission currents ranged from 10{endash}100 nA and required grid voltages rangingmore » from 20{endash}110 V. The grid currents were typically 1 to 10{sup 4} times the collector currents. {copyright} {ital 1997 American Institute of Physics.}« less

Degradation Study by Start-Up/Shut-Down Cycling of Superhydrophobic Electrosprayed Catalyst Layers Using a Localized Reference Electrode Technique.

PubMed

Ferreira-Aparicio, Paloma; Chaparro, Antonio M; Folgado, M Antonia; Conde, Julio J; Brightman, Edward; Hinds, Gareth

2017-03-29

Degradation of a polymer electrolyte membrane fuel cell (PEMFC) with electrosprayed cathode catalyst layers is investigated during cyclic start-up and shut-down events. The study is carried out within a single cell incorporating an array of reference electrodes that enables measurement of cell current as a function of local cathode potential (localized polarization curves). Accelerated degradation of the cell by start-up/shut-down cycling gives rise to inhomogeneous performance loss, which is more severe close to the gas outlet and occurs predominantly during start-up. The degradation consists primarily of loss of cathode catalyst activity and increase in cell internal resistance, which is attributed to carbon corrosion and Pt aggregation in both anode and cathode. Cells with an electrosprayed cathode catalyst layer show lower degradation rates during the first 100 cycles, compared with those of a conventional gas diffusion electrode. This difference in behavior is attributed to the high hydrophobicity of the electrosprayed catalyst layer microstructure, which retards the kinetics of corrosion of the carbon support. In the long term, however, the degradation rate is dominated by the Pt/C ratio in the cathode catalyst layer.

Secondary battery containing zinc electrode with modified separator and method

DOEpatents

Poa, David S.; Yao, Neng-Ping

1985-01-01

A battery containing a zinc electrode with a porous separator between the anode and cathode. The separator is a microporous substrate carrying therewith an organic solvent of benzene, toluene or xylene with a tertiary organic amine therein, wherein the tertiary amine has three carbon chains each containing from six to eight carbon atoms. The separator reduces the rate of zinc dentrite growth in the separator during battery operation prolonging battery life by preventing short circuits. A method of making the separator is also disclosed.

Secondary battery containing zinc electrode with modified separator and method

DOEpatents

Poa, D.S.

1984-02-16

A battery containing a zinc electrode with a porous separator between the anode and cathode. The separator is a microporous substrate carrying therewith an organic solvent of benzene, toluene or xylene with a tertiary organic amine therein, wherein the tertiary amine has three carbon chains each containing from six to eight carbon atoms. The separator reduces the rate of zinc dentrite growth in the separator during battery operation prolonging battery life by preventing short circuits. A method of making the separator is also disclosed.

Emission characteristics of dispenser cathodes with a fine-grained tungsten top layer

NASA Astrophysics Data System (ADS)

Kimura, S.; Higuchi, T.; Ouchi, Y.; Uda, E.; Nakamura, O.; Sudo, T.; Koyama, K.

1997-02-01

In order to improve the emission stability of the Ir-coated dispenser cathode under ion bombardment, a fine-grained tungsten top layer was applied on the substrate porous tungsten plug before Ir coating. The emission characteristics were studied after being assembled in a CRT gun. Cathode current was measured under pulse operation in a range of 0.1-9% duty. Remarkable anti-ion bombardment characteristics were observed over the range of 1-6% duty. The improved cathode showed 1.5 times higher emission current than that of a conventional Ir-coated dispenser cathode at 4% duty. AES analysis showed that the recovering rates of surface Ba and O atoms after ion bombardment were 2.5 times higher. From these results it is confirmed that the Ir coated cathode with a fine-grained tungsten top layer is provided with a good tolerance against the ion bombardment.

A high performance lithium ion capacitor achieved by the integration of a Sn-C anode and a biomass-derived microporous activated carbon cathode

NASA Astrophysics Data System (ADS)

Sun, Fei; Gao, Jihui; Zhu, Yuwen; Pi, Xinxin; Wang, Lijie; Liu, Xin; Qin, Yukun

2017-02-01

Hybridizing battery and capacitor materials to construct lithium ion capacitors (LICs) has been regarded as a promising avenue to bridge the gap between high-energy lithium ion batteries and high-power supercapacitors. One of the key difficulties in developing advanced LICs is the imbalance in the power capability and charge storage capacity between anode and cathode. Herein, we design a new LIC system by integrating a rationally designed Sn-C anode with a biomass-derived activated carbon cathode. The Sn-C nanocomposite obtained by a facile confined growth strategy possesses multiple structural merits including well-confined Sn nanoparticles, homogeneous distribution and interconnected carbon framework with ultra-high N doping level, synergically enabling the fabricated anode with high Li storage capacity and excellent rate capability. A new type of biomass-derived activated carbon featuring both high surface area and high carbon purity is also prepared to achieve high capacity for cathode. The assembled LIC (Sn-C//PAC) device delivers high energy densities of 195.7 Wh kg-1 and 84.6 Wh kg-1 at power densities of 731.25 W kg-1 and 24375 W kg-1, respectively. This work offers a new strategy for designing high-performance hybrid system by tailoring the nanostructures of Li insertion anode and ion adsorption cathode.

A high performance lithium ion capacitor achieved by the integration of a Sn-C anode and a biomass-derived microporous activated carbon cathode.

PubMed

Sun, Fei; Gao, Jihui; Zhu, Yuwen; Pi, Xinxin; Wang, Lijie; Liu, Xin; Qin, Yukun

2017-02-03

Hybridizing battery and capacitor materials to construct lithium ion capacitors (LICs) has been regarded as a promising avenue to bridge the gap between high-energy lithium ion batteries and high-power supercapacitors. One of the key difficulties in developing advanced LICs is the imbalance in the power capability and charge storage capacity between anode and cathode. Herein, we design a new LIC system by integrating a rationally designed Sn-C anode with a biomass-derived activated carbon cathode. The Sn-C nanocomposite obtained by a facile confined growth strategy possesses multiple structural merits including well-confined Sn nanoparticles, homogeneous distribution and interconnected carbon framework with ultra-high N doping level, synergically enabling the fabricated anode with high Li storage capacity and excellent rate capability. A new type of biomass-derived activated carbon featuring both high surface area and high carbon purity is also prepared to achieve high capacity for cathode. The assembled LIC (Sn-C//PAC) device delivers high energy densities of 195.7 Wh kg -1 and 84.6 Wh kg -1 at power densities of 731.25 W kg -1 and 24375 W kg -1 , respectively. This work offers a new strategy for designing high-performance hybrid system by tailoring the nanostructures of Li insertion anode and ion adsorption cathode.

A high performance lithium ion capacitor achieved by the integration of a Sn-C anode and a biomass-derived microporous activated carbon cathode

PubMed Central

Sun, Fei; Gao, Jihui; Zhu, Yuwen; Pi, Xinxin; Wang, Lijie; Liu, Xin; Qin, Yukun

2017-01-01

Hybridizing battery and capacitor materials to construct lithium ion capacitors (LICs) has been regarded as a promising avenue to bridge the gap between high-energy lithium ion batteries and high-power supercapacitors. One of the key difficulties in developing advanced LICs is the imbalance in the power capability and charge storage capacity between anode and cathode. Herein, we design a new LIC system by integrating a rationally designed Sn-C anode with a biomass-derived activated carbon cathode. The Sn-C nanocomposite obtained by a facile confined growth strategy possesses multiple structural merits including well-confined Sn nanoparticles, homogeneous distribution and interconnected carbon framework with ultra-high N doping level, synergically enabling the fabricated anode with high Li storage capacity and excellent rate capability. A new type of biomass-derived activated carbon featuring both high surface area and high carbon purity is also prepared to achieve high capacity for cathode. The assembled LIC (Sn-C//PAC) device delivers high energy densities of 195.7 Wh kg−1 and 84.6 Wh kg−1 at power densities of 731.25 W kg−1 and 24375 W kg−1, respectively. This work offers a new strategy for designing high-performance hybrid system by tailoring the nanostructures of Li insertion anode and ion adsorption cathode. PMID:28155853

Coating of porous carbon for use in lithium air batteries

DOEpatents

Amine, Khalil; Lu, Jun; Du, Peng; Lei, Yu; Elam, Jeffrey W

2015-04-14

A cathode includes a carbon material having a surface, the surface having a first thin layer of an inert material and a first catalyst overlaying the first thin layer, the first catalyst including metal or metal oxide nanoparticles, wherein the cathode is configured for use as the cathode of a lithium-air battery.

Phosphorescent organic light emitting diodes with high efficiency and brightness

DOEpatents

Forrest, Stephen R; Zhang, Yifan

2015-11-12

An organic light emitting device including a) an anode; b) a cathode; and c) an emissive layer disposed between the anode and the cathode, the emissive layer comprising an organic host compound and a phosphorescent compound exhibiting a Stokes Shift overlap greater than 0.3 eV. The organic light emitting device may further include a hole transport layer disposed between the emissive layer and the anode; and an electron transport layer disposed between the emissive layer and the cathode. In some embodiments, the phosphorescent compound exhibits a phosphorescent lifetime of less than 10 .mu.s. In some embodiments, the concentration of the phosphorescent compound ranges from 0.5 wt. % to 10 wt. %.

Diclofenac delays micropore closure following microneedle treatment in human subjects.

PubMed

Brogden, Nicole K; Milewski, Mikolaj; Ghosh, Priyanka; Hardi, Lucia; Crofford, Leslie J; Stinchcomb, Audra L

2012-10-28

Drugs absorbed poorly through the skin are commonly delivered via injection with a hypodermic needle, which is painful and increases the risk of transmitting infectious diseases. Microneedles (MNs) selectively and painlessly permeabilize the outermost skin layer, allowing otherwise skin-impermeable drugs to cross the skin through micron-sized pores and reach therapeutic concentrations. However, rapid healing of the micropores prevents further drug delivery, blunting the clinical utility of this unique transdermal technique. We present the first human study demonstrating that micropore lifetime can be extended following MN treatment. Subjects received one-time MN treatment and daily topical application of diclofenac sodium. Micropore closure was measured with impedance spectroscopy, and area under the admittance-time curve (AUC) was calculated. AUC was significantly higher at MN+diclofenac sodium sites vs. placebo, suggesting slower rates of micropore healing. Colorimetry measurements confirmed the absence of local erythema and irritation. This mechanistic human proof-of-concept study demonstrates that micropore lifetime can be prolonged with simple topical administration of a non-specific cyclooxygenase inhibitor, suggesting the involvement of subclinical inflammation in micropore healing. These results will allow for longer patch wear time with MN-enhanced delivery, thus increasing patient compliance and expanding the transdermal field to a wider variety of clinical conditions. Copyright © 2012 Elsevier B.V. All rights reserved.

Diclofenac delays micropore closure following microneedle treatment in human subjects

PubMed Central

Brogden, Nicole K.; Milewski, Mikolaj; Ghosh, Priyanka; Hardi, Lucia; Crofford, Leslie J.; Stinchcomb, Audra L.

2013-01-01

Drugs absorbed poorly through the skin are commonly delivered via injection with a hypodermic needle, which is painful and increases the risk of transmitting infectious diseases. Microneedles (MNs) selectively and painlessly permeabilize the outermost skin layer, allowing otherwise skin-impermeable drugs to cross the skin through micron-sized pores and reach therapeutic concentrations. However, rapid healing of the micropores prevents further drug delivery, blunting the clinical utility of this unique transdermal technique. We present the first human study demonstrating that micropore lifetime can be extended following MN treatment. Subjects received one-time MN treatment and daily topical application of diclofenac sodium. Micropore closure was measured with impedance spectroscopy, and area under the admittance–time curve (AUC) was calculated. AUC was significantly higher at MN + diclofenac sodium sites vs. placebo, suggesting slower rates of micropore healing. Colorimetry measurements confirmed the absence of local erythema and irritation. This mechanistic human proof-of-concept study demonstrates that micropore lifetime can be prolonged with simple topical administration of a non-specific cyclooxygenase inhibitor, suggesting the involvement of subclinical inflammation in micropore healing. These results will allow for longer patch wear time with MN-enhanced delivery, thus increasing patient compliance and expanding the transdermal field to a wider variety of clinical conditions. PMID:22929967

A proposed physical model for the impregnated tungsten cathode based on Auger surface studies of the Ba-O-W system

NASA Technical Reports Server (NTRS)

Forman, R.

1979-01-01

Auger spectra and work function measurements are used to study the surface reactions between tungsten surface and adsorbed layers of barium, and barium and oxygen. The barium on an impregnated tungsten cathod seems to be an intermediate state, probably a coadsorbed barium-oxygen layer on tungsten. A slightly revised version of the previously suggested (1976) impregnated tungsten cathode model is proposed. This revised model assumes that the cathode surface during life has an adsorbed surface layer of a monolayer or less of both barium and oxygen on the surface. At end of life, steep drop in electron emission and resultant cathode failure occur. Recent NASA life test results on TWT type tubes are reported and explained by the proposed model.

Solid oxide fuel cell having monolithic core

DOEpatents

Ackerman, John P.; Young, John E.

1984-01-01

A solid oxide fuel cell for electrochemically combining fuel and oxidant for generating galvanic output, wherein the cell core has an array of electrolyte and interconnect walls that are substantially devoid of any composite inert materials for support. Instead, the core is monolithic, where each electrolyte wall consists of thin layers of cathode and anode materials sandwiching a thin layer of electrolyte material therebetween, and each interconnect wall consists of thin layers of the cathode and anode materials sandwiching a thin layer of interconnect material therebetween. The electrolyte walls are arranged and backfolded between adjacent interconnect walls operable to define a plurality of core passageways alternately arranged where the inside faces thereof have only the anode material or only the cathode material exposed. Means direct the fuel to the anode-exposed core passageways and means direct the oxidant to the cathode-exposed core passageway; and means also direct the galvanic output to an exterior circuit. Each layer of the electrolyte and interconnect materials is of the order of 0.002-0.01 cm thick; and each layer of the cathode and anode materials is of the order of 0.002-0.05 cm thick.

Eliminating micro-porous layer from gas diffusion electrode for use in high temperature polymer electrolyte membrane fuel cell

NASA Astrophysics Data System (ADS)

Su, Huaneng; Xu, Qian; Chong, Junjie; Li, Huaming; Sita, Cordellia; Pasupathi, Sivakumar

2017-02-01

In this work, we report a simple strategy to improve the performance of high temperature polymer electrolyte membrane fuel cell (HT-PEMFC) by eliminating the micro-porous layer (MPL) from its gas diffusion electrodes (GDEs). Due to the absence of liquid water and the general use of high amount of catalyst, the MPL in a HT-PEMFC system works limitedly. Contrarily, the elimination of the MPL leads to an interlaced micropore/macropore composited structure in the catalyst layer (CL), which favors gas transport and catalyst utilization, resulting in a greatly improved single cell performance. At the normal working voltage (0.6 V), the current density of the GDE eliminated MPL reaches 0.29 A cm-2, and a maximum power density of 0.54 W cm-2 at 0.36 V is obtained, which are comparable to the best results yet reported for the HT-PEMFCs with similar Pt loading and operated using air. Furthermore, the MPL-free GDE maintains an excellent durability during a preliminary 1400 h HT-PEMFC operation, owing to its structure advantages, indicating the feasibility of this electrode for practical applications.

Tuning Electrochemical Properties of Li-Rich Layered Oxide Cathodes by Adjusting Co/Ni Ratios and Mechanism Investigation Using in situ X-ray Diffraction and Online Continuous Flow Differential Electrochemical Mass Spectrometry.

PubMed

Shen, ShouYu; Hong, YuHao; Zhu, FuChun; Cao, ZhenMing; Li, YuYang; Ke, FuSheng; Fan, JingJing; Zhou, LiLi; Wu, LiNa; Dai, Peng; Cai, MingZhi; Huang, Ling; Zhou, ZhiYou; Li, JunTao; Wu, QiHui; Sun, ShiGang

2018-04-18

Owing to high specific capacity of ∼250 mA h g -1 , lithium-rich layered oxide cathode materials (Li 1+ x Ni y Co z Mn (3- x-2 y-3 z)/4 O 2 ) have been considered as one of the most promising candidates for the next-generation cathode materials of lithium ion batteries. However, the commercialization of this kind of cathode materials seriously restricted by voltage decay upon cycling though Li-rich materials with high cobalt content have been widely studied and show good capacity. This research successfully suppresses voltage decay upon cycling while maintaining high specific capacity with low Co/Ni ratio in Li-rich cathode materials. Online continuous flow differential electrochemical mass spectrometry (OEMS) and in situ X-ray diffraction (XRD) techniques have been applied to investigate the structure transformation of Li-rich layered oxide materials during charge-discharge process. The results of OEMS revealed that low Co/Ni ratio lithium-rich layered oxide cathode materials released no lattice oxygen at the first charge process, which will lead to the suppression of the voltage decay upon cycling. The in situ XRD results displayed the structure transition of lithium-rich layered oxide cathode materials during the charge-discharge process. The Li 1.13 Ni 0.275 Mn 0.580 O 2 cathode material exhibited a high initial medium discharge voltage of 3.710 and a 3.586 V medium discharge voltage with the lower voltage decay of 0.124 V after 100 cycles.

Micropore extrusion-induced alignment transition from perpendicular to parallel of cylindrical domains in block copolymers.

PubMed

Qu, Ting; Zhao, Yongbin; Li, Zongbo; Wang, Pingping; Cao, Shubo; Xu, Yawei; Li, Yayuan; Chen, Aihua

2016-02-14

The orientation transition from perpendicular to parallel alignment of PEO cylindrical domains of PEO-b-PMA(Az) films has been demonstrated by extruding the block copolymer (BCP) solutions through a micropore of a plastic gastight syringe. The parallelized orientation of PEO domains induced by this micropore extrusion can be recovered to perpendicular alignment via ultrasonication of the extruded BCP solutions and subsequent annealing. A plausible mechanism is proposed in this study. The BCP films can be used as templates to prepare nanowire arrays with controlled layers, which has enormous potential application in the field of integrated circuits.

Organic photovoltaic device with interfacial layer and method of fabricating same

DOEpatents

Marks, Tobin J.; Hains, Alexander W.

2013-03-19

An organic photovoltaic device and method of forming same. In one embodiment, the organic photovoltaic device has an anode, a cathode, an active layer disposed between the anode and the cathode; and an interfacial layer disposed between the anode and the active layer, the interfacial layer comprising 5,5'-bis[(p-trichlorosilylpropylphenyl)phenylamino]-2,2'-bithiophene (PABTSi.sub.2).

Efficiency enhancement of polymer solar cells by applying poly(vinylpyrrolidone) as a cathode buffer layer via spin coating or self-assembly.

PubMed

Wang, Haitao; Zhang, Wenfeng; Xu, Chenhui; Bi, Xianghong; Chen, Boxue; Yang, Shangfeng

2013-01-01

A non-conjugated polymer poly(vinylpyrrolidone) (PVP) was applied as a new cathode buffer layer in P3HT:PCBM bulk heterojunction polymer solar cells (BHJ-PSCs), by means of either spin coating or self-assembly, resulting in significant efficiency enhancement. For the case of incorporation of PVP by spin coating, power conversion efficiency (PCE) of the ITO/PEDOT:PSS/P3HT:PCBM/PVP/Al BHJ-PSC device (3.90%) is enhanced by 29% under the optimum PVP spin-coating speed of 3000 rpm, which leads to the optimum thickness of PVP layer of ~3 nm. Such an efficiency enhancement is found to be primarily due to the increase of the short-circuit current (J(sc)) (31% enhancement), suggesting that the charge collection increases upon the incorporation of a PVP cathode buffer layer, which originates from the conjunct effects of the formation of a dipole layer between P3HT:PCBM active layer and Al electrodes, the chemical reactions of PVP molecules with Al atoms, and the increase of the roughness of the top Al film. Incorporation of PVP layer by doping PVP directly into the P3HT:PCBM active layer leads to an enhancement of PCE by 13% under the optimum PVP doping ratio of 3%, and this is interpreted by the migration of PVP molecules to the surface of the active layer via self-assembly, resulting in the formation of the PVP cathode buffer layer. While the formation of the PVP cathode buffer layer is fulfilled by both fabrication methods (spin coating and self-assembly), the dependence of the enhancement of the device performance on the thickness of the PVP cathode buffer layer formed by self-assembly or spin coating is different, because of the different aggregation microstructures of the PVP interlayer.

Importance of Ion Packing on the Dynamics of Ionic Liquids during Micropore Charging.

PubMed

He, Yadong; Qiao, Rui; Vatamanu, Jenel; Borodin, Oleg; Bedrov, Dmitry; Huang, Jingsong; Sumpter, Bobby G

2016-01-07

Molecular simulations of the diffusion of EMIM(+) and TFSI(-) ions in slit-shaped micropores under conditions similar to those during charging show that in pores that accommodate only a single layer of ions, ions diffuse increasingly faster as the pore becomes charged (with diffusion coefficients even reaching ∼5 × 10(-9) m(2)/s), unless the pore becomes very highly charged. In pores wide enough to fit more than one layer of ions, ion diffusion is slower than in the bulk and changes modestly as the pore becomes charged. Analysis of these results revealed that the fast (or slow) diffusion of ions inside a micropore during charging is correlated most strongly with the dense (or loose) ion packing inside the pore. The molecular details of the ions and the precise width of the pores modify these trends weakly, except when the pore is so narrow that the ion conformation relaxation is strongly constrained by the pore walls.

Importance of Ion Packing on the Dynamics of Ionic Liquids during Micropore Charging

DOE PAGES

He, Yadong; Qiao, Rui; Vatamanu, Jenel; ...

2015-12-07

In molecular simulations of the diffusion of EMIM+ and TESI- ions in slit-shaped micropores under conditions similar to those during charging show that in pores that accommodate only a single layer of ions, ions diffuse increasingly faster as the pore becomes charged (with diffusion coefficients even reaching similar to 5 x 10 -9 m 2/s), unless the pore becomes very highly charged. In pores wide enough to fit more than one layer of ions, ion diffusion is slower than in the bulk and changes modestly as the pore becomes charged. Moreover, analysis of these results revealed that the fast (ormore » slow) diffusion of ions inside a micropore during charging is correlated most strongly with the dense (or loose) ion packing inside the pore. Finally, the molecular details of the ions and the precise width of the pores modify these trends weakly, except when the pore is so narrow that the ion conformation relaxation is strongly constrained by the pore walls.« less

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

Bulk and contact resistances of gas diffusion layers in proton exchange membrane fuel cells

NASA Astrophysics Data System (ADS)

Ye, Donghao; Gauthier, Eric; Benziger, Jay B.; Pan, Mu

2014-06-01

A multi-electrode probe is employed to distinguish the bulk and contact resistances of the catalyst layer (CL) and the gas diffusion layer (GDL) with the bipolar plate (BPP). Resistances are compared for Vulcan carbon catalyst layers (CL), carbon paper and carbon cloth GDL materials, and GDLs with microporous layers (MPL). The Vulcan carbon catalyst layer bulk resistance is 100 times greater than the bulk resistance of carbon paper GDL (Toray TG-H-120). Carbon cloth (CCWP) has bulk and contact resistances twice those of carbon paper. Compression of the GDL decreases the GDL contact resistance, but has little effect on the bulk resistance. Treatment of the GDL with polytetrafluoroethylene (PTFE) increases the contact resistance, but has little effect on the bulk resistance. A microporous layer (MPL) added to the GDL decreases the contact resistance, but has little effect on the bulk resistance. An equivalent circuit model shows that for channels less than 1 mm wide the contact resistance is the major source of electronic resistance and is about 10% of the total ohmic resistance associated with the membrane electrode assembly.

Sorption of chlorophenols on microporous minerals: mechanism and influence of metal cations, solution pH, and humic acid.

PubMed

Yang, Hui; Hu, Yuanan; Cheng, Hefa

2016-10-01

Sorption of 2-chlorophenol (2-CP), 2,4-dichlorophenol (2,4-DCP), and 2,4,6-trichlorophenol (2,4,6-TCP) on a range of dealuminated zeolites were investigated to understand the mechanism of their sorption on microporous minerals, while the influence of common metal cations, solution pH, and humic acid was also studied. Sorption of chlorophenols was found to increase with the hydrophobicity of the sorbates and that of the microporous minerals, indicating the important role of hydrophobic interactions, while sorption was also stronger in the micropores of narrower sizes because of greater enhancement of the dispersion interactions. The presence of metal cations could enhance chlorophenol sorption due to the additional electrostatic attraction between metal cations exchanged into the mineral micropores and the chlorophenolates, and this effect was apparent on the mineral sorbent with a high density of surface cations (2.62 sites/nm(2)) in its micropores. Under circum-neutral or acidic conditions, neutral chlorophenol molecules adsorbed into the hydrophobic micropores through displacing the "loosely bound" water molecules, while their sorption was negligible under moderately alkaline conditions due to electrostatic repulsion between the negatively charged zeolite framework and anionic chlorophenolates. The influence of humic acid on sorption of chlorophenols on dealuminated Y zeolites suggests that its molecules did not block the micropores but created a secondary sorption sites by forming a "coating layer" on the external surface of the zeolites. These mechanistic insights could help better understand the interactions of ionizable chlorophenols and metal cations in mineral micropores and guide the selection and design of reusable microporous mineral sorbents for sorptive removal of chlorophenols from aqueous stream.

Organic photosensitive cells having a reciprocal-carrier exciton blocking layer

DOEpatents

Rand, Barry P [Princeton, NJ; Forrest, Stephen R [Princeton, NJ; Thompson, Mark E [Anaheim Hills, CA

2007-06-12

A photosensitive cell includes an anode and a cathode; a donor-type organic material and an acceptor-type organic material forming a donor-acceptor junction connected between the anode and the cathode; and an exciton blocking layer connected between the acceptor-type organic material of the donor-acceptor junction and the cathode, the blocking layer consisting essentially of a material that has a hole mobility of at least 10.sup.-7 cm.sup.2/V-sec or higher, where a HOMO of the blocking layer is higher than or equal to a HOMO of the acceptor-type material.

Effect of Lanthanum-Strontium Cathode Current-Collecting Layer on the Performance of Anode Supported Type Planar Solid Oxide Fuel Cells

NASA Astrophysics Data System (ADS)

Park, Sun-Young; Ji, Ho-Il; Kim, Hae-Ryoung; Yoon, Kyung Joong; Son, Ji-Won; Lee, Hae-Weon; Lee, Jong-Ho

2013-07-01

We applied screen-printed (La,Sr)CoO3 as a current-collecting layer of planar type unit-cell for lower temperature operation of SOFCs. In this study the effects of the cathode current-collecting layer on the performance of unit cell and symmetric half cell were investigated via AC and DC polarization experiments. According to our investigation, appropriately controlled current collecting layer was very effective to enhance the unit cell performance by reducing not only the ohmic resistance but also the polarization losses of SOFC cathode.

Same-View Nano-XAFS/STEM-EDS Imagings of Pt Chemical Species in Pt/C Cathode Catalyst Layers of a Polymer Electrolyte Fuel Cell.

PubMed

Takao, Shinobu; Sekizawa, Oki; Samjeské, Gabor; Nagamatsu, Shin-ichi; Kaneko, Takuma; Yamamoto, Takashi; Higashi, Kotaro; Nagasawa, Kensaku; Uruga, Tomoya; Iwasawa, Yasuhiro

2015-06-04

We have made the first success in the same-view imagings of 2D nano-XAFS and TEM/STEM-EDS under a humid N2 atmosphere for Pt/C cathode catalyst layers in membrane electrode assemblies (MEAs) of polymer electrolyte fuel cells (PEFCs) with Nafion membrane to examine the degradation of Pt/C cathodes by anode gas exchange cycles (start-up/shut-down simulations of PEFC vehicles). The same-view imaging under the humid N2 atmosphere provided unprecedented spatial information on the distribution of Pt nanoparticles and oxidation states in the Pt/C cathode catalyst layer as well as Nafion ionomer-filled nanoholes of carbon support in the wet MEA, which evidence the origin of the formation of Pt oxidation species and isolated Pt nanoparticles in the nanohole areas of the cathode layer with different Pt/ionomer ratios, relevant to the degradation of PEFC catalysts.

Preparation of hierarchical porous carbon from waste printed circuit boards for high performance electric double-layer capacitors

NASA Astrophysics Data System (ADS)

Du, Xuan; Wang, Li; Zhao, Wei; Wang, Yi; Qi, Tao; Li, Chang Ming

2016-08-01

Renewable clean energy and resources recycling have become inevitable choices to solve worldwide energy shortages and environmental pollution problems. It is a great challenge to recycle tons of waste printed circuit boards (PCB) produced every year for clean environment while creating values. In this work, low cost, high quality activated carbons (ACs) were synthesized from non-metallic fractions (NMF) of waste PCB to offer a great potential for applications of electrochemical double-layer capacitors (EDLCs). After recovering metal from waste PCB, hierarchical porous carbons were produced from NMF by carbonization and activation processes. The experimental results exhibit that some pores were formed after carbonization due to the escape of impurity atoms introduced by additives in NMF. Then the pore structure was further tailored by adjusting the activation parameters. Roles of micropores and non-micropores in charge storage were investigated when the hierarchical porous carbons were applied as electrode of EDLCs. The highest specific capacitance of 210 F g-1 (at 50 mA g-1) and excellent rate capability were achieved when the ACs possessing a proper micropores/non-micropores ratio. This work not only provides a promising method to recycle PCB, but also investigates the structure tailoring arts for a rational hierarchical porous structure in energy storage/conversion.

Transcutaneous vaccination via laser microporation

PubMed Central

Weiss, Richard; Hessenberger, Michael; Kitzmüller, Sophie; Bach, Doris; Weinberger, Esther E.; Krautgartner, Wolf D.; Hauser-Kronberger, Cornelia; Malissen, Bernard; Boehler, Christof; Kalia, Yogeshvar N.; Thalhamer, Josef; Scheiblhofer, Sandra

2012-01-01

Driven by constantly increasing knowledge about skin immunology, vaccine delivery via the cutaneous route has recently gained renewed interest. Considering its richness in immunocompetent cells, targeting antigens to the skin is considered to be more effective than intramuscular or subcutaneous injections. However, circumvention of the superficial layer of the skin, the stratum corneum, represents the major challenge for cutaneous immunization. An optimal delivery method has to be effective and reliable, but also highly adaptable to specific demands, should avoid the use of hypodermic needles and the requirement of specially trained healthcare workers. The P.L.E.A.S.E.® (Precise Laser Epidermal System) device employed in this study for creation of aqueous micropores in the skin fulfills these prerequisites by combining the precision of its laser scanning technology with the flexibility to vary the number, density and the depth of the micropores in a user-friendly manner. We investigated the potential of transcutaneous immunization via laser-generated micropores for induction of specific immune responses and compared the outcomes to conventional subcutaneous injection. By targeting different layers of the skin we were able to bias polarization of T cells, which could be modulated by addition of adjuvants. The P.L.E.A.S.E.® device represents a highly effective and versatile platform for transcutaneous vaccination. PMID:22750193

Microbial stratification structure within cathodic biofilm of the microbial fuel cell using the freezing microtome method.

PubMed

Li, Xiao; Lu, Yaobin; Luo, Haiping; Liu, Guangli; Zhang, Renduo

2017-10-01

The aim of this study was to investigate the microbial stratification structure within cathodic biofilm of the microbial fuel cell (MFC) using the freezing microtome method. Experiments were conducted in a single-chamber air-cathode MFC with 0.8g/L maltodextrin as substrate for ∼30d operation. The maximum power density was 945±10mW/m 2 in the MFC. Maltodextrin resulted in the relative abundance of Candidatus Saccharibacteria of 37.0% in the anodic biofilm. Different bacterial communities were identified in different layers within the cathodic biofilm. The relative abundance of Enterococcus was 3.7%, 10.5%, and 1.6% in the top (100-150μm), middle (50-100μm), and bottom (0-50μm) layers, respectively. Higher bacterial viability was observed within the top and bottom layers of the cathodic biofilm. Understanding the stratification of bacterial community in cathodic biofilm should be important to control the cathodic biofilm in the MFC. Copyright © 2017 Elsevier Ltd. All rights reserved.

Organic photosensitive optoelectronic device having a phenanthroline exciton blocking layer

DOEpatents

Thompson, Mark E [Anaheim Hills, CA; Li, Jian [Los Angeles, CA; Forrest, Stephen [Princeton, NJ; Rand, Barry [Princeton, NJ

2011-02-22

An organic photosensitive optoelectronic device, having an anode, a cathode, and an organic blocking layer between the anode and the cathode is described, wherein the blocking layer comprises a phenanthroline derivative, and at least partially blocks at least one of excitons, electrons, and holes.

Air cathode structure manufacture

DOEpatents

Momyer, William R.; Littauer, Ernest L.

1985-01-01

An improved air cathode structure for use in primary batteries and the like. The cathode structure includes a matrix active layer, a current collector grid on one face of the matrix active layer, and a porous, nonelectrically conductive separator on the opposite face of the matrix active layer, the collector grid and separator being permanently bonded to the matrix active layer. The separator has a preselected porosity providing low IR losses and high resistance to air flow through the matrix active layer to maintain high bubble pressure during operation of the battery. In the illustrated embodiment, the separator was formed of porous polypropylene. A thin hydrophobic film is provided, in the preferred embodiment, on the current collecting metal grid.

Fuel cell system with interconnect

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

Goettler, Richard; Liu, Zhien

The present invention includes a fuel cell system having a plurality of adjacent electrochemical cells formed of an anode layer, a cathode layer spaced apart from the anode layer, and an electrolyte layer disposed between the anode layer and the cathode layer. The fuel cell system also includes at least one interconnect, the interconnect being structured to conduct free electrons between adjacent electrochemical cells. Each interconnect includes a primary conductor embedded within the electrolyte layer and structured to conduct the free electrons.

Fuel cell system with interconnect

DOEpatents

Goettler, Richard; Liu, Zhien

2015-08-11

The present invention includes a fuel cell system having a plurality of adjacent electrochemical cells formed of an anode layer, a cathode layer spaced apart from the anode layer, and an electrolyte layer disposed between the anode layer and the cathode layer. The fuel cell system also includes at least one interconnect, the interconnect being structured to conduct free electrons between adjacent electrochemical cells. Each interconnect includes a primary conductor embedded within the electrolyte layer and structured to conduct the free electrons.

Fuel cell system with interconnect

DOEpatents

Goettler, Richard; Liu, Zhien

2015-03-10

The present invention includes a fuel cell system having a plurality of adjacent electrochemical cells formed of an anode layer, a cathode layer spaced apart from the anode layer, and an electrolyte layer disposed between the anode layer and the cathode layer. The fuel cell system also includes at least one interconnect, the interconnect being structured to conduct free electrons between adjacent electrochemical cells. Each interconnect includes a primary conductor embedded within the electrolyte layer and structured to conduct the free electrons.

Fuel cell system with interconnect

DOEpatents

Liu, Zhien; Goettler, Richard

2015-09-29

The present invention includes a fuel cell system having a plurality of adjacent electrochemical cells formed of an anode layer, a cathode layer spaced apart from the anode layer, and an electrolyte layer disposed between the anode layer and the cathode layer. The fuel cell system also includes at least one interconnect, the interconnect being structured to conduct free electrons between adjacent electrochemical cells. Each interconnect includes a primary conductor embedded within the electrolyte layer and structured to conduct the free electrons.

Abrasive-assisted Nickel Electroforming Process with Moving Cathode

NASA Astrophysics Data System (ADS)

REN, Jianhua; ZHU, Zengwei; XIA, Chunqiu; QU, Ningsong; ZHU, Di

2017-03-01

In traditional electroforming process for revolving parts with complex profiles, the drawbacks on surface of deposits, such as pinholes and nodules, will lead to varying physical and mechanical properties on different parts of electroformed components. To solve the problem, compositely moving cathode is employed in abrasive-assisted electroforming of revolving parts with complicated profiles. The cathode translates and rotates simultaneously to achieve uniform friction effect on deposits without drawbacks. The influences of current density and translation speed on the microstructure and properties of the electroformed nickel layers are investigated. It is found that abrasive-assisted electroforming with compound cathode motion can effectively remove the pinholes and nodules, positively affect the crystal nucleation, and refine the grains of layer. The increase of current density will lead to coarse microstructure and lower micro hardness, from 325 HV down to 189 HV. While, faster translational linear speed produces better surface quality and higher micro hardness, from 236 HV up to 283 HV. The weld-ability of the electroformed layers are also studied through the metallurgical analysis of welded joints between nickel layer and 304 stainless steel. The electrodeposited nickel layer shows fine performance in welding. The novel compound motion of cathode promotes the mechanical properties and refines the microstructure of deposited layer.

Contrast-enhancement in organic light-emitting diodes.

PubMed

Wu, Zhaoxin; Wang, Liduo; Qiu, Yong

2005-03-07

A high-contrast organic light-emitting diode (OLED) structure is presented. Because of poor contrast of conventional OLED resulting from high reflective metal cathode, the hybrid cathode structure was developed for low reflectivity. It consists the semitransparent cathode layers, passivation layers and a thick light-absorbing film. By optical reflectivity measurement and OLED electrical characterization tests for both OLED with the hybrid cathode and conventional OLED, it was found that the spectrum reflectance of OLED with hybrid cathode is among 8%-12%, about eight times lower than the conventional one when the two types of devices have similar turn-on voltages and current-voltage characteristics. The hybrid cathode for the high-contrast OLED is easily fabricated and its optical reflectance is slightly dependent on wavelength.

Composite membranes for fluid separations

DOEpatents

Blume, Ingo; Peinemann, Klaus-Viktor; Pinnau, Ingo; Wijmans, Johannes G.

1992-01-01

A method for designing and making composite membranes having a microporous support membrane coated with a permselective layer. The method involves calculating the minimum thickness of the permselective layer such that the selectivity of the composite membrane is close to the intrinsic selectivity of the perselective layer. The invention also provides high performance membranes with optimized properties.

Composite membranes for fluid separations

DOEpatents

Blume, Ingo; Peinemann, Klaus-Viktor; Pinnau, Ingo; Wijmans, Johannes G.

1991-01-01

A method for designing and making composite membranes having a microporous support membrane coated with a permselective layer. The method involves calculating the minimum thickness of the permselective layer such that the selectivity of the composite membrane is close to the intrinsic selectivity of the permselective layer. The invention also provides high performance membranes with optimized properties.

Composite membranes for fluid separations

DOEpatents

Blume, Ingo; Peinemann, Klaus-Viktor; Pinnau, Ingo; Wijmans, Johannes G.

1990-01-01

A method for designing and making composite membranes having a microporous support membrane coated with a permselective layer. The method involves calculating the minimum thickness of the permselective layer such that the selectivity of the composite membrane is close to the intrinsic selectivity of the permselective layer. The invention also provides high performance membranes with optimized properties.

Characteristics of Subfreezing Operation of Polymer Electrolyte Membrane Fuel Cells

NASA Astrophysics Data System (ADS)

Mishler, Jeffrey Harris

Polymer Electrolyte Membrane (PEM) Fuel Cells are capable of high efficiency operation, and are free of NOx, SOx, and CO2 emissions when using hydrogen fuel, and ideally suited for use in transportation applications due to their high power density and low operating temperatures. However, under subfreezing conditions which may be encountered during winter seasons in some areas, product water will freeze within the membrane, cathode side catalyst layer and gas diffusion media, leading to voltage loss and operation failure. Experiments were undertaken in order to characterize the amount and location of water during fuel cell operation. First, in-situ neutron radiography was undertaken on the fuel cells at a normal operating temperature for various operating current densities, inlet relative humidities, and diffusion media hydrophobicities. It was found that more hydrophobic cathode microporous layer (MPL) or hydrophilic anode MPL may result in a larger amount of water transporting back to the anode. The water profiles along the channels were measured and the point of liquid water emergence, where two phase flow begins, was compared to previous models. Secondly, under subfreezing temperatures, neutron imaging showed that water ice product accumulates because of lack of a water removal mechanism. Water was observed under both the lands and channels, and increased almost linearly with time. It is found that most ice exists in the cathode side. With evidence from experimental observation, a cold start model was developed and explained, following existing approaches in the literature. Three stages of cold start are explained: membrane saturation, ice storage in catalyst layer pores, and then ice melting. The voltage losses due to temperature change, increased transport resistance, and reduced electrochemical surface area. The ionic conductivity of the membrane at subfreezing temperatures was modeled. Voltage evolution over time for isothermal cold starts was predicted and validated against experimental data. The ice coverage coefficient was shown to be a key variable in matching with experimental data. From model analysis, it appears that the coulombs of charge passed before operation failure is an important parameter characterizing PEM fuel cell cold start. To investigate the coulombs of charge and its determining factors, PEM fuel cells were constructed to measure the effects of membrane configuration (thickness and initial state), catalyst layer configuration (thickness and ionomer-carbon ratio), current density, and temperature on the quantity. It was found that subfreezing temperature, ionomer-catalyst ratio, and catalyst-layer thickness significantly affect the amount of charge transferred before operational failure, whereas the membrane thickness and initial hydration level have limited effect for the considered cases. In addition, degradation of the catalyst layer was observed and quantified. These results improve the fundamental understanding of characteristics of subfreezing operation and thus are valuable for automobile applications of PEM fuel cells. The model directly relates the material properties to voltage loss, and predicts voltage evolution, thus providing a way for material optimization and diagnostics. Additionally, insights into component design and operating conditions can be used to better optimize the fuel cell for cold start-up of the vehicle.

Phosphorus Enrichment as a New Composition in the Solid Electrolyte Interphase of High-Voltage Cathodes and Its Effects on Battery Cycling

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

Yan, Pengfei; Zheng, Jianming; Kuppan, Saravanan

2015-11-10

Immersion of a solid into liquid often leads to the modification of both the structure and chemistry of surface of the solid, which subsequently affects the chemical and physical properties of the system. For the case of the rechargeable lithium ion battery, such a surface modification is termed as solid electrolyte interphase (SEI) layer, which has been perceived to play critical role for the stable operation of the batteries. However, the structure and chemical composition of SEI layer and its spatial distribution and dependence on the battery operating condition remain unclear. By using aberration corrected scanning transmission electron microscopy coupledmore » with ultra-high sensitive energy dispersive x-ray spectroscopy, we probed the structure and chemistry of SEI layer on several high voltage cathodes. We show that layer-structured cathodes, when cycled at a high cut off voltage, can form a P-rich SEI layer on their surface, which is a direct evidence of Li-salt (LiPF6) decomposition. Our systematical investigations indicate such cathode/Li-salt side reaction shows strong dependence on structure of the cathode materials, operating voltage and temperature, indicating the feasibility of SEI engineering. These findings provide us valuable insights into the complex interface between the high-voltage cathode and the electrolyte.« less

Erosion behavior of composite Al-Cr cathodes in cathodic arc plasmas in inert and reactive atmospheres

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

Franz, Robert, E-mail: robert.franz@unileoben.ac.at; Mendez Martin, Francisca; Hawranek, Gerhard

2016-03-15

Al{sub x}Cr{sub 1−x} composite cathodes with Al contents of x = 0.75, 0.5, and 0.25 were exposed to cathodic arc plasmas in Ar, N{sub 2}, and O{sub 2} atmospheres and their erosion behavior was studied. Cross-sectional analysis of the elemental distribution of the near-surface zone in the cathodes by scanning electron microscopy revealed the formation of a modified layer for all cathodes and atmospheres. Due to intermixing of Al and Cr in the heat-affected zone, intermetallic Al-Cr phases formed as evidenced by x-ray diffraction analysis. Cathode poisoning effects in the reactive N{sub 2} and O{sub 2} atmospheres were nonuniform as a resultmore » of the applied magnetic field configuration. With the exception of oxide islands on Al-rich cathodes, reactive layers were absent in the circular erosion zone, while nitrides and oxides formed in the less eroded center region of the cathodes.« less

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

PubMed

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

2017-09-22

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

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.

Cathode material for lithium ion accumulators prepared by screen printing for Smart Textile applications

NASA Astrophysics Data System (ADS)

Syrový, T.; Kazda, T.; Syrová, L.; Vondrák, J.; Kubáč, L.; Sedlaříková, M.

2016-03-01

The presented study is focused on the development of LiFePO4 based cathode for thin and flexible screen printed secondary lithium based accumulators. An ink formulation was developed for the screen printing technique, which enabled mass production of accumulator's cathode for Smart Label and Smart Textile applications. The screen printed cathode was compared with an electrode prepared by the bar coating technique using an ink formulation based on the standard approach of ink composition. Obtained LiFePO4 cathode layers were characterized by scanning electron microscopy (SEM), energy-dispersive X-ray spectroscopy (EDS) and galvanostatic charge/discharge measurements at different loads. The discharge capacity, capacity retention and stability at a high C rate of the LiFePO4 cathode were improved when Super P and PVDF were replaced by conductive polymers PEDOT:PSS. The achieved capacity during cycling at various C rates was approximately the same at the beginning and at the end, and it was about 151 mAh/g for cycling under 1C. The obtained results of this novelty electrode layer exceed the parameters of several electrode layers based on LiFePO4 published in literature in terms of capacity, cycling stability and overcomes them in terms of simplicity/industrial process ability of cathode layer fabrication and electrode material preparation.

Methods for batch fabrication of cold cathode vacuum switch tubes

DOEpatents

Walker, Charles A [Albuquerque, NM; Trowbridge, Frank R [Albuquerque, NM

2011-05-10

Methods are disclosed for batch fabrication of vacuum switch tubes that reduce manufacturing costs and improve tube to tube uniformity. The disclosed methods comprise creating a stacked assembly of layers containing a plurality of adjacently spaced switch tube sub-assemblies aligned and registered through common layers. The layers include trigger electrode layer, cathode layer including a metallic support/contact with graphite cathode inserts, trigger probe sub-assembly layer, ceramic (e.g. tube body) insulator layer, and metallic anode sub-assembly layer. Braze alloy layers are incorporated into the stacked assembly of layers, and can include active metal braze alloys or direct braze alloys, to eliminate costs associated with traditional metallization of the ceramic insulator layers. The entire stacked assembly is then heated to braze/join/bond the stack-up into a cohesive body, after which individual switch tubes are singulated by methods such as sawing. The inventive methods provide for simultaneously fabricating a plurality of devices as opposed to traditional methods that rely on skilled craftsman to essentially hand build individual devices.

Organic light emitting device architecture for reducing the number of organic materials

DOEpatents

D'Andrade, Brian [Westampton, NJ; Esler, James [Levittown, PA

2011-10-18

An organic light emitting device is provided. The device includes an anode and a cathode. A first emissive layer is disposed between the anode and the cathode. The first emissive layer includes a first non-emitting organic material, which is an organometallic material present in the first emissive layer in a concentration of at least 50 wt %. The first emissive layer also includes a first emitting organic material. A second emissive layer is disposed between the first emissive layer and the cathode, preferably, in direct contact with the first emissive layer. The second emissive material includes a second non-emitting organic material and a second emitting organic material. The first and second non-emitting materials, and the first and second emitting materials, are all different materials. A first non-emissive layer is disposed between the first emissive layer and the anode, and in direct contact with the first emissive layer. The first non- emissive layer comprises the first non-emissive organic material.

High performance and durability of order-structured cathode catalyst layer based on TiO2@PANI core-shell nanowire arrays

NASA Astrophysics Data System (ADS)

Chen, Ming; Wang, Meng; Yang, Zhaoyi; Wang, Xindong

2017-06-01

In this paper, an order-structured cathode catalyst layer consisting of Pt-TiO2@PANI core-shell nanowire arrays that in situ grown on commercial gas diffusion layer (GDL) are prepared and applied to membrane electrode assembly (MEA) of proton exchange membrane fuel cell (PEMFC). In order to prepare the TiO2@PANI core-shell nanowire arrays with suitable porosity and prominent conductivity, the morphologies of the TiO2 nanoarray and electrochemical polymerization process of aniline are schematically investigated. The MEA with order-structured cathode catalyst layer is assembled in the single cell to evaluate the electrochemical performance and durability of PEMFC. As a result, the PEMFC with order-structured cathode catalyst layer shows higher peak power density (773.54 mW cm-2) than conventional PEMFC (699.30 mW cm-2). Electrochemically active surface area (ECSA) and charge transfer impedance (Rct) are measured before and after accelerated degradation test (ADT), and the corresponding experimental results indicate the novel cathode structure exhibits a better stability with respect to conventional cathode. The enhanced electrochemical performance and durability toward PEMFC can be ascribed to the order-structured cathode nanoarray structure with high specific surface area increases the utilization of catalyst and reduces the tortuosity of transport pathways, and the synergistic effect between TiO2@PANI support and Pt nanoparticles promotes the high efficiency of electrochemical reaction and improves the stability of catalyst. This research provides a facile and controllable method to prepare order-structured membrane electrode with lower Pt loading for PEMFC in the future.

High-performing LiMgxCuyCo₁-x-yO₂ cathode material for lithium rechargeable batteries.

PubMed

Nithya, Chandrasekaran; Thirunakaran, Ramasamy; Sivashanmugam, Arumugam; Gopukumar, Sukumaran

2012-08-01

Sustainable power requirements of multifarious portable electronic applications demand the development of high energy and high power density cathode materials for lithium ion batteries. This paper reports a method for rapid synthesis of a cobalt based layered cathode material doped with mixed dopants Cu and Mg. The cathode material exhibits ordered layered structure and delivers discharge capacity of ∼200 mA h g(-1) at 0.2C rate with high capacity retention of 88% over the investigated 100 cycles.

Thermally conductive lithium ion electrodes and batteries

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

Shevchenko, Elena; Sumant, Anirudha V.; Balandin, Alexander

A thermally conductive electrochemical cell comprises a lithium ion-containing liquid electrolyte contacting a cathode and anode. The cathode and anode are in the form of electroactive sheets separated from each other by a membrane that is permeable to the electrolyte. One or more of the cathode and anode comprises two or more layers of carbon nanotubes, one of which layers includes electrochemically active nanoparticles and/or microparticles disposed therein or deposited on the nanotubes thereof. The majority of the carbon nanotubes in each of the layers are oriented generally parallel to the layers. Optionally, one or more of the layers includesmore » an additional carbon material such as graphene, nanoparticulate diamond, microparticulate diamond, and a combination thereof.« less

Thermal Conductivity Changes Due to Degradation of Cathode Film Subjected to Charge-Discharge Cycles in a Li Ion Battery

NASA Astrophysics Data System (ADS)

Jagannadham, K.

2018-05-01

A battery device with graphene platelets as anode, lithium nickel manganese oxide as cathode, and solid-state electrolyte consisting of layers of lithium phosphorous oxynitride and lithium lanthanum titanate is assembled on the stainless steel substrate. The battery in a polymer enclosure is subjected to several electrical tests consisting of charge and discharge cycles at different current and voltage levels. Thermal conductivity of the cathode layer is determined at the end of charge-discharge cycles using transient thermoreflectance. The microstructure and composition of the cathode layer and the interface between the cathode, the anode, and the electrolyte are characterized using scanning electron microscopy and elemental mapping. The decrease in the thermal conductivity of the same cathode observed after each set of electrical test cycles is correlated with the volume changes and formation of low ionic and thermal conductivity lithium oxide and lithium oxychloride at the interface and along porous regions. The interface between the metal current collector and the cathode is also found to be responsible for the increase in thermal resistance. The results indicate that changes in the thermal conductivity of the electrodes provide a measure of the resistance to heat transfer and degradation of ionic transport in the cathode accompanying the charge-discharge cycles in the batteries.

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

DOE PAGES

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

2017-02-15

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

Intragranular cracking as a critical barrier for high-voltage usage of layer-structured cathode for lithium-ion batteries

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

Yan, Pengfei; Zheng, Jianming; Gu, Meng

LiNi 1/3Mn 1/3Co 1/3O 2 (NMC333) layered cathode is often fabricated as secondary particles of consisting of densely packed primary particles, which offers advantage of high energy density and alleviation of cathode side reactions/corrosions, but introduces other drawbacks, such as intergranular cracking. Here, we report unexpected observations on the nucleation and growth of intragranular cracks in the commercial NMC333 layered cathode by using advanced S/TEM. We found that the formation of the intragranular cracks is directly associated with high voltage cycling, which is an electrochemically driven and diffusion controlled process. The intragranular cracks were noticed to be characteristically initiated frommore » grain interior, a consequence of dislocation based crack incubation mechanism. This observation is in sharp contrast with the general theoretical models, predicting the initiation of intragranular cracks from grain boundaries or particle surface. As a result, our study indicates that maintain a structural stability is the key step toward high voltage operation of layered cathode materials.« less

Intragranular cracking as a critical barrier for high-voltage usage of layer-structured cathode for lithium-ion batteries

DOE PAGES

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

2017-01-16

LiNi 1/3Mn 1/3Co 1/3O 2 (NMC333) layered cathode is often fabricated as secondary particles of consisting of densely packed primary particles, which offers advantage of high energy density and alleviation of cathode side reactions/corrosions, but introduces other drawbacks, such as intergranular cracking. Here, we report unexpected observations on the nucleation and growth of intragranular cracks in the commercial NMC333 layered cathode by using advanced S/TEM. We found that the formation of the intragranular cracks is directly associated with high voltage cycling, which is an electrochemically driven and diffusion controlled process. The intragranular cracks were noticed to be characteristically initiated frommore » grain interior, a consequence of dislocation based crack incubation mechanism. This observation is in sharp contrast with the general theoretical models, predicting the initiation of intragranular cracks from grain boundaries or particle surface. As a result, our study indicates that maintain a structural stability is the key step toward high voltage operation of layered cathode materials.« less

Synthesis-microstructure-performance relationship of layered transition metal oxides as cathode for rechargeable sodium batteries prepared by high-temperature calcination.

PubMed

Xie, Man; Luo, Rui; Lu, Jun; Chen, Renjie; Wu, Feng; Wang, Xiaoming; Zhan, Chun; Wu, Huiming; Albishri, Hassan M; Al-Bogami, Abdullah S; El-Hady, Deia Abd; Amine, Khalil

2014-10-08

Research on sodium batteries has made a comeback because of concern regarding the limited resources and cost of lithium for Li-ion batteries. From the standpoint of electrochemistry and economics, Mn- or Fe-based layered transition metal oxides should be the most suitable cathode candidates for affordable sodium batteries. Herein, this paper reports a novel cathode material, layered Na1+x(Fey/2Niy/2Mn1-y)1-xO2 (x = 0.1-0.5), synthesized through a facile coprecipitation process combined with subsequent calcination. For such cathode material calcined at 800 °C for 20 h, the Na/Na1+x(Fey/2Niy/2Mn1-y)1-xO2 (x = 0.4) electrode exhibited a good capacity of 99.1 mAh g(-1) (cycled at 1.5-4.0 V) and capacity retention over 87% after 50 cycles. Optimization of this material would make layered transition metal oxides a strong candidate for the Na-ion battery cathode.

Isolating the effect of pore size distribution on electrochemical double-layer capacitance using activated fluid coke

NASA Astrophysics Data System (ADS)

Zuliani, Jocelyn E.; Tong, Shitang; Kirk, Donald W.; Jia, Charles Q.

2015-12-01

Electrochemical double-layer capacitors (EDLCs) use physical ion adsorption in the capacitive electrical double layer of high specific surface area (SSA) materials to store electrical energy. Previous work shows that the SSA-normalized capacitance increases when pore diameters are less than 1 nm. However, there still remains uncertainty about the charge storage mechanism since the enhanced SSA-normalized capacitance is not observed in all microporous materials. In previous studies, the total specific surface area and the chemical composition of the electrode materials were not controlled. The current work is the first reported study that systematically compares the performance of activated carbon prepared from the same raw material, with similar chemical composition and specific surface area, but different pore size distributions. Preparing samples with similar SSAs, but different pores sizes is not straightforward since increasing pore diameters results in decreasing the SSA. This study observes that the microporous activated carbon has a higher SSA-normalized capacitance, 14.1 μF cm-2, compared to the mesoporous material, 12.4 μF cm-2. However, this enhanced SSA-normalized capacitance is only observed above a threshold operating voltage. Therefore, it can be concluded that a minimum applied voltage is required to induce ion adsorption in these sub-nanometer micropores, which increases the capacitance.

Microstructure and corrosion resistance of nitrogen-rich surface layers on AISI 304 stainless steel by rapid nitriding in a hollow cathode discharge

NASA Astrophysics Data System (ADS)

Li, Yang; He, Yongyong; Zhang, Shangzhou; Wang, Wei; Zhu, Yijie

2018-01-01

Nitriding treatments have been successfully applied to austenitic stainless steels to improve their hardness and tribological properties. However, at temperatures above 450 °C, conventional plasma nitriding processes decrease the corrosion resistance due to the formation of CrN phases within the modified layer. In this work, AISI 304 austenitic stainless steels were efficiently treated by rapid plasma nitriding at a high temperature of 530 °C in a hollow cathode discharge. The enhanced ionization obtained in the hollow cathode configuration provided a high current density and, consequently, a high temperature could be attained in a short time. The nitrided layers were characterized by X-ray diffraction, scanning electron microscopy, atomic force microscopy, transmission electron microscopy and X-ray photoelectron spectroscopy. The results indicated that the dual-layer structure of the nitrided layer consists of a high-N face-centered cubic structure with a free CrN precipitate outer (top) layer and a nitrogen-expanded austenite S-phase bottom layer. The rapid nitriding-assisted hollow cathode discharge technique permits the use of high temperatures, as high as 530 °C, without promoting degradation in the corrosion resistance of stainless steel.

Development of in vivo impedance spectroscopy techniques for measurement of micropore formation following microneedle insertion

PubMed Central

Brogden, Nicole K.; Ghosh, Priyanka; Hardi, Lucia; Crofford, Leslie J.; Stinchcomb, Audra L.

2013-01-01

Microneedles provide a minimally invasive means to enhance skin permeability by creating micron-scale channels (micropores) that provide a drug delivery pathway. Adequate formation of the micropores is critical to the success of this unique drug delivery technique. The objective of these studies was to develop sensitive and reproducible impedance spectroscopy techniques to monitor micropore formation in animal models and human subjects. Hairless guinea pigs, a Yucatan miniature pig, and human volunteers were treated with 100 microneedle insertions per site following an overnight pre-hydration period. Repeated measurements were made pre- and post-microneedle treatment using dry and gel Ag/AgCl electrodes applied with light vs. direct pressure to hold the electrode to the skin surface. Impedance measurements dropped significantly post-microneedle application at all sites (p < 0.05, irrespective of electrode type or gel application), confirming micropore formation. In the Yucatan pig and human subjects, gel electrodes with direct pressure yielded the lowest variability (demonstrated by lower %RSD), whereas dry electrodes with direct pressure were superior in the guinea pigs. These studies confirm that impedance measurements are suitable for use in both clinical and animal research environments to monitor formation of new micropores that will allow for drug delivery through the impermeable skin layers. PMID:23589356

Development of in vivo impedance spectroscopy techniques for measurement of micropore formation following microneedle insertion.

PubMed

Brogden, Nicole K; Ghosh, Priyanka; Hardi, Lucia; Crofford, Leslie J; Stinchcomb, Audra L

2013-06-01

Microneedles (MNs) provide a minimally invasive means to enhance skin permeability by creating micron-scale channels (micropores) that provide a drug delivery pathway. Adequate formation of the micropores is critical to the success of this unique drug delivery technique. The objective of the current work was to develop sensitive and reproducible impedance spectroscopy techniques to monitor micropore formation in animal models and human subjects. Hairless guinea pigs, a Yucatan miniature pig, and human volunteers were treated with 100 MN insertions per site following an overnight prehydration period. Repeated measurements were made pre- and post-MN treatment using dry and gel Ag/AgCl electrodes applied with light verses direct pressure to hold the electrode to the skin surface. Impedance measurements dropped significantly post-MN application at all sites (p < 0.05, irrespective of electrode type or gel application), confirming micropore formation. In the Yucatan pig and human subjects, gel electrodes with direct pressure yielded the lowest variability (demonstrated by lower %relative standard deviation), whereas dry electrodes with direct pressure were superior in the guinea pigs. These studies confirm that impedance measurements are suitable for use in both clinical and animal research environments to monitor the formation of new micropores that will allow for drug delivery through the impermeable skin layers. Copyright © 2013 Wiley Periodicals, Inc.

Decay of the zincate concentration gradient at an alkaline zinc cathode after charging

NASA Technical Reports Server (NTRS)

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

1979-01-01

The transport of the zincate ion to the alkaline zinc cathode was studied by observing the decay of the zincate concentration gradient at a horizontal zinc cathode after charging. This decay was found to approximate first order kinetics as expected from a proposed boundary layer model. The concentrations were calculated from polarization voltages. The decay half life was shown to be a linear function of the thickness of porous zinc deposit on the cathode indicating a very rapid transport of zincate through porous zinc metal. The rapid transport is attributed to an electrochemical mechanism. From the linear dependence of the half life on the thickness the boundary layer thickness was found to be about 0.010 cm when the cathode was at the bottom of the cell. No significant dependence of the boundary layer thickness on the viscosity of electrolyte was observed. The data also indicated a relatively sharp transition between the diffusion and convection transport regions. When the cathode was at the top of the cell, the boundary layer thickness was found to be roughly 0.080 cm. The diffusion of zincate ion through asbestos submerged in alkaline electrolyte was shown to be comparable with that predicted from the bulk diffusion coefficient of the zincate ion in alkali.

Countering the Segregation of Transition-Metal Ions in LiMn1/3 Co1/3 Ni1/3 O2 Cathode for Ultralong Life and High-Energy Li-Ion Batteries.

PubMed

Luo, Dong; Fang, Shaohua; Tamiya, Yu; Yang, Li; Hirano, Shin-Ichi

2016-08-01

High-voltage layered lithium transition-metal oxides are very promising cathodes for high-energy Li-ion batteries. However, these materials often suffer from a fast degradation of cycling stability due to structural evolutions. It seriously impedes the large-scale application of layered lithium transition-metal oxides. In this work, an ultralong life LiMn1/3 Co1/3 Ni1/3 O2 microspherical cathode is prepared by constructing an Mn-rich surface. Its capacity retention ratio at 700 mA g(-1) is as large as 92.9% after 600 cycles. The energy dispersive X-ray maps of electrodes after numerous cycles demonstrate that the ultralong life of the as-prepared cathode is attributed to the mitigation of TM-ions segregation. Additionally, it is discovered that layered lithium transition-metal oxide cathodes with an Mn-rich surface can mitigate the segregation of TM ions and the corrosion of active materials. This study provides a new strategy to counter the segregation of TM ions in layered lithium transition-metal oxides and will help to the design and development of high-energy cathodes with ultralong life. © 2016 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Carbon nanotube polymer composition and devices

DOEpatents

Liu, Gao [Oakland, CA; Johnson, Stephen [Richmond, CA; Kerr, John B [Oakland, CA; Minor, Andrew M [El Cerrito, CA; Mao, Samuel S [Castro Valley, CA

2011-06-14

A thin film device and compound having an anode, a cathode, and at least one light emitting layer between the anode and cathode, the at least one light emitting layer having at least one carbon nanotube and a conductive polymer.

Solid oxide fuel cell cathode with oxygen-reducing layer

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

Surdoval, Wayne A.; Berry, David A.; Shultz, Travis

The disclosure provides a SOFC comprised of an electrolyte, anode, and cathode, where the cathode comprises an MIEC and an oxygen-reducing layer. The oxygen-reducing layer is in contact with the MIEC, and the MIEC is generally between and separating the oxygen-reducing layer and the electrolyte. The oxygen-reducing layer is comprised of single element oxides, single element carbonates, or mixtures thereof, and has a thickness of less than about 30 nm. In a particular embodiment, the thickness is less than 5 nm. In another embodiment, the thickness is about 3 monolayers or less. The oxygen-reducing layer may be a continuous filmmore » or a discontinuous film with various coverage ratios. The oxygen-reducing layer at the thicknesses described may be generated on the MIEC surface using means known in the art such as, for example, ALD processes.« less

Cooling Performance of a Partially-Confined FC-72 Spray: The Effect of Dissolved Air (Postprint)

DTIC Science & Technology

2007-01-01

plate FC = FC-72 fluid htr = heater conductive layer int = interface between heater substrate and insulating support post m = measured s = heater... microporous enhanced surface and a plain reference surface, and developed correlations for nucleate boiling and CHF. The results of the experiment...8Rainey, K. N., You, S. M., and Lee, S., “Effect of Pressure, Subcooling, and Dissolved Gas on Pool Boiling Heat Transfer from Microporous Surfaces

Application of a self-supporting microporous layer to gas diffusion layers of proton exchange membrane fuel cells

NASA Astrophysics Data System (ADS)

Ito, Hiroshi; Heo, Yun; Ishida, Masayoshi; Nakano, Akihiro; Someya, Satoshi; Munakata, Tetsuo

2017-02-01

The intrinsic effect of properties of a self-supporting microporous layer (MPL) on the performance of proton exchange membrane fuel cells (PEMFCs) is identified. First, a self-supporting MPL is fabricated and applied to a gas diffusion layer (GDL) of a PEMFC, when the GDL is either an integrated sample composed of a gas diffusion backing (GDB, i.e., carbon paper) combined with MPL or a sample with only MPL. Cell performance tests reveal that, the same as the MPL fabricated by the coating method, the self-supporting MPL on the GDB improves the cell performance at high current density. Furthermore, the GDL composed only of the MPL (i.e., GDB-free GDL) shows better performance than does the integrated GDB/MPL GDL. These results along with literature data strongly suggest that the low thermal conductivity of MPL induces a high temperature throughout the GDL, and thus vapor diffusion is dominant in the transport of product water through the MPL.

Nanofiber based triple layer hydro-philic/-phobic membrane - a solution for pore wetting in membrane distillation

PubMed Central

Prince, J. A.; Rana, D.; Matsuura, T.; Ayyanar, N.; Shanmugasundaram, T. S.; Singh, G.

2014-01-01

The innovative design and synthesis of nanofiber based hydro-philic/phobic membranes with a thin hydro-phobic nanofiber layer on the top and a thin hydrophilic nanofiber layer on the bottom of the conventional casted micro-porous layer which opens up a solution for membrane pore wetting and improves the pure water flux in membrane distillation. PMID:25377488

Perfluorinated ionomer-enveloped sulfur cathodes for lithium-sulfur batteries.

PubMed

Song, Jongchan; Choo, Min-Ju; Noh, Hyungjun; Park, Jung-Ki; Kim, Hee-Tak

2014-12-01

Nafion is known to suppress the polysulfide (PS) shuttle effect, a major obstacle to achieving high capacity and long cycle life for lithium-sulfur batteries. However, elaborate control of the layer's configuration is required for high performance. In this regard, we designed a Nafion-enveloped sulfur cathode, where the Nafion layer is formed on the skin of the cathode, covering its surface and edge while not restricting the porosity. Discharge capacity and efficiency were enhanced with the enveloping configuration, demonstrating suppression of shuttle. The edge protection exhibited better cycling stability than an edge-open configuration. In the absence of the Nafion envelope, charged sulfur concentrated on the top region of the cathode because of the relatively lower PS concentration at the cathode surface. Surprisingly, for the Nafion-enveloped cathode, sulfur was evenly distributed along the cathode, indicating that the configuration imparts a uniform PS concentration within the cathode. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Impact of polymer electrolyte membrane fuel cell microporous layer nano-scale features on thermal conductance

NASA Astrophysics Data System (ADS)

Botelho, S. J.; Bazylak, A.

2015-04-01

In this study, the microporous layer (MPL) of the polymer electrolyte membrane (PEM) fuel cell was analysed at the nano-scale. Atomic force microscopy (AFM) was utilized to image the top layer of MPL particles, and a curve fitting algorithm was used to determine the particle size and filling radius distributions for SGL-10BB and SGL-10BC. The particles in SGL-10BC (approximately 60 nm in diameter) have been found to be larger than those in SGL-10BB (approximately 40 nm in diameter), highlighting structural variability between the two materials. The impact of the MPL particle interactions on the effective thermal conductivity of the bulk MPL was analysed using a discretization of the Fourier equation with the Gauss-Seidel iterative method. It was found that the particle spacing and filling radius dominates the effective thermal conductivity, a result which provides valuable insight for future MPL design.

Gold Nanoclusters@Ru(bpy)₃²⁺-Layered Double Hydroxide Ultrathin Film as a Cathodic Electrochemiluminescence Resonance Energy Transfer Probe.

PubMed

Yu, Yingchang; Lu, Chao; Zhang, Meining

2015-08-04

Herein, it is the first report that a cathodic electrochemiluminescence (ECL) resonance energy transfer (ERET) system is fabricated by layer-by-layer (LBL) electrostatic assembly of CoAl layered double hydroxide (LDH) nanosheets with a mixture of blue BSA-gold nanoclusters (AuNCs) and Ru(bpy)3(2+) (denoted as AuNCs@Ru) on an Au electrode. The possible ECL mechanism indicates that the appearance of CoAl-LDH nanosheets generates a long-range stacking order of the AuNCs@Ru on an Au electrode, facilitating the occurrence of the ERET between BSA-AuNC donors and Ru(bpy)3(2+) acceptors on the as-prepared AuNCs@Ru-LDH ultrathin films (UTFs). Furthermore, it is observed that the cathodic ECL intensity can be quenched efficiently in the presence of 6-mercaptopurine (6-MP) in a linear range of 2.5-100 nM with a detection limit of 1.0 nM. On the basis of these interesting phenomena, a facile cathodic ECL sensor has successfully distinguished 6-MP from other thiol-containing compounds (e.g., cysteine and glutathione) in human serum and urine samples. The proposed sensing scheme opens a way for employing the layered UTFs as a platform for the cathodic ECL of Ru(bpy)3(2+).

Sulfur-carbon nanocomposite cathodes improved by an amphiphilic block copolymer for high-rate lithium-sulfur batteries.

PubMed

Fu, Yongzhu; Su, Yu-Sheng; Manthiram, Arumugam

2012-11-01

A sulfur-carbon nanocomposite consisting of a commercial high-surface-area carbon (i.e., Black Pearls 2000, BET surface area >1000 m² g⁻¹) and sulfur has been synthesized by an in situ deposition method. The nanocomposite is in the form of agglomerated nanoparticles, with the micropores within the carbon filled with sulfur and the mesopores on the carbon surface almost completely covered by sulfur. The BET surface area of the nanocomposite containing a sulfur content of 63.5 wt % is significantly reduced to only 40 m² g⁻¹. Cathodes containing the nanocomposite and Pluronic F-127 block copolymer, which partially replaces the polyvinylidene fluoride binder, were prepared and evaluated in lithium cells by cyclic voltammetry and galvanostatic cycling. The nanocomposite cathodes with the copolymer show improved electrochemical stability and cyclability. The Pluronic copolymer helps retain a uniform nanocomposite structure within the electrodes, improving the electrochemical contact, which was manifested by scanning electron microscopy and electrochemical impedance spectroscopy. The sulfur-Black Pearls nanocomposite with the Pluronic copolymer as an additive in the electrodes is promising for high-rate rechargeable lithium-sulfur batteries.

Carbon-Coated Current Collectors for High-Power Li-Ion Secondary Batteries

DTIC Science & Technology

2012-08-29

deposition condition. Surface analysis indicates that this thin C layer does not contain interfacial Al-carbide layer. LiFePO4 electrode using this C...layer does not contain an interfacial Al-carbide layer. LiFePO4 electrode using this C-coated Al current collector exhibits higher capacity under 10 C...cathode. LiFePO4 (LFPO) was used as active materials for test, and this cathode material was purchased from Aleees company. The LFPO active layer

Transparent Carbon Nanotube layers as cathodes in OLEDs

NASA Astrophysics Data System (ADS)

Papadimitratos, Alexios; Nasibulin, Albert; Kauppinen, Esko; Zakhidov, Anvar; Solarno Inc Collaboration; Aalto University Collaboration; UT Dallas Collaboration

2011-03-01

Organic Light Emitting diodes (OLEDs) have attracted high interest in recent years due to their potential use in future lighting and display applications. Reported work on OLEDs traditionally utilizes low work function materials as cathodes that are expensive to fabricate because of the high vacuum processing. Transparent carbon nanotube (CNT) sheets have excellent mechanical and electrical properties. We have already shown earlier that multi-wall (MWCNT) as well as single CNT (SWCNT) sheets can be used as effective anodes in bright OLEDs [,]. The true advantage of using the CNT sheets lies in flexible devices and new architectures with CNT sheet as layers in tandem devices with parallel connection. In this work, we are investigating the possibility of using SWCNT as cathodes in OLEDs. SWCNT sheets have been reported to show lower work function compared to MWCNT. Our work attempts to demonstrate transparent OLED devices with CNT anodes and cathodes. In the process, OLEDs with CNT cathodes have been fabricated in normal and inverted configurations using inorganic oxides (MoO3,ZnO) as invertion layers.

A versatile single molecular precursor for the synthesis of layered oxide cathode materials for Li-ion batteries.

PubMed

Li, Maofan; Liu, Jiajie; Liu, Tongchao; Zhang, Mingjian; Pan, Feng

2018-02-01

A carbonyl-bridged single molecular precursor LiTM(acac) 3 [transition metal (TM) = cobalt/manganese/nickel (Co/Mn/Ni), acac = acetylacetone], featuring a one-dimensional chain structure, was designed and applied to achieve the layered oxide cathode materials: LiTMO 2 (TM = Ni/Mn/Co, NMC). As examples, layered oxides, primary LiCoO 2 , binary LiNi 0.8 Co 0.2 O 2 and ternary LiNi 0.5 Mn 0.3 Co 0.2 O 2 were successfully prepared to be used as cathode materials. When they are applied to lithium-ion batteries (LIBs), all exhibit good electrochemical performance because of their unique morphology and great uniformity of element distribution. This versatile precursor is predicted to accommodate many other metal cations, such as aluminum (Al 3+ ), iron (Fe 2+ ), and sodium (Na + ), because of the flexibility of organic ligand, which not only facilitates the doping-modification of the NMC system, but also enables synthesis of Na-ion layered oxides. This opens a new direction of research for the synthesis of high-performance layered oxide cathode materials for LIBs.

The design of cathode for organic photovoltaic devices

NASA Astrophysics Data System (ADS)

Song, De; Shi, Feng; Xia, Xuan; Li, Ye; Duanmu, Qingduo

2016-11-01

We have discussed the effect of the residual gas in the Al metal cathode deposition process and consequently influence the performance of organic photovoltaic devices (such as organic photoelectron detector or solar cell). We believe that the origin of degradation in Jsc and FF from the Al cathode device should be the formation of AlOx in the C60-Al interface, which contaminate the interface and plays a role like an energy barrier that block the charge collect process. To solve this problem the Ag and Alq3 layer had been inserted before the Al. Owing to the advantageous of Alq3 and Ag layer, the device which Al cathode prepared at a lower vacuum condition exhibits a comparable performance to that device which Al cathode deposited in regular situation. As an additional benefit, since the introducing of Alq3/Ag layer in the VOPc/C60 organic photovoltaic device performs a better near-infrared response, this phenomenon has been confirmed by means of both simulation and experimental data. So the design of our new cathode structure provides a degree of freedom to modulate the light absorption for organic photovoltaic devices in short-wave and long-wave.

Optical properties of lamps with cold emission cathode

NASA Astrophysics Data System (ADS)

Kalenik, Jerzy; Czerwosz, ElŻbieta; Biernacki, Krzysztof; Rymarczyk, Joanna; Stepińska, Izabela

2016-12-01

A luminescent lamp was constructed and tested. Phosphor excited by electrons is the source of light. The source of electrons is field emission cathode. The cathode is covered with nickel-carbon layer containing carbon nanotubes that enhance electron emission from the cathode. Results of luminance measurements are presented. Luminance is high enough for lighting application.

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.

Process For Patterning Dispenser-Cathode Surfaces

NASA Technical Reports Server (NTRS)

Garner, Charles E.; Deininger, William D.

1989-01-01

Several microfabrication techniques combined into process cutting slots 100 micrometer long and 1 to 5 micrometer wide into tungsten dispenser cathodes for traveling-wave tubes. Patterned photoresist serves as mask for etching underlying aluminum. Chemically-assisted ion-beam etching with chlorine removes exposed parts of aluminum layer. Etching with fluorine or chlorine trifluoride removes tungsten not masked by aluminum layer. Slots enable more-uniform low-work function coating dispensed to electron-emitting surface. Emission of electrons therefore becomes more uniform over cathode surface.

Organic light emitting diodes with structured electrodes

DOEpatents

Mao, Samuel S.; Liu, Gao; Johnson, Stephen G.

2012-12-04

A cathode that contain nanostructures that extend into the organic layer of an OLED has been described. The cathode can have an array of nanotubes or a layer of nanoclusters extending out from its surface. In another arrangement, the cathode is patterned and etched to form protruding nanostructures using a standard lithographic process. Various methods for fabricating these structures are provided, all of which are compatible with large-scale manufacturing. OLEDs made with these novel electrodes have greatly enhanced electron injection, have good environmental stability.

Ion distribution and selectivity of ionic liquids in microporous electrodes.

PubMed

Neal, Justin N; Wesolowski, David J; Henderson, Douglas; Wu, Jianzhong

2017-05-07

The energy density of an electric double layer capacitor, also known as supercapacitor, depends on ion distributions in the micropores of its electrodes. Herein we study ion selectivity and partitioning of symmetric, asymmetric, and mixed ionic liquids among different pores using the classical density functional theory. We find that a charged micropore in contact with mixed ions of the same valence is always selective to the smaller ions, and the ion selectivity, which is strongest when the pore size is comparable to the ion diameters, drastically falls as the pore size increases. The partitioning behavior in ionic liquids is fundamentally different from those corresponding to ion distributions in aqueous systems whereby the ion selectivity is dominated by the surface energy and entropic effects insensitive to the degree of confinement.

Low-voltage electric-double-layer paper transistors gated by microporous SiO2 processed at room temperature

NASA Astrophysics Data System (ADS)

Sun, Jia; Wan, Qing; Lu, Aixia; Jiang, Jie

2009-11-01

Battery drivable low-voltage SnO2-based paper thin-film transistors with a near-zero threshold voltage (Vth=0.06 V) gated by microporous SiO2 dielectric with electric-double-layer (EDL) effect are fabricated at room temperature. The operating voltage is found to be as low as 1.5 V due to the huge gate specific capacitance (1.34 μF/cm2 at 40 Hz) related to EDL formation. The subthreshold gate voltage swing and current on/off ratio is found to be 82 mV/decade and 2.0×105, respectively. The electron field-effect mobility is estimated to be 47.3 cm2/V s based on the measured gate specific capacitance at 40 Hz.

Microporous layer based on SiC for high temperature proton exchange membrane fuel cells

NASA Astrophysics Data System (ADS)

Lobato, Justo; Zamora, Héctor; Cañizares, Pablo; Plaza, Jorge; Rodrigo, Manuel Andrés

2015-08-01

This work reports the evaluation of Silicon Carbide (SiC) for its application in microporous layers (MPL) of HT-PEMFC electrodes and compares results with those obtained using conventional MPL based on Vulcan XC72. Influence of the support load on the MPL prepared with SiC was evaluated, and the MPL were characterized by XRD, Hg porosimetry and cyclic voltammetries. In addition, a short lifetest was carried out to evaluate performance in accelerated stress conditions. Results demonstrate that SiC is a promising alternative to carbonaceous materials because of its higher electrochemical and thermal stability and the positive effect on mass transfer associated to its different pore size distribution. Ohmic resistance is the most significant challenge to be overcome in further studies.

Cross-stacked carbon nanotube film as an additional built-in current collector and adsorption layer for high-performance lithium sulfur batteries.

PubMed

Sun, Li; Kong, Weibang; Li, Mengya; Wu, Hengcai; Jiang, Kaili; Li, Qunqing; Zhang, Yihe; Wang, Jiaping; Fan, Shoushan

2016-02-19

Cross-stacked carbon nanotube (CNT) film is proposed as an additional built-in current collector and adsorption layer in sulfur cathodes for advanced lithium sulfur (Li-S) batteries. On one hand, the CNT film with high conductivity, microstructural rough surface, high flexibility and mechanical durability retains stable and direct electronic contact with the sulfur cathode materials, therefore decreasing internal resistivity and suppressing polarization of the cathode. On the other hand, the highly porous structure and the high surface area of the CNT film provide abundant adsorption points to support and confine sulfur cathode materials, alleviate their aggregation and promote high sulfur utilization. Moreover, the lightweight and compact structure of the CNT film adds no extra weight or volume to the sulfur cathode, benefitting the improvement of energy densities. Based on these characteristics, the sulfur cathode with a 100-layer cross-stacked CNT film presents excellent rate performances with capacities of 986, 922 and 874 mAh g(-1) at cycling rates of 0.2C, 0.5C and 1C for sulfur loading of 60 wt%, corresponding to an improvement of 52%, 109% and 146% compared to that without a CNT film. Promising cycling performances are also demonstrated, offering great potential for scaled-up production of sulfur cathodes for Li-S batteries.

Aramid Nanofiber Composites for Energy Storage Applications

NASA Astrophysics Data System (ADS)

Tung, Siu on

Lithium ion batteries and non-aqueous redox flow batteries represent two of the most important energy storage technologies to efficient electric vehicles and power grid, which are essential to decreasing U.S. dependence on fossil fuels and sustainable economic growth. Many of the developmental roadblocks for these batteries are related to the separator, an electrically insulating layer between the cathode and anode. Lithium dendrite growth has limited the performance and threatened the safety of lithium ion batteries by piercing the separator and causing internal shorts. In non-aqueous redox flow batteries, active material crossover through microporous separators and the general lack of a suitable ion conducting membrane has led to low operating efficiencies and rapid capacity fade. Developing new separators for these batteries involve the combination of different and sometimes seemingly contradictory properties, such as high ionic conductivity, mechanical stability, thermal stability, chemical stability, and selective permeability. In this dissertation, I present work on composites made from Kevlar-drived aramid nanofibers (ANF) through rational design and fabrication techniques. For lithium ion batteries, a dendrite suppressing layer-by-layer composite of ANF and polyethylene oxide is present with goals of high ionic conductivity, improved safety and thermal stability. For non-aqueous redox flow batteries, a nanoporous ANF separator with surface polyelectrolyte modification is used to achieve high coulombic efficiencies and cycle life in practical flow cells. Finally, manufacturability of ANF based separators is addressed through a prototype machine for continuous ANF separator production and a novel separator coated on anode assembly. In combination, these studies serve as a foundation for addressing the challenges in separator engineering for lithium ion batteries and redox flow batteries.

Alcohol-soluble interfacial fluorenes for inverted polymer solar cells: sequence induced spatial conformation dipole moment.

PubMed

Chen, Lie; Liu, Xiangfu; Wei, Yingkai; Wu, Feiyan; Chen, Yiwang

2016-01-21

Three fluorene-based alcohol-soluble organic small molecule electrolytes (SMEs) with different conjugated backbones, namely, TFTN-Br, FTFN-Br and FTTFN-Br, were designed as cathode interfacial layers for inverted polymer solar cells (i-PSCs). The insertion of SMEs to the ITO/active layer interfaces effectively lowered the energy barrier for electron transport and improved the inherent compatibility between the hydrophilic ITO and hydrophobic active layers. Due to these advantages, the device based on poly(3-hexylthiophene) (P3HT):(6,6)-phenyl-C61 butyric acid methyl ester (PC61BM) with TFTN-Br as the cathode interfacial layer achieved an improved power conversion efficiency (PCE) of 3.8%, which is a 26% improvement when compared to the standard device comprising ZnO cathode interfacial layers (PCE = 3.0%). Devices with FTFN-Br and FTTFN-Br also showed an improved PCE of 3.1% and 3.5%, respectively. The variation in device performance enhancement was found to be primarily correlated with the different conformation of their assembly onto the electrode caused by the joint sequence of the polar group of the SMEs, consequently impacting the dipole moment and interface morphology. In addition, introducing SMEs as the cathode interfacial layer also produced devices with long-term stability.

Micro-porous layer stochastic reconstruction and transport parameter determination

NASA Astrophysics Data System (ADS)

El Hannach, Mohamed; Singh, Randhir; Djilali, Ned; Kjeang, Erik

2015-05-01

The Micro-Porous Layer (MPL) is a porous, thin layer commonly used in fuel cells at the interfaces between the catalyst layers and gas diffusion media. It is generally made from spherical carbon nanoparticles and PTFE acting as hydrophobic agent. The scale and brittle nature of the MPL structure makes it challenging to study experimentally. In the present work, a 3D stochastic model is developed to virtually reconstruct the MPL structure. The carbon nanoparticle and PTFE phases are fully distinguished by the algorithm. The model is shown to capture the actual structural morphology of the MPL and is validated by comparing the results to available experimental data. The model shows a good capability in generating a realistic MPL successfully using a set of parameters introduced to capture specific morphological features of the MPL. A numerical model that resolves diffusive transport at the pore scale is used to compute the effective transport properties of the reconstructed MPLs. A parametric study is conducted to illustrate the capability of the model as an MPL design tool that can be used to guide and optimize the functionality of the material.

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.

Probing the Complexities of Structural Changes in Layered Oxide Cathode Materials for Li-Ion Batteries during Fast Charge–Discharge Cycling and Heating

DOE PAGES

Hu, Enyuan; Wang, Xuelong; Yu, Xiqian; ...

2018-01-19

The rechargeable lithium-ion battery (LIB) is the most promising energy storage system to power electric vehicles with high energy density and long cycling life. However, in order to meet customers’ demands for fast charging, the power performances of current LIBs need to be improved. From the cathode aspect, layer-structured cathode materials are widely used in today’s market and will continue to play important roles in the near future. The high rate capability of layered cathode materials during charging and discharging is critical to the power performance of the whole cell and the thermal stability is closely related to the safetymore » issues. Therefore, the in-depth understanding of structural changes of layered cathode materials during high rate charging/discharging and the thermal stability during heating are essential in developing new materials and improving current materials. Since structural changes take place from the atomic level to the whole electrode level, combination of characterization techniques covering multilength scales is quite important. Finally, in many cases, this means using comprehensive tools involving diffraction, spectroscopy, and imaging to differentiate the surface from the bulk and to obtain structural/chemical information with different levels of spatial resolution.« less

In-situ time-of-flight neutron diffraction study of the structure evolution of electrode materials in a commercial battery with LiNi0.8Co0.15Al0.05O2 cathode

NASA Astrophysics Data System (ADS)

Bobrikov, I. A.; Samoylova, N. Yu.; Sumnikov, S. V.; Ivanshina, O. Yu.; Vasin, R. N.; Beskrovnyi, A. I.; Balagurov, A. M.

2017-12-01

A commercial lithium-ion battery with LiNi0.8Co0.15Al0.05O2 (NCA) cathode has been studied in situ using high-intensity and high-resolution neutron diffraction. Structure and phase composition of the battery electrodes have been probed during charge-discharge in different cycling modes. The dependence of the anode composition on the charge rate has been determined quantitatively. Different kinetics of Li (de)intercalation in the graphite anode during charge/discharge process have been observed. Phase separation of the cathode material has not been detected in whole voltage range. Non-linear dependencies of the unit cell parameters, atomic and layer spacing on the lithium content in the cathode have been observed. Measured dependencies of interatomic spacing and interlayer spacing, and unit cell parameters of the cathode structure on the lithium content could be qualitatively explained by several factors, such as variations of oxidation state of cation in oxygen octahedra, Coulomb repulsion of oxygen layers, changes of average effective charge of oxygen layers and van der Waals interactions between MeO2-layers at high level of the NCA delithiation.

Blue photon management by inhouse grown ZnO:Al cathode for enhanced photostability in polymer solar cells

DOE PAGES

Bhattacharya, Joydeep; Peer, Akshit; Joshi, Pranav H.; ...

2018-02-21

Here, we report the improvement in photostability of P3HT:PC 60BM based bulk heterojunction solar cells deposited on Al-doped ZnO as a cathode layer replacing ITO as regularly used TCO in cells with N-I-P configuration. We experimentally and theoretically demonstrate that use of thicker ZnO:Al as cathode can successfully cut down the rate of photodegradation in short circuit current by ~40% and open circuit voltage by ~30% compared to the control device made on ITO based cathode. This effective reduction in photodegradation is understood to be coming from the absorption of ultraviolet and blue photon in the cathode layer itself. Themore » loss in short circuit current due to the loss of blue photon in EQE is compensated by higher FF (lower series resistance) due to thicker ZnO:Al layer resulting in final device efficiency almost uncompromised with added benefit of reduced photo degradation. The experimental results are supported with optical simulations which show more absorption in the short wavelength region for the thicker ZnO films, compared to ITO films, deposited on glass substrates. This work also proposes using ZnO:Al cathode as a template for random textured front surface to potentially increase short circuit current by increase in photon absorption in active layer matrix by light scattering techniques. Our results provide an inexpensive pathway for improving the stability of organic photovoltaics without compromising the device performance.« less

Blue photon management by inhouse grown ZnO:Al cathode for enhanced photostability in polymer solar cells

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

Bhattacharya, Joydeep; Peer, Akshit; Joshi, Pranav H.

Here, we report the improvement in photostability of P3HT:PC 60BM based bulk heterojunction solar cells deposited on Al-doped ZnO as a cathode layer replacing ITO as regularly used TCO in cells with N-I-P configuration. We experimentally and theoretically demonstrate that use of thicker ZnO:Al as cathode can successfully cut down the rate of photodegradation in short circuit current by ~40% and open circuit voltage by ~30% compared to the control device made on ITO based cathode. This effective reduction in photodegradation is understood to be coming from the absorption of ultraviolet and blue photon in the cathode layer itself. Themore » loss in short circuit current due to the loss of blue photon in EQE is compensated by higher FF (lower series resistance) due to thicker ZnO:Al layer resulting in final device efficiency almost uncompromised with added benefit of reduced photo degradation. The experimental results are supported with optical simulations which show more absorption in the short wavelength region for the thicker ZnO films, compared to ITO films, deposited on glass substrates. This work also proposes using ZnO:Al cathode as a template for random textured front surface to potentially increase short circuit current by increase in photon absorption in active layer matrix by light scattering techniques. Our results provide an inexpensive pathway for improving the stability of organic photovoltaics without compromising the device performance.« less

Effect of Transition Metal Ordering on the Electronic Properties of LiNi1 - y - xCoyMnxO2 Cathode Materials for Li-ion Batteries

NASA Astrophysics Data System (ADS)

Longo, Roberto; Kong, Fantai; Kc, Santosh; Yeon, Dong-Hee; Yoon, Jaegu; Park, Jin-Hwan; Doo, Seok-Kwang; Cho, Kyeongjae; MSL Team; SAIT Team

2015-03-01

Current Li-ion batteries use layered oxides as cathode materials, specially LiCoO2 or LiNi1 - y - xCoyMnxO2(NCM), and graphite as anode. Co layered oxides suffer from the high cost and toxicity of cobalt, together with certain instability at high operational temperatures. To overcome these difficulties, the synthesis of novel materials composed of layered oxides with different sets of Transition Metals (TM) has become the most successful way to solve the particular drawbacks of every single-oxide family. Although layered materials can deliver larger capacity than other families of cathode materials, the energy density has yet to be increased in order to match the expectations deposited on the NCM oxides. To acquire a high capacity, they need to be cycled at high operational voltages, resulting in voltage and capacity fading over a large number of cycles. In this work, we examine the phase diagram of the Li-Ni-Co-Mn-O system and the effect of TM ordering on the electronic properties of NCM cathode materials, using density-functional theory. Our findings will provide conceptual guidance in the experimental search for the mechanisms driving the voltage and capacity fading of the NCM family of cathode materials, in an attempt to solve such structural instability problems and, thus, improving the performance of the NCM cathode materials. This work was supported by Samsung GRO project.

Atomic Resolution Structural and Chemical Imaging Revealing the Sequential Migration of Ni, Co, and Mn upon the Battery Cycling of Layered Cathode

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

Yan, Pengfei; Zheng, Jianming; Zhang, Ji-Guang

Layered lithium transition metal oxides (LTMO) are promising candidate cathode materials for next generation high energy density lithium ion battery. The challenge for using this category of cathode is the capacity and voltage fading, which is believed to be associated with the layered structure disordering, a process that is initiated from the surface or solid-electrolyte interface and facilitated by transition metal (TM) reduction and oxygen vacancy formation. However, the atomic level dynamic mechanism of such a layered structure disordering is still not fully clear. In this work, utilizing atomic resolution electron energy loss spectroscopy (EELS), we map, for the firstmore » time at atomic scale, the spatial evolution of Ni, Co and Mn in a cycled LiNi1/3M1/3Co1/3O2 layered cathode. In combination with atomic level structural imaging, we discovered the direct correlation of TM ions migration behavior with lattice disordering, featuring the residing of TM ions in the tetrahedral site and a sequential migration of Ni, Co, and Mn upon the increased lattice disordering of the layered structure. This work highlights that Ni ions, though acting as the dominant redox species in many LTMO, are labile to migrate to cause lattice disordering upon battery cycling; while the Mn ions are more stable as compared with Ni and Co and can act as pillar to stabilize layered structure. Direct visualization of the behavior of TM ions during the battery cycling provides insight for designing of cathode with structural stability and correspondingly a superior performance.« less

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

Pascal, Tod A.; Villaluenga, Irune; Wujcik, Kevin H.

Impregnation of porous carbon matrices with liquid sulfur has been exploited to fabricate composite cathodes for lithium-sulfur batteries, aimed at confining soluble sulfur species near conducting carbon to prevent both loss of active material into the electrolyte and parasitic reactions at the lithium metal anode. Here, through extensive computer simulations, we uncover the strongly favorable interfacial free energy between liquid sulfur and graphitic surfaces that underlies this phenomenon. Previously unexplored curvature-dependent enhancements are shown to favor the filling of smaller pores first and effect a quasi-liquid sulfur phase in microporous domains (diameters <2 nm) that persists ~30° below the expectedmore » freezing point. Evidence of interfacial sulfur on carbon is shown to be a 0.3 eV red shift in the simulated and measured interfacial X-ray absorption spectra. Our results elucidate the critical morphology and thermodynamic properties necessary for future cathode design and highlight the importance of molecular-scale details in defining emergent properties of functional nanoscale interfaces.« less

Acidic and alkaline pretreatments of activated carbon and their effects on the performance of air-cathodes in microbial fuel cells.

PubMed

Wang, Xin; Gao, Ningshengjie; Zhou, Qixing; Dong, Heng; Yu, Hongbing; Feng, Yujie

2013-09-01

Activated carbon (AC) is a high performing and cost effective catalyst for oxygen reduction reactions (ORRs) of air-cathodes in microbial fuel cells (MFCs). Acidic (HNO3) and alkaline (KOH) pretreatments on AC at low temperature (85°C) are conducted to enhance the performance of MFCs. The alkaline pretreatment increased the power density by 16% from 804±70 to 957±31 mW m(-2), possibly due to the decrease of ohmic resistance (from 20.58 to 19.20 Ω) and the increase of ORR activities provided by the adsorbed hydroxide ion and extra micropore area/volume after alkaline pretreatment. However, acidic pretreatment decreased the power output to 537±36 mW m(-2), which can be mainly attributed to the corrosion by adsorbed proton at the interface of AC powder and stainless steel mesh and the decreased pore area. Copyright © 2013 Elsevier Ltd. All rights reserved.

Spatially resolved surface valence gradient and structural transformation of lithium transition metal oxides in lithium-ion batteries.

PubMed

Liu, Hanshuo; Bugnet, Matthieu; Tessaro, Matteo Z; Harris, Kristopher J; Dunham, Mark J R; Jiang, Meng; Goward, Gillian R; Botton, Gianluigi A

2016-10-26

Layered lithium transition metal oxides are one of the most important types of cathode materials in lithium-ion batteries (LIBs) that possess high capacity and relatively low cost. Nevertheless, these layered cathode materials suffer structural changes during electrochemical cycling that could adversely affect the battery performance. Clear explanations of the cathode degradation process and its initiation, however, are still under debate and not yet fully understood. We herein systematically investigate the chemical evolution and structural transformation of the LiNi x Mn y Co 1-x-y O 2 (NMC) cathode material in order to understand the battery performance deterioration driven by the cathode degradation upon cycling. Using high-resolution electron energy loss spectroscopy (HR-EELS) we clarify the role of transition metals in the charge compensation mechanism, particularly the controversial Ni 2+ (active) and Co 3+ (stable) ions, at different states-of-charge (SOC) under 4.6 V operation voltage. The cathode evolution is studied in detail from the first-charge to long-term cycling using complementary diagnostic tools. With the bulk sensitive 7 Li nuclear magnetic resonance (NMR) measurements, we show that the local ordering of transition metal and Li layers (R3[combining macron]m structure) is well retained in the bulk material upon cycling. In complement to the bulk measurements, we locally probe the valence state distribution of cations and the surface structure of NMC particles using EELS and scanning transmission electron microscopy (STEM). The results reveal that the surface evolution of NMC is initiated in the first-charging step with a surface reduction layer formed at the particle surface. The NMC surface undergoes phase transformation from the layered structure to a poor electronic and ionic conducting transition-metal oxide rock-salt phase (R3[combining macron]m → Fm3[combining macron]m), accompanied by irreversible lithium and oxygen loss. In addition to the electrochemical cycling effect, electrolyte exposure also shows non-negligible influence on cathode surface degradation. These chemical and structural changes of the NMC cathode could contribute to the first-cycle coulombic inefficiency, restrict the charge transfer characteristics and ultimately impact the cell capacity.

Structure that encapsulates lithium metal for high energy density battery anode

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

Cui, Yi; Yan, Kai; Chu, Steven

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

Solid oxide fuel cell having monolithic core

DOEpatents

Ackerman, J.P.; Young, J.E.

1983-10-12

A solid oxide fuel cell is described for electrochemically combining fuel and oxidant for generating galvanic output, wherein the cell core has an array of electrolyte and interconnect walls that are substantially devoid of any composite inert materials for support. Instead, the core is monolithic, where each electrolyte wall consists of thin layers of cathode and anode materials sandwiching a thin layer of electrolyte material therebetween. The electrolyte walls are arranged and backfolded between adjacent interconnect walls operable to define a plurality of core passageways alternately arranged where the inside faces thereof have only the anode material or only the cathode material exposed. Means direct the fuel to the anode-exposed core passageways and means direct the oxidant to the anode-exposed core passageways and means direct the oxidant to the cathode-exposed core passageway; and means also direct the galvanic output to an exterior circuit. Each layer of the electrolyte and interconnect materials is of the order of 0.002 to 0.01 cm thick; and each layer of the cathode and anode materials is of the order of 0.002 to 0.05 cm thick.

Preparation of Layered-Spinel Microsphere/Reduced Graphene Oxide Cathode Materials for Ultrafast Charge-Discharge Lithium-Ion Batteries.

PubMed

Luo, Dong; Fang, Shaohua; Yang, Li; Hirano, Shin-Ichi

2017-12-22

Although Li-rich layered oxides (LLOs) have the highest capacity of any cathodes used, the rate capability of LLOs falls short of meeting the requirements of electric vehicles and smart grids. Herein, a layered-spinel microsphere/reduced graphene oxide heterostructured cathode (LS@rGO) is prepared in situ. This cathode is composed of a spinel phase, two layered structures, and a small amount of reduced graphene oxide (1.08 wt % of carbon). The assembly delivers a considerable charge capacity (145 mA h g -1 ) at an ultrahigh charge- discharge rate of 60 C (12 A g -1 ). The rate capability of LS@rGO is influenced by the introduced spinel phase and rGO. X-ray absorption and X-ray photoelectron spectroscopy data indicate that Cr ions move from octahedral lattice sites to tetrahedral lattice sites, and that Mn ions do not participate in the oxidation reaction during the initial charge process. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Two-Ply Composite Membranes with Separation Layers from Chitosan and Sulfoethylcellulose on a Microporous Support Based on Poly(diphenylsulfone-N-phenylphthalimide).

PubMed

Kononova, Svetlana V; Kruchinina, Elena V; Petrova, Valentina A; Baklagina, Yulia G; Romashkova, Kira A; Orekhov, Anton S; Klechkovskaya, Vera V; Skorik, Yury A

2017-12-14

Two-ply composite membranes with separation layers from chitosan and sulfoethylcellulose were developed on a microporous support based on poly(diphenylsulfone- N -phenylphthalimide) and investigated by use of X-ray diffraction and scanning electron microscopy methods. The pervaporation properties of the membranes were studied for the separation of aqueous alcohol (ethanol, propan-2-ol) mixtures of different compositions. When the mixtures to be separated consist of less than 15 wt % water in propan-2-ol, the membranes composed of polyelectrolytes with the same molar fraction of ionogenic groups (-NH₃⁺ for chitosan and -SO₃ - for sulfoethylcellulose) show high permselectivity (the water content in the permeate was 100%). Factors affecting the structure of a non-porous layer of the polyelectrolyte complex formed on the substrate surface and the contribution of that complex to changes in the transport properties of membranes are discussed. The results indicate significant prospects for the use of chitosan and sulfoethylcellulose for the formation of highly selective pervaporation membranes.

Enhanced lifetime for thin-dielectric microdischarge-arrays operating in DC

NASA Astrophysics Data System (ADS)

Dussart, Remi; Felix, Valentin; Overzet, Lawrence; Aubry, Olivier; Stolz, Arnaud; Lefaucheux, Philippe; Gremi-Univ Orleans-Cnrs Collaboration; University Of Texas At Dallas Collaboration

2016-09-01

Micro-hollow cathode discharge arrays using silicon as the cathode have a very limited lifetime because the silicon bubbles and initiates micro-arcing. To avoid this destructive behavior, the same configuration was kept but, another material was selected for the cathode. Using micro and nanotechnologies ordinarily used in microelectronic and MEMS device fabrication, we made arrays of cathode boundary layer (CBL)-type microreactors consisting of nickel electrodes separated by a 6 µm thick SiO2 layer. Microdischarges were ignited in arrays of 100 µm diameter holes at different pressures (200750 Torr) in different gases. Electrical and optical measurements were made to characterize the arrays. Unlike the microdischarges produced using silicon cathodes, the Ni cathode discharges remain very stable with essentially no micro-arcing. DC currents between 50 and 900 µA flowed through each microreactor with a discharge voltage of typically 200 V. Stable V-I characteristics showing both the normal and abnormal regimes were observed and are consistent with the spread of the plasma over the cathode area. Due to their stability and lifetime, new applications of these DC, CBL-type microreactors can now be envisaged.

Effect of cathode cooling efficiency and oxygen plasma gas pressure on the hafnium cathode wall temperature

NASA Astrophysics Data System (ADS)

Ashtekar, Koustubh; Diehl, Gregory; Hamer, John

2012-10-01

The hafnium cathode is widely used in DC plasma arc cutting (PAC) under an oxygen gas environment to cut iron and iron alloys. The hafnium erosion is always a concern which is controlled by the surface temperature. In this study, the effect of cathode cooling efficiency and oxygen gas pressure on the hafnium surface temperature are quantified. The two layer cathode sheath model is applied on the refractive hafnium surface while oxygen species (O2, O, O+, O++, e-) are considered within the thermal dis-equilibrium regime. The system of non-linear equations comprising of current density balance, heat flux balance at both the cathode surface and the sheath-ionization layer is coupled with the plasma gas composition solver. Using cooling heat flux, gas pressure and current density as inputs; the cathode wall temperature, electron temperature, and sheath voltage drop are calculated. Additionally, contribution of emitted electron current (Je) and ions current (Ji) to the total current flux are estimated. Higher gas pressure usually reduces Ji and increases Je that reduces the surface temperature by thermionic cooling.

Interlocking wettable ceramic tiles

DOEpatents

Tabereaux, Jr., Alton T.; Fredrickson, Guy L.; Groat, Eric; Mroz, Thomas; Ulicny, Alan; Walker, Mark F.

2005-03-08

An electrolytic cell for the reduction of aluminum having a layer of interlocking cathode tiles positioned on a cathode block. Each tile includes a main body and a vertical restraining member to prevent movement of the tiles away from the cathode block during operation of the cell. The anode of the electrolytic cell may be positioned about 1 inch from the interlocking cathode tiles.

Insight into self-discharge of layered lithium-rich oxide cathode in carbonate-based electrolytes with and without additive

NASA Astrophysics Data System (ADS)

Li, Jianhui; Xing, Lidan; Zhang, Liping; Yu, Le; Fan, Weizhen; Xu, Mengqing; Li, Weishan

2016-08-01

Self-discharge behavior of layered lithium-rich oxide as cathode of lithium ion battery in a carbonated-based electrolyte is understood, and a simple boron-containing compound, trimethyl borate (TMB), is used as an electrolyte additive to suppress this self-discharge. It is found that layered lithium-rich oxide charged under 4.8 V in additive-free electrolyte suffers severe self-discharge and TMB is an effective electrolyte additive for self-discharge suppression. Physical characterizations from XRD, SEM, TEM, XPS and ICP-MS demonstrate that the crystal structure of the layered lithium-rich oxide collapses due to the chemical interaction between the charged oxide and electrolyte. When TMB is applied, the structural integrity of the oxide is maintained due to the protective cathode film generated from the preferential oxidation of TMB.

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.

A novel metal organic framework-derived carbon-based catalyst for oxygen reduction reaction in a microbial fuel cell

NASA Astrophysics Data System (ADS)

Zhang, Lihua; Hu, Yongyou; Chen, Junfeng; Huang, Wantang; Cheng, Jianhua; Chen, Yuancai

2018-04-01

To improve the power generation of microbial fuel cell (MFC), the cathode is modified to increase its oxygen reduction reaction (ORR) activity by using a Cu, N-incorporated carbon-based material as catalyst, which obtained from pyrolyzing ORR active Cu (II)-based metal organic framework (MOF; Cu-bipy-BTC, bipy = 2,2‧-bipyridine, BTC = 1,3,5-tricarboxylate). MOF-800 (the product of pyrolyzing Cu-bipy-BTC at 800 °C) shows porous structure with micropores ranging from 0.5 to 1.3 nm and mesopores ranging from 27 to 46 nm. It also exhibits improved ORR electrocatalytic activity with a higher current density of -3.06 mA cm-2 compared to Cu-bipy-BTC. Moreover, the charge transfer resistance of MOF-800 cathode (1.38 Ω) is much smaller than that of Cu-bipy-BTC cathode (176.8 Ω). A maximum power density of 326 ± 11 mW m-2 is achieved by MOF-800-MFC, which is 2.6 times of that of Cu-bipy-BTC-MFC and comparable with Pt/C-MFC (402 ± 17 mW m-2). The results imply the enhancements of ORR catalytic activity and electrical conductivity of MOF-800 are due to the enhanced porous structure and abundant active sites (C-N, Cu-Nχ), which result in the improved power generation of MFC. This study provides technical and theoretical validation for the MFC performance improvement by ORR active MOF-derived catalysts modified cathodes.

Visualizing nanoscale 3D compositional fluctuation of lithium in advanced lithium-ion battery cathodes

DOE PAGES

Devaraj, Arun; Gu, Meng; Colby, Robert J.; ...

2015-08-14

The distribution and concentration of lithium in Li-ion battery cathodes at different stages of cycling is a pivotal factor in determining battery performance. Non-uniform distribution of the transition metal cations has been shown to affect cathode performance; however, the Li is notoriously challenging to characterize with typical high-spatial-resolution imaging techniques. Here, for the first time, laser–assisted atom probe tomography is applied to two advanced Li-ion battery oxide cathode materials—layered Li 1.2Ni 0.2Mn 0.6O 2 and spinel LiNi 0.5Mn 1.5O 4—to unambiguously map the three dimensional (3D) distribution of Li at sub-nanometer spatial resolution and correlate it with the distribution ofmore » the transition metal cations (M) and the oxygen. The as-fabricated layered Li 1.2Ni 0.2Mn 0.6O 2 is shown to have Li-rich Li 2MO 3 phase regions and Li-depleted Li(Ni 0.5Mn 0.5)O 2 regions while in the cycled layered Li 1.2Ni 0.2Mn 0.6O 2 an overall loss of Li and presence of Ni rich regions, Mn rich regions and Li rich regions are shown in addition to providing the first direct evidence for Li loss on cycling of layered LNMO cathodes. The spinel LiNi 0.5Mn 1.5O 4 cathode is shown to have a uniform distribution of all cations. These results were additionally validated by correlating with energy dispersive spectroscopy mapping of these nanoparticles in a scanning transmission electron microscope. Thus, we have opened the door for probing the nanoscale compositional fluctuations in crucial Li-ion battery cathode materials at an unprecedented spatial resolution of sub-nanometer scale in 3D which can provide critical information for understanding capacity decay mechanisms in these advanced cathode materials.« less

Zeolite-templated carbons - three-dimensional microporous graphene frameworks.

PubMed

Nishihara, H; Kyotani, T

2018-05-31

Zeolite-templated carbons (ZTCs) are ordered microporous carbons synthesized by using zeolite as a sacrificial template. Unlike well-known ordered mesoporous carbons obtained by using mesoporous silica templates, ZTCs consist of curved and single-layer graphene frameworks, thereby affording uniform micropore size (ca. 1.2 nm), developed microporosity (∼1.7 cm3 g-1), very high surface area (∼4000 m2 g-1), good compatibility with chemical modification, and remarkable softness/elasticity. Thus, ZTCs have been used in many applications such as hydrogen storage, methane storage, CO2 capture, liquid-phase adsorption, catalysts, electrochemical capacitors, batteries, and fuel cells. Herein, the relevant research studies are summarized, and the properties as well as the performances of ZTCs are compared with those of other materials including metal-organic frameworks, to elucidate the intrinsic advantages of ZTCs and their future development.

Electrochemical performance of La2O3/Li2O/TiO2 nano-particle coated cathode material LiFePO4.

PubMed

Wang, Hong; Yang, Chi; Liu, Shu-Xin

2014-09-01

Cathode material, LiFePO4 was modified by coating with a thin layer of La2O3/Li2O/TiO2 nano-particles for improving its performance for lithium ion batteries. The morphology and structure of the modified cathode material were characterized by powder X-ray diffraction, scanning electron microcopy and AES. The performance of the battery with the modified cathode material, including cycling stability, C-rate discharge was examined. The results show that the battery composed of the coated cathode materials can discharge at a large current density and show stable cycling performance in the range from 2.5 to 4.0 V. The rate of Li ion diffusion increases in the battery with the La2O3/Li2O/TiO2-coated LiFePO4 as a cathode and the coating layer may acts as a faster ion conductor (La(2/3-x)Li(3x)TiO3).

High-efficiency AlxGa1-xAs/GaAs cathode for photon-enhanced thermionic emission solar energy converters

NASA Astrophysics Data System (ADS)

Feng, Cheng; Zhang, Yijun; Qian, Yunsheng; Wang, Ziheng; Liu, Jian; Chang, Benkang; Shi, Feng; Jiao, Gangcheng

2018-04-01

A theoretical emission model for AlxGa1-xAs/GaAs cathode with complex structure based on photon-enhanced thermionic emission is developed by utilizing one-dimensional steady-state continuity equations. The cathode structure comprises a graded-composition AlxGa1-xAs window layer and an exponential-doping GaAs absorber layer. In the deduced model, the physical properties changing with the Al composition are taken into consideration. Simulated current-voltage characteristics are presented and some important factors affecting the conversion efficiency are also illustrated. Compared with the graded-composition and uniform-doping cathode structure, and the uniform-composition and uniform-doping cathode structure, the graded-composition and exponential-doping cathode structure can effectively improve the conversion efficiency, which is ascribed to the twofold built-in electric fields. More strikingly, this graded bandgap structure is especially suitable for photon-enhanced thermionic emission devices since a higher conversion efficiency can be achieved at a lower temperature.

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).

Optimization of the Energy Level Alignment between the Photoactive Layer and the Cathode Contact Utilizing Solution-Processed Hafnium Acetylacetonate as Buffer Layer for Efficient Polymer Solar Cells.

PubMed

Yu, Lu; Li, Qiuxiang; Shi, Zhenzhen; Liu, Hao; Wang, Yaping; Wang, Fuzhi; Zhang, Bing; Dai, Songyuan; Lin, Jun; Tan, Zhan'ao

2016-01-13

The insertion of an appropriate interfacial buffer layer between the photoactive layer and the contact electrodes makes a great impact on the performance of polymer solar cells (PSCs). Ideal interfacial buffer layers could minimize the interfacial traps and the interfacial barriers caused by the incompatibility between the photoactive layer and the electrodes. In this work, we utilized solution-processed hafnium(IV) acetylacetonate (Hf(acac)4) as an effective cathode buffer layer (CBL) in PSCs to optimize the energy level alignment between the photoactive layer and the cathode contact, with the short-circuit current density (Jsc), open-circuit voltage (Voc), and fill factor (FF) all simultaneously improved with Hf(acac)4 CBL, leading to enhanced power conversion efficiencies (PCEs). Ultraviolet photoemission spectroscopy (UPS) and scanning Kelvin probe microscopy (SKPM) were performed to confirm that the interfacial dipoles were formed with the same orientation direction as the built-in potential between the photoactive layer and Hf(acac)4 CBL, benefiting the exciton separation and electron transport/extraction. In addition, the optical characteristics and surface morphology of the Hf(acac)4 CBL were also investigated.

Cathode for aluminum producing electrolytic cell

DOEpatents

Brown, Craig W.

2004-04-13

A method of producing aluminum in an electrolytic cell comprising the steps of providing an anode in a cell, preferably a non-reactive anode, and also providing a cathode in the cell, the cathode comprised of a base material having low electrical conductivity reactive with molten aluminum to provide a highly electrically conductive layer on the base material. Electric current is passed from the anode to the cathode and alumina is reduced and aluminum is deposited at the cathode. The cathode base material is selected from boron carbide, and zirconium oxide.

A novel TFC forward osmosis (FO) membrane supported by polyimide (PI) microporous nanofiber membrane

NASA Astrophysics Data System (ADS)

Chi, Xiang-Yu; Zhang, Ping-Yun; Guo, Xue-Jiao; Xu, Zhen-Liang

2018-01-01

A novel interfacial polymerization (IP) procedure on polyimide (PI) microporous nanofiber membrane support with mean pore size 1.27 μm was reported. Using m-phenylenediamine (MPD) as aqueous phase monomer, trimesoyl chloride (TMC) as organic phase monomer, ethanol as aqueous phase co-solvent, thin-film composite (TFC) forward osmosis (FO) membrane was fabricated by two IP procedures. The first IP procedure with the unconventional order (ie, the membrane was immersed in the TMC organic phase first, then in the co-solvent ethanol-water MPD aqueous phase) was used to diminish the pore size of PI microporous nanofiber membrane support for the formation of the polyamide layer. The secondary IP procedure was employed to form the relatively dense polyamide layer with conventional order (ie, the membrane was immersed in the co-solvent ethanol-water MPD aqueous phase first, then in the TMC organic phase). The experimental results showed that higher ethanol concentration led to the relatively higher pure water permeability in RO process and osmotic water flux in FO process, whereas NaCl rejection in RO process decreased and reverse salt flux increased. The specific salt flux (Js/Jv) of TFC FO PI nanofiber membrane (PIN-2-4) could be as low as 0.095 g/L in FO mode. These results could be attributed to influence of the addition of ethanol into aqueous phase on the surface morphology, hydrophilicity and polyamide layer structure.

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)

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

Evaporation Source for Deposition of Protective Layers inside Tubes

NASA Astrophysics Data System (ADS)

Musa, Geavit; Mustata, Ion; Dinescu, Gheorghe; Bajeu, George; Raiciu, Elena

1992-09-01

A heated cathode arc can be ignited in vacuum in the vapours of the anode material due to the accelerated electron beam from the cathode. A small assembly, consisting of an electron gun as the cathode and a refractory metal crucible, containing the material to be evaporated, as the anode, can be moved along the axis of the tube whose inside wall is to be covered with a protective layer. The vacuum arc ignited between the electrodes in the vapours of the evaporating anode material ensures a high deposition rate with low thermal energy transport to the tube wall. This new method can be used for the deposition of various metal layers inside different kinds of tubes (metallic, glass, ceramics or plastics).

Efficient polymer light-emitting diode with air-stable aluminum cathode

NASA Astrophysics Data System (ADS)

Abbaszadeh, D.; Wetzelaer, G. A. H.; Doumon, N. Y.; Blom, P. W. M.

2016-03-01

The fast degradation of polymer light-emitting diodes (PLEDs) in ambient conditions is primarily due to the oxidation of highly reactive metals, such as barium or calcium, which are used as cathode materials. Here, we report the fabrication of PLEDs using an air-stable partially oxidized aluminum (AlOx) cathode. Usually, the high work function of aluminum (4.2 eV) imposes a high barrier for injecting electrons into the lowest unoccupied molecular orbital (LUMO) of the emissive polymer (2.9 eV below the vacuum level). By partially oxidizing aluminum, its work function is decreased, but not sufficiently low for efficient electron injection. Efficient injection is obtained by inserting an electron transport layer of poly[(9,9-di-n-octylfluorenyl-2,7-diyl)-alt-(benzo[2,1,3]thiadiazol-4,8-diyl)] (F8BT), which has its LUMO at 3.3 eV below vacuum, between the AlOx cathode and the emissive polymer. The intermediate F8BT layer not only serves as a hole-blocking layer but also provides an energetic staircase for electron injection from AlOx into the emissive layer. PLEDs with an AlOx cathode and F8BT interlayer exhibit a doubling of the efficiency as compared to conventional Ba/Al PLEDs, and still operate even after being kept in ambient atmosphere for one month without encapsulation.

Power Conversion Efficiency and Device Stability Improvement of Inverted Perovskite Solar Cells by Using a ZnO:PFN Composite Cathode Buffer Layer.

PubMed

Jia, Xiaorui; Zhang, Lianping; Luo, Qun; Lu, Hui; Li, Xueyuan; Xie, Zhongzhi; Yang, Yongzhen; Li, Yan-Qing; Liu, Xuguang; Ma, Chang-Qi

2016-07-20

We have demonstrated in this article that both power conversion efficiency (PCE) and performance stability of inverted planar heterojunction perovskite solar cells can be improved by using a ZnO:PFN nanocomposite (PFN: poly[(9,9-bis(3'-(N,N-dimethylamion)propyl)-2,7-fluorene)-alt-2,7-(9,9-dioctyl)-fluorene]) as the cathode buffer layer (CBL). This nanocomposite could form a compact and defect-less CBL film on the perovskite/PC61BM surface (PC61BM: phenyl-C61-butyric acid methyl ester). In addition, the high conductivity of the nanocomposite layer makes it works well at a layer thickness of 150 nm. Both advantages of the composite layer are helpful in reducing interface charge recombination and improving device performance. The power conversion efficiency (PCE) of the best ZnO:PFN CBL based device was measured to be 12.76%, which is higher than that of device without CBL (9.00%), or device with ZnO (7.93%) or PFN (11.30%) as the cathode buffer layer. In addition, the long-term stability is improved by using ZnO:PFN composite cathode buffer layer when compare to that of the reference cells. Almost no degradation of open circuit voltage (VOC) and fill factor (FF) was found for the device having ZnO:PFN, suggesting that ZnO:PFN is able to stabilize the interface property and consequently improve the solar cell performance stability.

Suppressing Manganese Dissolution from Lithium Manganese Oxide Spinel Cathodes with Single-Layer Graphene

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

Jaber-Ansari, Laila; Puntambekar, Kanan P.; Kim, Soo

2015-06-24

Spinel-structured LiMn 2 O 4 (LMO) is a desirable cathode material for Li-ion batteries due to its low cost, abundance, and high power capability. However, LMO suffers from limited cycle life that is triggered by manganese dissolution into the electrolyte during electrochemical cycling. Here, it is shown that single-layer graphene coatings suppress manganese dissolution, thus enhancing the performance and lifetime of LMO cathodes. Relative to lithium cells with uncoated LMO cathodes, cells with graphene-coated LMO cathodes provide improved capacity retention with enhanced cycling stability. X-ray photoelectron spectroscopy reveals that graphene coatings inhibit manganese depletion from the LMO surface. Additionally, transmissionmore » electron microscopy demonstrates that a stable solid electrolyte interphase is formed on graphene, which screens the LMO from direct contact with the electrolyte. Density functional theory calculations provide two mechanisms for the role of graphene in the suppression of manganese dissolution. First, common defects in single-layer graphene are found to allow the transport of lithium while concurrently acting as barriers for manganese diffusion. Second, graphene can chemically interact with Mn 3+ at the LMO electrode surface, promoting an oxidation state change to Mn 4+ , which suppresses dissolution.« less

Mn-Based Cathode with Synergetic Layered-Tunnel Hybrid Structures and Their Enhanced Electrochemical Performance in Sodium Ion Batteries.

PubMed

Wu, Zhen-Guo; Li, Jun-Tao; Zhong, Yan-Jun; Guo, Xiao-Dong; Huang, Ling; Zhong, Ben-He; Agyeman, Daniel-Adjei; Lim, Jin-Myoung; Kim, Du-Ho; Cho, Maeng-Hyo; Kang, Yong-Mook

2017-06-28

A synergistic approach for advanced cathode materials is proposed. Sodium manganese oxide with a layered-tunnel hybrid structure was designed, synthesized, and subsequently investigated. The layered-tunnel hybrid structure provides fast Na ion diffusivity and high structural stability thanks to the tunnel phase, enabling high rate capability and greatly improved cycling stability compared to that of the pure P2 layered phase while retaining the high specific capacity of the P2 layered phase. The hybrid structure provided a decent discharge capacity of 133.4 mAh g -1 even at 8 C, which exceeds the reported best rate capability for Mn-based cathodes. It also displayed an impressive cycling stability, maintaining 83.3 mAh g -1 after 700 cycles at 10 C. Theoretical calculation and the potentiostatic intermittent titration technique (PITT) demonstrated that this hybrid structure helps enhance Na ion diffusivity during charge and discharge, attaining, as a result, an unprecendented electrochemical performance.

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

Kumar, Pankaj, E-mail: pankaj@mail.nplindia.ernet.in; Centre for Organic Electronics, Physics, University of Newcastle, Callaghan NSW-2308; Bilen, Chhinder

The degradation and thermal regeneration of poly(3-hexylethiophene) (P3HT):[6,6]-phenyl-C{sub 61}-butyric acid methyl ester (PCBM) and P3HT:indene-C{sub 60} bisadduct (ICBA) polymer solar cells, with Ca/Al and Ca/Ag cathodes and indium tin oxide/poly(ethylene-dioxythiophene):polystyrene sulfonate anode have been investigated. Degradation occurs via a combination of three primary pathways: (1) cathodic oxidation, (2) active layer phase segregation, and (3) anodic diffusion. Fully degraded devices were subjected to thermal annealing under inert atmosphere. Degraded solar cells possessing Ca/Ag electrodes were observed to regenerate their performance, whereas solar cells having Ca/Al electrodes exhibited no significant regeneration of device characteristics after thermal annealing. Moreover, the solar cells withmore » a P3HT:ICBA active layer exhibited enhanced regeneration compared to P3HT:PCBM active layer devices as a result of reduced changes to the active layer morphology. Devices combining a Ca/Ag cathode and P3HT:ICBA active layer demonstrated ∼50% performance restoration over several degradation/regeneration cycles.« less

Semitransparent Flexible Organic Solar Cells Employing Doped-Graphene Layers as Anode and Cathode Electrodes.

PubMed

Shin, Dong Hee; Jang, Chan Wook; Lee, Ha Seung; Seo, Sang Woo; Choi, Suk-Ho

2018-01-31

Semitransparent flexible photovoltaic cells are advantageous for effective use of solar energy in many areas such as building-integrated solar-power generation and portable photovoltaic chargers. We report semitransparent and flexible organic solar cells (FOSCs) with high aperture, composed of doped graphene layers, ZnO, P3HT:PCBM, and PEDOT:PSS as anode/cathode transparent conductive electrodes (TCEs), electron transport layer, photoactive layer, and hole transport layer, respectively, fabricated based on simple solution processing. The FOSCs do not only harvest solar energy from ultraviolet-visible region but are also less sensitive to near-infrared photons, indicating semitransparency. For the anode/cathode TCEs, graphene is doped with bis(trifluoromethanesulfonyl)-amide or triethylene tetramine, respectively. Power conversion efficiency (PCE) of 3.12% is obtained from the fundamental FOSC structure, and the PCE is further enhanced to 4.23% by adding an Al reflective mirror on the top or bottom side of the FOSCs. The FOSCs also exhibit remarkable mechanical flexibilities through bending tests for various curvature radii.

Green fabrication of composite cathode with attractive performance for solid oxide fuel cells through facile inkjet printing

NASA Astrophysics Data System (ADS)

Li, Chao; Chen, Huili; Shi, Huangang; Tade, Moses O.; Shao, Zongping

2015-01-01

The inkjet printing technique has numerous advantages and is attractive in solid oxide fuel cell (SOFC) fabrication, especially for the dense thin electrolyte layer because of its ultrafine powder size. In this study, we exploited the technique for the fabrication of a porous SDC/SSC composite cathode layer using environmentally friendly water-based ink. An optimized powder synthesis method was applied to the preparation of the well-dispersed suspension. In view of the easy sintering of the thin film layer prepared by inkjet printing, 10 wt.% pore former was introduced to the ink. The results indicate that the cell with the inkjet printing cathode layer exhibits a fantastic electrochemical performance, with a PPD as high as 940 mW cm-2 at 750 °C, which is comparable to that of a cell prepared using the conventional wet powder spraying method, suggesting a promising application of inkjet printing on electrode layer fabrication.

Stable interstitial layer to alleviate fatigue fracture of high nickel cathode for lithium-ion batteries

NASA Astrophysics Data System (ADS)

Yang, Chengkai; Shao, Ruiwen; Mi, Yingying; Shen, Lanyao; Zhao, Binglu; wang, Qian; Wu, Kai; Lui, Wen; Gao, Peng; Zhou, Henghui

2018-02-01

High nickel cathodes can deliver higher capacity with lower cost than conventional LiCoO2, however, the irreversible structural and morphology degradation with long-term cycling hinder their further application. In this paper, LiNi0.815Co0.15Al0.035O2 agglomerates are treated by LiNi0.333Co0.333Mn0.333O2 coating to get a stable interstitial layer without capacity loss. The interstitial layer is about 10 nm in thickness and has a layered (R-3m) structure, which can improve the chemical and mechanical stability of cathode materials with capacity retention of 88.5% after 200 cycles. The structural analysis and in-situ compression test proves that the morphology degradation is a fatigue process within long-term electrochemical reaction, and the coated sample has an excellent elastic recovery capacity thus leading to long cycle life.

Serially connected solid oxide fuel cells having monolithic cores

DOEpatents

Herceg, Joseph E.

1987-01-01

A solid oxide fuel cell for electrochemically combining fuel and oxidant for generating galvanic output, wherein the cell core has an array of cell segments electrically serially connected in the flow direction, each segment consisting of electrolyte walls and interconnect that are substantially devoid of any composite inert materials for support. Instead, the core is monolithic, where each electrolyte wall consists of thin layers of cathode and anode materials sandwiching a thin layer of electrolyte material therebetween. Means direct the fuel to the anode-exposed core passageways and means direct the oxidant to the cathode-exposed core passageways; and means also direct the galvanic output to an exterior circuit. Each layer of the electrolyte composite materials is of the order of 0.002-0.01 cm thick; and each layer of the cathode and anode materials is of the order of 0.002-0.05 cm thick. Between 2 and 50 cell segments may be connected in series.

Effects of CO{sub 2} activation on electrochemical performance of microporous carbons derived from poly(vinylidene fluoride)

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

Lee, Seul-Yi; Park, Soo-Jin, E-mail: sjpark@inha.ac.kr

In this work, we have prepared microporous carbons (MPCs) derived from poly(vinylidene fluoride) (PVDF), and the physical activation of MPCs using CO{sub 2} gas is subsequently carried out with various activation temperatures to investigate the electrochemical performance. PVDF is successfully converted into MPCs with a high specific surface area and well-developed micropores. After CO{sub 2} activation, the specific surface areas of MPCs (CA-MPCs) are enhanced by 12% compared with non-activated MPCs. With increasing activation temperature, the micropore size distributions of A-MPCs also become narrower and shift to larger pore size. It is also confirmed that the CO{sub 2} activation hadmore » developed the micropores and introduced the oxygen-containing groups to MPCs′ surfaces. From the results, the specific capacitances of the electrodes in electric double layer capacitors (EDLCs) based on CA-MPCs are distinctly improved through CO{sub 2} activation. The highest specific capacitance of the A-MPCs activated at 700 °C is about 125 F/g, an enhancement of 74% in comparison with NA-MPCs, at a discharge current of 2 A/g in a 6 M KOH electrolyte solution. We also found that micropore size of 0.67 nm has a specific impact on the capacitance behaviors, besides the specific surface area of the electrode samples. - Graphical abstract: The A-MPC samples with high specific surface area (ranging from 1030 to 1082 m{sup 2}/g), corresponding to micropore sizes of 0.67 and 0.72 nm, and with the amount of oxygen-containing groups ranging from 3.2% to 4.4% have been evaluated as electrodes for EDLC applications. . Display Omitted - Highlights: • Microporous carbons (MPCs) were synthesized without activation process. • Next, we carried out the CO{sub 2} activation of MPCs with activation temperatures. • It had developed the micropores and introduced the O-functional groups to MPCs. • The highest specific capacitance: 125 F/g, an increase of 74% compared to MPCs.« less

Nanoscale surface modification of Li-rich layered oxides for high-capacity cathodes in Li-ion batteries

NASA Astrophysics Data System (ADS)

Lan, Xiwei; Xin, Yue; Wang, Libin; Hu, Xianluo

2018-03-01

Li-rich layered oxides (LLOs) have been developed as a high-capacity cathode material for Li-ion batteries, but the structural complexity and unique initial charging behavior lead to several problems including large initial capacity loss, capacity and voltage fading, poor cyclability, and inferior rate capability. Since the surface conditions are critical to electrochemical performance and the drawbacks, nanoscale surface modification for improving LLO's properties is a general strategy. This review mainly summarizes the surface modification of LLOs and classifies them into three types of surface pre-treatment, surface gradient doping, and surface coating. Surface pre-treatment usually introduces removal of Li2O for lower irreversible capacity while surface doping is aimed to stabilize the structure during electrochemical cycling. Surface coating layers with different properties, protective layers to suppress the interface side reaction, coating layers related to structural transformation, and electronic/ionic conductive layers for better rate capability, can avoid the shortcomings of LLOs. In addition to surface modification for performance enhancement, other strategies can also be investigated to achieve high-performance LLO-based cathode materials.

Prospects for spinel-stabilized, high-capacity lithium-ion battery cathodes

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

Croy, Jason R.; Park, Joong Sun; Shin, Youngho

Herein we report early results on efforts to optimize the electrochemical performance of a cathode composed of a lithium- and manganese-rich “layered-layered-spinel” material for lithium-ion battery applications. Pre-pilot scale synthesis leads to improved particle properties compared with lab-scale efforts, resulting in high capacities (≳200 mAh/g) and good energy densities (>700 Wh/kg) in tests with lithium-ion cells. Subsequent surface modifications give further improvements in rate capabilities and high-voltage stability. These results bode well for advances in the performance of this class of lithium- and manganese-rich cathode materials.

Prospects for spinel-stabilized, high-capacity lithium-ion battery cathodes

DOE PAGES

Croy, Jason R.; Park, Joong Sun; Shin, Youngho; ...

2016-10-13

Herein we report early results on efforts to optimize the electrochemical performance of a cathode composed of a lithium- and manganese-rich “layered-layered-spinel” material for lithium-ion battery applications. Pre-pilot scale synthesis leads to improved particle properties compared with lab-scale efforts, resulting in high capacities (≳200 mAh/g) and good energy densities (>700 Wh/kg) in tests with lithium-ion cells. Subsequent surface modifications give further improvements in rate capabilities and high-voltage stability. These results bode well for advances in the performance of this class of lithium- and manganese-rich cathode materials.

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).

Novel approaches for fabrication of thin film layers for solid oxide electrolyte fuel cells

NASA Technical Reports Server (NTRS)

Murugesamoorthi, K. A.; Srinivasan, S.; Cocke, D. L.; Appleby, A. J.

1990-01-01

The main objectives of the SOFC (solid oxide fuel cell) project are to (1) identify viable and cost-effective techniques to prepare cell components for stable MSOFCs (monolithic SOFCs); (2) fabricate half and single cells; and (3) evaluate their performances. The approach used to fabricate stable MSOFCs is as follows: (1) the electrolyte layer is prepared in the form of a honeycomb structure by alloy oxidation and other cell components are deposited on it; (2) the electrolyte and anode layers are deposited on the cathode layer, which has a porous, honeycomb structure; and (3) the electrolyte and cathode layers are deposited on the anode layer. The current status of the project is reported.

Air stable organic-inorganic nanoparticles hybrid solar cells

DOEpatents

Qian, Lei; Yang, Jihua; Xue, Jiangeng; Holloway, Paul H.

2015-09-29

A solar cell includes a low work function cathode, an active layer of an organic-inorganic nanoparticle composite, a ZnO nanoparticle layer situated between and physically contacting the cathode and active layers; and a transparent high work function anode that is a bilayer electrode. The inclusion of the ZnO nanoparticle layer results in a solar cell displaying a conversion efficiency increase and reduces the device degradation rate. Embodiments of the invention are directed to novel ZnO nanoparticles that are advantageous for use as the ZnO nanoparticle layers of the novel solar cells and a method to prepare the ZnO nanoparticles.

Temperature management of photo cathodes at MAMI and MESA

NASA Astrophysics Data System (ADS)

Aulenbacher, K.; Friederich, S.; Tyukin, V.

2018-05-01

Production of highly polarized electron current is limited by cathode heating which leads to the destruction of the active layer. For the new electron accelerator MESA a more efficient solution for the cathode cooling problem is required, with the goal to achieve acceptable temperatures at an incident power of about 1 Watt. The current status of temperature management of photo cathodes at MAMI and MESA is presented.

Probing the Complexities of Structural Changes in Layered Oxide Cathode Materials for Li-Ion Batteries during Fast Charge-Discharge Cycling and Heating.

PubMed

Hu, Enyuan; Wang, Xuelong; Yu, Xiqian; Yang, Xiao-Qing

2018-02-20

The rechargeable lithium-ion battery (LIB) is the most promising energy storage system to power electric vehicles with high energy density and long cycling life. However, in order to meet customers' demands for fast charging, the power performances of current LIBs need to be improved. From the cathode aspect, layer-structured cathode materials are widely used in today's market and will continue to play important roles in the near future. The high rate capability of layered cathode materials during charging and discharging is critical to the power performance of the whole cell and the thermal stability is closely related to the safety issues. Therefore, the in-depth understanding of structural changes of layered cathode materials during high rate charging/discharging and the thermal stability during heating are essential in developing new materials and improving current materials. Since structural changes take place from the atomic level to the whole electrode level, combination of characterization techniques covering multilength scales is quite important. In many cases, this means using comprehensive tools involving diffraction, spectroscopy, and imaging to differentiate the surface from the bulk and to obtain structural/chemical information with different levels of spatial resolution. For example, hard X-ray spectroscopy can yield the bulk information and soft X-ray spectroscopy can give the surface information; X-ray based imaging techniques can obtain spatial resolution of tens of nanometers, and electron-based microcopy can go to angstroms. In addition to challenges associated with different spatial resolution, the dynamic nature of structural changes during high rate cycling and heating requires characterization tools to have the capability of collecting high quality data in a time-resolved fashion. Thanks to the advancement in synchrotron based techniques and high-resolution electron microscopy, high temporal and spatial resolutions can now be achieved. In this Account, we focus on the recent works studying kinetic and thermal properties of layer-structured cathode materials, especially the structural changes during high rate cycling and the thermal stability during heating. Advanced characterization techniques relating to the rate capability and thermal stability will be introduced. The different structure evolution behavior of cathode materials cycled at high rate will be compared with that cycled at low rate. Different response of individual transition metals and the inhomogeneity in chemical distribution will be discussed. For the thermal stability, the relationship between structural changes and oxygen release will be emphatically pointed out. In all these studies being reviewed, advanced characterization techniques are critically applied to reveal complexities at multiscale in layer-structured cathode materials.

A multi-scaled hybrid orthopedic implant: bone ECM-shaped Sr-HA nanofibers on the microporous walls of a macroporous titanium scaffold.

PubMed

Han, Yong; Zhou, Jianhong; Zhang, Lan; Xu, Kewei

2011-07-08

We report here, for the first time, a novel multi-scaled hybrid orthopedic implant material consisting of a macroporous Ti scaffold, whose macropores' walls have a microporous titania layer which is fully covered with nanofibers of Sr-doped hydroxyapatite (Sr-HA). The microporous titania layer is formed on and within the Ti scaffold by micro-arc oxidation, which firmly binds to the Ti substrate and contains Ca2+, Sr2+ and PO4(3-) ions. It is then hydrothermally treated to form Sr-HA nanofibers. During the hydrothermal treatment, Sr-HA nanoprisms nucleate from Ca0.5Sr0.5TiO3 pre-formed on the TiO2 and grow in length to nanofibers at the expense of Ca2+, Sr2+ and PO4(3-) ions that migrate from the TiO2. These Sr-HA nanofibers construct a network structure similar to the hierarchical organization of bone extracellular matrix (ECM), and the resulting nanofibrous surface displays a firm adhesion to substrate, superhydrophilicity and apatite-inducing ability. The induced apatite prefers to nucleate on the basal-faceted surfaces of Sr-HA nanofibers. The nanofiber-walled scaffold has a great potential for load-bearing orthotopic use.

A multi-scaled hybrid orthopedic implant: bone ECM-shaped Sr-HA nanofibers on the microporous walls of a macroporous titanium scaffold

NASA Astrophysics Data System (ADS)

Han, Yong; Zhou, Jianhong; Zhang, Lan; Xu, Kewei

2011-07-01

We report here, for the first time, a novel multi-scaled hybrid orthopedic implant material consisting of a macroporous Ti scaffold, whose macropores' walls have a microporous titania layer which is fully covered with nanofibers of Sr-doped hydroxyapatite (Sr-HA). The microporous titania layer is formed on and within the Ti scaffold by micro-arc oxidation, which firmly binds to the Ti substrate and contains Ca2 + , Sr2 + and PO43 - ions. It is then hydrothermally treated to form Sr-HA nanofibers. During the hydrothermal treatment, Sr-HA nanoprisms nucleate from Ca0.5Sr0.5TiO3 pre-formed on the TiO2 and grow in length to nanofibers at the expense of Ca2 + , Sr2 + and PO43 - ions that migrate from the TiO2. These Sr-HA nanofibers construct a network structure similar to the hierarchical organization of bone extracellular matrix (ECM), and the resulting nanofibrous surface displays a firm adhesion to substrate, superhydrophilicity and apatite-inducing ability. The induced apatite prefers to nucleate on the basal-faceted surfaces of Sr-HA nanofibers. The nanofiber-walled scaffold has a great potential for load-bearing orthotopic use.

Methanol-tolerant cathode catalyst composite for direct methanol fuel cells

DOEpatents

Zhu, Yimin; Zelenay, Piotr

2006-09-05

A direct methanol fuel cell (DMFC) having a methanol fuel supply, oxidant supply, and its membrane electrode assembly (MEA) formed of an anode electrode and a cathode electrode with a membrane therebetween, a methanol oxidation catalyst adjacent the anode electrode and the membrane, an oxidant reduction catalyst adjacent the cathode electrode and the membrane, comprises an oxidant reduction catalyst layer of Pt.sub.3Cr/C so that oxidation at the cathode of methanol that crosses from the anode through the membrane to the cathode is reduced with a concomitant increase of net electrical potential at the cathode electrode.

Methanol-Tolerant Cathode Catalyst Composite For Direct Methanol Fuel Cells

DOEpatents

Zhu, Yimin; Zelenay, Piotr

2006-03-21

A direct methanol fuel cell (DMFC) having a methanol fuel supply, oxidant supply, and its membrane electrode assembly (MEA) formed of an anode electrode and a cathode electrode with a membrane therebetween, a methanol oxidation catalyst adjacent the anode electrode and the membrane, an oxidant reduction catalyst adjacent the cathode electrode and the membrane, comprises an oxidant reduction catalyst layer of a platinum-chromium alloy so that oxidation at the cathode of methanol that crosses from the anode through the membrane to the cathode is reduced with a concomitant increase of net electrical potential at the cathode electrode.

Development and Characterization of Gas Diffusion Layer Using Carbon Slurry Dispersed by Ammonium Lauryl Sulfate for Proton Exchange Member Fuel Cells

NASA Astrophysics Data System (ADS)

Villacorta, Rashida

Gas diffusion layers (GDLs) are a critical and essential part of proton exchange membrane fuel cells (PEMFCs). They carry out various important functions such as transportation of reactants to and from the reaction sites. The material properties and structural characteristics of the substrate and the microporous layer strongly influence fuel cell performance. The microporous layer of the GDLs was fabricated with the carbon slurry dispersed in water containing ammonium lauryl sulfate (ALS) using the wire rod coating method. GDLs were fabricated with different materials to compose the microporous layer and evaluated the effects on PEMFC power output performance. The consistency of the carbon slurry was achieved by adding 25 wt. % of PTFE, a binding agent with a 75:25 ratio of carbon (Pureblack and vapor grown carbon fiber). The GDLs were investigated in PEMFC under various relative humidity (RH) conditions using H2/O2 and H2/Air. GDLs were also fabricated with the carbon slurry dispersed in water containing sodium dodecyl sulfate (SDS) and multiwalled carbon nanotubes (MWCNTs) with isopropyl alcohol (IPA) based for fuel cell performance comparison. MWCNTs and SDS exhibits the highest performance at 60% and 70% RH with a peak power density of 1100 mW.cm-2 and 850 mW.cm-2 using air and oxygen as an oxidant. This means that the gas diffusion characteristics of these two samples were optimum at 60 and 70 % RH with high limiting current density range. It was also found that the composition of the carbon slurry, specifically ALS concentration has the highest peak power density of 1300 and 500mW.cm-2 for both H2/O 2 and H2/Air at 100% RH. However, SDS and MWCNTs demonstrates the lowest power density using air and oxygen as an oxidants at 100% RH.

Gas diffusion layers coated with a microporous layer containing hydrophilic carbon nanotubes for performance enhancement of polymer electrolyte fuel cells under both low and high humidity conditions

NASA Astrophysics Data System (ADS)

Kitahara, Tatsumi; Nakajima, Hironori; Okamura, Kosuke

2015-06-01

Gas diffusion layers (GDLs) coated with a hydrophobic microporous layer (MPL) composed of carbon black and polytetrafluoroethylene (PTFE) have been commonly used to improve the water management characteristics of polymer electrolyte fuel cells (PEFCs). However, the hydrophobic MPL coated GDL designed to prevent dehydration of the membrane under low humidity conditions is generally inferior at reducing flooding under high humidity conditions. It is therefore important to develop a robust MPL coated GDL that can enhance the PEFC performance regardless of the humidity conditions. In the present study, a GDL coated with an MPL containing hydrophilic carbon nanotubes (CNTs) was developed. The less hydrophobic pores incorporating CNTs are effective at conserving the membrane humidity under low humidity conditions. The MPL with CNTs is also effective at expelling excess water from the catalyst layer while maintaining oxygen flow pathways from the GDL substrate, allowing the mean flow pore diameter to be decreased to 2 μm without reducing the ability of the MPL to prevent flooding under high humidity conditions. An MPL coated GDL with a CNT content of 4 mass% exhibits significantly higher performance under both low and high humidity conditions than a hydrophobic MPL coated GDL.

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

Advanced materials and design for low temperature SOFCs

DOEpatents

Wachsman, Eric D.; Yoon, Heesung; Lee, Kang Taek; Camaratta, Matthew; Ahn, Jin Soo

2016-05-17

Embodiments of the invention are directed to SOFC with a multilayer structure comprising a porous ceramic cathode, optionally a cathodic triple phase boundary layer, a bilayer electrolyte comprising a cerium oxide comprising layer and a bismuth oxide comprising layer, an anion functional layer, and a porous ceramic anode with electrical interconnects, wherein the SOFC displays a very high power density at temperatures below 700.degree. C. with hydrogen or hydrocarbon fuels. The low temperature conversion of chemical energy to electrical energy allows the fabrication of the fuel cells using stainless steel or other metal alloys rather than ceramic conductive oxides as the interconnects.

Synergistic effects of dendritic cell targeting and laser-microporation on enhancing epicutaneous skin vaccination efficacy.

PubMed

Machado, Yoan; Duinkerken, Sanne; Hoepflinger, Veronika; Mayr, Melissa; Korotchenko, Evgeniia; Kurtaj, Almedina; Pablos, Isabel; Steiner, Markus; Stoecklinger, Angelika; Lübbers, Joyce; Schmid, Maximillian; Ritter, Uwe; Scheiblhofer, Sandra; Ablinger, Michael; Wally, Verena; Hochmann, Sarah; Raninger, Anna M; Strunk, Dirk; van Kooyk, Yvette; Thalhamer, Josef; Weiss, Richard

2017-11-28

Due to its unique immunological properties, the skin is an attractive target tissue for allergen-specific immunotherapy. In our current work, we combined a dendritic cell targeting approach with epicutaneous immunization using an ablative fractional laser to generate defined micropores in the upper layers of the skin. By coupling the major birch pollen allergen Bet v 1 to mannan from S. cerevisiae via mild periodate oxidation we generated hypoallergenic Bet-mannan neoglycoconjugates, which efficiently targeted CD14 + dendritic cells and Langerhans cells in human skin explants. Mannan conjugation resulted in sustained release from the skin and retention in secondary lymphoid organs, whereas unconjugated antigen showed fast renal clearance. In a mouse model, Bet-mannan neoglycoconjugates applied via laser-microporated skin synergistically elicited potent humoral and cellular immune responses, superior to intradermal injection. The induced antibody responses displayed IgE-blocking capacity, highlighting the therapeutic potential of the approach. Moreover, application via micropores, but not by intradermal injection, resulted in a mixed TH1/TH17-biased immune response. Our data clearly show that applying mannan-neoglycoconjugates to an organ rich in dendritic cells using laser-microporation is superior to intradermal injection. Due to their low IgE binding capacity and biodegradability, mannan neoglycoconjugates therefore represent an attractive formulation for allergen-specific epicutaneous immunotherapy. Copyright © 2017 Elsevier B.V. All rights reserved.

Organic photovoltaic cell incorporating electron conducting exciton blocking layers

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

Forrest, Stephen R.; Lassiter, Brian E.

2014-08-26

The present disclosure relates to photosensitive optoelectronic devices including a compound blocking layer located between an acceptor material and a cathode, the compound blocking layer including: at least one electron conducting material, and at least one wide-gap electron conducting exciton blocking layer. For example, 3,4,9,10 perylenetetracarboxylic bisbenzimidazole (PTCBI) and 1,4,5,8-napthalene-tetracarboxylic-dianhydride (NTCDA) function as electron conducting and exciton blocking layers when interposed between the acceptor layer and cathode. Both materials serve as efficient electron conductors, leading to a fill factor as high as 0.70. By using an NTCDA/PTCBI compound blocking layer structure increased power conversion efficiency is achieved, compared to anmore » analogous device using a conventional blocking layers shown to conduct electrons via damage-induced midgap states.« less

Improved Cathode Structure for a Direct Methanol Fuel Cell

NASA Technical Reports Server (NTRS)

Valdez, Thomas; Narayanan, Sekharipuram

2005-01-01

An improved cathode structure on a membrane/electrode assembly has been developed for a direct methanol fuel cell, in a continuing effort to realize practical power systems containing such fuel cells. This cathode structure is intended particularly to afford better cell performance at a low airflow rate. A membrane/electrode assembly of the type for which the improved cathode structure was developed (see Figure 1) is fabricated in a process that includes brush painting and spray coating of catalyst layers onto a polymer-electrolyte membrane and onto gas-diffusion backings that also act as current collectors. The aforementioned layers are then dried and hot-pressed together. When completed, the membrane/electrode assembly contains (1) an anode containing a fine metal black of Pt/Ru alloy, (2) a membrane made of Nafion 117 or equivalent (a perfluorosulfonic acid-based hydrophilic, proton-conducting ion-exchange polymer), (3) a cathode structure (in the present case, the improved cathode structure described below), and (4) the electrically conductive gas-diffusion backing layers, which are made of Toray 060(TradeMark)(or equivalent) carbon paper containing between 5 and 6 weight percent of poly(tetrafluoroethylene). The need for an improved cathode structure arises for the following reasons: In the design and operation of a fuel-cell power system, the airflow rate is a critical parameter that determines the overall efficiency, cell voltage, and power density. It is desirable to operate at a low airflow rate in order to obtain thermal and water balance and to minimize the size and mass of the system. The performances of membrane/electrode assemblies of prior design are limited at low airflow rates. Methanol crossover increases the required airflow rate. Hence, one way to reduce the required airflow rate is to reduce the effect of methanol crossover. Improvement of the cathode structure - in particular, addition of hydrophobic particles to the cathode - has been demonstrated to mitigate the effects of crossover and decrease the airflow required.

Micro hollow cathode discharge jets utilizing solid fuel

NASA Astrophysics Data System (ADS)

Nikic, Dejan

2017-10-01

Micro hollow cathode discharge devices with a solid fuel layer embedded between the electrodes have demonstrated an enhanced jetting process. Outlined are series of experiments in various pressure and gas conditions as well as vacuum. Examples of use of these devices in series and parallel configurations are presented. Evidence of utilization of solid fuel is obtained through optical spectroscopy and analysis of remaining fuel layer.

Tetrakis(1-imidazolyl) borate (BIM4) based zwitterionic and related molecules used as electron injection layers

DOEpatents

Li, Huaping; Xu, Yunhua; Bazan, Guillermo C

2013-02-05

Tetrakis(1-imidazolyl)borate (BIm4) based zwitterionic and/or related molecules for the fabrication of PLEDs is provided. Device performances with these materials approaches that of devices with Ba/Al cathodes for which the cathode contact is ohmic. Methods of producing such materials, and electron injection layers and devices containing these materials are also provided.

An Integrated, Layered-Spinel Composite Cathode for Energy Storage Applications

NASA Technical Reports Server (NTRS)

Hagh, Nader; Skandan, Ganesh

2012-01-01

At low operating temperatures, commercially available electrode materials for lithium-ion batteries do not fully meet the energy and power requirements for NASA fs exploration activities. The composite cathode under development is projected to provide the required energy and power densities at low temperatures and its usage will considerably reduce the overall volume and weight of the battery pack. The newly developed composite electrode material can provide superior electrochemical performance relative to a commercially available lithium cobalt system. One advantage of using a composite cathode is its higher energy density, which can lead to smaller and lighter battery packs. In the current program, different series of layered-spinel composite materials with at least two different systems in an integrated structure were synthesized, and the volumetric and gravimetric energy densities were evaluated. In an integrated network of a composite electrode, the effect of the combined structures is to enhance the capacity and power capabilities of the material to levels greater than what is possible in current state-of-the-art cathode systems. The main objective of the current program is to implement a novel cathode material that meets NASA fs low temperature energy density requirements. An important feature of the composite cathode is that it has at least two components (e.g., layered and spinel) that are structurally integrated. The layered material by itself is electrochemically inactive; however, upon structural integration with a spinel material, the layered material can be electrochemically activated, thereby delivering a large amount of energy with stable cycling. A key aspect of the innovation has been the development of a scalable process to produce submicronand micron-scale particles of these composite materials. An additional advantage of using such a composite electrode material is its low irreversible loss (.5%), which is primarily due to the unique activation of the composite. High columbic efficiency (greater than 99%) upon cycling may indicate the formation of a stable SEI (solid-electrolyte interface) layer, which can contribute to long cycle life. The innovation in the current program, when further developed, will enable the system to maintain high energy and power densities at low temperatures, improve efficiency, and further stabilize and enhance the safety of the cell.

Efficient polymer light-emitting diode with air-stable aluminum cathode

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

Abbaszadeh, D.; Dutch Polymer Institute, P.O. Box 902, 5600 AX Eindhoven; Wetzelaer, G. A. H.

2016-03-07

The fast degradation of polymer light-emitting diodes (PLEDs) in ambient conditions is primarily due to the oxidation of highly reactive metals, such as barium or calcium, which are used as cathode materials. Here, we report the fabrication of PLEDs using an air-stable partially oxidized aluminum (AlO{sub x}) cathode. Usually, the high work function of aluminum (4.2 eV) imposes a high barrier for injecting electrons into the lowest unoccupied molecular orbital (LUMO) of the emissive polymer (2.9 eV below the vacuum level). By partially oxidizing aluminum, its work function is decreased, but not sufficiently low for efficient electron injection. Efficient injection is obtainedmore » by inserting an electron transport layer of poly[(9,9-di-n-octylfluorenyl-2,7-diyl)-alt-(benzo[2,1,3] thiadiazol-4,8-diyl)] (F8BT), which has its LUMO at 3.3 eV below vacuum, between the AlO{sub x} cathode and the emissive polymer. The intermediate F8BT layer not only serves as a hole-blocking layer but also provides an energetic staircase for electron injection from AlO{sub x} into the emissive layer. PLEDs with an AlO{sub x} cathode and F8BT interlayer exhibit a doubling of the efficiency as compared to conventional Ba/Al PLEDs, and still operate even after being kept in ambient atmosphere for one month without encapsulation.« less

Non-conventional Pt-Cu alloy/carbon paper electrochemical catalyst formed by electrodeposition using hydrogen bubble as template

NASA Astrophysics Data System (ADS)

Kim, Youngkwang; Lee, Hyunjoon; Lim, Taeho; Kim, Hyun-Jong; Kwon, Oh Joong

2017-10-01

With emerging stability issues in fuel cell technology, a non-conventional catalyst not supported on carbon materials has been highlighted because it can avoid negative influences of carbon support materials on the stability, such as carbon corrosion. The nanostructured thin film catalyst is representative of non-conventional catalysts, which shows improved stability, enhanced mass specific activity, and fast mass transfer at high current densities. However, the nanostructured thin film catalyst usually requires multi-step processes for fabrication, making its mass production complex and irreproducible. We introduce a Pt-Cu alloy nanostructured thin film catalyst, which can be simply prepared by electrodeposition. By using hydrogen bubbles as a template, a three-dimensional free-standing foam of Cu was electrodeposited directly on the micro-porous layer/carbon paper and it was then displaced with Pt by simple immersion. The structure characterization revealed that a porous thin Pt-Cu alloy catalyst layer was successfully formed on the micro-porous layer/carbon paper. The synthesized Pt-Cu alloy catalyst exhibited superior durability compared to a conventional Pt/C in single cell test.

A forward analysis on the applicability of tracer breakthrough profiles in revealing the pore structure of tight gas sandstone and carbonate rocks

NASA Astrophysics Data System (ADS)

Mehmani, Ayaz; Mehmani, Yashar; Prodanović, Maša.; Balhoff, Matthew

2015-06-01

We explore tracer breakthrough profiles (TBP) as a macroscopic property to infer the pore-space topology of tight gas sandstone and carbonate rocks at the core scale. The following features were modeled via three-dimensional multiscale networks: microporosity within dissolved grains and pore-filling clay, cementation in the absence and presence of microporosity (each classified into uniform, pore-preferred, and throat-preferred modes), layering, vug, and microcrack inclusion. A priori knowledge of the extent and location of each process was assumed to be known. With the exception of an equal importance of macropores and pore-filling micropores, TBPs show little sensitivity to the fraction of micropores present. In general, significant sensitivity of the TBPs was observed for uniform and throat-preferred cementation. Layering parallel to the fluid flow direction had a considerable impact on TBPs whereas layering perpendicular to flow did not. Microcrack orientations seemed of minor importance in affecting TBPs. This article was corrected on 9 Nov 2015. See the end of the full text for details.

A Solvent-Free Surface Suspension Melt Technique for Making Biodegradable PCL Membrane Scaffolds for Tissue Engineering Applications.

PubMed

Suntornnond, Ratima; An, Jia; Tijore, Ajay; Leong, Kah Fai; Chua, Chee Kai; Tan, Lay Poh

2016-03-21

In tissue engineering, there is limited availability of a simple, fast and solvent-free process for fabricating micro-porous thin membrane scaffolds. This paper presents the first report of a novel surface suspension melt technique to fabricate a micro-porous thin membrane scaffolds without using any organic solvent. Briefly, a layer of polycaprolactone (PCL) particles is directly spread on top of water in the form of a suspension. After that, with the use of heat, the powder layer is transformed into a melted layer, and following cooling, a thin membrane is obtained. Two different sizes of PCL powder particles (100 µm and 500 µm) are used. Results show that membranes made from 100 µm powders have lower thickness, smaller pore size, smoother surface, higher value of stiffness but lower ultimate tensile load compared to membranes made from 500 µm powder. C2C12 cell culture results indicate that the membrane supports cell growth and differentiation. Thus, this novel membrane generation method holds great promise for tissue engineering.

A Polysulfide-Infiltrated Carbon Cloth Cathode for High-Performance Flexible Lithium–Sulfur Batteries

PubMed Central

Song, Ji-Yoon; Lee, Hyeon-Haeng; Hong, Won Gi; Huh, Yun Suk; Lee, Yun Sung; Kim, Hae Jin; Jun, Young-Si

2018-01-01

For practical application of lithium–sulfur batteries (LSBs), it is crucial to develop sulfur cathodes with high areal capacity and cycle stability in a simple and inexpensive manner. In this study, a carbon cloth infiltrated with a sulfur-containing electrolyte solution (CC-S) was utilized as an additive-free, flexible, high-sulfur-loading cathode. A freestanding carbon cloth performed double duty as a current collector and a sulfur-supporting/trapping material. The active material in the form of Li2S6 dissolved in a 1 M LiTFSI-DOL/DME solution was simply infiltrated into the carbon cloth (CC) during cell fabrication, and its optimal loading amount was found to be in a range between 2 and 10 mg/cm2 via electrochemical characterization. It was found that the interwoven carbon microfibers retained structural integrity against volume expansion/contraction and that the embedded uniform micropores enabled a high loading and an efficient trapping of sulfur species during cycling. The LSB coin cell employing the CC-S electrode with an areal sulfur loading of 6 mg/cm2 exhibited a high areal capacity of 4.3 and 3.2 mAh/cm2 at C/10 for 145 cycles and C/3 for 200 cycles, respectively, with minor capacity loss (<0.03%/cycle). More importantly, such high performance could also be realized in flexible pouch cells with dimensions of 2 cm × 6 cm before and after 300 bending cycles. Simple and inexpensive preparation of sulfur cathodes using CC-S electrodes, therefore, has great potential for the manufacture of high-performance flexible LSBs. PMID:29414863

A Polysulfide-Infiltrated Carbon Cloth Cathode for High-Performance Flexible Lithium-Sulfur Batteries.

PubMed

Song, Ji-Yoon; Lee, Hyeon-Haeng; Hong, Won Gi; Huh, Yun Suk; Lee, Yun Sung; Kim, Hae Jin; Jun, Young-Si

2018-02-07

For practical application of lithium-sulfur batteries (LSBs), it is crucial to develop sulfur cathodes with high areal capacity and cycle stability in a simple and inexpensive manner. In this study, a carbon cloth infiltrated with a sulfur-containing electrolyte solution (CC-S) was utilized as an additive-free, flexible, high-sulfur-loading cathode. A freestanding carbon cloth performed double duty as a current collector and a sulfur-supporting/trapping material. The active material in the form of Li₂S₆ dissolved in a 1 M LiTFSI-DOL/DME solution was simply infiltrated into the carbon cloth (CC) during cell fabrication, and its optimal loading amount was found to be in a range between 2 and 10 mg/cm² via electrochemical characterization. It was found that the interwoven carbon microfibers retained structural integrity against volume expansion/contraction and that the embedded uniform micropores enabled a high loading and an efficient trapping of sulfur species during cycling. The LSB coin cell employing the CC-S electrode with an areal sulfur loading of 6 mg/cm² exhibited a high areal capacity of 4.3 and 3.2 mAh/cm² at C/10 for 145 cycles and C/3 for 200 cycles, respectively, with minor capacity loss (<0.03%/cycle). More importantly, such high performance could also be realized in flexible pouch cells with dimensions of 2 cm × 6 cm before and after 300 bending cycles. Simple and inexpensive preparation of sulfur cathodes using CC-S electrodes, therefore, has great potential for the manufacture of high-performance flexible LSBs.

Fabrication of high-transmission microporous membranes by proton beam writing-based molding technique

NASA Astrophysics Data System (ADS)

Wang, Liping; Meyer, Clemens; Guibert, Edouard; Homsy, Alexandra; Whitlow, Harry J.

2017-08-01

Porous membranes are widely used as filters in a broad range of micro and nanofluidic applications, e.g. organelle sorters, permeable cell growth substrates, and plasma filtration. Conventional silicon fabrication approaches are not suitable for microporous membranes due to the low mechanical stability of thin film substrates. Other techniques like ion track etching are limited to the production of randomly distributed and randomly orientated pores with non-uniform pore sizes. In this project, we developed a procedure for fabricating high-transmission microporous membranes by proton beam writing (PBW) with a combination of spin-casting and soft lithography. In this approach, focused 2 MeV protons were used to lithographically write patterns consisting of hexagonal arrays of high-density pillars of few μm size in a SU-8 layer coated on a silicon wafer. After development, the pillars were conformably coated with a thin film of poly-para-xylylene (Parylene)-C release agent and spin-coated with polydimethylsiloxane (PDMS). To facilitate demolding, a special technique based on the use of a laser-cut sealing tape ring was developed. This method facilitated the successful delamination of 20-μm thick PDMS membrane with high-density micropores from the mold without rupture or damage.

Plasma Emission Characteristics from a High Current Hollow Cathode in an Ion Thruster Discharge Chamber

NASA Technical Reports Server (NTRS)

Foster, John E.; Patterson, Michael J.

2002-01-01

The presence of energetic ions produced by a hollow cathodes operating at high emission currents (greater than 5A) has been documented in the literature. In order to further elucidate these findings, an investigation of a high current cathode operating in an ion thruster discharge chamber has been undertaken. Using Langmuir probes, a low energy charged particle analyzer and emission spectroscopy, the behavior of the near-cathode plasma and the emitted ion energy distribution was characterized. The presence of energetic ions was confirmed. It was observed that these ions had energies in excess of the discharge voltage and thus cannot be simply explained by ions falling out of plasma through a potential difference of this order. Additionally, evidence provided by Langmuir probes suggests the existence of a double layer essentially separating the hollow cathode plasma column from the main discharge. The radial potential difference associated with this double layer was measured to be of order the ionization potential.

Sintered wire cesium dispenser photocathode

DOEpatents

Montgomery, Eric J; Ives, R. Lawrence; Falce, Louis R

2014-03-04

A photoelectric cathode has a work function lowering material such as cesium placed into an enclosure which couples a thermal energy from a heater to the work function lowering material. The enclosure directs the work function lowering material in vapor form through a low diffusion layer, through a free space layer, and through a uniform porosity layer, one side of which also forms a photoelectric cathode surface. The low diffusion layer may be formed from sintered powdered metal, such as tungsten, and the uniform porosity layer may be formed from wires which are sintered together to form pores between the wires which are continuous from the a back surface to a front surface which is also the photoelectric surface.

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.

Electrochemical power-producing cell. [Li/Se

DOEpatents

Cairns, E.J.; Chilenskas, A.A.; Steunenberg, R.K.; Shimotake, H.

1972-05-30

An electrochemical power-producing cell including a molten lithium metal anode, a molten selenium metal cathode, a paste electrolyte separating the anode from the cathode, an anode current collector, and a single layer of niobium expanded metal formed in corrugated shape as cathode current collector is described. In addition, means are provided for sealing the anode and the cathode from loss of lithium and selenium, respectively, and an insulator is provided between the anode housing and the paste electrolyte disk.

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

Hu, Enyuan; Wang, Xuelong; Yu, Xiqian

The rechargeable lithium-ion battery (LIB) is the most promising energy storage system to power electric vehicles with high energy density and long cycling life. However, in order to meet customers’ demands for fast charging, the power performances of current LIBs need to be improved. From the cathode aspect, layer-structured cathode materials are widely used in today’s market and will continue to play important roles in the near future. The high rate capability of layered cathode materials during charging and discharging is critical to the power performance of the whole cell and the thermal stability is closely related to the safetymore » issues. Therefore, the in-depth understanding of structural changes of layered cathode materials during high rate charging/discharging and the thermal stability during heating are essential in developing new materials and improving current materials. Since structural changes take place from the atomic level to the whole electrode level, combination of characterization techniques covering multilength scales is quite important. Finally, in many cases, this means using comprehensive tools involving diffraction, spectroscopy, and imaging to differentiate the surface from the bulk and to obtain structural/chemical information with different levels of spatial resolution.« less

A novel cobalt-free layered GdBaFe 2O 5+ δ cathode for proton conducting solid oxide fuel cells

NASA Astrophysics Data System (ADS)

Ding, Hanping; Xue, Xingjian

While cobalt-containing perovskite-type cathode materials facilitate the activation of oxygen reduction, they also suffer from problems like poor chemical stability in CO 2 and high thermal expansion coefficients. In this research, a cobalt-free layered GdBaFe 2O 5+ δ (GBF) perovskite was developed as a cathode material for protonic ceramic membrane fuel cells (PCMFCs) based on proton conducting electrolyte of stable BaZr 0.1Ce 0.7Y 0.2O 3- δ (BZCY7). The button cells of Ni-BZCY7|BZCY7|GBF were fabricated and characterized using complex impedance technique from 600 to 700 °C. An open-circuit potential of 1.007 V, maximum power density of 417 mW cm -2, and a low electrode polarization resistance of 0.18 Ω cm 2 were achieved at 700 °C. The results indicate that layered GBF perovskite is a good candidate for cobalt-free cathode material, while the developed Ni-BZCY7|BZCY7|GBF cell is a promising functional material system for solid oxide fuel cells.

Carbon nanotube: nanodiamond Li-ion battery cathodes with increased thermal conductivity

NASA Astrophysics Data System (ADS)

Salgado, Ruben; Lee, Eungiee; Shevchenko, Elena V.; Balandin, Alexander A.

2016-10-01

Prevention of excess heat accumulation within the Li-ion battery cells is a critical design consideration for electronic and photonic device applications. Many existing approaches for heat removal from batteries increase substantially the complexity and overall weight of the battery. Some of us have previously shown a possibility of effective passive thermal management of Li-ion batteries via improvement of thermal conductivity of cathode and anode material1. In this presentation, we report the results of our investigation of the thermal conductivity of various Li-ion cathodes with incorporated carbon nanotubes and nanodiamonds in different layered structures. The cathodes were synthesized using the filtration method, which can be utilized for synthesis of commercial electrode-active materials. The thermal measurements were conducted with the "laser flash" technique. It has been established that the cathode with the carbon nanotubes-LiCo2 and carbon nanotube layered structure possesses the highest in-plane thermal conductivity of 206 W/mK at room temperature. The cathode containing nanodiamonds on carbon nanotubes structure revealed one of the highest cross-plane thermal conductivity values. The in-plane thermal conductivity is up to two orders-of-magnitude greater than that in conventional cathodes based on amorphous carbon. The obtained results demonstrate a potential of carbon nanotube incorporation in cathode materials for the effective thermal management of Li-ion high-powered density batteries.

Inhibition of microbial growth on air cathodes of single chamber microbial fuel cells by incorporating enrofloxacin into the catalyst layer.

PubMed

Liu, Weifeng; Cheng, Shaoan; Sun, Dan; Huang, Haobin; Chen, Jie; Cen, Kefa

2015-10-15

The inevitable growth of aerobic bacteria on the surface of air cathodes is an important factor reducing the performance stability of air cathode single-chamber membrane-free microbial fuel cells (MFCs). Thus searching for effective methods to inhibit the cathodic microbial growth is critical for the practical application of MFCs. In this study, enrofloxacin (ENR), a broad spectrum fluoroquinolone antibiotic, was incorporated into the catalyst layer of activated carbon air cathodes (ACACs) to inhibit the cathodic microbial growth. The biomass content on ACACs was substantially reduced by 60.2% with ENR treatment after 91 days of MFCs operation. As a result of the inhibited microbial growth, the oxygen reduction catalytic performance of the ENR treated ACACs was much stable compared to the fast performance decline of the untreated control. Consequently, a quite stable electricity production was obtained for the MFCs with the ENR treated ACACs, in contrast with a 22.5% decrease in maximum power density of the MFCs with the untreated cathode. ENR treatment of ACACs showed minimal effects on the anode performance. These results indicate that incorporating antibiotics into ACACs should be a simple and effective strategy to inhibit the microbial growth and improve the long-term stability of the performance of air cathode and the electricity production of MFCs. Copyright © 2015 Elsevier B.V. All rights reserved.

Single step transformation of sulphur to Li2S2/Li2S in Li-S batteries

PubMed Central

Helen, M.; Reddy, M. Anji; Diemant, Thomas; Golla-Schindler, Ute; Behm, R. Jürgen; Kaiser, Ute; Fichtner, Maximilian

2015-01-01

Lithium-sulphur batteries have generated tremendous research interest due to their high theoretical energy density and potential cost-effectiveness. The commercial realization of Li-S batteries is still hampered by reduced cycle life associated with the formation of electrolyte soluble higher-order polysulphide (Li2Sx, x = 4–8) intermediates, leading to capacity fading, self-discharge, and a multistep voltage profile. Herein, we have realized a practical approach towards a direct transformation of sulphur to Li2S2/Li2S in lithium-sulphur batteries by alteration of the reaction pathway. A coconut shell derived ultramicroporous carbon-sulphur composite cathode has been used as reaction directing template for the sulphur. The lithiation/delithiation and capacity fading mechanism of microporous carbon confined sulphur composite was revealed by analyzing the subsurface using X-ray photoelectron spectroscopy. No higher-order polysulphides were detected in the electrolyte, on the surface, and in the subsurface of the cathode composite. The altered reaction pathway is reflected by a single-step profile in the discharge/charge of a lithium-sulphur cell. PMID:26173723

Serially connected solid oxide fuel cells having monolithic cores

DOEpatents

Herceg, J.E.

1985-05-20

Disclosed is a solid oxide fuel cell for electrochemically combining fuel and oxidant for generating galvanic output. The cell core has an array of cell segments electrically serially connected in the flow direction, each segment consisting of electrolyte walls and interconnect that are substantially devoid of any composite inert materials for support. Instead, the core is monolithic, where each electrolyte wall consists of thin layers of cathode and anode materials sandwiching a thin layer of electrolyte material therebetween. Means direct the fuel to the anode-exposed core passageways and means direct the oxidant to the cathode-exposed core passageways; and means also direct the galvanic output to an exterior circuit. Each layer of the electrolyte composite materials is of the order of 0.002 to 0.01 cm thick; and each layer of the cathode and anode materials is of the order of 0.002 to 0.05 cm thick. Between 2 and 50 cell segments may be connected in series.

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.

Enhancing substrate utilization and power production of a microbial fuel cell with nitrogen-doped carbon aerogel as cathode catalyst.

PubMed

Tardy, Gábor Márk; Lóránt, Bálint; Lóka, Máté; Nagy, Balázs; László, Krisztina

2017-07-01

Catalytic efficiency of a nitrogen-doped, mesoporous carbon aerogel cathode catalyst was investigated in a two-chambered microbial fuel cell (MFC) applying graphite felt as base material for cathode and anode, utilizing peptone as carbon source. This mesoporous carbon aerogel containing catalyst layer on the cathode increased the maximum power density normalized to the anode volume to 2.7 times higher compared to the maximum power density obtained applying graphite felt cathode without the catalyst layer. At high (2 and 3) cathode/anode volume ratios, maximum power density exceeded 40 W m -3 . At the same time, current density and specific substrate utilization rate increased by 58% resulting in 31.9 A m -3 and 18.8 g COD m -3  h -1 , respectively (normalized to anode volume). Besides the increase of the power and the rate of biodegradation, the investigated catalyst decreased the internal resistance from the range of 450-600 to 350-370 Ω. Although Pt/C catalyst proved to be more efficient, a considerable decrease in the material costs might be achieved by substituting it with nitrogen-doped carbon aerogel in MFCs. Such cathode still displays enhanced catalytic effect.

Layered materials with improved magnesium intercalation for rechargeable magnesium ion cells

DOEpatents

Doe, Robert Ellis; Downie, Craig Michael; Fischer, Christopher; Lane, George Hamilton; Morgan, Dane; Nevin, Josh; Ceder, Gerbrand; Persson, Kristin Aslaug; Eaglesham, David

2015-10-27

Electrochemical devices which incorporate cathode materials that include layered crystalline compounds for which a structural modification has been achieved which increases the diffusion rate of multi-valent ions into and out of the cathode materials. Examples in which the layer spacing of the layered electrode materials is modified to have a specific spacing range such that the spacing is optimal for diffusion of magnesium ions are presented. An electrochemical cell comprised of a positive intercalation electrode, a negative metal electrode, and a separator impregnated with a nonaqeuous electrolyte solution containing multi-valent ions and arranged between the positive electrode and the negative electrode active material is described.

The effect of doping (Mn,B)3O4 materials as protective layers in different metallic interconnects for Solid Oxide Fuel Cells

NASA Astrophysics Data System (ADS)

Miguel-Pérez, Verónica; Martínez-Amesti, Ana; Nó, María Luisa; Larrañaga, Aitor; Arriortua, María Isabel

2013-12-01

Spinel oxides with the general formula of (Mn,B)3O4 (B = Co, Fe) were used as barrier materials between the cathode and the metallic interconnect to reduce the rate of cathode degradation by Cr poisoning. The effect of doping at the B position was investigated terms of microstructure and electrical conductivity to determine its behaviour and effectiveness as a protective layer in contact with three metallic materials (Crofer 22 APU, SS430 and Conicro 4023 W 188). The analysis showed that the use of these materials considerably decreased the reactivity and diffusion of Cr between the cathode and the metallic interconnects. The protective layer doped with Fe at the B position exhibited the least amount of reactivity with the interconnector and cathode materials. The worst results were observed for SS430 cells coated with a protective layer perhaps due to their low Cr content. The Crofer 22 APU and Conicro 4023 W 188 samples exhibited very similar conductivity results in the presence of the MnCo1.9Fe0.1O4 protective coating. As a result, these two material combinations are a promising option for use as bipolar plates in SOFC.

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

One-dimensional conduction through supporting electrolytes: two-scale cathodic Debye layer.

PubMed

Almog, Yaniv; Yariv, Ehud

2011-10-01

Supporting-electrolyte solutions comprise chemically inert cations and anions, produced by salt dissolution, together with a reactive ionic species that may be consumed and generated on bounding ion-selective surfaces (e.g., electrodes or membranes). Upon application of an external voltage, a Faraday current is thereby established. It is natural to analyze this ternary-system process through a one-dimensional transport problem, employing the thin Debye-layer limit. Using a simple model of ideal ion-selective membranes, we have recently addressed this problem for moderate voltages [Yariv and Almog, Phys. Rev. Lett. 105, 176101 (2010)], predicting currents that scale as a fractional power of Debye thickness. We address herein the complementary problem of moderate currents. We employ matched asymptotic expansions, separately analyzing the two inner thin Debye layers adjacent to the ion-selective surfaces and the outer electroneutral region outside them. A straightforward calculation following comparable singular-perturbation analyses of binary systems is frustrated by the prediction of negative ionic concentrations near the cathode. Accompanying numerical simulations, performed for small values of Debye thickness, indicate a number unconventional features occurring at that region, such as inert-cation concentration amplification and electric-field intensification. The current-voltage correlation data of the electrochemical cell, obtained from compilation of these simulations, does not approach a limit as the Debye thickness vanishes. Resolution of these puzzles reveals a transformation of the asymptotic structure of the cathodic Debye layer. This reflects the emergence of an internal boundary layer, adjacent to the cathode, wherein field and concentration scaling differs from those of the Gouy-Chapman theory. The two-scale feature of the cathodic Debye layer is manifested through a logarithmic voltage scaling with Debye thickness. Accounting for this scaling, the complied current-voltage data collapses upon a single curve. This curve practically coincides with an asymptotically calculated universal current-voltage relation.

Fullerene derivative-doped zinc oxide nanofilm as the cathode of inverted polymer solar cells with low-bandgap polymer (PTB7-Th) for high performance.

PubMed

Liao, Sih-Hao; Jhuo, Hong-Jyun; Cheng, Yu-Shan; Chen, Show-An

2013-09-14

Modification of a ZnO cathode by doping it with a hydroxyl-containing derivative - giving a ZnO-C60 cathode - provides a fullerene-derivative-rich surface and enhanced electron conduction. Inverted polymer solar cells with the ZnO-C60 cathode display markedly improved power conversion efficiency compared to those with a pristine ZnO cathode, especially when the active layer includes the low-bandgap polymer PTB7-Th. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Formation of an Anti-Core–Shell Structure in Layered Oxide Cathodes for Li-Ion Batteries

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

Zhang, Hanlei; Omenya, Fredrick; Whittingham, M. Stanley

The layered → rock-salt phase transformation in the layered dioxide cathodes for Li-ion batteries is believed to result in a “core-shell” structure of the primary particles, in which the core region maintains as the layered phase while the surface region undergoes the phase transformation to the rock-salt phase. Using transmission electron microscopy, here we demonstrate the formation of an “anti-core-shell” structure in cycled primary particles with a formula of LiNi0.80Co0.15Al0.05O2, in which the surface and subsurface regions remain as the layered structure while the rock-salt phase forms as domains in the bulk with a thin layer of the spinel phasemore » between the rock-salt core and the skin of the layered phase. Formation of this anti-core-shell structure is attributed to the oxygen loss at the surface that drives the migration of oxygen from the bulk to the surface, thereby resulting in localized areas of significantly reduced oxygen levels in the bulk of the particle, which subsequently undergoes the phase transformation to the rock-salt domains. The formation of the anti-core-shell rock-salt domains is responsible for the reduced capacity, discharge voltage and ionic conductivity in cycled cathode.« 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.

Layered Li-Mn-M-oxides as cathodes for Li-ion batteries:. Recent trends

NASA Astrophysics Data System (ADS)

Shaju, K. M.; Subba Rao, G. V.; Chowdari, B. V. R.

2002-12-01

There is an increasing demand for manganese (Mn) based mixed oxides which can effectively replace the presently used LiCoO2 as cathode in Li-ion batteries (LIB). The well-studied spinel, LiMn2O4 and its doped derivatives give a capacity of 100-120 mAh/g, but show capacity-fading on cycling especially above 55°C. The layered LiMnO2, isostructural to LiCoO2 (so called O3-structure) can be a viable cathode. However, studies have shown that it undergoes conversion to spinel structure on cycling and thus gives capacity-fading. Other alternative systems recently studied are: O2-structured layered Li-M-Mn-oxides with the general formula Li(2/3)+x(MyMn1-y)O2, M = Li, Ni, Co; x ≤ 0.33 and y = 0.1-0.67, O3-Li(Ni1/2Mn1/2)O2, Li(NixCo1-2xMnx)O2, and M'-substituted Li2MnO3 (M' = Ni, Co, Cr). Some of them are shown to have stable cycling performance, good rate-capability and structural stability over charge-discharge cycling in the 2.5-4.6 V region. Further, the electrochemical processes in the above mixed oxides have been shown to involve Ni2+/4+ or Cr3+/6+ redox couple, thus invoking novel ideas to develop new cathode materials. A brief review of the work done on the above O2- and O3-layered Li-Mn-M-oxides (M = metal) as cathodes for LIB is presented.

Relationship between the specific surface area of rust and the electrochemical behavior of rusted steel in a wet-dry acid corrosion environment

NASA Astrophysics Data System (ADS)

Liu, Wei; Zhao, Qing-he; Li, Shuan-zhu

2017-01-01

The relationship between the specific surface area (SSA) of rust and the electrochemical behavior of rusted steel under wet-dry acid corrosion conditions was investigated. The results showed that the corrosion current density first increased and then decreased with increasing SSA of the rust during the corrosion process. The structure of the rust changed from single-layer to double-layer, and the γ-FeOOH content decreased in the inner layer of the rust with increasing corrosion time; by contrast, the γ-FeOOH content in the outer layer was constant. When the SSA of the rust was lower than the critical SSA corresponding to the relative humidity during the drying period, condensed water in the micropores of the rust could evaporate, which prompted the diffusion of O2 into the rust and the following formation process of γ-FeOOH, leading to an increase of corrosion current density with increasing corrosion time. However, when the SSA of the rust reached or exceeded the critical SSA, condensate water in the micro-pores of the inner layer of the rust could not evaporate which inhibited the diffusion of O2 and decreased the γ-FeOOH content in the inner rust, leading to a decrease of corrosion current density with increasing corrosion time.

Method of fabricating an optoelectronic device having a bulk heterojunction

DOEpatents

Shtein, Max [Princeton, NJ; Yang, Fan [Princeton, NJ; Forrest, Stephen R [Princeton, NJ

2008-09-02

A method of fabricating an organic optoelectronic device having a bulk heterojunction comprises the steps of: depositing a first layer over a first electrode by organic vapor phase deposition, wherein the first layer comprises a first organic small molecule material; depositing a second layer on the first layer such that the second layer is in physical contact with the first layer, wherein the interface of the second layer on the first layer forms a bulk heterojunction; and depositing a second electrode over the second layer to form the optoelectronic device. In another embodiment, a first layer having protrusions is deposited over the first electrode, wherein the first layer comprises a first organic small molecule material. For example, when the first layer is an electron donor layer, the first electrode is an anode, the second layer is an electron acceptor layer, and the second electrode is a cathode. As a further example, when the first layer is an electron acceptor layer, the first electrode is a cathode, the second layer is an electron donor layer, and the second electrode is an anode.

A sodium-ion battery exploiting layered oxide cathode, graphite anode and glyme-based electrolyte

NASA Astrophysics Data System (ADS)

Hasa, Ivana; Dou, Xinwei; Buchholz, Daniel; Shao-Horn, Yang; Hassoun, Jusef; Passerini, Stefano; Scrosati, Bruno

2016-04-01

Room-temperature rechargeable sodium-ion batteries (SIBs), in view of the large availability and low cost of sodium raw materials, represent an important class of electrochemical systems suitable for application in large-scale energy storage. In this work, we report a novel, high power SIB formed by coupling the layered P2-Na0.7CoO2 cathode with the graphite anode in an optimized ether-based electrolyte. The study firstly addresses the electrochemical optimization of the two electrode materials and then the realization and characterization of the novel SIB based on their combination. The cell represents an original sodium rocking chair battery obtained combining the intercalation/de-intercalation processes of sodium within the cathode and anode layers. We show herein that this battery, favored by suitable electrode/electrolyte combination, offers unique performance in terms of cycle life, efficiency and, especially, power capability.

Stabilizing nanostructured solid oxide fuel cell cathode with atomic layer deposition.

PubMed

Gong, Yunhui; Palacio, Diego; Song, Xueyan; Patel, Rajankumar L; Liang, Xinhua; Zhao, Xuan; Goodenough, John B; Huang, Kevin

2013-09-11

We demonstrate that the highly active but unstable nanostructured intermediate-temperature solid oxide fuel cell cathode, La0.6Sr0.4CoO3-δ (LSCo), can retain its high oxygen reduction reaction (ORR) activity with exceptional stability for 4000 h at 700 °C by overcoating its surfaces with a conformal layer of nanoscale ZrO2 films through atomic layer deposition (ALD). The benefits from the presence of the nanoscale ALD-ZrO2 overcoats are remarkable: a factor of 19 and 18 reduction in polarization area-specific resistance and degradation rate over the pristine sample, respectively. The unique multifunctionality of the ALD-derived nanoscaled ZrO2 overcoats, that is, possessing porosity for O2 access to LSCo, conducting both electrons and oxide-ions, confining thermal growth of LSCo nanoparticles, and suppressing surface Sr-segregation is deemed the key enabler for the observed stable and active nanostructured cathode.

Determination of optimal parameters for dual-layer cathode of polymer electrolyte fuel cell using computational intelligence-aided design.

PubMed

Chen, Yi; Huang, Weina; Peng, Bei

2014-01-01

Because of the demands for sustainable and renewable energy, fuel cells have become increasingly popular, particularly the polymer electrolyte fuel cell (PEFC). Among the various components, the cathode plays a key role in the operation of a PEFC. In this study, a quantitative dual-layer cathode model was proposed for determining the optimal parameters that minimize the over-potential difference η and improve the efficiency using a newly developed bat swarm algorithm with a variable population embedded in the computational intelligence-aided design. The simulation results were in agreement with previously reported results, suggesting that the proposed technique has potential applications for automating and optimizing the design of PEFCs.

Directed Vertical Diffusion of Photovoltaic Active Layer Components into Porous ZnO-Based Cathode Buffer Layers.

PubMed

Kang, Jia-Jhen; Yang, Tsung-Yu; Lan, Yi-Kang; Wu, Wei-Ru; Su, Chun-Jen; Weng, Shih-Chang; Yamada, Norifumi L; Su, An-Chung; Jeng, U-Ser

2018-04-01

Cathode buffer layers (CBLs) can effectively further the efficiency of polymer solar cells (PSCs), after optimization of the active layer. Hidden between the active layer and cathode of the inverted PSC device configuration is the critical yet often unattended vertical diffusion of the active layer components across CBL. Here, a novel methodology of contrast variation with neutron and anomalous X-ray reflectivity to map the multicomponent depth compositions of inverted PSCs, covering from the active layer surface down to the bottom of the ZnO-based CBL, is developed. Uniquely revealed for a high-performance model PSC are the often overlooked porosity distributions of the ZnO-based CBL and the differential diffusions of the polymer PTB7-Th and fullerene derivative PC 71 BM of the active layer into the CBL. Interface modification of the ZnO-based CBL with fullerene derivative PCBEOH for size-selective nanochannels can selectively improve the diffusion of PC 71 BM more than that of the polymer. The deeper penetration of PC 71 BM establishes a gradient distribution of fullerene derivatives over the ZnO/PCBE-OH CBL, resulting in markedly improved electron mobility and device efficiency of the inverted PSC. The result suggests a new CBL design concept of progressive matching of the conduction bands. © 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

A Chemical-Adsorption Strategy to Enhance the Reaction Kinetics of Lithium-Rich Layered Cathodes via Double-Shell Surface Modification.

PubMed

Guo, Lichao; Li, Jiajun; Cao, Tingting; Wang, Huayu; Zhao, Naiqin; He, Fang; Shi, Chunsheng; He, Chunnian; Liu, Enzuo

2016-09-21

Sluggish surface reaction kinetics hinders the power density of Li-ion battery. Thus, various surface modification techniques have been applied to enhance the electronic/ionic transfer kinetics. However, it is challenging to obtain a continuous and uniform surface modification layer on the prime particles with structure integration at the interface. Instead of classic physical-adsorption/deposition techniques, we propose a novel chemical-adsorption strategy to synthesize double-shell modified lithium-rich layered cathodes with enhanced mass transfer kinetics. On the basis of experimental measurement and first-principles calculation, MoO2S2 ions are proved to joint the layered phase via chemical bonding. Specifically, the Mo-O or Mo-S bonds can flexibly rotate to bond with the cations in the layered phase, leading to the good compatibility between the thiomolybdate adsorption layer and layered cathode. Followed by annealing treatment, the lithium-excess-spinel inner shell forms under the thiomolybdate adsorption layer and functions as favorable pathways for lithium and electron. Meanwhile, the nanothick MoO3-x(SO4)x outer shell protects the transition metal from dissolution and restrains electrolyte decomposition. The double-shell modified sample delivers an enhanced discharge capacity almost twice as much as that of the unmodified one at 1 A g(-1) after 100 cycles, demonstrating the superiority of the surface modification based on chemical adsorption.

Highly Monodisperse Microporous Polymeric and Carbonaceous Nanospheres with Multifunctional Properties

PubMed Central

Ouyang, Yi; Shi, Huimin; Fu, Ruowen; Wu, Dingcai

2013-01-01

Fabrication of monodisperse porous polymeric nanospheres with diameters below 500 nm remains a great challenge, due to serious crosslinking between neighboring nanospheres during pore-making process. Here we show how a versatile hypercrosslinking strategy can be used to prepare monodisperse microporous polystyrene nanospheres (MMPNSs) with diameters as low as ca. 190 nm. In our approach, an unreactive crosslinked PS outer skin as protective layer can be in-situ formed at the very beginning of hypercrosslinking treatment to minimize the undesired inter-sphere crosslinking. The as-prepared MMPNSs with a well-developed microporous network demonstrate unusual multifunctional properties, including remarkable colloidal stability in aqueous solution, good adsorption-release property for drug, and large adsorption capacity toward organic vapors. Surprisingly, MMPNSs can be directly transformed into high-surface-area monodisperse carbon nanospheres with good colloidal stability via a facile hydrothermal-assisted carbonization procedure. These findings provide a new benchmark for fabricating well-defined porous nanospheres with great promise for various applications. PMID:23478487

Efficient small molecular organic light emitting diode with graphene cathode covered by a Sm layer with nano-hollows and n-doped by Bphen:Cs2CO3 in the hollows

NASA Astrophysics Data System (ADS)

Yao, Li; Li, Lei; Qin, Laixiang; Ma, Yaoguang; Wang, Wei; Meng, Hu; Jin, Weifeng; Wang, Yilun; Xu, Wanjin; Ran, Guangzhao; You, Liping; Qin, Guogang

2017-03-01

Graphene is a favorable candidate for electrodes of organic light emitting diodes (OLEDs). Graphene has quite a high work function of ˜4.5 eV, and has been extensively studied when used as anodes of OLEDs. In order to use graphene as a cathode, the electron injection barrier between the graphene cathode and the electron transport layer has to be low enough. Using 4,7-diphenyl-1,10-phenanthroline (Bphen):Cs2CO3 to n-dope graphene is a very good method, but the electron injection barrier between the n-doped graphene and Bphen:Cs2CO3 is still too high to be ˜1.0 eV. In this work, in order to further reduce the electron injection barrier, a novel method is suggested. On the graphene cathode, a Sm layer with a lot of nano-hollows, and subsequently a layer of Bphen:Cs2CO3, are deposited. The Bphen:Cs2CO3 can n-dope graphene in the nano-hollows, and the Fermi level of the graphene rises. The nano Sm layer is very easily oxidized. Oxygen adsorbed on the surface of graphene may react with Sm to form an O--Sm+ dipole layer. On the areas of the Sm oxide dipole layer without nano-hollows, the electron injection barrier can be further lowered by the dipole layer. Electrons tend to mainly inject through the lower electron barrier where the dipole layer exists. Based on this idea, an effective inverted small molecular OLED with the structure of graphene/1 nm Sm layer with a lot of nano-hollows/Bphen:Cs2CO3/Alq3:C545T/NPB/MoO3/Al is presented. The maximum current efficiency and maximum power efficiency of the OLED with a 1 nm Sm layer are about two and three times of those of the reference OLED without any Sm layer, respectively.

Understanding the Role of Temperature and Cathode Composition on Interface and Bulk: Optimizing Aluminum Oxide Coatings for Li-Ion Cathodes.

PubMed

Han, Binghong; Paulauskas, Tadas; Key, Baris; Peebles, Cameron; Park, Joong Sun; Klie, Robert F; Vaughey, John T; Dogan, Fulya

2017-05-03

Surface coating of cathode materials with Al 2 O 3 has been shown to be a promising method for cathode stabilization and improved cycling performance at high operating voltages. However, a detailed understanding on how coating process and cathode composition change the chemical composition, morphology, and distribution of coating within the cathode interface and bulk lattice is still missing. In this study, we use a wet-chemical method to synthesize a series of Al 2 O 3 -coated LiNi 0.5 Co 0.2 Mn 0.3 O 2 and LiCoO 2 cathodes treated under various annealing temperatures and a combination of structural characterization techniques to understand the composition, homogeneity, and morphology of the coating layer and the bulk cathode. Nuclear magnetic resonance and electron microscopy results reveal that the nature of the interface is highly dependent on the annealing temperature and cathode composition. For Al 2 O 3 -coated LiNi 0.5 Co 0.2 Mn 0.3 O 2 , higher annealing temperature leads to more homogeneous and more closely attached coating on cathode materials, corresponding to better electrochemical performance. Lower Al 2 O 3 coating content is found to be helpful to further improve the initial capacity and cyclability, which can greatly outperform the pristine cathode material. For Al 2 O 3 -coated LiCoO 2 , the incorporation of Al into the cathode lattice is observed after annealing at high temperatures, implying the transformation from "surface coatings" to "dopants", which is not observed for LiNi 0.5 Co 0.2 Mn 0.3 O 2 . As a result, Al 2 O 3 -coated LiCoO 2 annealed at higher temperature shows similar initial capacity but lower retention compared to that annealed at a lower temperature, due to the intercalation of surface alumina into the bulk layered structure forming a solid solution.

Understanding the Role of Temperature and Cathode Composition on Interface and Bulk: Optimizing Aluminum Oxide Coatings for Li-Ion Cathodes

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

Han, Binghong; Paulauskas, Tadas; Key, Baris

Here, surface coating of cathode materials with Al 2O 3 has been shown to be a promising method for cathode stabilization and improved cycling performance at high operating voltages. However, a detailed understanding on how coating process and cathode composition changes the chemical composition, morphology and distribution of coating within cathode interface and bulk lattice, is still missing. In this study, we use a wet-chemical method to synthesize a series of Al 2O 3-coated LiNi 0.5Co 0.2Mn 0.3O 2 and LiCoO 2 cathodes treated under various annealing temperatures and a combination of structural characterization techniques to understand the composition, homogeneitymore » and morphology of coating layer and the bulk cathode. Nuclear magnetic resonance and electron microscopy results reveal that the nature of the interface is highly depended on the annealing temperature and cathode composition. For Al 2O 3-coated LiNi 0.5Co 0.2Mn 0.3O 2, higher annealing temperature leads to more homogeneous and more closely attached coating on cathode materials, corresponding to better electrochemical performance. Lower Al 2O 3 coating content is found to be helpful to further improve the initial capacity and cyclability, which can greatly outperform the pristine cathode material. For Al 2O 3-coated LiCoO 2, the incorporation of Al into the cathode lattice is observed after annealing at high temperatures, implying the transformation from “surface coatings” to “dopants”, which is not observed for LiNi 0.5Co 0.2Mn 0.3O 2. As a result, Al 2O 3-coated LiCoO 2 annealed at higher temperature shows similar initial capacity but lower retention compared to that annealed at a lower temperature, due to the intercalation of surface alumina into the bulk layered structure forming a solid solution.« less

Understanding the Role of Temperature and Cathode Composition on Interface and Bulk: Optimizing Aluminum Oxide Coatings for Li-Ion Cathodes

DOE PAGES

Han, Binghong; Paulauskas, Tadas; Key, Baris; ...

2017-04-07

Here, surface coating of cathode materials with Al 2O 3 has been shown to be a promising method for cathode stabilization and improved cycling performance at high operating voltages. However, a detailed understanding on how coating process and cathode composition changes the chemical composition, morphology and distribution of coating within cathode interface and bulk lattice, is still missing. In this study, we use a wet-chemical method to synthesize a series of Al 2O 3-coated LiNi 0.5Co 0.2Mn 0.3O 2 and LiCoO 2 cathodes treated under various annealing temperatures and a combination of structural characterization techniques to understand the composition, homogeneitymore » and morphology of coating layer and the bulk cathode. Nuclear magnetic resonance and electron microscopy results reveal that the nature of the interface is highly depended on the annealing temperature and cathode composition. For Al 2O 3-coated LiNi 0.5Co 0.2Mn 0.3O 2, higher annealing temperature leads to more homogeneous and more closely attached coating on cathode materials, corresponding to better electrochemical performance. Lower Al 2O 3 coating content is found to be helpful to further improve the initial capacity and cyclability, which can greatly outperform the pristine cathode material. For Al 2O 3-coated LiCoO 2, the incorporation of Al into the cathode lattice is observed after annealing at high temperatures, implying the transformation from “surface coatings” to “dopants”, which is not observed for LiNi 0.5Co 0.2Mn 0.3O 2. As a result, Al 2O 3-coated LiCoO 2 annealed at higher temperature shows similar initial capacity but lower retention compared to that annealed at a lower temperature, due to the intercalation of surface alumina into the bulk layered structure forming a solid solution.« less

Layered materials with improved magnesium intercalation for rechargeable magnesium ion cells

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

Doe, Robert E.; Downie, Craig M.; Fischer, Christopher

2016-01-19

Electrochemical devices which incorporate cathode materials that include layered crystalline compounds for which a structural modification has been achieved which increases the diffusion rate of multi-valent ions into and out of the cathode materials. Examples in which the layer spacing of the layered electrode materials is modified to have a specific spacing range such that the spacing is optimal for diffusion of magnesium ions are presented. An electrochemical cell comprised of a positive intercalation electrode, a negative metal electrode, and a separator impregnated with a nonaqueous electrolyte solution containing multi-valent ions and arranged between the positive electrode and the negativemore » electrode active material is described.« less

Construction of Uniform Cobalt-Based Nanoshells and Its Potential for Improving Li-Ion Battery Performance.

PubMed

Piao, Jun-Yu; Liu, Xiao-Chan; Wu, Jinpeng; Yang, Wanli; Wei, Zengxi; Ma, Jianmin; Duan, Shu-Yi; Lin, Xi-Jie; Xu, Yan-Song; Cao, An-Min; Wan, Li-Jun

2018-06-28

Surface cobalt doping is an effective and economic way to improve the electrochemical performance of cathode materials. Herein, by tuning the precipitation kinetics of Co 2+ , we demonstrate an aqueous-based protocol to grow uniform basic cobaltous carbonate coating layer onto different substrates, and the thickness of the coating layer can be adjusted precisely in nanometer accuracy. Accordingly, by sintering the cobalt-coated LiNi 0.5 Mn 1.5 O 4 cathode materials, an epitaxial cobalt-doped surface layer will be formed, which will act as a protective layer without hindering charge transfer. Consequently, improved battery performance is obtained because of the suppression of interfacial degradation.

Layered materials with improved magnesium intercalation for rechargeable magnesium ion cells

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

Doe, Robert Ellis; Downie, Craig Michael; Fischer, Christopher

2016-07-26

Electrochemical devices which incorporate cathode materials that include layered crystalline compounds for which a structural modification has been achieved which increases the diffusion rate of multi-valent ions into and out of the cathode materials. Examples in which the layer spacing of the layered electrode materials is modified to have a specific spacing range such that the spacing is optimal for diffusion of magnesium ions are presented. An electrochemical cell comprised of a positive intercalation electrode, a negative metal electrode, and a separator impregnated with a nonaqueous electrolyte solution containing multi-valent ions and arranged between the positive electrode and the negativemore » electrode active material is described.« less

Delithiated states of layered cathode materials: doping and dispersion interaction effects on the structure

NASA Astrophysics Data System (ADS)

Eremin, Roman; Zolotarev, Pavel; Bobrikov, Ivan

2018-04-01

Here we present results of density functional theory (DFT) study of delithiated structures of layered LiNiO2 (LNO, Li12Ni12O24 model) cathode material and its doped analogue LiNi0.833Co0.083Al0.083O2 (N10C1A1, Li12Ni10CoAlO24 model). The paper is aimed at independent elucidation of doping and dispersion interaction effects on the structural stability of cathode materials studied. For this purpose, the LNO and N10C1A1 configurational spaces consisting of 87 and 4512 crystallographically independent configurations (obtained starting from 2×2×1 supercell of R-3m structure of LNO) are optimized within a number of DFT models. Based on a comparison of the calculated dependencies for the lattice parameters with the results of in situ neutron diffraction experiments, the most pronounced effect of cathode material stabilization is due to the dispersion interaction. In turn, the doping effect is found to affect cathode structure behavior at the latest stages of delithiation only.

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

Liu, Jr., Jie Jerry; Sista, Srinivas Prasad; Shi, Xiaolei

Optoelectronic devices with enhanced internal outcoupling include a substrate, an anode, a cathode, an electroluminescent layer, and an electron transporting layer comprising inorganic nanoparticles dispersed in an organic matrix.

Structural integrity--Searching the key factor to suppress the voltage fade of Li-rich layered cathode materials through 3D X-ray imaging and spectroscopy techniques

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

Xu, Yahong; Hu, Enyuan; Yang, Feifei

Li-rich layered materials are important cathode compounds used in commercial lithium ion batteries, which, however, suffers from some drawbacks including the so-called voltage fade upon electrochemical cycling. Here, our study employs novel transmission X-ray microscopy to investigate the electrochemical reaction induced morphological and chemical changes in the Li-rich Li 2Ru 0.5Mn 0.5O 3 cathode particles at the meso to nano scale. We performed combined X-ray spectroscopy, diffraction and microscopy experiments to systematically study this cathode material's evolution upon cycling as well as to establish a comprehensive understanding of the structural origin of capacity fade through 2D and 3D fine lengthmore » scale morphology and heterogeneity change of this material. This work suggests that atomic manipulation (e.g. doping, substitution etc.) or nano engineering (e.g. nano-sizing, heterogeneous structure) are important strategies to mitigate the internal strain and defects induced by extensive lithium insertion/extraction. It also shows that maintaining the structural integrity is the key in designing and synthesizing lithium-rich layered materials with better cycle stability.« less

Structural integrity—Searching the key factor to supress the voltage fade of Li-rich layered cathode materials through 3D X-ray imaging and spectroscopy techniques

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

Xu, Yahong; Hu, Enyuan; Yang, Feifei

Li-rich layered materials are important cathode compounds used in commercial lithium ion batteries, which, however, suffers from some drawbacks including the so-called voltage fade upon electrochemical cycling. This study employs novel transmission X-ray microscopy to investigate the electrochemical reaction induced morphological and chemical changes in the Li-rich Li 2Ru 0.5Mn 0.5O 3 cathode particles at the meso to nano scale. Combined X-ray spectroscopy, diffraction and microscopy experiments are performed to systematically study this cathode material's evolution upon cycling as well as to establish a comprehensive understanding of the structural origin of capacity fade through 2D and 3D fine length scalemore » morphology and heterogeneity change of this material. This work suggests that atomic manipulation (e.g. doping, substitution etc.) or nano engineering (e.g. nano-sizing, heterogeneous structure) are important strategies to mitigate the internal strain and defects induced by extensive lithium insertion/extraction. In conclusion, it also shows that maintaining the structural integrity is the key in designing and synthesizing lithium-rich layered materials with better cycle stability.« less

Structural integrity—Searching the key factor to supress the voltage fade of Li-rich layered cathode materials through 3D X-ray imaging and spectroscopy techniques

DOE PAGES

Xu, Yahong; Hu, Enyuan; Yang, Feifei; ...

2016-08-17

Li-rich layered materials are important cathode compounds used in commercial lithium ion batteries, which, however, suffers from some drawbacks including the so-called voltage fade upon electrochemical cycling. This study employs novel transmission X-ray microscopy to investigate the electrochemical reaction induced morphological and chemical changes in the Li-rich Li 2Ru 0.5Mn 0.5O 3 cathode particles at the meso to nano scale. Combined X-ray spectroscopy, diffraction and microscopy experiments are performed to systematically study this cathode material's evolution upon cycling as well as to establish a comprehensive understanding of the structural origin of capacity fade through 2D and 3D fine length scalemore » morphology and heterogeneity change of this material. This work suggests that atomic manipulation (e.g. doping, substitution etc.) or nano engineering (e.g. nano-sizing, heterogeneous structure) are important strategies to mitigate the internal strain and defects induced by extensive lithium insertion/extraction. In conclusion, it also shows that maintaining the structural integrity is the key in designing and synthesizing lithium-rich layered materials with better cycle stability.« less

High-Capacity, High-Voltage Composite Oxide Cathode Materials

NASA Technical Reports Server (NTRS)

Hagh, Nader M.

2015-01-01

This SBIR project integrates theoretical and experimental work to enable a new generation of high-capacity, high-voltage cathode materials that will lead to high-performance, robust energy storage systems. At low operating temperatures, commercially available electrode materials for lithium-ion (Li-ion) batteries do not meet energy and power requirements for NASA's planned exploration activities. NEI Corporation, in partnership with the University of California, San Diego, has developed layered composite cathode materials that increase power and energy densities at temperatures as low as 0 degC and considerably reduce the overall volume and weight of battery packs. In Phase I of the project, through innovations in the structure and morphology of composite electrode particles, the partners successfully demonstrated an energy density exceeding 1,000 Wh/kg at 4 V at room temperature. In Phase II, the team enhanced the kinetics of Li-ion transport and electronic conductivity at 0 degC. An important feature of the composite cathode is that it has at least two components that are structurally integrated. The layered material is electrochemically inactive; however, upon structural integration with a spinel material, the layered material can be electrochemically activated and deliver a large amount of energy with stable cycling.

Stable blue phosphorescent organic light emitting devices

DOEpatents

Forrest, Stephen R.; Thompson, Mark; Giebink, Noel

2014-08-26

Novel combination of materials and device architectures for organic light emitting devices is provided. An organic light emitting device, is provided, having an anode, a cathode, and an emissive layer disposed between the anode and the cathode. The emissive layer includes a host and a phosphorescent emissive dopant having a peak emissive wavelength less than 500 nm, and a radiative phosphorescent lifetime less than 1 microsecond. Preferably, the phosphorescent emissive dopant includes a ligand having a carbazole group.

Ice electrode electrolytic cell

DOEpatents

Glenn, D.F.; Suciu, D.F.; Harris, T.L.; Ingram, J.C.

1993-04-06

This invention relates to a method and apparatus for removing heavy metals from waste water, soils, or process streams by electrolytic cell means. The method includes cooling a cell cathode to form an ice layer over the cathode and then applying an electric current to deposit a layer of the heavy metal over the ice. The metal is then easily removed after melting the ice. In a second embodiment, the same ice-covered electrode can be employed to form powdered metals.

Ice electrode electrolytic cell

DOEpatents

Glenn, David F.; Suciu, Dan F.; Harris, Taryl L.; Ingram, Jani C.

1993-01-01

This invention relates to a method and apparatus for removing heavy metals from waste water, soils, or process streams by electrolytic cell means. The method includes cooling a cell cathode to form an ice layer over the cathode and then applying an electric current to deposit a layer of the heavy metal over the ice. The metal is then easily removed after melting the ice. In a second embodiment, the same ice-covered electrode can be employed to form powdered metals.

Fullerene surfactants and their use in polymer solar cells

DOEpatents

Jen, Kwan-Yue; Yip, Hin-Lap; Li, Chang-Zhi

2015-12-15

Fullerene surfactant compounds useful as interfacial layer in polymer solar cells to enhance solar cell efficiency. Polymer solar cell including a fullerene surfactant-containing interfacial layer intermediate cathode and active layer.

Ceramic composite separators coated with moisturized ZrO(2) nanoparticles for improving the electrochemical performance and thermal stability of lithium ion batteries.

PubMed

Kim, Ki Jae; Kwon, Hyuk Kwon; Park, Min-Sik; Yim, Taeeun; Yu, Ji-Sang; Kim, Young-Jun

2014-05-28

We introduce a ceramic composite separator prepared by coating moisturized ZrO2 nanoparticles with a poly(vinylidene fluoride-co-hexafluoropropylene) (PVdF-12wt%HFP) copolymer on a polyethylene separator. The effect of moisturized ZrO2 nanoparticles on the morphology and the microstructure of the polymeric coating layer is investigated. A large number of micropores formed around the embedded ZrO2 nanoparticles in the coating layer as a result of the phase inversion caused by the adsorbed moisture. The formation of micropores highly affects the ionic conductivity and electrolyte uptake of the ceramic composite separator and, by extension, the rate discharge properties of lithium ion batteries. In particular, thermal stability of the ceramic composite separators coated with the highly moisturized ZrO2 nanoparticles (a moisture content of 16 000 ppm) is dramatically improved without any degradation in electrochemical performance compared to the performance of pristine polyethylene separators.

In situ NMR and electrochemical quartz crystal microbalance techniques reveal the structure of the electrical double layer in supercapacitors

NASA Astrophysics Data System (ADS)

Griffin, John M.; Forse, Alexander C.; Tsai, Wan-Yu; Taberna, Pierre-Louis; Simon, Patrice; Grey, Clare P.

2015-08-01

Supercapacitors store charge through the electrosorption of ions on microporous electrodes. Despite major efforts to understand this phenomenon, a molecular-level picture of the electrical double layer in working devices is still lacking as few techniques can selectively observe the ionic species at the electrode/electrolyte interface. Here, we use in situ NMR to directly quantify the populations of anionic and cationic species within a working microporous carbon supercapacitor electrode. Our results show that charge storage mechanisms are different for positively and negatively polarized electrodes for the electrolyte tetraethylphosphonium tetrafluoroborate in acetonitrile; for positive polarization charging proceeds by exchange of the cations for anions, whereas for negative polarization, cation adsorption dominates. In situ electrochemical quartz crystal microbalance measurements support the NMR results and indicate that adsorbed ions are only partially solvated. These results provide new molecular-level insight, with the methodology offering exciting possibilities for the study of pore/ion size, desolvation and other effects on charge storage in supercapacitors.

Composition analysis of a polymer electrolyte membrane fuel cell microporous layer using scanning transmission X-ray microscopy and near edge X-ray absorption fine structure analysis

NASA Astrophysics Data System (ADS)

George, Michael G.; Wang, Jian; Banerjee, Rupak; Bazylak, Aimy

2016-03-01

The novel application of scanning transmission X-ray microscopy (STXM) to the microporous layer (MPL) of a polymer electrolyte membrane fuel cell is investigated. A spatially resolved chemical component distribution map is obtained for the MPL of a commercially available SGL 25 BC sample. This is achieved with near edge X-ray absorption fine structure spectroscopic analysis. Prior to analysis the sample is embedded in non-reactive epoxy and ultra-microtomed to a thickness of 100 nm. Polytetrafluoroethylene (PTFE), carbon particle agglomerates, and supporting epoxy resin distributions are identified and reconstructed for a scanning area of 6 μm × 6 μm. It is observed that the spatial distribution of PTFE is strongly correlated to the carbon particle agglomerations. Additionally, agglomerate structures of PTFE are identified, possibly indicating the presence of a unique mesostructure in the MPL. STXM analysis is presented as a useful technique for the investigation of chemical species distributions in the MPL.

Thermal conductivity of microporous layers: Analytical modeling and experimental validation

NASA Astrophysics Data System (ADS)

Andisheh-Tadbir, Mehdi; Kjeang, Erik; Bahrami, Majid

2015-11-01

A new compact relationship is developed for the thermal conductivity of the microporous layer (MPL) used in polymer electrolyte fuel cells as a function of pore size distribution, porosity, and compression pressure. The proposed model is successfully validated against experimental data obtained from a transient plane source thermal constants analyzer. The thermal conductivities of carbon paper samples with and without MPL were measured as a function of load (1-6 bars) and the MPL thermal conductivity was found between 0.13 and 0.17 W m-1 K-1. The proposed analytical model predicts the experimental thermal conductivities within 5%. A correlation generated from the analytical model was used in a multi objective genetic algorithm to predict the pore size distribution and porosity for an MPL with optimized thermal conductivity and mass diffusivity. The results suggest that an optimized MPL, in terms of heat and mass transfer coefficients, has an average pore size of 122 nm and 63% porosity.

Suppressing the chromium disproportionation reaction in O3-type layered cathode materials for high capacity sodium-ion batteries

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

Cao, Ming -Hui; Wang, Yong; Shadike, Zulipiya

Chromium-based layered cathode materials suffer from the irreversible disproportionation reaction of Cr 4+ to Cr 3+ and Cr 6+, which hinders the reversible multi-electron redox of Cr ions in layered cathodes, and limits their capacity and reversibility. To address this problem, a novel O3-type layer-structured transition metal oxide of NaCr 1/3Fe 1/3Mn 1/3O 2 (NCFM) was designed and studied as a cathode material. A high reversible capacity of 186 mA h g –1 was achieved at a current rate of 0.05C in a voltage range of 1.5 to 4.2 V. X-ray diffraction revealed an O3 → (O3 + P3) →more » (P3 + O3'') → O3'' phase-transition pathway for NCFM during charge. X-ray absorption, X-ray photoelectron and electron energy-loss spectroscopy measurements revealed the electronic structure changes of NCFM during Na + deintercalation/intercalation processes. It is confirmed that the disproportionation reaction of Cr 4+ to Cr 3+ and Cr 6+ can be effectively suppressed by Fe 3+ and Mn 4+ substitution. Lastly, these results demonstrated that the reversible multi-electron oxidation/reduction of Cr ions can be achieved in NCFM during charge and discharge accompanied by CrO 6 octahedral distortion and recovery.« less

Suppressing the chromium disproportionation reaction in O3-type layered cathode materials for high capacity sodium-ion batteries

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

Cao, Ming-Hui; Wang, Yong; Shadike, Zulipiya

Chromium-based layered cathode materials suffer from the irreversible disproportionation reaction of Cr4+ to Cr3+ and Cr6+, which hinders the reversible multi-electron redox of Cr ions in layered cathodes, and limits their capacity and reversibility. To address this problem, a novel O3-type layer-structured transition metal oxide of NaCr1/3Fe1/3Mn1/3O2 (NCFM) was designed and studied as a cathode material. A high reversible capacity of 186 mA h g-1 was achieved at a current rate of 0.05C in a voltage range of 1.5 to 4.2 V. X-ray diffraction revealed an O3 → (O3 + P3) → (P3 + O3'') → O3'' phase-transition pathway formore » NCFM during charge. X-ray absorption, X-ray photoelectron and electron energy-loss spectroscopy measurements revealed the electronic structure changes of NCFM during Na+ deintercalation/intercalation processes. It is confirmed that the disproportionation reaction of Cr4+ to Cr3+ and Cr6+ can be effectively suppressed by Fe3+ and Mn4+ substitution. These results demonstrated that the reversible multi-electron oxidation/reduction of Cr ions can be achieved in NCFM during charge and discharge accompanied by CrO6 octahedral distortion and recovery.« less

Suppressing the chromium disproportionation reaction in O3-type layered cathode materials for high capacity sodium-ion batteries

DOE PAGES

Cao, Ming -Hui; Wang, Yong; Shadike, Zulipiya; ...

2017-02-14

Chromium-based layered cathode materials suffer from the irreversible disproportionation reaction of Cr 4+ to Cr 3+ and Cr 6+, which hinders the reversible multi-electron redox of Cr ions in layered cathodes, and limits their capacity and reversibility. To address this problem, a novel O3-type layer-structured transition metal oxide of NaCr 1/3Fe 1/3Mn 1/3O 2 (NCFM) was designed and studied as a cathode material. A high reversible capacity of 186 mA h g –1 was achieved at a current rate of 0.05C in a voltage range of 1.5 to 4.2 V. X-ray diffraction revealed an O3 → (O3 + P3) →more » (P3 + O3'') → O3'' phase-transition pathway for NCFM during charge. X-ray absorption, X-ray photoelectron and electron energy-loss spectroscopy measurements revealed the electronic structure changes of NCFM during Na + deintercalation/intercalation processes. It is confirmed that the disproportionation reaction of Cr 4+ to Cr 3+ and Cr 6+ can be effectively suppressed by Fe 3+ and Mn 4+ substitution. Lastly, these results demonstrated that the reversible multi-electron oxidation/reduction of Cr ions can be achieved in NCFM during charge and discharge accompanied by CrO 6 octahedral distortion and recovery.« less

Polymeric hydrogen diffusion barrier, high-pressure storage tank so equipped, method of fabricating a storage tank and method of preventing hydrogen diffusion

DOEpatents

Lessing, Paul A [Idaho Falls, ID

2008-07-22

An electrochemically active hydrogen diffusion barrier which comprises an anode layer, a cathode layer, and an intermediate electrolyte layer, which is conductive to protons and substantially impermeable to hydrogen. A catalytic metal present in or adjacent to the anode layer catalyzes an electrochemical reaction that converts any hydrogen that diffuses through the electrolyte layer to protons and electrons. The protons and electrons are transported to the cathode layer and reacted to form hydrogen. The hydrogen diffusion barrier is applied to a polymeric substrate used in a storage tank to store hydrogen under high pressure. A storage tank equipped with the electrochemically active hydrogen diffusion barrier, a method of fabricating the storage tank, and a method of preventing hydrogen from diffusing out of a storage tank are also disclosed.

Polymeric hydrogen diffusion barrier, high-pressure storage tank so equipped, method of fabricating a storage tank and method of preventing hydrogen diffusion

DOEpatents

Lessing, Paul A.

2004-09-07

An electrochemically active hydrogen diffusion barrier which comprises an anode layer, a cathode layer, and an intermediate electrolyte layer, which is conductive to protons and substantially impermeable to hydrogen. A catalytic metal present in or adjacent to the anode layer catalyzes an electrochemical reaction that converts any hydrogen that diffuses through the electrolyte layer to protons and electrons. The protons and electrons are transported to the cathode layer and reacted to form hydrogen. The hydrogen diffusion barrier is applied to a polymeric substrate used in a storage tank to store hydrogen under high pressure. A storage tank equipped with the electrochemically active hydrogen diffusion barrier, a method of fabricating the storage tank, and a method of preventing hydrogen from diffusing out of a storage tank are also disclosed.

Triple-conducting layered perovskites as cathode materials for proton-conducting solid oxide fuel cells.

PubMed

Kim, Junyoung; Sengodan, Sivaprakash; Kwon, Goeun; Ding, Dong; Shin, Jeeyoung; Liu, Meilin; Kim, Guntae

2014-10-01

We report on an excellent anode-supported H(+) -SOFC material system using a triple conducting (H(+) /O(2-) /e(-) ) oxide (TCO) as a cathode material for H(+) -SOFCs. Generally, mixed ionic (O(2-) ) and electronic conductors (MIECs) have been selected as the cathode material of H(+) -SOFCs. In an H(+) -SOFC system, however, MIEC cathodes limit the electrochemically active sites to the interface between the proton conducting electrolyte and the cathode. New approaches to the tailoring of cathode materials for H(+) -SOFCs should therefore be considered. TCOs can effectively extend the electrochemically active sites from the interface between the cathode and the electrolyte to the entire surface of the cathode. The electrochemical performance of NBSCF/BZCYYb/BZCYYb-NiO shows excellent long term stability for 500 h at 1023 K with high power density of 1.61 W cm(-2) . © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Polarization-induced local pore-wall functionalization for biosensing: from micropore to nanopore.

PubMed

Liu, Jie; Pham, Pascale; Haguet, Vincent; Sauter-Starace, Fabien; Leroy, Loïc; Roget, André; Descamps, Emeline; Bouchet, Aurélie; Buhot, Arnaud; Mailley, Pascal; Livache, Thierry

2012-04-03

The use of biological-probe-modified solid-state pores in biosensing is currently hindered by difficulties in pore-wall functionalization. The surface to be functionalized is small and difficult to target and is usually chemically similar to the bulk membrane. Herein, we demonstrate the contactless electrofunctionalization (CLEF) approach and its mechanism. This technique enables the one-step local functionalization of the single pore wall fabricated in a silica-covered silicon membrane. CLEF is induced by polarization of the pore membrane in an electric field and requires a sandwich-like composition and a conducting or semiconducting core for the pore membrane. The defects in the silica layer of the micropore wall enable the creation of an electric pathway through the silica layer, which allows electrochemical reactions to take place locally on the pore wall. The pore diameter is not a limiting factor for local wall modification using CLEF. Nanopores with a diameter of 200 nm fabricated in a silicon membrane and covered with native silica layer have been successfully functionalized with this method, and localized pore-wall modification was obtained. Furthermore, through proof-of-concept experiments using ODN-modified nanopores, we show that functionalized nanopores are suitable for translocation-based biosensing.

Architectures and criteria for the design of high efficiency organic photovoltaic cells

DOEpatents

Rand, Barry; Forrest, Stephen R; Pendergrast Burk, Diane

2015-03-31

A method for fabricating an organic photovoltaic cell includes providing a first electrode; depositing a series of at least seven layers onto the first electrode, each layer consisting essentially of a different organic semiconductor material, the organic semiconductor material of at least an intermediate layer of the sequence being a photoconductive material; and depositing a second electrode onto the sequence of at least seven layers. One of the first electrode and the second electrode is an anode and the other is a cathode. The organic semiconductor materials of the series of at least seven layers are arranged to provide a sequence of decreasing lowest unoccupied molecular orbitals (LUMOs) and a sequence of decreasing highest occupied molecular orbitals (HOMOs) across the series from the anode to the cathode.

Direct electron injection into an oxide insulator using a cathode buffer layer

PubMed Central

Lee, Eungkyu; Lee, Jinwon; Kim, Ji-Hoon; Lim, Keon-Hee; Seok Byun, Jun; Ko, Jieun; Dong Kim, Young; Park, Yongsup; Kim, Youn Sang

2015-01-01

Injecting charge carriers into the mobile bands of an inorganic oxide insulator (for example, SiO2, HfO2) is a highly complicated task, or even impossible without external energy sources such as photons. This is because oxide insulators exhibit very low electron affinity and high ionization energy levels. Here we show that a ZnO layer acting as a cathode buffer layer permits direct electron injection into the conduction bands of various oxide insulators (for example, SiO2, Ta2O5, HfO2, Al2O3) from a metal cathode. Studies of current–voltage characteristics reveal that the current ohmically passes through the ZnO/oxide-insulator interface. Our findings suggests that the oxide insulators could be used for simply fabricated, transparent and highly stable electronic valves. With this strategy, we demonstrate an electrostatic discharging diode that uses 100-nm SiO2 as an active layer exhibiting an on/off ratio of ∼107, and protects the ZnO thin-film transistors from high electrical stresses. PMID:25864642

Effect of Li2O/Al cathode in Alq3 based organic light-emitting diodes.

PubMed

Shin, Eun Chul; Ahn, Hui Chul; Han, Wone Keun; Kim, Tae Wan; Lee, Won Jae; Hong, Jin Woong; Chung, Dong Hoe; Song, Min Jong

2008-09-01

An effect of bilayer cathode Li20/Al was studied in Alq3 based organic light-emitting diodes with a variation of Li2O layer thickness. The current-luminance-voltage characteristics of ITO/TPD/Alq3/Li2O/Al device were measured at ambient condition to investigate the effect of Li2O/Al. It was found that when the thickness of Li2O layer is in the range of 0.5-1 nm, there are improvements in luminance, efficiency, and turn-on voltage of the device. A current density and a luminance are increased by about 100 times, a turn-on voltage is lowered from 6 V to 3 V, a maximum current efficiency is improved by a factor of 2.3, and a maximum power efficiency is improved by a factor of 3.2 for a device with a use of thin Li2O layer compared to those of the one without the Li2Otron-barrier height for electron injection from the cathode to the emissive layer.

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.

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

How the charge-neutrality level of interface states controls energy level alignment in cathode contacts of organic bulk-heterojunction solar cells.

PubMed

Guerrero, Antonio; Marchesi, Luís F; Boix, Pablo P; Ruiz-Raga, Sonia; Ripolles-Sanchis, Teresa; Garcia-Belmonte, Germà; Bisquert, Juan

2012-04-24

Electronic equilibration at the metal-organic interface, leading to equalization of the Fermi levels, is a key process in organic optoelectronic devices. How the energy levels are set across the interface determines carrier extraction at the contact and also limits the achievable open-circuit voltage under illumination. Here, we report an extensive investigation of the cathode energy equilibration of organic bulk-heterojunction solar cells. We show that the potential to balance the mismatch between the cathode metal and the organic layer Fermi levels is divided into two contributions: spatially extended band bending in the organic bulk and voltage drop at the interface dipole layer caused by a net charge transfer. We scan the operation of the cathode under a varied set of conditions, using metals of different work functions in the range of ∼2 eV, different fullerene acceptors, and several cathode interlayers. The measurements allow us to locate the charge-neutrality level within the interface density of sates and calculate the corresponding dipole layer strength. The dipole layer withstands a large part of the total Fermi level mismatch when the polymer:fullerene blend ratio approaches ∼1:1, producing the practical alignment between the metal Fermi level and the charge-neutrality level. Origin of the interface states is linked with fullerene reduced molecules covering the metal contact. The dipole contribution, and consequently the band bending, is highly sensitive to the nature and amount of fullerene molecules forming the interface density of states. Our analysis provides a detailed picture of the evolution of the potentials in the bulk and the interface of the solar cell when forward voltage is applied or when photogeneration takes place.

Developing Battery Computer Aided Engineering Tools for Military Vehicles

DTIC Science & Technology

2013-12-01

Task 1.b Modeling Bullet penetration. The purpose of Task 1.a was to extend the chemical kinetics models of CoO2 cathodes developed under CAEBAT to...lithium- ion batteries. The new finite element model captures swelling/shrinking in cathodes /anodes due to thermal expansion and lithium intercalation...Solid Electrolyte Interphase (SEI) layer decomposition 80 2 Anode — electrolyte 100 3 Cathode — electrolyte 130 4 Electrolyte decomposition 180

Determination of Optimal Parameters for Dual-Layer Cathode of Polymer Electrolyte Fuel Cell Using Computational Intelligence-Aided Design

PubMed Central

Chen, Yi; Huang, Weina; Peng, Bei

2014-01-01

Because of the demands for sustainable and renewable energy, fuel cells have become increasingly popular, particularly the polymer electrolyte fuel cell (PEFC). Among the various components, the cathode plays a key role in the operation of a PEFC. In this study, a quantitative dual-layer cathode model was proposed for determining the optimal parameters that minimize the over-potential difference and improve the efficiency using a newly developed bat swarm algorithm with a variable population embedded in the computational intelligence-aided design. The simulation results were in agreement with previously reported results, suggesting that the proposed technique has potential applications for automating and optimizing the design of PEFCs. PMID:25490761

Electricity generation of microbial fuel cell with waterproof breathable membrane cathode

NASA Astrophysics Data System (ADS)

Xing, Defeng; Tang, Yu; Mei, Xiaoxue; Liu, Bingfeng

2015-12-01

Simplification of fabrication and reduction of capital cost are important for scale-up and application of microbial electrochemical systems (MES). A fast and inexpensive method of making cathode was developed via assembling stainless steel mesh (SSM) with waterproof breathable membrane (WBM). Three assemble types of cathodes were fabricated; Pt@SSM/WBM (SSM as cathode skeleton, WBM as diffusion layer, platinum (Pt) catalyst applied on SSM), SSM/Pt@WBM and Pt@WBM. SSM/Pt@WBM cathode showed relatively preferable with long-term stability and favorable power output (24.7 W/m3). Compared to conventional cathode fabrication, air-cathode was made for 0.5 h. The results indicated that the novel fabrication method could remarkably reduce capital cost and simplify fabrication procedures with a comparable power output, making MFC more prospective for future application.

Li- and Mn-Rich Cathode Materials: Challenges to Commercialization

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

Zheng, Jianming; Myeong, Seungjun; Cho, Woongrae

2016-12-14

The lithium- and manganese-rich (LMR) layered structure cathode exhibit one of the highest specific energy (~900 Wh kg-1) among all the cathode materials. However, the practical applications of LMR cathodes are still hindered by several significant challenges including voltage fade, large initial capacity loss, poor rate capability and limited cycle life. Herein, we review the recent progresses and understandings on the application of LMR cathode materials from practical point of view. Several key parameters of LMR cathodes that affect the LMR/graphite full cell operation are systematically analysed. These factors include the first cycle capacity loss, voltage fade, powder tap density,more » electrode density of LMR based cathode etc. New approaches to minimize the detrimental effect of these factors are highlighted in this work. We also provided the perspectives for the future research on LMR cathode materials, focusing on addressing the fundamental problems of LMR cathodes while always keeping practical considerations in mind.« less

Materials Genomics Screens for Adaptive Ion Transport Behavior by Redox-Switchable Microporous Polymer Membranes in Lithium-Sulfur Batteries.

PubMed

Ward, Ashleigh L; Doris, Sean E; Li, Longjun; Hughes, Mark A; Qu, Xiaohui; Persson, Kristin A; Helms, Brett A

2017-05-24

Selective ion transport across membranes is critical to the performance of many electrochemical energy storage devices. While design strategies enabling ion-selective transport are well-established, enhancements in membrane selectivity are made at the expense of ionic conductivity. To design membranes with both high selectivity and high ionic conductivity, there are cues to follow from biological systems, where regulated transport of ions across membranes is achieved by transmembrane proteins. The transport functions of these proteins are sensitive to their environment: physical or chemical perturbations to that environment are met with an adaptive response. Here we advance an analogous strategy for achieving adaptive ion transport in microporous polymer membranes. Along the polymer backbone are placed redox-active switches that are activated in situ, at a prescribed electrochemical potential, by the device's active materials when they enter the membrane's pore. This transformation has little influence on the membrane's ionic conductivity; however, the active-material blocking ability of the membrane is enhanced. We show that when used in lithium-sulfur batteries, these membranes offer markedly improved capacity, efficiency, and cycle-life by sequestering polysulfides in the cathode. The origins and implications of this behavior are explored in detail and point to new opportunities for responsive membranes in battery technology development.

Materials Genomics Screens for Adaptive Ion Transport Behavior by Redox-Switchable Microporous Polymer Membranes in Lithium–Sulfur Batteries

PubMed Central

2017-01-01

Selective ion transport across membranes is critical to the performance of many electrochemical energy storage devices. While design strategies enabling ion-selective transport are well-established, enhancements in membrane selectivity are made at the expense of ionic conductivity. To design membranes with both high selectivity and high ionic conductivity, there are cues to follow from biological systems, where regulated transport of ions across membranes is achieved by transmembrane proteins. The transport functions of these proteins are sensitive to their environment: physical or chemical perturbations to that environment are met with an adaptive response. Here we advance an analogous strategy for achieving adaptive ion transport in microporous polymer membranes. Along the polymer backbone are placed redox-active switches that are activated in situ, at a prescribed electrochemical potential, by the device’s active materials when they enter the membrane’s pore. This transformation has little influence on the membrane’s ionic conductivity; however, the active-material blocking ability of the membrane is enhanced. We show that when used in lithium–sulfur batteries, these membranes offer markedly improved capacity, efficiency, and cycle-life by sequestering polysulfides in the cathode. The origins and implications of this behavior are explored in detail and point to new opportunities for responsive membranes in battery technology development. PMID:28573201

Materials Challenges and Opportunities of Lithium-ion Batteries for Electrical Energy Storage

NASA Astrophysics Data System (ADS)

Manthiram, Arumugam

2011-03-01

Electrical energy storage has emerged as a topic of national and global importance with respect to establishing a cleaner environment and reducing the dependence on foreign oil. Batteries are the prime candidates for electrical energy storage. They are the most viable near-term option for vehicle applications and the efficient utilization of intermittent energy sources like solar and wind. Lithium-ion batteries are attractive for these applications as they offer much higher energy density than other rechargeable battery systems. However, the adoption of lithium-ion battery technology for vehicle and stationary storage applications is hampered by high cost, safety concerns, and limitations in energy, power, and cycle life, which are in turn linked to severe materials challenges. This presentation, after providing an overview of the current status, will focus on the physics and chemistry of new materials that can address these challenges. Specifically, it will focus on the design and development of (i) high-capacity, high-voltage layered oxide cathodes, (ii) high-voltage, high-power spinel oxide cathodes, (iii) high-capacity silicate cathodes, and (iv) nano-engineered, high-capacity alloy anodes. With high-voltage cathodes, a critical issue is the instability of the electrolyte in contact with the highly oxidized cathode surface and the formation of solid-electrolyte interfacial (SEI) layers that degrade the performance. Accordingly, surface modification of cathodes with nanostructured materials and self-surface segregation during the synthesis process to suppress SEI layer formation and enhance the energy, power, and cycle life will be emphasized. With the high-capacity alloy anodes, a critical issue is the huge volume change occurring during the charge-discharge process and the consequent poor cycle life. Dispersion of the active alloy nanoparticles in an inactive metal oxide-carbon matrix to mitigate this problem and realize long cycle life will be presented.

Systems and Methods for Fabricating Carbon Nanotube-Based Vacuum Electronic Devices

NASA Technical Reports Server (NTRS)

Manohara, Harish (Inventor); Toda, Risaku (Inventor); Del Castillo, Linda Y. (Inventor); Murthy, Rakesh (Inventor)

2015-01-01

Systems and methods in accordance with embodiments of the invention proficiently produce carbon nanotube-based vacuum electronic devices. In one embodiment a method of fabricating a carbon nanotube-based vacuum electronic device includes: growing carbon nanotubes onto a substrate to form a cathode; assembling a stack that includes the cathode, an anode, and a first layer that includes an alignment slot; disposing a microsphere partially into the alignment slot during the assembling of the stack such that the microsphere protrudes from the alignment slot and can thereby separate the first layer from an adjacent layer; and encasing the stack in a vacuum sealed container.

Synthesis, characterization and rate capability performance of the micro-porous MnO{sub 2} nanowires as cathode material in lithium batteries

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

R, Ranjusha; S, Sonia T.; S, Roshny

Graphical abstract: Translating MnO{sub 2} nanowires as cathode materials in coin cell and studying their discharge behavior and cycling stability at different C-rates. - Highlights: • MnO{sub 2} nanowires have been synthesized via hydrothermal route. • The nanowires were employed as cathode materials in Li-batteries. • Discharge and cycling stability were studied at different C-rates. • Specific capacity and power density of 251 mAh g{sup −1} and 200 W kg{sup −1} were attained. - Abstract: A peculiar architecture of one-dimensional MnO{sub 2} nanowires was synthesized by an optimized hydrothermal route and has been lucratively exploited to fabricate highly efficient microporousmore » electrode overlays for lithium batteries. These fabricated electrodes comprised of interconnected nanoscale units with wire-shaped profile which exhibits high aspect ratio in the order of 10{sup 2}. Their outstanding intercalation/de-intercalation prerogatives have also been studied to fabricate lithium coin cells which revealed a significant specific capacity and power density of 251 mAh g{sup −1} and 200 W kg{sup −1}, respectively. A detailed electrochemical study was performed to elucidate how surface morphology and redox reaction behaviors underlying these electrodes influence the cyclic behavior of the electrode. Rate capability tests at different C-rates were performed to evaluate the capacity and cycling performance of these coin cells.« less

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

Atmospheric Plasma Spraying Low-Temperature Cathode Materials for Solid Oxide Fuel Cells

NASA Astrophysics Data System (ADS)

Harris, J.; Kesler, O.

2010-01-01

Atmospheric plasma spraying (APS) is attractive for manufacturing solid oxide fuel cells (SOFCs) because it allows functional layers to be built rapidly with controlled microstructures. The technique allows SOFCs that operate at low temperatures (500-700 °C) to be fabricated by spraying directly onto robust and inexpensive metallic supports. However, standard cathode materials used in commercial SOFCs exhibit high polarization resistances at low operating temperatures. Therefore, alternative cathode materials with high performance at low temperatures are essential to facilitate the use of metallic supports. Coatings of lanthanum strontium cobalt ferrite (LSCF) were fabricated on steel substrates using axial-injection APS. The thickness and microstructure of the coating layers were evaluated, and x-ray diffraction analysis was performed on the coatings to detect material decomposition and the formation of undesired phases in the plasma. These results determined the envelope of plasma spray parameters in which coatings of LSCF can be manufactured, and the range of conditions in which composite cathode coatings could potentially be manufactured.

Multi-variable mathematical models for the air-cathode microbial fuel cell system

NASA Astrophysics Data System (ADS)

Ou, Shiqi; Kashima, Hiroyuki; Aaron, Douglas S.; Regan, John M.; Mench, Matthew M.

2016-05-01

This research adopted the version control system into the model construction for the single chamber air-cathode microbial fuel cell (MFC) system, to understand the interrelation of biological, chemical, and electrochemical reactions. The anodic steady state model was used to consider the chemical species diffusion and electric migration influence to the MFC performance. In the cathodic steady state model, the mass transport and reactions in a multi-layer, abiotic cathode and multi-bacteria cathode biofilm were simulated. Transport of hydroxide was assumed for cathodic pH change. This assumption is an alternative to the typical notion of proton consumption during oxygen reduction to explain elevated cathode pH. The cathodic steady state model provided the power density and polarization curve performance results that can be compared to an experimental MFC system. Another aspect considered was the relative contributions of platinum catalyst and microbes on the cathode to the oxygen reduction reaction (ORR). Simulation results showed that the biocatalyst in a cathode that includes a Pt/C catalyst likely plays a minor role in ORR, contributing up to 8% of the total power calculated by the models.

Molecular dynamics simulations of Li transport between cathode crystals

NASA Astrophysics Data System (ADS)

Garofalini, S. H.

The molecular dynamics (MD) computer simulation technique has been used to study the effect of an amorphous intergranular film (IGF) present in a polycrystalline cathode on Li transport. The solid electrolyte is a model lithium silicate glass while the cathode is a nanocrystalline vanadia with an amorphous V 2O 5 IGF separating the crystals. Thin (˜1 to a few nanometer thick) IGFs are known to be present in most polycrystalline oxide materials. However, the role of such a film on Li transport in oxide cathodes has not been addressed. Current scanning probe microscopy (SPM) studies have shown that the orientation of the layered nanocrystalline vanadia crystals near the cathode/solid electrolyte interface is not optimized for Li ion transport. While the precise structure of the material between the crystals has not been identified, initially it can be initially considered as likely to be a thin non-crystalline (amorphous) film. This is based on the ubiquitous presence of such a structure in other polycrystalline oxides. Also, and with more relevance to the materials used in thin film batteries, an amorphous film can be expected to form between nanocrystals that crystallized from an amorphous matrix, as would be the case in a deposited thin film cathode. Consistent with simulations of Li transport in amorphous vanadia, the current simulations show that Li ions diffuse more rapidly into the amorphous intergranular thin film than into the layered vanadia with the (0 0 1) planes parallel to the cathode/electrolyte interface.

Barium: An Efficient Cathode Layer for Bulk-heterojunction Solar Cells

PubMed Central

Gupta, Vinay; Kyaw, Aung Ko Ko; Wang, Dong Hwan; Chand, Suresh; Bazan, Guillermo C.; Heeger, Alan J.

2013-01-01

We report Barium (Ba) cathode layer for bulk-heterojunction solar cells which enhanced the fill factor (FF) of p-DTS(FBTTh2)2/PC71BM BHJ solar cell up to 75.1%, one of the highest value reported for an organic solar cell. The external quantum efficiency exceeds 80%. Analysis of recombination mechanisms using the current-voltage (J–V) characteristics at various light intensities in the BHJ solar cell layer reveals that Ba prevents trap assisted Shockley-Read-Hall (SRH) recombination at the interface and with different thicknesses of the Ba, the recombination shifts towards bimolecular from monomolecular. Moreover, Ba increases shunt resistance and decreases the series resistance significantly. This results in an increase in the charge collection probability leading to high FF. This work identifies a new cathode interlayer which outclasses the all the reported interlayers in increasing FF leading to high power conversion efficiency and have significant implications in improving the performance of BHJ solar cells. PMID:23752562

Effect of cathodic polarization on coating doxycycline on titanium surfaces.

PubMed

Geißler, Sebastian; Tiainen, Hanna; Haugen, Håvard J

2016-06-01

Cathodic polarization has been reported to enhance the ability of titanium based implant materials to interact with biomolecules by forming titanium hydride at the outermost surface layer. Although this hydride layer has recently been suggested to allow the immobilization of the broad spectrum antibiotic doxycycline on titanium surfaces, the involvement of hydride in binding the biomolecule onto titanium remains poorly understood. To gain better understanding of the influence this immobilization process has on titanium surfaces, mirror-polished commercially pure titanium surfaces were cathodically polarized in the presence of doxycycline and the modified surfaces were thoroughly characterized using atomic force microscopy, electron microscopy, secondary ion mass spectrometry, and angle-resolved X-ray spectroscopy. We demonstrated that no hydride was created during the polarization process. Doxycycline was found to be attached to an oxide layer that was modified during the electrochemical process. A bacterial assay using bioluminescent Staphylococcus epidermidis Xen43 showed the ability of the coating to reduce bacterial colonization and planktonic bacterial growth. Copyright © 2016 Elsevier B.V. All rights reserved.

Study on the water flooding in the cathode of direct methanol fuel cells.

PubMed

Im, Hun Suk; Kim, Sang-Kyung; Lim, Seongyop; Peck, Dong-Hyun; Jung, Doohwan; Hong, Won Hi

2011-07-01

Water flooding phenomena in the cathode of direct methanol fuel cells were analyzed by using electrochemical impedance spectroscopy. Two kinds of commercial gas diffusion layers with different PTFE contents of 5 wt% (GDL A5) and 20 wt% (GDL B20) were used to investigate the water flooding under various operating conditions. Water flooding was divided into two types: catalyst flooding and backing flooding. The cathode impedance spectra of each gas diffusion layer was obtained and compared under the same conditions. The diameter of the capacitive semicircle became larger with increasing current density for both, and this increase was greater for GDL B20 than GDL A5. Catalyst flooding is dominant and backing flooding is negligible when the air flow rate is high and current density is low. An equivalent model was suggested and fitted to the experimental data. Parameters for catalyst flooding and backing flooding were individually obtained. The capacitance of the catalyst layer decreases as the air flow rate decreases when the catalyst flooding is dominant.

Physical and technological principles of designing layer-gradient multicomponent surfaces by combining the methods of ion-diffusion saturation and magnetron- and vacuum-arc deposition

NASA Astrophysics Data System (ADS)

Savostikov, V. M.; Potekaev, A. I.; Tabachenko, A. N.

2011-12-01

Using a technological system proposed by the authors, a combined process is developed for formation of stratified-gradient surface layers and multicomponent coatings. It is implemented under the conditions of a combined serial-parallel operation of a hot-cathode gas plasma generator and a duomagnetron with two targets and two electric-arc evaporators. The extended functional potential is ensured by using advanced multi-element and multi-phase cathode targets made of borides, carbides, silicides, and sulfides of metals produced by the SHS-process followed by their immediate compaction. The variations in composition, structure, and physicomechanical properties in the cross-section of the stratified-gradient surface layers and coating is provided by a predetermined alternating replacement of the sputtered cathode targets of the plasma sources, the plasma flow intensity ratios, and variation in the particle energy incident on the substrate, which is determined by the accelerating voltage on the substrate.

Integrated Semiconductor-based Diagnostics System for Multiplexed Genomic Amplification and Electrochemical Detection of Biothreat Agents

DTIC Science & Technology

2009-01-01

microporous disc with adhesive backing. Figure 6. Illustration of the bottom polypropylene layer with the PCR chamber. PCR Chamber UNCLASSIFIED...consistent heating in the PCR chamber. Using insulation and a modified commercial temperature sensor, consistent thermal cycling was achieved with this

Characterization of metal-supported axial injection plasma sprayed solid oxide fuel cells with aqueous suspension plasma sprayed electrolyte layers

NASA Astrophysics Data System (ADS)

Waldbillig, D.; Kesler, O.

A method for manufacturing metal-supported SOFCs with atmospheric plasma spraying (APS) is presented, making use of aqueous suspension feedstock for the electrolyte layer and dry powder feedstock for the anode and cathode layers. The cathode layer was deposited first directly onto a metal support, in order to minimize contact resistance, and to allow the introduction of added porosity. The electrolyte layers produced by suspension plasma spraying (SPS) were characterized in terms of thickness, permeability, and microstructure, and the impact of substrate morphology on electrolyte properties was investigated. Fuel cells produced by APS were electrochemically tested at temperatures ranging from 650 to 750 °C. The substrate morphology had little effect on open circuit voltage, but substrates with finer porosity resulted in lower kinetic losses in the fuel cell polarization.

Zirconia coating stabilized super-iron alkaline cathodes

NASA Astrophysics Data System (ADS)

Yu, Xingwen; Licht, Stuart

A low-level zirconia coating significantly stabilizes high energy alkaline super-iron cathodes, and improves the energy storage capacity of super-iron batteries. Zirconia coating is derived from ZrCl 4 in an organic medium through the conversion of ZrCl 4 to ZrO 2. In alkaline battery system, ZrO 2 provides an intact shield for the cathode materials and the hydroxide shuttle through the coating sustains alkaline cathode redox chemistry. Most super-iron cathodes are solid-state stable, such as K 2FeO 4 and Cs 2FeO 4, but tend to be passivated in alkaline electrolyte due to the formation of Fe(III) over layer. Zirconia coating effectively enhances the stability of these super-iron cathodes. However, for solid-state unstable super-iron cathode (e.g. BaFeO 4), only a little stabilization effect of zirconia coating is observed.

A High-Performance Sodium-Ion Full Cell with a Layered Oxide Cathode and a Phosphorous-Based Composite Anode

DOE PAGES

Oh, Seung-Min; Oh, Pilgun; Kim, Sang-Ok; ...

2016-12-29

A low-cost sodium-ion full cell with a O3-type layered Na[Cu 0.2(Fe 1/3Mn2/3) 0.8]O 2 cathode and an alloy-type P-TiP2-C anode is presented. The cathode is synthesized by an oxalate coprecipitation method and optimized cathodes shows a high specific capacity of 135 mAh g -1 at 0.1C rate with a high rate capability of 90 mAh g-1 at 1C rate and 70 mAh g -1 at 2C rate with good cyclability. The full cell exhibits better capacity retention than the half cell with the cathode due to the elimination of the degradation caused by sodium-metal anode. The dramatically enhanced electrochemical performancemore » of the Na[Cu 0.2(Fe 1/3Mn 2/3) 0.8]O 2 / P-TiP 2-C full cell compared to that of the sample with no Cu is attributed to the structural stabilization imparted by Cu by suppressing the phase change from the O3 structure to the P3 structure during cycling.« less

Insights into the Influence of Work Functions of Cathodes on Efficiencies of Perovskite Solar Cells.

PubMed

Yue, Shizhong; Lu, Shudi; Ren, Kuankuan; Liu, Kong; Azam, Muhammad; Cao, Dawei; Wang, Zhijie; Lei, Yong; Qu, Shengchun; Wang, Zhanguo

2017-05-01

Though various efforts on modification of electrodes are still undertaken to improve the efficiency of perovskite solar cells, attributing to the large scope of these methods, it is of significance to unveil the working principle systematically. Herein, inverted perovskite solar cells based on indium tin oxide (ITO)/poly(3,4-ethylenedioxythiophene) polystyrene sulfonate (PEDOT:PSS)/CH 3 NH 3 PbI 3 /phenyl-C61-butyric acid methyl ester (PC 61 BM)/buffer metal/Al are constructed. Through the choice of different buffer metals to tune work function of the cathode, the contact nature of the active layer with the cathode could be manipulated well. In comparison with the device using Au/Al as the electrode that shows an unfavorable band bending for conducting the excited electrons to the cathode, the one with Ca/Al presents a dramatically improved efficiency over 17.1%, ascribed to the favorable band bending at the interface of the cathode with the active layer. Details for tuning the band bending and the corresponding charge transfer mechanism are given in a systematic manner. Thus, a general guideline for constructing perovskite photovoltaic devices efficiently is provided. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Substrate-Independent Epitaxial Growth of the Metal-Organic Framework MOF-508a.

PubMed

Wilson, M; Barrientos-Palomo, S N; Stevens, P C; Mitchell, N L; Oswald, G; Nagaraja, C M; Badyal, J P S

2018-01-31

Plasmachemical deposition is a substrate-independent method for the conformal surface functionalization of solid substrates. Structurally well-defined pulsed plasma deposited poly(1-allylimidazole) layers provide surface imidazole linker groups for the directed liquid-phase epitaxial (layer-by-layer) growth of metal-organic frameworks (MOFs) at room temperature. For the case of microporous [Zn (benzene-1,4-dicarboxylate)-(4,4'-bipyridine) 0.5 ] (MOF-508), the MOF-508a polymorph containing two interpenetrating crystal lattice frameworks undergoes orientated Volmer-Weber growth and displays CO 2 gas capture behavior at atmospheric concentrations in proportion to the number of epitaxially grown MOF-508 layers.

Binary Hierarchical Porous Graphene/Pyrolytic Carbon Nanocomposite Matrix Loaded with Sulfur as a High-Performance Li-S Battery Cathode.

PubMed

Zhang, Hang; Gao, Qiuming; Qian, Weiwei; Xiao, Hong; Li, Zeyu; Ma, Li; Tian, Xuehui

2018-06-06

A N,O-codoped hierarchical porous nanocomposite consisting of binary reduced graphene oxide and pyrolytic carbon (rGO/PC) from chitosan is fabricated. The optimized rGO/PC possesses micropores with size distribution concentrated around 1.1 nm and plenty of meso/macropores. The Brunauer-Emmett-Teller specific surface area is 480.8 m 2 g -1 , and it possesses impressively large pore volume of 2.14 cm 3 g -1 . On the basis of the synergistic effects of the following main factors: (i) the confined space effect in the hierarchical porous binary carbonaceous matrix; (ii) the anchor effects by strong chemical bonds with codoped N and O atoms; and (iii) the good flexibility and conductivity of rGO, the rGO/PC/S holding 75 wt % S exhibits high performance as Li-S battery cathode. Specific capacity of 1625 mA h g -1 can be delivered at 0.1 C (1 C = 1675 mA g -1 ), whereas 848 mA h g -1 can be maintained after 300 cycles at 1 C. Even at high rate of 5 C, 412 mA h g -1 can be restrained after 1000 cycles.

Porous metal-organic framework Cu3(BTC)2 as catalyst used in air-cathode for high performance of microbial fuel cell.

PubMed

Tian, Pei; Liu, Di; Li, Kexun; Yang, Tingting; Wang, Junjie; Liu, Yi; Zhang, Song

2017-11-01

Metal-organic framework Cu 3 (BTC) 2 , prepared by an easy hydrothermal method, was used as the oxygen-based catalyst in microbial fuel cell (MFC). The maximum power density of Cu 3 (BTC) 2 modified air-cathode MFC was 1772±15mWm -2 , almost 1.8 times higher than the control. BET results disclosed high specific surface area of 2159.7m 2 g -1 and abundant micropores structure. Regular octahedron and porous surface of Cu 3 (BTC) 2 were observed in SEM. XPS testified the existence of divalent copper in the extended 3D frameworks, which importantly acted as the Lewis-acid sites or redox centers in ORR. Additionally, the total resistance decreased by 42% from 17.60 to 10.24Ω compared with bare AC electrode. The rotating disk electrode test results showed a four-electron transfer pathway for Cu 3 (BTC) 2 , which was crucial for electrochemical catalytic activity. All the structural and electrochemical advantages make Cu 3 (BTC) 2 a promising catalyst for ORR in MFC. Copyright © 2017. Published by Elsevier Ltd.

Cation-substituted spinel oxide and oxyfluoride cathodes for lithium ion batteries

DOEpatents

Manthiram, Arumugam; Choi, Wongchang

2014-05-13

The present invention includes compositions and methods of making cation-substituted and fluorine-substituted spinel cathode compositions by firing a LiMn.sub.2-y-zLi.sub.yM.sub.zO.sub.4 oxide with NH.sub.4HF.sub.2 at low temperatures of between about 300 and 700.degree. C. for 2 to 8 hours and a .eta. of more than 0 and less than about 0.50, mixed two-phase compositions consisting of a spinel cathode and a layered oxide cathode, and coupling them with unmodified or surface modified graphite anodes in lithium ion cells.

Nitrogen-doped carbonaceous catalysts for gas-diffusion cathodes for alkaline aluminum-air batteries

NASA Astrophysics Data System (ADS)

Davydova, E. S.; Atamanyuk, I. N.; Ilyukhin, A. S.; Shkolnikov, E. I.; Zhuk, A. Z.

2016-02-01

Cobalt tetramethoxyphenyl porphyrin and polyacrylonitrile - based catalysts for oxygen reduction reaction were synthesized and characterized by means of SEM, TEM, XPS, BET, limited evaporation method, rotating disc and rotating ring-disc electrode methods. Half-cell and Al-air cell tests were carried out to determine the characteristics of gas-diffusion cathodes. Effect of active layer thickness and its composition on the characteristics of the gas-diffusion cathodes was investigated. Power density of 300 mW cm-2 was achieved for alkaline Al-air cell with an air-breathing polyacrylonitrile-based cathode.

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

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

Post-test characterization of a solid oxide fuel cell stack operated for more than 30,000 hours: The cell

NASA Astrophysics Data System (ADS)

Menzler, Norbert H.; Sebold, Doris; Guillon, Olivier

2018-01-01

A four-layer solid oxide fuel cell stack with planar anode-supported cells was operated galvanostatically at 700 °C and 0.5Acm-2 for nearly 35,000 h. One of the four planes started to degrade more rapidly after ∼28,000 h and finally more progressively after ∼33,000 h. The stack was then shut down and a post-test analysis was carefully performed. The cell was characterized with respect to cathodic impurities and clarification of the reason(s) for failure. Wet chemical analysis revealed very low chromium incorporation into the cathode. However, SEM and TEM observations on polished and fractured surfaces showed catastrophic failure in the degraded layer. The cathode-barrier-electrolyte cell layer system delaminated from the entire cell over large areas. The source of delamination was the formation of a porous, sponge-like secondary phase consisting of zirconia, yttria and manganese (oxide). Large secondary phase islands grew from the electrolyte-anode interface towards the anode and cracked the bonding between both layers. The manganese originated from the contact or protection layers used on the air side. This stack result shows that volatile species - in this case manganese - should be avoided, especially when long-term applications are envisaged.

Nanostructured high-energy cathode materials for advanced lithium batteries

NASA Astrophysics Data System (ADS)

Sun, Yang-Kook; Chen, Zonghai; Noh, Hyung-Joo; Lee, Dong-Ju; Jung, Hun-Gi; Ren, Yang; Wang, Steve; Yoon, Chong Seung; Myung, Seung-Taek; Amine, Khalil

2012-11-01

Nickel-rich layered lithium transition-metal oxides, LiNi1-xMxO2 (M = transition metal), have been under intense investigation as high-energy cathode materials for rechargeable lithium batteries because of their high specific capacity and relatively low cost. However, the commercial deployment of nickel-rich oxides has been severely hindered by their intrinsic poor thermal stability at the fully charged state and insufficient cycle life, especially at elevated temperatures. Here, we report a nickel-rich lithium transition-metal oxide with a very high capacity (215 mA h g-1), where the nickel concentration decreases linearly whereas the manganese concentration increases linearly from the centre to the outer layer of each particle. Using this nano-functional full-gradient approach, we are able to harness the high energy density of the nickel-rich core and the high thermal stability and long life of the manganese-rich outer layers. Moreover, the micrometre-size secondary particles of this cathode material are composed of aligned needle-like nanosize primary particles, resulting in a high rate capability. The experimental results suggest that this nano-functional full-gradient cathode material is promising for applications that require high energy, long calendar life and excellent abuse tolerance such as electric vehicles.

Nanostructured high-energy cathode materials for advanced lithium batteries.

PubMed

Sun, Yang-Kook; Chen, Zonghai; Noh, Hyung-Joo; Lee, Dong-Ju; Jung, Hun-Gi; Ren, Yang; Wang, Steve; Yoon, Chong Seung; Myung, Seung-Taek; Amine, Khalil

2012-11-01

Nickel-rich layered lithium transition-metal oxides, LiNi(1-x)M(x)O(2) (M = transition metal), have been under intense investigation as high-energy cathode materials for rechargeable lithium batteries because of their high specific capacity and relatively low cost. However, the commercial deployment of nickel-rich oxides has been severely hindered by their intrinsic poor thermal stability at the fully charged state and insufficient cycle life, especially at elevated temperatures. Here, we report a nickel-rich lithium transition-metal oxide with a very high capacity (215 mA h g(-1)), where the nickel concentration decreases linearly whereas the manganese concentration increases linearly from the centre to the outer layer of each particle. Using this nano-functional full-gradient approach, we are able to harness the high energy density of the nickel-rich core and the high thermal stability and long life of the manganese-rich outer layers. Moreover, the micrometre-size secondary particles of this cathode material are composed of aligned needle-like nanosize primary particles, resulting in a high rate capability. The experimental results suggest that this nano-functional full-gradient cathode material is promising for applications that require high energy, long calendar life and excellent abuse tolerance such as electric vehicles.

Conceptual design and experiments of electrochemistry-flushing technology for the remediation of historically Cr(Ⅵ)-contaminated soil.

PubMed

Li, Dong; Sun, Delin; Hu, Siyang; Hu, Jing; Yuan, Xingzhong

2016-02-01

A conceptual design and experiments, electrochemistry-flushing (E-flushing), using electrochemistry to enhance flushing efficiency for the remediation of Cr(Ⅵ)-contaminated soil is presented. The rector contained three compartments vertically superposed. The upper was airtight cathode compartment containing an iron-cathode. The middle was soil layer. The bottom was anode compartment containing an iron-anode and connected to a container by circulation pumps. H2 and OH(-) ions were produced at cathode. H2 increased the gas pressure in cathode compartment and drove flushing solution into soil layer forming flushing process. OH(-) ions entered into soil layer by eletromigration and hydraulic flow to enhance the desorption of Cr(Ⅵ). High potential gradient was applied to accelerate the electromigration of desorbed Cr(Ⅵ) ions and produced joule heat to increase soil temperature to enhance Cr(Ⅵ) desorption. In anode compartment, Fe(2+) ions produced at iron-anode reduced the desorbed Cr(Ⅵ) into Cr(3+) ions, which reacted with OH(-) ions forming Cr(OH)3. Experimental results show that Cr(Ⅵ) removal efficiency of E-flushing experiments was more than double of flushing experiments and reached the maximum of removal efficiency determined by desorption kinetics. All electrochemistry processes were positively used in E-flushing technology. Copyright © 2015 Elsevier Ltd. All rights reserved.

The effect of diamond-like carbon coating on LiNi0.8Co0.15Al0.05O2 particles for all solid-state lithium-ion batteries based on Li2S-P2S5 glass-ceramics

NASA Astrophysics Data System (ADS)

Visbal, Heidy; Aihara, Yuichi; Ito, Seitaro; Watanabe, Taku; Park, Youngsin; Doo, Seokgwang

2016-05-01

There have been several reports on improvements of the performance of all solid-state battery using lithium metal oxide coatings on the cathode active material. However, the mechanism of the performance improvement remains unclear. To better understand the effect of the surface coating, we studied the impact of diamond-like carbon (DLC) coating on LiNi0.8Co0.15Al0.05O2 (NCA) by chemical vapor deposition (CVD). The DLC coated NCA showed good cycle ability and rate performance. This result is further supported by reduction of the interfacial resistance of the cathode and electrolyte observed in impedance spectroscopy. The DLC layer was analyzed by transmission electron microscopy electron energy loss spectroscopy (TEM-EELS). After 100 cycles the sample was analyzed by X-ray photo spectroscopy (XPS), and Time-of-Flight Secondary Ion Mass Spectrometry (TOF-SIMS). These analyses showed that the thickness of the coating layer was around 4 nm on average, acting to hinder the side reactions between the cathode particle and the solid electrolyte. The results of this study will provide useful insights for understanding the nature of the buffer layer for the cathode materials.

Honeycomb-Ordered Na 3Ni 1.5M 0.5BiO 6 (M = Ni, Cu, Mg, Zn) as High-Voltage Layered Cathodes for Sodium-Ion Batteries

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

Wang, Peng -Fei; Guo, Yu -Jie; Duan, Hui

Developing high-voltage layered cathodes for sodium-ion batteries (SIBs) has always been a severe challenge. Herein, a new family of honeycomb-layered Na 3Ni 1.5M 0.5BiO 6 (M = Ni, Cu, Mg, Zn) with a monoclinic superstructure has been shown to combine good Na + (de)intercalation activity with a competitive 3.3 V high voltage. By coupling the electrochemical process with ex situ X-ray absorption spectroscopy as well as in situ X-ray diffraction, the charge compensation mechanism and structural evolution of these new cathodes are clearly investigated. Interestingly, both Ni 2+/Ni 3+ and Cu 2+/Cu 3+ participate in the redox reaction upon cycling,more » and the succession of single-phase, two-phase, or three-phase regions upon Na+ extraction/insertion were identified with rather good accuracy. Furthermore, this research strategy could provide insights into the structure–function–property relationships on a new series of honeycomb-ordered materials with the general formula Na 3Ni 1.5M 0.5BiO 6 and also serve as a bridge to guide future design of high-performance cathodes for SIBs.« less

Honeycomb-Ordered Na 3Ni 1.5M 0.5BiO 6 (M = Ni, Cu, Mg, Zn) as High-Voltage Layered Cathodes for Sodium-Ion Batteries

DOE PAGES

Wang, Peng -Fei; Guo, Yu -Jie; Duan, Hui; ...

2017-11-01

Developing high-voltage layered cathodes for sodium-ion batteries (SIBs) has always been a severe challenge. Herein, a new family of honeycomb-layered Na 3Ni 1.5M 0.5BiO 6 (M = Ni, Cu, Mg, Zn) with a monoclinic superstructure has been shown to combine good Na + (de)intercalation activity with a competitive 3.3 V high voltage. By coupling the electrochemical process with ex situ X-ray absorption spectroscopy as well as in situ X-ray diffraction, the charge compensation mechanism and structural evolution of these new cathodes are clearly investigated. Interestingly, both Ni 2+/Ni 3+ and Cu 2+/Cu 3+ participate in the redox reaction upon cycling,more » and the succession of single-phase, two-phase, or three-phase regions upon Na+ extraction/insertion were identified with rather good accuracy. Furthermore, this research strategy could provide insights into the structure–function–property relationships on a new series of honeycomb-ordered materials with the general formula Na 3Ni 1.5M 0.5BiO 6 and also serve as a bridge to guide future design of high-performance cathodes for SIBs.« less

Cathodic protection of two concrete bridge decks using titanium-mesh anodes : interim report.

DOT National Transportation Integrated Search

1991-01-01

Expanded titanium mesh with a layer of precious metal oxides sintered around it has recently been introduced to fulfill the need for a durable anode in the cathodic protection (CP) of concrete bridge decks. In addition to being resistant to chemical ...

Luminance enhancement in quantum dot light-emitting diodes fabricated with Field’s metal as the cathode

NASA Astrophysics Data System (ADS)

Basilio, Carlos; Oliva, Jorge; Lopez-Luke, Tzarara; Pu, Ying-Chih; Zhang, Jin Z.; Rodriguez, C. E.; de la Rosa, E.

2017-03-01

This work reports the fabrication and characterization of blue-green quantum dot light-emitting diodes (QD-LEDs) by using core/shell/shell Cd1-x Zn x Se/ZnSe/ZnS quantum dots. Poly [(9,9-bis(3‧-(N,N-dimethylamino)propyl)-2,7-fluorene)-alt-2,7-(9,9-dioctylfluorene)] (PFN) was introduced in order to enhance the electron injection and also acted as a protecting layer during the deposition of the cathode (a Field’s metal sheet) on the organic/inorganic active layers at low temperature (63 °C). This procedure permitted us to eliminate the process of thermal evaporation for the deposition of metallic cathodes, which is typically used in the fabrication of OLEDs. The performance of devices made with an aluminum cathode was compared with that of devices which employed Field’s metal (FM) as the cathode. We found that the luminance and efficiency of devices with FM was ~70% higher with respect to those that employed aluminum as the cathode and their consumption of current was similar up to 13 V. We also demonstrated that the simultaneous presence of 1,2-ethanedethiol (EDT) and PFN enhanced the luminance in our devices and improved the current injection in QD-LEDs. Hence, the architecture for QD-LEDs presented in this work could be useful for the fabrication of low-cost luminescent devices.

Correlating highpower conversion efficiency of PTB7:PC 71BM inverted organic solar cells with nanoscale structures [Unraveling the correlation between the structural aspects and power conversion efficiency in PTB7:PC 71BM inverted organic solar cells

DOE PAGES

Das, Sanjib; Browning, Jim; Gu, Gong; ...

2015-07-16

Advances in materials design and device engineering led to inverted organic solar cells (i-OSCs) with superior power conversion efficiencies (PCEs) to their conventional counterparts, in addition to the well-known better ambient stability. Despite the significant progress, however, it has so far been unclear how the morphologies of the photoactive layer and its interface with the cathode modifying layer impact device performance. Here, we report an in-depth morphology study of the i-OSC active and cathode modifying layers, employing a model system with the well-established bulk-heterojunction, PTB7:PC 71BM as the active layer and poly-[(9,9-bis(3 -( N,N-dimethylamino)propyl)-2,7-fluorene)- alt-2,7-(9,9-dioctylfluorene)] (PFN) as the cathode surfacemore » modifying layer. We have also identified the role of a processing additive, 1,8-diiodooctane (DIO), used in the spin-casting of the active layer to increase PCE. Using a variety of characterization techniques, we demonstrate that the high PCEs of i-OSCs are due to the smearing (diffusion) of electron-accepting PC 71BM into the PFN layer, resulting in improved electron transport. The PC 71BM diffusion occurs after spin-casting the active layer onto the PFN layer, when residual solvent molecules act as a plasticizer. Furthermore, the DIO additive, with a higher boiling point than the host solvent, has a longer residence time in the spin-cast active layer, resulting in more PC 71BM smearing and therefore more efficient electron transport. This work provides important insight and guidance to further enhancement of i-OSC performance by materials and interface engineering.« less

Ultrabright fluorescent OLEDS using triplet sinks

DOEpatents

Zhang, Yifan; Forrest, Stephen R; Thompson, Mark

2013-06-04

A first device is provided. The first device further comprises an organic light emitting device. The organic light emitting device further comprises an anode, a cathode, and an emissive layer disposed between the anode and the cathode. The emissive layer further comprises an organic host compound, an organic emitting compound capable of fluorescent emission at room temperature, and an organic dopant compound. The triplet energy of the dopant compound is lower than the triplet energy of the host compound. The dopant compound does not strongly absorb the fluorescent emission of the emitting compound.

High efficiency and brightness fluorescent organic light emitting diode by triplet-triplet fusion

DOEpatents

Forrest, Stephen; Zhang, Yifan

2015-02-10

A first device is provided. The first device further comprises an organic light emitting device. The organic light emitting device further comprises an anode, a cathode, and an emissive layer disposed between the anode and the cathode. The emissive layer may include an organic host compound and at least one organic emitting compound capable of fluorescent emission at room temperature. Various configurations are described for providing a range of current densities in which T-T fusion dominates over S-T annihilation, leading to very high efficiency fluorescent OLEDs.

Lithium-ion batteries having conformal solid electrolyte layers

DOEpatents

Kim, Gi-Heon; Jung, Yoon Seok

2014-05-27

Hybrid solid-liquid electrolyte lithium-ion battery devices are disclosed. Certain devices comprise anodes and cathodes conformally coated with an electron insulating and lithium ion conductive solid electrolyte layer.

Transport equations in an enzymatic glucose fuel cell

NASA Astrophysics Data System (ADS)

Jariwala, Soham; Krishnamurthy, Balaji

2018-01-01

A mathematical model is developed to study the effects of convective flux and operating temperature on the performance of an enzymatic glucose fuel cell with a membrane. The model assumes isothermal operating conditions and constant feed rate of glucose. The glucose fuel cell domain is divided into five sections, with governing equations describing transport characteristics in each region, namely - anode diffusion layer, anode catalyst layer (enzyme layer), membrane, cathode catalyst layer and cathode diffusion layer. The mass transport is assumed to be one-dimensional and the governing equations are solved numerically. The effects flow rate of glucose feed on the performance of the fuel cell are studied as it contributes significantly to the convective flux. The effects of operating temperature on the performance of a glucose fuel cell are also modeled. The cell performances are compared using cell polarization curves, which were found compliant with experimental observations.

Surface morphology and interdiffusion of LiF in Alq3-based organic light-emitting devices.

PubMed

Lee, Young Joo; Li, Xiaolong; Kang, Da-Yeon; Park, Seong-Sik; Kim, Jinwoo; Choi, Jeong-Woo; Kim, Hyunjung

2008-09-01

Highly efficient organic light-emitting devices (OLEDs) have been realized by insertion of a thin insulating lithium fluoride (LiF) layer between aluminum (Al) cathode and an electron transport layer, tris-(8-hydroxyquinoline) aluminum (Alq(3)). In this paper, we study the surface morphology of LiF on Alq(3) by synchrotron X-ray scattering and atomic force microscopy (AFM) as a function of thickness of LiF. We also study the interdiffusion of LiF into Al cathode as well as into Alq(3) layer as a function of temperature. Initially, LiF molecules are distributed randomly as clusters on the Alq(3) layer and then gradually form a layer as increasing LiF thickness. The interdiffusion of LiF into Al occurs more actively than into Alq(3) in annealing process. LiF on Alq(3) induces the ordering of Al to (111) direction strongly with increasing LiF thickness.

Graphene oxide as a dual-function conductive binder for PEEK-derived microporous carbons in high performance supercapacitors

NASA Astrophysics Data System (ADS)

Kim, Christine H. J.; Zhang, Hongbo; Liu, Jie

2015-06-01

Microporous carbons (MPCs) are promising electrode materials for supercapacitors because of their high surface area and accessible pores. However, their low electrical conductivity and mechanical instability result in limited power density and poor cycle life. This work proposes a unique two-layered film made of polyetheretherketone-derived MPCs and reduced graphene oxide (rGO) as an electrode for supercapacitors. Electrochemical characterizations of films show that such a layered structure is more effective in increasing the accessibility of ions to the hydrophilic MPCs and establishing conductive paths through the rGO network than a simple mixed composite film. The two-layered structure increases the capacitance by ˜124% (237 F g-1) with excellent cycling stability (˜93% after 6000 cycles). More importantly, we demonstrate that such performance improvements result from an optimal balance between electrical conductivity and ion accessibility, which maximizes the synergistic effects of MPC and rGO. The MPCs, which are exposed to the surface, provide a highly accessible surface area for ion adsorption. The rGO serves a dual function as a conductive filler to increase the electrical conductivity and as a binder to interconnect individual MPC particles into a robust and flexible film. These findings provide a rational basis for the design of MPC-based electrodes in high performance supercapacitors.

Improving the Performance of Layered Oxide Cathode Materials with Football-Like Hierarchical Structure for Na-Ion Batteries by Incorporating Mg2+ into Vacancies in Na-Ion Layers.

PubMed

Li, Zheng-Yao; Wang, Huibo; Chen, Dongfeng; Sun, Kai; Yang, Wenyun; Yang, Jinbo; Liu, Xiangfeng; Han, Songbai

2018-04-09

The development of advanced cathode materials is still a great interest for sodium-ion batteries. The feasible commercialization of sodium-ion batteries relies on the design and exploitation of suitable electrode materials. This study offers a new insight into material design to exploit high-performance P2-type cathode materials for sodium-ion batteries. The incorporation of Mg 2+ into intrinsic Na + vacancies in Na-ion layers can lead to a high-performance P2-type cathode material for sodium-ion batteries. The materials prepared by the coprecipitation approach show a well-defined morphology of secondary football-like hierarchical structures. Neutron power diffraction and refinement results demonstrate that the incorporation of Mg 2+ into intrinsic vacancies can enlarge the space for Na-ion diffusion, which can increase the d-spacing of the (0 0 2) peak and the size of slabs but reduce the chemical bond length to result in an enhanced rate capability and cycling stability. The incorporation of Mg 2+ into available vacancies and a unique morphology make Na 0.7 Mg 0.05 Mn 0.8 Ni 0.1 Co 0.1 O 2 a promising cathode, which can be charged and discharged at an ultra-high current density of 2000 mA g -1 with an excellent specific capacity of 60 mAh g -1 . This work provides a new insight into the design of electrode materials for sodium-ion batteries. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Morphology and microstructure evolution of Ti-50 at.% Al cathodes during cathodic arc deposition of Ti-Al-N coatings

NASA Astrophysics Data System (ADS)

Syed, Bilal; Zhu, Jianqiang; Polcik, Peter; Kolozsvari, Szilard; Hâkansson, Greger; Johnson, Lars; Ahlgren, Mats; Jöesaar, Mats; Odén, Magnus

2017-06-01

Today's research on the cathodic arc deposition technique and coatings therefrom primarily focuses on the effects of, e.g., nitrogen partial pressure, growth temperature, and substrate bias. Detailed studies on the morphology and structure of the starting material—the cathode—during film growth and its influence on coating properties at different process conditions are rare. This work aims to study the evolution of the converted layer, its morphology, and microstructure, as a function of the cathode material grain size during deposition of Ti-Al-N coatings. The coatings were reactively grown in pure N2 discharges from powder metallurgically manufactured Ti-50 at.% Al cathodes with grain size distribution averages close to 1800, 100, 50, and 10 μm, respectively, and characterized with respect to microstructure, composition, and mechanical properties. The results indicate that for the cathode of 1800 μm grain size the disparity in the work function among parent phases plays a dominant role in the pronounced erosion of Al, which yields the coatings rich in macro-particles and of high Al content. We further observed that a reduction in the grain size of Ti-50 at.% Al cathodes to 10 μm provides favorable conditions for self-sustaining reactions between Ti and Al phases upon arcing to form γ phase. The combination of self-sustaining reaction and the arc process not only result in the formation of hole-like and sub-hole features on the converted layer but also generate coatings of high Al content and laden with macro-particles.

Materials characterization of impregnated W and W-Ir cathodes after oxygen poisoning

NASA Astrophysics Data System (ADS)

Polk, James E.; Capece, Angela M.

2015-05-01

Electric thrusters use hollow cathodes as the electron source for generating the plasma discharge and for beam neutralization. These cathodes contain porous tungsten emitters impregnated with BaO material to achieve a lower surface work function and are operated with xenon propellant. Oxygen contaminants in the xenon plasma can poison the emitter surface, resulting in a higher work function and increased operating temperature. This could lead directly to cathode failure by preventing discharge ignition or could accelerate evaporation of the BaO material. Exposures over hundreds of hours to very high levels of oxygen can result in increased temperatures, oxidation of the tungsten substrate, and the formation of surface layers of barium tungstates. In this work, we present results of a cathode test in which impregnated tungsten and tungsten-iridium emitters were operated with 100 ppm of oxygen in the xenon plasma for several hundred hours. The chemical and morphological changes were studied using scanning electron microscopy, energy dispersive spectroscopy, and laser profilometry. The results provide strong evidence that high concentrations of oxygen accelerate the formation of tungstate layers in both types of emitters, a phenomenon not inherent to normal cathode operation. Deposits of pure tungsten were observed on the W-Ir emitter, indicating that tungsten is preferentially removed from the surface and transported in the insert plasma. A W-Ir cathode surface will therefore evolve to a pure W composition, eliminating the work function benefit of W-Ir. However, the W-Ir emitter exhibited less erosion and redeposition at the upstream end than the pure W emitter.

Multi-variable mathematical models for the air-cathode microbial fuel cell system

DOE PAGES

Ou, Shiqi; Kashima, Hiroyuki; Aaron, Douglas S.; ...

2016-03-10

This research adopted the version control system into the model construction for the single chamber air-cathode microbial fuel cell (MFC) system, to understand the interrelation of biological, chemical, and electrochemical reactions. The anodic steady state model was used to consider the chemical species diffusion and electric migration influence to the MFC performance. In the cathodic steady state model, the mass transport and reactions in a multi-layer, abiotic cathode and multi-bacteria cathode biofilm were simulated. Transport of hydroxide was assumed for cathodic pH change. This assumption is an alternative to the typical notion of proton consumption during oxygen reduction to explainmore » elevated cathode pH. The cathodic steady state model provided the power density and polarization curve performance results that can be compared to an experimental MFC system. Another aspect we considered was the relative contributions of platinum catalyst and microbes on the cathode to the oxygen reduction reaction (ORR). We found simulation results showed that the biocatalyst in a cathode that includes a Pt/C catalyst likely plays a minor role in ORR, contributing up to 8% of the total power calculated by the models.« less

Durability and regeneration of activated carbon air-cathodes in long-term operated microbial fuel cells

NASA Astrophysics Data System (ADS)

Zhang, Enren; Wang, Feng; Yu, Qingling; Scott, Keith; Wang, Xu; Diao, Guowang

2017-08-01

The performance of activated carbon catalyst in air-cathodes in microbial fuel cells was investigated over one year. A maximum power of 1722 mW m-2 was produced within the initial one-month microbial fuel cell operation. The air-cathodes produced a maximum power >1200 mW m-2 within six months, but gradually became a limiting factor for the power output in prolonged microbial fuel cell operation. The maximum power decreased by 55% when microbial fuel cells were operated over one year due to deterioration in activated carbon air-cathodes. While salt/biofilm removal from cathodes experiencing one-year operation increased a limiting performance enhancement in cathodes, a washing-drying-pressing procedure could restore the cathode performance to its original levels, although the performance restoration was temporary. Durable cathodes could be regenerated by re-pressing activated carbon catalyst, recovered from one year deteriorated air-cathodes, with new gas diffusion layer, resulting in ∼1800 mW m-2 of maximum power production. The present study indicated that activated carbon was an effective catalyst in microbial fuel cell cathodes, and could be recovered for reuse in long-term operated microbial fuel cells by simple methods.

Xenon-Ion Drilling of Tungsten Films

NASA Technical Reports Server (NTRS)

Garner, C. E.

1986-01-01

High-velocity xenon ions used to drill holes of controlled size and distribution through tungsten layer that sheaths surface of controlled-porosity dispenser cathode of traveling wave-tube electron emitter. Controlled-porosity dispenser cathode employs barium/calcium/ aluminum oxide mixture that migrates through pores in cathode surface, thus coating it and reducing its work function. Rapid, precise drilling technique applied to films of other metals and used in other applications where micron-scale holes required. Method requires only few hours, as opposed to tens of hours by prior methods.

A Smart Microwave Vacuum Electron Device (MVED) Using Field Emitters

DTIC Science & Technology

2012-01-31

operation of the device. By using a larger retardation value, the slow wave phase velocity is decreased allowing a lower E/B drift velocity. By reducing...the drift velocity the device is able to run at a lower cathode potential reducing the risk of high voltage arcing. This new slow wave circuit will...sole electrode above the cathode by using a thin dielectric layer ( mylar ) on top of the cathode and placing the sole electrode on the dielectric

Cation-substituted spinel oxide and oxyfluoride cathodes for lithium ion batteries

DOEpatents

Manthiram, Arumugam; Choi, Wonchang

2010-05-18

The present invention includes compositions and methods of making cation-substituted and fluorine-substituted spinel cathode compositions by firing a LiMn_2-y-zLi_yM_zO₄ oxide with NH₄HF₂ at low temperatures of between about 300 and 700.degree. C. for 2 to 8 hours and a .eta. of more than 0 and less than about 0.50, mixed two-phase compositions consisting of a spinel cathode and a layered oxide cathode, and coupling them with unmodified or surface modified graphite anodes in lithium ion cells.

The effect of zirconium-based surface treatment on the cathodic disbonding resistance of epoxy coated mild steel

NASA Astrophysics Data System (ADS)

Ghanbari, A.; Attar, M. M.

2014-10-01

The effect of zirconium-based surface treatment on the cathodic disbonding resistance and adhesion performance of an epoxy coated mild steel substrate was investigated. The obtained data from pull-off, cathodic disbonding test and electrochemical impedance spectroscopy (EIS) indicated that the zirconium conversion layer significantly improved the adhesion strength and cathodic disbonding resistance of the epoxy coating. This may be attributed to formation of some polar zirconium compounds on the surface and increment of surface roughness, that were evident in the results of field emission scanning electron microscopy (FE-SEM) and atomic force microscopy (AFM), respectively.

Intermediate connector for stacked organic light emitting devices

DOEpatents

D& #x27; Andrade, Brian

2013-02-12

A device is provided, having an anode, a cathode, and an intermediate connector disposed between the anode and the cathode. A first organic layer including an emissive sublayer is disposed between the anode and the intermediate connector, and a second including an emissive sublayer is disposed between the intermediate connector and the cathode. The intermediate connector includes a first metal having a work function lower than 4.0 eV and a second metal having a work function lower than 5.0 eV. The work function of the first metal is at least 0.5 eV less than the work function of the second metal. The first metal is in contact with a sublayer of the second organic layer that includes a material well adapted to receive holes from a low work function metal.

Process for forming a nickel foil with controlled and predetermined permeability to hydrogen

DOEpatents

Engelhaupt, Darell E.

1981-09-22

The present invention provides a novel process for forming a nickel foil having a controlled and predetermined hydrogen permeability. This process includes the steps of passing a nickel plating bath through a suitable cation exchange resin to provide a purified nickel plating bath free of copper and gold cations, immersing a nickel anode and a suitable cathode in the purified nickel plating bath containing a selected concentration of an organic sulfonic acid such as a napthalene-trisulfonic acid, electrodepositing a nickel layer having the thickness of a foil onto the cathode, and separating the nickel layer from the cathode to provide a nickel foil. The anode is a readily-corrodible nickel anode. The present invention also provides a novel nickel foil having a greater hydrogen permeability than palladium at room temperature.

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.

Investigations of direct methanol fuel cell (DMFC) fading mechanisms

NASA Astrophysics Data System (ADS)

Sarma, Loka Subramanyam; Chen, Ching-Hsiang; Wang, Guo-Rung; Hsueh, Kan-Lin; Huang, Chiou-Ping; Sheu, Hwo-Shuenn; Liu, Ding-Goa; Lee, Jyh-Fu; Hwang, Bing-Joe

In this report, we present the microscopic investigations on various fading mechanisms of a direct methanol fuel cell (DMFC). High energy X-ray diffraction (XRD), X-ray absorption spectroscopy (XAS), energy dispersive X-ray spectroscopy (EDX), and Raman spectroscopic analysis were applied to a membrane-electrode-assembly (MEA) before and after fuel cell operation to figure out the various factors causing its fading. High energy XRD analysis of the fresh and faded MEA revealed that the agglomeration of the catalyst particles in the cathode layer of the faded MEA was more significant than in the anode layer of the faded MEA. The XAS analysis demonstrated that the alloying extent of Pt (J Pt) and Ru (J Ru) in the anode catalyst was increased and decreased, respectively, from the fresh to the faded MEA, indicating that the Ru environment in the anode catalyst was significantly changed after the fuel cell operation. Based on the X-ray absorption edge jump measurements at the Ru K-edge on the anode catalyst of the fresh and the faded MEA it was found that Ru was dissolved from the Pt-Ru catalyst after the fuel cell operation. Both the Ru K-edge XAS and EDX analysis on the cathode catalyst layer of the faded MEA confirms the presence of Ru environment in the cathode catalyst due to the Ru crossover from the anode to the cathode side. The changes in the membrane and the gas diffusion layer (GDL) after the fuel cell operation were observed from the Raman spectroscopy analysis.

Carbon corrosion of proton exchange membrane fuel cell catalyst layers studied by scanning transmission X-ray microscopy

NASA Astrophysics Data System (ADS)

Hitchcock, Adam P.; Berejnov, Viatcheslav; Lee, Vincent; West, Marcia; Colbow, Vesna; Dutta, Monica; Wessel, Silvia

2014-11-01

Scanning Transmission X-ray Microscopy (STXM) at the C 1s, F 1s and S 2p edges has been used to investigate degradation of proton exchange membrane fuel cell (PEM-FC) membrane electrode assemblies (MEA) subjected to accelerated testing protocols. Quantitative chemical maps of the catalyst, carbon support and ionomer in the cathode layer are reported for beginning-of-test (BOT), and end-of-test (EOT) samples for two types of carbon support, low surface area carbon (LSAC) and medium surface area carbon (MSAC), that were exposed to accelerated stress testing with upper potentials (UPL) of 1.0, 1.2, and 1.3 V. The results are compared in order to characterize catalyst layer degradation in terms of the amounts and spatial distributions of these species. Pt agglomeration, Pt migration and corrosion of the carbon support are all visualized, and contribute to differing degrees in these samples. It is found that there is formation of a distinct Pt-in-membrane (PTIM) band for all EOT samples. The cathode thickness shrinks due to loss of the carbon support for all MSAC samples that were exposed to the different upper potentials, but only for the most aggressive testing protocol for the LSAC support. The amount of ionomer per unit volume significantly increases indicating it is being concentrated in the cathode as the carbon corrosion takes place. S 2p spectra and mapping of the cathode catalyst layer indicates there are still sulfonate groups present, even in the most damaged material.

Towards developing a backing layer for proton exchange membrane electrolyzers

NASA Astrophysics Data System (ADS)

Lettenmeier, P.; Kolb, S.; Burggraf, F.; Gago, A. S.; Friedrich, K. A.

2016-04-01

Current energy policies require the urgent replacement of fossil energy carriers by carbon neutral ones, such as hydrogen. The backing or micro-porous layer plays an important role in the performance of hydrogen proton exchange membrane (PEM) fuel cells, reducing contact resistance and improving reactant/product management. Such carbon-based coating cannot be used in PEM electrolysis since it oxidizes to CO2 at high voltages. A functional titanium macro-porous layer (MPL) on the current collectors of a PEM electrolyzer is developed by thermal spraying. It improves the contact with the catalyst layers by ca. 20 mΩ cm2, increasing significantly the efficiency of the device when operating at high current densities.

Nanoprocess and nanoscale surface functionalization on cathode materials for advanced lithium-ion batteries.

PubMed

Alaboina, Pankaj Kumar; Uddin, Md-Jamal; Cho, Sung-Jin

2017-10-26

Nanotechnology-driven development of cathode materials is an essential part to revolutionize the evolution of the next generation lithium ion batteries. With the progress of nanoprocess and nanoscale surface modification investigations on cathode materials in recent years, the advanced battery technology future seems very promising - Thanks to nanotechnology. In this review, an overview of promising nanoscale surface deposition methods and their significance in surface functionalization on cathodes is extensively summarized. Surface modified cathodes are provided with a protective layer to overcome the electrochemical performance limitations related to side reactions with electrolytes, reduce self-discharge reactions, improve thermal and structural stability, and further enhance the overall battery performance. The review addresses the importance of nanoscale surface modification on battery cathodes and concludes with a comparison of the different nanoprocess techniques discussed to provide a direction in the race to build advanced lithium-ion batteries.

Free-Standing Porous Carbon Nanofiber/Carbon Nanotube Film as Sulfur Immobilizer with High Areal Capacity for Lithium-Sulfur Battery.

PubMed

Zhang, Ye-Zheng; Zhang, Ze; Liu, Sheng; Li, Guo-Ran; Gao, Xue-Ping

2018-03-14

Low sulfur utilization and poor cycle life of the sulfur cathode with high sulfur loadings remain a great challenge for lithium-sulfur (Li-S) battery. Herein, the free-standing carbon film consisting of porous carbon nanofibers (PCNFs) and carbon nanotubes (CNTs) is successfully fabricated by the electrospinning technology. The PCNF/CNT film with three-dimensional and interconnected structure is promising for the uniformity of the high-loading sulfur, good penetration of the electrolyte, and reliable accommodation of volumetric expansion of the sulfur cathode. In addition, the abundant N/O-doped elements in PCNF/CNT film are helpful to chemically trap soluble polysulfides in the charge-discharge processes. Consequently, the obtained monolayer S/PCNF/CNT film as the cathode shows high specific capacity, excellent cycle stability, and rate stability with the sulfur loading of 3.9 mg cm -2 . Moreover, the high areal capacity of 13.5 mA h cm -2 is obtained for the cathode by stacking three S/PCNF/CNT layers with the high sulfur loading of 12 mg cm -2 . The stacking-layered cathode with high sulfur loading provides excellent cycle stability, which is beneficial to fabricate high-energy-density Li-S battery in future.

Tuning Li2MO3 phase abundance and suppressing migration of transition metal ions to improve the overall performance of Li- and Mn-rich layered oxide cathode

NASA Astrophysics Data System (ADS)

Zhang, Shiming; Tang, Tian; Ma, Zhihua; Gu, Haitao; Du, Wubing; Gao, Mingxia; Liu, Yongfeng; Jian, Dechao; Pan, Hongge

2018-03-01

The poor cycling stability of Li- and Mn-rich layered oxide cathodes used in lithium-ion batteries (LIBs) has severely limited their practical application. Unfortunately, current strategies to improve their lifecycle sacrifice initial capacity. In this paper, we firstly report the synergistic improvement of the electrochemical performance of a Li1.2Ni0.13Co0.13Mn0.54O2 (LNCMO) cathode material, including gains for capacity, cycling stability, and rate capability, by the partial substitution of Li+ ions by Mg2+ ions. Electrochemical performance is evaluated by a galvanostatic charge and discharge test and electrochemical impedance spectroscopy (EIS). Structure and morphology are characterized by X-ray diffraction (XRD) and high-resolution transmission electron microscopy (HRTEM). Compared with the substitution of transition metal (TM) ions with Mg2+ ions reported previously, the substitution of Li+ ions by Mg2+ ions not only drastically ameliorates the capacity retention and rate performance challenges of LNCMO cathodes but also markedly suppresses their voltage fading, due to the inhibition of the migration of TM ions during cycling, while also increasing the capacity of the cathode due to an increased abundance of the Li2MO3 phase.

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

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

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

2017-01-01

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

High Performance Proton-Conducting Solid Oxide Fuel Cells with a Layered Perovskite GdBaCuCoO5+ x Cathode

NASA Astrophysics Data System (ADS)

Zhang, Xiaozhen; Jiang, Yuhua; Hu, Xuebing; Sun, Liangliang; Ling, Yihan

2018-03-01

Proton-conducting solid oxide fuel cell (H-SOFC) based on layered perovskite type GdBaCuCoO5+x (GBCC) cathode was fabricated with in situ drop-coating BaZr0.1Ce0.7Y0.2O3-δ (BZCY) electrolyte membrane. The influences of Cu doping into Co sites of GdBaCo2O5+ x on the electrical conductivity and conduction mechanism, thermal expansion property and electrochemical performance of cathode materials and corresponding single cell were investigated. Results show that the electrical conductivity decreased and the conduction mechanism would gradually transform to the semiconductor-like behavior. A high maximum power density of 480 mW cm-2 was obtained for the anode supported NiO-BZCY/NiO-BZCY/BZCY/GBCC single cells with wet H2 fuel at 700 °C. The corresponding polarization resistance was as low as 0.17 Ω cm2. The excellent electrochemical performance of as-prepared single cell indicates that GBCC is a good candidate of cathode materials for H-SOFCs.

Emission and evaporation properties of 75 at.% Re-25 at.% W mixed matrix impregnated cathode

NASA Astrophysics Data System (ADS)

Lai, Chen; Wang, Jinshu; Zhou, Fan; Liu, Wei; den Engelsen, Daniel; Miao, Naihua

2018-01-01

We present a comprehensive study on the phase, emission performance, surface composition, chemical states and evaporation properties of a 75 at.% Re-25 at.% W (75Re) mixed matrix impregnated cathode by several modern analyzers, including XRD, electron emission test device, in situ AES, XPS and Quartz Crystal Oscillation Instrument (QCOI). On the basis of experimental results, the adsorption energy and charge transfer of the Ba-O dipole adsorbed on cathode surface was investigated by the first-principles density functional theory calculations. The in situ AES analyses indicate that the atomic ratio of Ba:O of the active emission layer on the cathode surface converged to 3:2 for a conventional Ba-W cathode and to about 3:1 for the 75Re cathode. Due to the larger adsorption energy of Ba and Ba-O on 75Re cathode surface, the total evaporation rate of Ba and BaO in the 75Re cathode is much lower than that for the Ba-W cathode, which is agreed favorably with the experimental evaporation data. Our characterizations and calculations suggest that rhenium in the matrix of impregnated cathodes improves the stability of Ba-O dipole on the cathode surface and enhances the emission capability substantially.

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

Huang, Jinsong; Dong, Qingfeng; Sao, Yuchuan

Continuous processes for fabricating a perovskite device are described that include using a doctor blade for continuously forming a perovskite layer and using a conductive tape lamination process to form an anode or a cathode layer on the perovskite device.

Gas block mechanism for water removal in fuel cells

DOEpatents

Issacci, Farrokh; Rehg, Timothy J.

2004-02-03

The present invention is directed to apparatus and method for cathode-side disposal of water in an electrochemical fuel cell. There is a cathode plate. Within a surface of the plate is a flow field comprised of interdigitated channels. During operation of the fuel cell, cathode gas flows by convection through a gas diffusion layer above the flow field. Positioned at points adjacent to the flow field are one or more porous gas block mediums that have pores sized such that water is sipped off to the outside of the flow field by capillary flow and cathode gas is blocked from flowing through the medium. On the other surface of the plate is a channel in fluid communication with each porous gas block mediums. The method for water disposal in a fuel cell comprises installing the cathode plate assemblies at the cathode sides of the stack of fuel cells and manifolding the single water channel of each of the cathode plate assemblies to the coolant flow that feeds coolant plates in the stack.

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

PubMed Central

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

2017-01-01

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

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

NASA Astrophysics Data System (ADS)

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

2017-04-01

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

Exfoliation and reassembly of cobalt oxide nanosheets into a reversible lithium-ion battery cathode.

PubMed

Compton, Owen C; Abouimrane, Ali; An, Zhi; Palmeri, Marc J; Brinson, L Catherine; Amine, Khalil; Nguyen, SonBinh T

2012-04-10

An exfoliation-reassembly-activation (ERA) approach to lithium-ion battery cathode fabrication is introduced, demonstrating that inactive HCoO(2) powder can be converted into a reversible Li(1-x) H(x) CoO(2) thin-film cathode. This strategy circumvents the inherent difficulties often associated with the powder processing of the layered solids typically employed as cathode materials. The delamination of HCoO(2) via a combination of chemical and mechanical exfoliation generates a highly processable aqueous dispersion of [CoO(2) ](-) nanosheets that is critical to the ERA approach. Following vacuum-assisted self-assembly to yield a thin-film cathode and ion exchange to activate this material, the generated cathodes exhibit excellent cyclability and discharge capacities approaching that of low-temperature-prepared LiCoO(2) (~83 mAh g(-1) ), with this good electrochemical performance attributable to the high degree of order in the reassembled cathode. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

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

Tris(trimethylsilyl) Phosphite as an Efficient Electrolyte Additive To Improve the Surface Stability of Graphite Anodes.

PubMed

Yim, Taeeun; Han, Young-Kyu

2017-09-27

Tris(trimethylsilyl) phosphite (TMSP) has received considerable attention as a functional additive for various cathode materials in lithium-ion batteries, but the effect of TMSP on the surface stability of a graphite anode has not been studied. Herein, we demonstrate that TMSP serves as an effective solid electrolyte interphase (SEI)-forming additive for graphite anodes in lithium-ion batteries (LIBs). TMSP forms SEI layers by chemical reactions between TMSP and a reductively decomposed ethylene carbonate (EC) anion, which is strikingly different from the widely known mechanism of the SEI-forming additives. TMSP is stable under cathodic polarization, but it reacts chemically with radical anion intermediates derived from the electrochemical reduction of the carbonate solvents to generate a stable SEI layer. These TMSP-derived SEI layers improve the interfacial stability of the graphite anode, resulting in a retention of 96.8% and a high Coulombic efficiency of 95.2%. We suggest the use of TMSP as a functional additive that effectively stabilizes solid electrolyte interfaces of both the anode and cathode in lithium-ion batteries.

Catalyst inks and method of application for direct methanol fuel cells

DOEpatents

Zelenay, Piotr; Davey, John; Ren, Xiaoming; Gottesfeld, Shimshon; Thomas, Sharon C.

2004-02-24

Inks are formulated for forming anode and cathode catalyst layers and applied to anode and cathode sides of a membrane for a direct methanol fuel cell. The inks comprise a Pt catalyst for the cathode and a Pt--Ru catalyst for the anode, purified water in an amount 4 to 20 times that of the catalyst by weight, and a perfluorosulfonic acid ionomer in an amount effective to provide an ionomer content in the anode and cathode surfaces of 20% to 80% by volume. The inks are prepared in a two-step process while cooling and agitating the solutions. The final solution is placed in a cooler and continuously agitated while spraying the solution over the anode or cathode surface of the membrane as determined by the catalyst content.

Mechanistic Insight in the Function of Phosphite Additives for Protection of LiNi0.5Co0.2Mn0.3O2 Cathode in High Voltage Li-Ion Cells.

PubMed

He, Meinan; Su, Chi-Cheung; Peebles, Cameron; Feng, Zhenxing; Connell, Justin G; Liao, Chen; Wang, Yan; Shkrob, Ilya A; Zhang, Zhengcheng

2016-05-11

Triethlylphosphite (TEP) and tris(2,2,2-trifluoroethyl) phosphite (TTFP) have been evaluated as electrolyte additives for high-voltage Li-ion battery cells using a Ni-rich layered cathode material LiNi0.5Co0.2Mn0.3O2 (NCM523) and the conventional carbonate electrolyte. The repeated charge/discharge cycling for cells containing 1 wt % of these additives was performed using an NCM523/graphite full cell operated at the voltage window from 3.0-4.6 V. During the initial charge process, these additives decompose on the cathode surface at a lower oxidation potential than the baseline electrolyte. Impedance spectroscopy and post-test analyses indicate the formation of protective coatings by both additives on the cathode surface that prevent oxidative breakdown of the electrolyte. However, only TTFP containing cells demonstrate the improved capacity retention and Coulombic efficiency. For TEP, the protective coating is also formed, but low Li(+) ion mobility through the interphase layer results in inferior performance. These observations are rationalized through the inhibition of electrocatalytic centers present on the cathode surface and the formation of organophosphate deposits isolating the cathode surface from the electrolyte. The difference between the two phosphites clearly originates in the different properties of the resulting phosphate coatings, which may be in Li(+) ion conductivity through such materials.

Mechanistic Insight in the Function of Phosphite Additives for Protection of LiNi 0.5 Co 0.2 Mn 0.3 O 2 Cathode in High Voltage Li-Ion Cells

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

He, Meinan; Su, Chi-Cheung; Peebles, Cameron

Triethlylphosphite (TEP) and tris(2,2,2-trifluoroethyl) phosphite (TTFP) have been evaluated as electrolyte additives for high-voltage Li-ion battery cells using a Ni-rich layered cathode material LiNi0.5Co0.2Mn0.3O2 (NCM523) and the conventional carbonate electrolyte. The repeated charge/discharge cycling for cells containing 1 wt% of these additives was performed using an NCM523/graphite full cell operated at the voltage window from 3.0 to 4.6 V. During the initial charge process, these additives decompose on the cathode surface at a lower oxidation potential than the baseline electrolyte. Impedance spectroscopy and post-test analyses indicate the formation of protective coatings by both additives on the cathode surface that preventmore » oxidative breakdown of the electrolyte. However, only TTFP containing cells demonstrate the improved capacity retention and Coulombic efficiency. For TEP, the protective coating is also formed, but low Li+ ion mobility through the interphase layer results in inferior performance. These observations are rationalized through the inhibition of electrocatalytic centers present on the cathode surface and the formation of organophosphate deposits isolating the cathode surface from the electrolyte. The difference between the two phosphites clearly originates in the different properties of the resulting phosphate coatings, which may be in Li+ ion conductivity through such materials.« less

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.

Electrochromic counter electrode

DOEpatents

Lee, Se-Hee; Tracy, C. Edwin; Pitts, J. Roland; Jorgensen, Gary J.

2005-02-22

The present invention discloses an amorphous material comprising nickel oxide doped with tantalum that is an anodically coloring electrochromic material. The material of the present invention is prepared in the form of an electrode (200) having a thin film (202) of an electrochromic material of the present invention residing on a transparent conductive film (203). The material of the present invention is also incorporated into an electrochromic device (100) as a thin film (102) in conjunction with a cathodically coloring prior art electrochromic material layer (104) such that the devices contain both anodically coloring (102) and cathodically coloring (104) layers. The materials of the electrochromic layers in these devices exhibit broadband optical complimentary behavior, ionic species complimentary behavior, and coloration efficiency complimentary behavior in their operation.

Comparison of trimethylgallium and triethylgallium as “Ga” source materials for the growth of ultrathin GaN films on Si (100) substrates via hollow-cathode plasma-assisted atomic layer deposition

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

Alevli, Mustafa, E-mail: mustafaalevli@marmara.edu.tr; Haider, Ali; Kizir, Seda

2016-01-15

GaN films grown by hollow cathode plasma-assisted atomic layer deposition using trimethylgallium (TMG) and triethylgallium (TEG) as gallium precursors are compared. Optimized and saturated TMG/TEG pulse widths were used in order to study the effect of group-III precursors. The films were characterized by grazing incidence x-ray diffraction, atomic force microscopy, x-ray photoelectron spectroscopy, and spectroscopic ellipsometry. Refractive index follows the same trend of crystalline quality, mean grain, and crystallite sizes. GaN layers grown using TMG precursor exhibited improved structural and optical properties when compared to GaN films grown with TEG precursor.

Hollow nanoparticle cathode materials for sodium electrochemical cells and batteries

DOEpatents

Shevchenko, Elena; Rajh, Tijana; Johnson, Christopher S.; Koo, Bonil

2016-07-12

A cathode comprises, in its discharged state, a layer of hollow .gamma.-Fe.sub.2O.sub.3 nanoparticles disposed between two layers of carbon nanotubes, and preferably including a metallic current collector in contact with one of the layers of carbon nanotubes. Individual particles of the hollow .gamma.-Fe.sub.2O.sub.3 nanoparticles comprise a crystalline shell of .gamma.-Fe.sub.2O.sub.3 including cation vacancies within the crystal structure of the shell (i.e., iron vacancies of anywhere between 3% to 90%, and preferably 44 to 77% of available octahedral iron sites). Sodium ions are intercalated within at least some of the cation vacancies within the crystalline shell of the hollow .gamma.-Fe.sub.2O.sub.3 nanoparticles.

Materials genomics screens for adaptive ion transport behavior by redox-switchable microporous polymer membranes in lithium–sulfur batteries

DOE PAGES

Ward, Ashleigh L.; Doris, Sean E.; Li, Longjun; ...

2017-04-27

Selective ion transport across membranes is critical to the performance of many electrochemical energy storage devices. While design strategies enabling ion-selective transport are well-established, enhancements in membrane selectivity are made at the expense of ionic conductivity. To design membranes with both high selectivity and high ionic conductivity, there are cues to follow from biological systems, where regulated transport of ions across membranes is achieved by transmembrane proteins. The transport functions of these proteins are sensitive to their environment: physical or chemical perturbations to that environment are met with an adaptive response. Here we advance an analogous strategy for achieving adaptivemore » ion transport in microporous polymer membranes. Along the polymer backbone are placed redox-active switches that are activated in situ, at a prescribed electrochemical potential, by the device’s active materials when they enter the membrane’s pore. This transformation has little influence on the membrane’s ionic conductivity; however, the active-material blocking ability of the membrane is enhanced. We show that when used in lithium-sulfur batteries, these membranes offer markedly improved capacity, efficiency, and cycle-life by sequestering polysulfides in the cathode. Furthermore, the origins and implications of this behavior are explored in detail and point to new opportunities for responsive membranes in battery technology development« less

Materials genomics screens for adaptive ion transport behavior by redox-switchable microporous polymer membranes in lithium–sulfur batteries

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

Ward, Ashleigh L.; Doris, Sean E.; Li, Longjun

Selective ion transport across membranes is critical to the performance of many electrochemical energy storage devices. While design strategies enabling ion-selective transport are well-established, enhancements in membrane selectivity are made at the expense of ionic conductivity. To design membranes with both high selectivity and high ionic conductivity, there are cues to follow from biological systems, where regulated transport of ions across membranes is achieved by transmembrane proteins. The transport functions of these proteins are sensitive to their environment: physical or chemical perturbations to that environment are met with an adaptive response. Here we advance an analogous strategy for achieving adaptivemore » ion transport in microporous polymer membranes. Along the polymer backbone are placed redox-active switches that are activated in situ, at a prescribed electrochemical potential, by the device’s active materials when they enter the membrane’s pore. This transformation has little influence on the membrane’s ionic conductivity; however, the active-material blocking ability of the membrane is enhanced. We show that when used in lithium-sulfur batteries, these membranes offer markedly improved capacity, efficiency, and cycle-life by sequestering polysulfides in the cathode. Furthermore, the origins and implications of this behavior are explored in detail and point to new opportunities for responsive membranes in battery technology development« less

Polymer and small molecule based hybrid light source

DOEpatents

Choong, Vi-En; Choulis, Stelios; Krummacher, Benjamin Claus; Mathai, Mathew; So, Franky

2010-03-16

An organic electroluminescent device, includes: a substrate; a hole-injecting electrode (anode) coated over the substrate; a hole injection layer coated over the anode; a hole transporting layer coated over the hole injection layer; a polymer based light emitting layer, coated over the hole transporting layer; a small molecule based light emitting layer, thermally evaporated over the polymer based light emitting layer; and an electron-injecting electrode (cathode) deposited over the electroluminescent polymer layer.

Positioning of the sensor cell on the sensing area using cell trapping pattern in incubation type planar patch clamp biosensor.

PubMed

Wang, Zhi-Hong; Takada, Noriko; Uno, Hidetaka; Ishizuka, Toru; Yawo, Hiromu; Urisu, Tsuneo

2012-08-01

Positioning the sensor cell on the micropore of the sensor chip and keeping it there during incubation are problematic tasks for incubation type planar patch clamp biosensors. To solve these problems, we formed on the Si sensor chip's surface a cell trapping pattern consisting of a lattice pattern with a round area 5 μm deep and with the micropore at the center of the round area. The surface of the sensor chip was coated with extra cellular matrix collagen IV, and HEK293 cells on which a chimera molecule of channel-rhodopsin-wide-receiver (ChR-WR) was expressed, were then seeded. We examined the effects of this cell trapping pattern on the biosensor's operation. In the case of a flat sensor chip without a cell trapping pattern, it took several days before the sensor cell covered the micropore and formed an almost confluent state. As a result, multi-cell layers easily formed and made channel current measurements impossible. On the other hand, the sensor chip with cell trapping pattern easily trapped cells in the round area, and formed the colony consisted of the cell monolayer covering the micropore. A laser (473 nm wavelength) induced channel current was observed from the whole cell arrangement formed using the nystatin perforation technique. The observed channel current characteristics matched measurements made by using a pipette patch clamp. Copyright © 2012 Elsevier B.V. All rights reserved.

Electrochemical investigation of stainless steel corrosion in a proton exchange membrane electrolyzer cell

DOE PAGES

Mo, Jingke; Steen, Stuart M.; Zhang, Feng-Yuan; ...

2015-08-05

The lack of a fundamental understanding of the corrosion mechanisms in the electrochemical environments of proton exchange membrane (PEM) electrolyzer and/or fuel cells (ECs/FCs) has seriously hindered the improvement of performance and efficiency of PEM ECs/FCs. In this study, a stainless steel mesh was purposely used as an anode gas diffusion layer that was intentionally operated with high positive potentials under harsh oxidative environments in a PEMEC to study the corrosion mechanism of metal migration. A significant amount of iron and nickel cations were determined to transport through the anode catalyst layer, the PEM and the cathode catalyst layer duringmore » the PEMEC operation. The formation/deposition of iron oxide and nickel oxide on the carbon paper gas diffusion layer at the cathode side is first revealed by both scanning electron microscope and X-ray diffraction. The results indicate the corrosion elements of iron and nickel are transported from anode to cathode through the catalyst-coated membrane, and deposited on carbon fibers as oxides. This phenomenon could also open a new corrosion-based processing approach to potentially fabricate multifunctional oxide structures on carbon fiber devices. This study has demonstrated a new accelerated test method for investigating the corrosion and durability of metallic materials as well.« less

Electrochemical investigation of stainless steel corrosion in a proton exchange membrane electrolyzer cell

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

Mo, Jingke; Steen, Stuart M.; Zhang, Feng-Yuan

The lack of a fundamental understanding of the corrosion mechanisms in the electrochemical environments of proton exchange membrane (PEM) electrolyzer and/or fuel cells (ECs/FCs) has seriously hindered the improvement of performance and efficiency of PEM ECs/FCs. In this study, a stainless steel mesh was purposely used as an anode gas diffusion layer that was intentionally operated with high positive potentials under harsh oxidative environments in a PEMEC to study the corrosion mechanism of metal migration. A significant amount of iron and nickel cations were determined to transport through the anode catalyst layer, the PEM and the cathode catalyst layer duringmore » the PEMEC operation. The formation/deposition of iron oxide and nickel oxide on the carbon paper gas diffusion layer at the cathode side is first revealed by both scanning electron microscope and X-ray diffraction. The results indicate the corrosion elements of iron and nickel are transported from anode to cathode through the catalyst-coated membrane, and deposited on carbon fibers as oxides. This phenomenon could also open a new corrosion-based processing approach to potentially fabricate multifunctional oxide structures on carbon fiber devices. This study has demonstrated a new accelerated test method for investigating the corrosion and durability of metallic materials as well.« less

A Comprehensive Physical Impedance Model of Polymer Electrolyte Fuel Cell Cathodes in Oxygen-free Atmosphere.

PubMed

Obermaier, Michael; Bandarenka, Aliaksandr S; Lohri-Tymozhynsky, Cyrill

2018-03-21

Electrochemical impedance spectroscopy (EIS) is an indispensable tool for non-destructive operando characterization of Polymer Electrolyte Fuel Cells (PEFCs). However, in order to interpret the PEFC's impedance response and understand the phenomena revealed by EIS, numerous semi-empirical or purely empirical models are used. In this work, a relatively simple model for PEFC cathode catalyst layers in absence of oxygen has been developed, where all the equivalent circuit parameters have an entire physical meaning. It is based on: (i) experimental quantification of the catalyst layer pore radii, (ii) application of De Levie's analytical formula to calculate the response of a single pore, (iii) approximating the ionomer distribution within every pore, (iv) accounting for the specific adsorption of sulfonate groups and (v) accounting for a small H 2 crossover through ~15 μm ionomer membranes. The derived model has effectively only 6 independent fitting parameters and each of them has clear physical meaning. It was used to investigate the cathode catalyst layer and the double layer capacitance at the interface between the ionomer/membrane and Pt-electrocatalyst. The model has demonstrated excellent results in fitting and interpretation of the impedance data under different relative humidities. A simple script enabling fitting of impedance data is provided as supporting information.

High performance planar p-i-n perovskite solar cells with crown-ether functionalized fullerene and LiF as double cathode buffer layers

NASA Astrophysics Data System (ADS)

Liu, Xiaodong; Lei, Ming; Zhou, Yi; Song, Bo; Li, Yongfang

2015-08-01

Double cathode buffer layers (CBLs) composed of fullerene derivative functionalized with a crown-ether end group in its side chain (denoted as PCBC) and a LiF layer were introduced between the PCBM acceptor layer and the top cathode in planar p-i-n perovskite solar cells (pero-SCs) based on CH3NH3PbI3-XClX. The devices with the PCBC/LiF double CBLs showed significant improvements in power conversion efficiency (PCE) and long-term stability when compared to the device with LiF single CBL. Through optimizing the spin-coating speed of PCBC, a maximum PCE of 15.53% has been achieved, which is approximately 15% higher than that of the device with single LiF CBL. The remarkable improvement in PCE can be attributed to the formation of a better ohmic contact in the CBL between PCBC and LiF/Al electrode arising from the dipole moment of PCBC, leading to the enhanced fill factor and short-circuit current density (Jsc). Besides the PCE, the long-term stability of the devices with PCBC interlayer is also superior to that of the device with LiF single CBL, which is due to the more effective protection for the perovskite/PCBM interface.

Fabrication of three-dimensional buckypaper catalyst layer with Pt nanoparticles supported on polyelectrolyte functionalized carbon nanotubes for proton exchange membrane fuel cells

NASA Astrophysics Data System (ADS)

Zhu, Shiyao; Zheng, Junsheng; Huang, Jun; Dai, Ningning; Li, Ping; Zheng, Jim P.

2018-07-01

Polyelectrolyte poly(diallyldimethylammonium chloride) (PDDA) functionalized carbon nanotubes (CNTs) supported Pt electrocatalyst was synthesized as a substitute for commonly used Pt/C and Pt/CNTs (modified by harsh acid-oxidation treatment) catalysts. In addition, this catalyst was fabricated as the cathode catalyst layer (CL) with a unique double-layered structure for proton exchange membrane fuel cells (PEMFCs). Thermogravimetric analysis shows an enhanced thermal stability of Pt/PDDA-CNTs. The Pt/PDDA-CNTs catalyst with an average Pt particle size of ∼3.1 nm exhibits the best electrocatalytic activity and a significantly enhanced electrochemical stability. Scanning electron microscope, energy dispersive spectrometer and mercury intrusion porosimetry results demonstrate the gradient distribution of Pt content and pore size along the thickness of buckypaper catalyst layer (BPCL). The accelerated degradation test results of BPCLs indicate that this gradient structure can ensure a high Pt utilization in the BPCLs (up to 90%) and further improve the catalyst durability. In addition, the membrane electrode assembly (MEA) fabricated with cathode BPCL-PDDA shows the best single cell performance and long-term stability, and a reduction of Pt loading can be achieved. The feasibility of BPCL for improving the Pt utilization is also demonstrated by the cathode cyclic voltammetry in MEA.

Surface chemical analysis and ab initio investigations of CsI coated C fiber cathodes for high power microwave sources

NASA Astrophysics Data System (ADS)

Vlahos, Vasilios; Morgan, Dane; LaCour, Matthew; Golby, Ken; Shiffler, Don; Booske, John H.

2010-02-01

CsI coated C fiber cathodes are promising electron emitters utilized in field emission applications. Ab initio calculations, in conjunction with experimental investigations on CsI-spray coated C fiber cathodes, were performed in order to better understand the origin of the low turn-on E-field obtained, as compared to uncoated C fibers. One possible mechanism for lowering the turn-on E-field is surface dipole layers reducing the work function. Ab initio modeling revealed that surface monolayers of Cs, CsI, Cs2O, and CsO are all capable of producing low work function C fiber cathodes (1 eV<Φ<1.5 eV), yielding a reduction in the turn-on E-field by as much as ten times, when compared to the bare fiber. Although a CsI-containing aqueous solution is spray deposited on the C fiber surface, energy dispersive x-ray spectroscopy and scanning auger microscopy measurements show coabsorption of Cs and I into the fiber interior and Cs and O on the fiber surface, with no surface I. It is therefore proposed that a cesium oxide (CsxOy) surface coating is responsible, at least in part, for the low turn E-field and superior emission characteristics of this type of fiber cathode. This CsxOy layer could be formed during preconditioning heating. CsxOy surface layers cannot only lower the fiber work function by the formation of surface dipoles (if they are thin enough) but may also enhance surface emission through their ability to emit secondary electrons due to a process of grazing electron impact. These multiple electron emission processes may explain the reported 10-100 fold reduction in the turn-on E-field of coated C fibers.

Nb and Pd co-doped La0.57Sr0.38Co0.19Fe0.665Nb0.095Pd0.05O3-δ as a stable, high performance electrode for barrier-layer-free Y2O3-ZrO2 electrolyte of solid oxide fuel cells

NASA Astrophysics Data System (ADS)

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

2018-02-01

La0.6Sr0.2Co0.2Fe0.8O3-δ (LSCF) is the most intensively investigated high performance cathode for intermediate temperature solid oxide fuel cells (IT-SOFCs), but strontium segregation and migration at the electrode/electrolyte interface is a critical issue limiting the electrocatalytic activity and stability of LSCF based cathodes. Herein, we report a Nb and Pd co-doped LSCF (La0.57Sr0.38Co0.19Fe0.665Nb0.095Pd0.05O3-δ, LSCFNPd) perovskite as stable and active cathode on a barrier-layer-free anode-supported yttria-stabilized zirconia (YSZ) electrolyte cell using direct assembly method without pre-sintering at high temperatures. The cell exhibits a peak power density of 1.3 W cm-2 at 750 °C and excellent stability with no degradation during polarization at 500 mA cm-2 and 750 °C for 175 h. Microscopic and spectroscopic analysis show that the electrochemical polarization promotes the formation of electrode/electrolyte interface in operando and exsolution of Pd/PdO nanoparticles. The Nb doping in the B-site of LSCF significantly reduces the Sr surface segregation, enhancing the stability of the cathode, while the exsoluted Pd/PdO nanoparticles increases the electrocatalytic activity for the oxygen reduction reaction. The present study opens up a new route for the development of cobaltite-based perovskite cathodes with high activity and stability for barrier-layer-free YSZ electrolyte based IT-SOFCs.

Calcium intercalation into layered fluorinated sodium iron phosphate

DOE PAGES

Lipson, Albert L.; Kim, Soojeong; Pan, Baofei; ...

2017-10-09

Here, the energy density and cost of battery systems could be improved by moving to alternative battery chemistries such as Ca-ion. However, in order to switch chemistries many problems need to be solved including the identification of cathode materials with high energy density, and electrolytes that can plate and strip calcium metal. Herein, the feasibility and cycling performance of Ca 2+ intercalation into a desodiated layered Na 2FePO 4F host is described. This is the first demonstration of Ca 2+ intercalation into a polyanionic framework, which implies that other polyanionic framework materials may be active for Ca 2+ intercalation. Althoughmore » substantial effort is still needed to identify a high energy density cathode material, this study and others demonstrate the feasibility of Ca 2+ intercalation into multiple materials making it more probable that such a cathode material can be found.« less

Calcium intercalation into layered fluorinated sodium iron phosphate

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

Lipson, Albert L.; Kim, Soojeong; Pan, Baofei

Here, the energy density and cost of battery systems could be improved by moving to alternative battery chemistries such as Ca-ion. However, in order to switch chemistries many problems need to be solved including the identification of cathode materials with high energy density, and electrolytes that can plate and strip calcium metal. Herein, the feasibility and cycling performance of Ca 2+ intercalation into a desodiated layered Na 2FePO 4F host is described. This is the first demonstration of Ca 2+ intercalation into a polyanionic framework, which implies that other polyanionic framework materials may be active for Ca 2+ intercalation. Althoughmore » substantial effort is still needed to identify a high energy density cathode material, this study and others demonstrate the feasibility of Ca 2+ intercalation into multiple materials making it more probable that such a cathode material can be found.« less

Advanced Lithium-ion Batteries with High Specific Energy and Improved Safety for Nasa's Missions

NASA Technical Reports Server (NTRS)

West, William; Smart, Marshall; Soler, Jess; Krause, Charlie; Hwang, Constanza; Bugga, Ratnakumar

2012-01-01

High Energy Materials ( Cathodes, anodes and high voltage and safe electrolyte are required to meet the needs of the future space missions. A. Cathodes: The layered layered composites of of Li2MnO3 and LiMO2 are promising Power capability of the materials, however requires further improvement. Suitable morphology is critical for good performance and high tap (packing) density. Surface coatings help in the interfacial kinetics and stability. B. Electrolytes: Small additions of Flame Retardant Additives improves flammability without affecting performance (Rate and cycle life). 1.0 M in EC+EMC+TPP was shown to have good performance against the high voltage cathode; Performance demonstrated in large capacity prototype MCMB- LiNiCoO2 Cells. Formulations with higher proportions are looking promising. Still requires further validation through abuse tests (e.g., on 18650 cells).

Cassettes for solid-oxide fuel cell stacks and methods of making the same

DOEpatents

Weil, K. Scott; Meinhardt, Kerry D; Sprenkle, Vincent L

2012-10-23

Solid-oxide fuel cell (SOFC) stack assembly designs are consistently investigated to develop an assembly that provides optimal performance, and durability, within desired cost parameters. A new design includes a repeat unit having a SOFC cassette and being characterized by a three-component construct. The three components include an oxidation-resistant, metal window frame hermetically joined to an electrolyte layer of a multi-layer, anode-supported ceramic cell and a pre-cassette including a separator plate having a plurality of vias that provide electrical contact between an anode-side collector within the pre-cassette and a cathode-side current collector of an adjacent cell. The third component is a cathode-side seal, which includes a standoff that supports a cathode channel spacing between each of the cassettes in a stack. Cassettes are formed by joining the pre-cassette and the window frame.

Fractional-dimensional Child-Langmuir law for a rough cathode

NASA Astrophysics Data System (ADS)

Zubair, M.; Ang, L. K.

2016-07-01

This work presents a self-consistent model of space charge limited current transport in a gap combined of free-space and fractional-dimensional space (Fα), where α is the fractional dimension in the range 0 < α ≤ 1. In this approach, a closed-form fractional-dimensional generalization of Child-Langmuir (CL) law is derived in classical regime which is then used to model the effect of cathode surface roughness in a vacuum diode by replacing the rough cathode with a smooth cathode placed in a layer of effective fractional-dimensional space. Smooth transition of CL law from the fractional-dimensional to integer-dimensional space is also demonstrated. The model has been validated by comparing results with an experiment.

Computational Studies of Thermodynamics and Kinetics of Metal Oxides in Li-Ion Batteries and Earth's Lower Mantle Materials

NASA Astrophysics Data System (ADS)

Xu, Shenzhen

Metal oxide materials are ubiquitous in nature and in our daily lives. For example, the Earth's mantle layer that makes up about 80% of our Earth's volume is composed of metal oxide materials, the cathode materials in the lithium-ion batteries that provide power for most of our mobile electronic devices are composed of metal oxides, the chemical components of the passivation layers on many kinds of metal materials that protect the metal from further corrosion are metal oxides. This thesis is composed of two major topics about the metal oxide materials in nature. The first topic is about our computational study of the iron chemistry in the Earth's lower mantle metal oxide materials, i.e. the bridgmanite (Fe-bearing MgSiO3 where iron is the substitution impurity element) and the ferropericlase (Fe-bearing MgO where iron is the substitution impurity element). The second topic is about our multiscale modeling works for understanding the nanoscale kinetic and thermodynamic properties of the metal oxide cathode interfaces in Li-ion batteries, including the intrinsic cathode interfaces (intergrowth of multiple types of cathode materials, compositional gradient cathode materials, etc.), the cathode/coating interface systems and the cathode/electrolyte interface systems. This thesis uses models based on density functional theory quantum mechanical calculations to explore the underlying physics behind several types of metal oxide materials existing in the interior of the Earth or used in the applications of lithium-ion batteries. The exploration of this physics can help us better understand the geochemical and seismic properties of our Earth and inspire us to engineer the next generation of electrochemical technologies.

Experimental investigation of high temperature high voltage thermionic diode for the space power nuclear reactor

NASA Astrophysics Data System (ADS)

Onufriyev, Valery. V.

2001-02-01

It is well known that the rise of arc from the dense glow discharge is connected with the thermion and secondary processes on the cathode surface (Granovsky, 1971; Leob, 1953; Engel, 1935). First model of breakdown of the cathode layer is connected with the increase of the cathode temperature in consequence of the ion bombardment that leads to the grows its thermo-emissive current. Other model shows the main role of the secondary effects on the cathode surface-the increase of the secondary ion emission coefficient-γi with the grows of glow discharge voltage. But the author of this investigation work of breakdown in Cs vapor (a transmission the glow discharge into self-maintaining arc discharge) discovered the next peculiarity: the value of breakdown voltage is constant when the values of vapor temperature (its pressure pcs) and cathode temperature Tk is constant too (Ub=constant with Tk=constant and pcs=constant) and it is not a statistical value (Onufryev, Grishin, 1996) (that was observed in gas glow discharges other authors (Granovsky, 1971; Leob, 1953; Engel, 1935)). The investigations of thermion high voltage high temperature diode (its breakdown characteristics in closed state and voltage-current characteristics in disclosed state) showed that the value of the breakdown voltage is depended on the vapor pressure in inter-electrode gap (IEG)-pcs and cathode temperature-Tk and is independent on IEG length-Δieg. On this base it was settled that the main role in transition of glow discharge to self-maintaining arc discharge plays an ion cathode layer but more exactly-the region of excited atoms-``Aston glow.'' .

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.

Electrospun Nanofiber-Coated Membrane Separators for Lithium-Ion Batteries

NASA Astrophysics Data System (ADS)

Lee, Hun

Lithium-ion batteries are widely used as a power source for portable electronic devices and hybrid electric vehicles due to their excellent energy and power densities, long cycle life, and enhanced safety. A separator is considered to be the critical component in lithium-ion rechargeable batteries. The separator is placed between the positive and negative electrodes in order to prevent the physical contact of electrodes while allowing the transportation of ions. In most commercial lithium-ion batteries, polyolefin microporous membranes are commonly used as the separator due to their good chemical stability and high mechanical strength. However, some of their intrinsic natures, such as low electrolyte uptake, poor adhesion property to the electrodes, and low ionic conductivity, can still be improved to achieve higher performance of lithium-ion batteries. In order to improve these intrinsic properties, polyolefin microporous membranes can be coated with nanofibers by using electrospinning technique. Electrospinning is a simple and efficient method to prepare nanofibers which can absorb a significant amount of liquid electrolyte to achieve low internal resistance and battery performance. This research presents the preparation and investigation of composite membrane separators prepared by coating nanofibers onto polyolefin microporous membranes via electrospinning technique. Polyvinylidene fluoride polymers and copolymers were used for the preparation of electrospun nanofiber coatings because they have excellent electrochemical stability, good adhesion property, and high temperature resistance. The nanofiber coatings prepared by electrospinning form an interconnected and randomly orientated structure on the surface of the polyolefin microporous membranes. The size of the nanofibers is on a scale that does not interfere with the micropores in the membrane substrates. The resultant nanofiber-coated membranes have the potential to combine advantages of both the polyolefin separator membranes and the nanoscale fibrous polymer coatings. The polyolefin microporous membranes serve as the supporting substrate which provides the required mechanical strength for the assembling process of lithium-ion batteries. The electrospun nanofiber coatings improve the wettability of the composite membrane separators to the liquid electrolyte, which is desirable for the lithium-ion batteries with high kinetics and good cycling performance. The results show that the nanofiber-coated membranes have enhanced adhesion properties to the battery electrode which can help prevent the formation of undesirable gaps between the separators and electrodes during prolonged charge-discharge cycles, especially in large-format batteries. The improvement on adhesive properties of nanofiber-coated membranes was evaluated by peel test. Nanofiber coatings applied to polyolefin membrane substrates improve the adhesion of separator membranes to battery electrodes. Electrolyte uptakes, ionic conductivities and interfacial resistances of the nanofiber-coated membrane separators were studied by soaking the membrane separators with a liquid electrolyte solution of 1 M lithium hexafluorophosphate dissolved in ethylene carbonate/dimethylcarbonate/ethylmethyl carbonate (1:1:1 vol). The nanofiber coatings on the surface of the membrane substrates increase the electrolyte uptake capacity due to the high surface area and capillary effect of nanofibers. The nanofiber-coated membranes soaked in the liquid electrolyte solution exhibit high ionic conductivities and low interfacial resistances to the lithium electrode. The cells containing LiFePO 4 cathode and the nanofiber-coated membranes as the separator show high discharge specific capacities and good cycling stability at room temperature. The nanofiber coatings on the membrane substrates contribute to high ionic conductivity and good electrochemical performance in lithium-ion batteries. Therefore, these nanofiber-coated composite membranes can be directly used as novel battery separators for high performance of lithium-ion batteries. Coating polyolefin microporous membranes with electrospun nanofibers is a promising approach to obtain highperformance separators for advanced lithium-ion batteries.

New general pore size distribution model by classical thermodynamics application: Activated carbon

USGS Publications Warehouse

Lordgooei, M.; Rood, M.J.; Rostam-Abadi, M.

2001-01-01

A model is developed using classical thermodynamics to characterize pore size distributions (PSDs) of materials containing micropores and mesopores. The thermal equation of equilibrium adsorption (TEEA) is used to provide thermodynamic properties and relate the relative pore filling pressure of vapors to the characteristic pore energies of the adsorbent/adsorbate system for micropore sizes. Pore characteristic energies are calculated by averaging of interaction energies between adsorbate molecules and adsorbent pore walls as well as considering adsorbate-adsorbate interactions. A modified Kelvin equation is used to characterize mesopore sizes by considering variation of the adsorbate surface tension and by excluding the adsorbed film layer for the pore size. The modified-Kelvin equation provides similar pore filling pressures as predicted by density functional theory. Combination of these models provides a complete PSD of the adsorbent for the micropores and mesopores. The resulting PSD is compared with the PSDs from Jaroniec and Choma and Horvath and Kawazoe models as well as a first-order approximation model using Polanyi theory. The major importance of this model is its basis on classical thermodynamic properties, less simplifying assumptions in its derivation compared to other methods, and ease of use.

A high-capacity, low-cost layered sodium manganese oxide material as cathode for sodium-ion batteries.

PubMed

Guo, Shaohua; Yu, Haijun; Jian, Zelang; Liu, Pan; Zhu, Yanbei; Guo, Xianwei; Chen, Mingwei; Ishida, Masayoshi; Zhou, Haoshen

2014-08-01

A layered sodium manganese oxide material (NaMn3 O5 ) is introduced as a novel cathode materials for sodium-ion batteries. Structural characterizations reveal a typical Birnessite structure with lamellar stacking of the synthetic nanosheets. Electrochemical tests reveal a particularly large discharge capacity of 219 mAh g(-1) in the voltage rang of 1.5-4.7 V vs. Na/Na(+) . With an average potential of 2.75 V versus sodium metal, layered NaMn3 O5 exhibits a high energy density of 602 Wh kg(-1) , and also presents good rate capability. Furthermore, the diffusion coefficient of sodium ions in the layered NaMn3 O5 electrode is investigated by using the galvanostatic intermittent titration technique. The results greatly contribute to the development of room-temperature sodium-ion batteries based on earth-abundant elements. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

An Electrostatically Self-Assembled Thin Film Made of Zn-Substituted Tungstoborate and Rhodamine B with Photoelectrochemical Properties.

PubMed

Mao, Xu; Zhang, Jia-Ning; Gao, Li-Hua; Su, Yu; Chen, Peng-Xia; Wang, Ke-Zhi

2016-04-01

An electrostatically self-assembled multilayer thin film consisting of alternating layers of Keggin polyoxometalate of Zn-substituted tungstoborate (BW11Zn) and Rhodamine B (RhB) has successfully been prepared on a quartz and indium-tin oxide (ITO) glass substrate. The ultraviolet-visible (UV-vis) absorption spectra demonstrated that the electrostatically self-assembled film of (BW11Zn/RhB)n was uniformly deposited layer by layer, and the RhB molecules in the film formed the J-aggregation. The photoelectrochemical investigations showed that the films generated stable cathodic photocurrents that originated from RhB, and the maximal cathodic photocurrent density generated by an eight-layer film was 4.9 µA/cm2 while the film was irradiated with 100 mW/cm2 polychromatic light of 730 nm > λ > 325 nm at an applied potential of 0 V versus a saturated calomel electrode.

Role of ultrathin metal fluoride layer in organic photovoltaic cells: mechanism of efficiency and lifetime enhancement.

PubMed

Lim, Kyung-Geun; Choi, Mi-Ri; Kim, Ji-Hoon; Kim, Dong Hun; Jung, Gwan Ho; Park, Yongsup; Lee, Jong-Lam; Lee, Tae-Woo

2014-04-01

Although rapid progress has been made recently in bulk heterojunction organic solar cells, systematic studies on an ultrathin interfacial layer at the electron extraction contact have not been conducted in detail, which is important to improve both the device efficiency and the lifetime. We find that an ultrathin BaF2 layer at the electron extraction contact strongly influences the open-circuit voltage (Voc ) as the nanomorphology evolves with increasing BaF2 thickness. A vacuum-deposited ultrathin BaF2 layer grows by island growth, so BaF2 layers with a nominal thickness less than that of single-coverage layer (≈3 nm) partially cover the polymeric photoactive layer. As the nominal thickness of the BaF2 layer increased to that of a single-coverage layer, the Voc and power conversion efficiency (PCE) of the organic photovoltaic cells (OPVs) increased but the short-circuit current remained almost constant. The fill factor and the PCE decreased abruptly as the thickness of the BaF2 layer exceeded that of a single-coverage layer, which was ascribed to the insulating nature of BaF2 . We find the major cause of the increased Voc observed in these devices is the lowered work function of the cathode caused by the reaction and release of Ba from thin BaF2 films upon deposition of Al. The OPV device with the BaF2 layer showed a slightly improved maximum PCE (4.0 %) and a greatly (approximately nine times) increased device half-life under continuous simulated solar irradiation at 100 mW cm(-2) as compared with the OPV without an interfacial layer (PCE=2.1 %). We found that the photodegradation of the photoactive layer was not a major cause of the OPV degradation. The hugely improved lifetime with cathode interface modification suggests a significant role of the cathode interfacial layer that can help to prolong device lifetimes. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Activated carbon derived from chitosan as air cathode catalyst for high performance in microbial fuel cells

NASA Astrophysics Data System (ADS)

Liu, Yi; Zhao, Yong; Li, Kexun; Wang, Zhong; Tian, Pei; Liu, Di; Yang, Tingting; Wang, Junjie

2018-02-01

Chitosan with rich of nitrogen is used as carbon precursor to synthesis activated carbon through directly heating method in this study. The obtained carbon is activated by different amount of KOH at different temperatures, and then prepared as air cathodes for microbial fuel cells. Carbon sample treated with double amount of KOH at 850 °C exhibits maximum power density (1435 ± 46 mW m-2), 1.01 times improved, which ascribes to the highest total surface area, moderate micropore and mesoporous structure and the introduction of nitrogen. The electrochemical impedance spectroscopy and powder resistivity state that carbon treated with double amount of KOH at 850 °C possesses lower resistance. The other electrochemical measurements demonstrate that the best kinetic activity make the above treated sample to show the best oxygen reduction reaction activity. Besides, the degree of graphitization of samples increases with the activated temperature increasing, which is tested by Raman. According to elemental analysis and X-ray photoelectron spectroscopy, all chitosan samples are nitrogen-doped carbon, and high content nitrogen (pyridinic-N) improves the electrochemical activity of carbon treated with KOH at 850 °C. Thus, carbon materials derived from chitosan would be an optimized catalyst for oxygen reduction reaction in microbial fuel cell.

Tellurium-Impregnated Porous Cobalt-Doped Carbon Polyhedra as Superior Cathodes for Lithium-Tellurium Batteries.

PubMed

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

2017-08-22

Lithium-tellurium (Li-Te) batteries are attractive for energy storage owing to their high theoretical volumetric capacity of 2621 mAh cm -3 . In this work, highly nanoporous cobalt and nitrogen codoped carbon polyhedra (C-Co-N) derived from a metal-organic framework (MOF) is synthesized and employed as tellurium host for Li-Te batteries. The Te@C-Co-N cathode with a high Te loading of 77.2 wt % exhibits record-breaking electrochemical performances including an ultrahigh initial capacity of 2615.2 mAh cm -3 approaching the theoretical capacity of Te (2621 mAh cm -3 ), a superior cycling stability with a high capacity retention of 93.6%, a ∼99% Columbic efficiency after 800 cycles as well as rate capacities of 2160, 1327.6, and 894.8 mAh cm -3 at 4, 10, and 20 C, respectively. The redox chemistry of tellurium is revealed by in operando Raman spectroscopic analysis and density functional theory simulations. The results illustrate that the performances are attributed to the highly conductive C-Co-N matrix with an advantageous structure of abundant micropores, which provides highly efficient channels for electron transfer and ionic diffusion as well as sufficient surface area to efficiently host tellurium while mitigating polytelluride dissolution and suppressing volume expansion.

Delay in micro-discharges appearance during PEO of Al: Evidence of a mechanism of charge accumulation at the electrolyte/oxide interface

NASA Astrophysics Data System (ADS)

Martin, J.; Nominé, A.; Brochard, F.; Briançon, J.-L.; Noël, C.; Belmonte, T.; Czerwiec, T.; Henrion, G.

2017-07-01

PEO was conducted on Al by applying a pulsed bipolar current. The role of the cathodic polarization on the appearance of micro-discharges (MDs) and on the subsequent formation of the PEO oxide layers is investigated. Various ratios of the charge quantity RCQ = Qp/Qn (defined as the anodic Qp to cathodic Qn charge quantity ratio over one current pulse period) in the range [0.5; 6.0] were selected by changing the waveform parameters of the cathodic current while keeping the waveform of the anodic current unchanged. Results show that the appearance of MDs is delayed with respect to the rising edge of the anodic current; this delay strongly depends on both the processing time and the applied cathodic charge quantity. It is also evidenced that shorter delays promoted by high RCQ values (RCQ > 1) are associated with stronger MDs (large size and long life) that have detrimental effects on the formed PEO oxide layers. Thicker and the more compact oxide layer morphology is achieved with the intermediate RCQ value (RCQ = 0.9) for which the delay of the MDs appearance is high and the MDs softer. Low RCQ (RCQ < 0.9) results in an earlier extinction of the MDs as the process goes on, which leads to poorly oxidized metal. A mechanism of charge accumulation taking place at the oxide/electrolyte interface and arising before the occurrence of dielectric breakdown is proposed to explain the ignition of MDs during pulsed bipolar PEO of aluminium. A close examination of the voltage-time response which can be adequately simulated with an equivalent RC circuit evidences the capacitive behaviour of the oxide layer and therefore confirms this proposed mechanism of charge accumulation.

Understanding the Intrinsic Electrochemistry of Ni-Rich Layered Cathodes

NASA Astrophysics Data System (ADS)

Sallis, Shawn

The demand for energy is continually increasing overtime and the key to meeting future demand in a sustainable way is with energy storage. Li-ion batteries employing layered transition metal oxide cathodes are one of the most technologically important energy storage technologies. However, current Li-ion batteries are unable to access their full theoretical capacity and suffer from performance limiting degradation over time partially originating from the cathode and partially from the interface with the electrolyte. Understanding the fundamental limitations of layered transition metal oxide cathodes requires a complete understanding of the surface and bulk of the materials in their most delithiated state. In this thesis, we employ LiNi0.8Co0.15Al 0.05O2 (NCA) as a model system for Ni-rich layered oxide cathodes. Unlike its parent compound, LiCoO2, NCA is capable of high states of delithiation with minimal structural transitions. Furthermore, commercially available NCA has little to no transition metals in the Li layer. X-ray spectroscopies are an ideal tool for studying cathodes at high states of delithiation due their elemental selectivity, range of probing depths, and sensitivity to both chemical and electronic state information. The oxidation state of the transition metals at the surface can be probed via X-ray photoelectron spectroscopy (XPS) while both bulk and surface oxidation states as well as changes in metal oxygen bonding can be probed using X-ray absorption spectroscopy (XAS). Using X-ray spectroscopy in tandem with electrochemical, transport and microscopy measurements of the same materials, the impedance growth with increasing delithiation was correlated with the formation of a disordered NiO phase on the surface of NCA which was precipitated by the release of oxygen. Furthermore, the surface degradation was strongly impacted by the type of Li salt used in the electrolyte, with the standard commercial salt LiPF6 suffering from exothermic decomposition at high voltages and temperatures. Substituting LiPF6with LiBF4 suppressed NCA surface degradation and the dissolution of the transition metals into the electrolyte which is responsible for the impedance growth. Even in the most extreme conditions (4.75V vs Li +/Li0 at 60 °C for > 100 hrs) the degradation (i.e. metal reduction) was restricted to the first 10-30 nm and no evidence of oxygen loss was observed in the bulk. However, the transition metal ions were found to cease oxidizing above 4.25 V vs Li+/Li0 despite it being possible to extract 20% more lithium. Using a newly developed high efficiency resonant inelastic x-ray scattering (RIXS) spectrometer to probe the O K-edge of NCA electrodes at various conditions, it was concluded that oxygen participates in the charge compensation at the highest states of delithiation instead of the transition metals. These results are intrinsic to the physical and electronic structure of NCA and appear general to the other layered transition metal oxides currently under consideration for use as cathodes in Li-ion batteries.

Oriented graphite layer formation in Ti/C and TiC/C multilayers deposited by high current pulsed cathodic arc

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

Persson, P. O. A.; Ryves, L.; Tucker, M. D.

2008-10-01

Ti/C and TiC/C multilayers with periods ranging from 2 to 18 nm were grown by filtered high current pulsed cathodic arc. The growth was monitored in situ by ellipsometry and cantilever stress measurements. The ellipsometry results reveal that the optical properties of the carbon vary as a function of thickness. Correspondingly, the stress in each carbon layer as measured in situ exhibits two well defined values: initially the stress is low and then takes on a higher value for the remainder of the layer. Transmission electron microscopy shows that the initial growth of carbon on Ti or TiC layer ismore » oriented with graphitic basal planes aligned parallel to the interface. After 2-4 nm of growth, the graphitic structure transforms to amorphous carbon. Electron energy loss spectroscopy shows that the carbon layer simultaneously undergoes a transition from sp{sup 2} rich to sp{sup 3} rich material.« less

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

Freestanding membrane composed of micro-ring array with ultrahigh sidewall aspect ratio for application in lightweight cathode arrays

NASA Astrophysics Data System (ADS)

Wang, Lanlan; Liu, Hongzhong; Jiang, Weitao; Gao, Wei; Chen, Bangdao; Li, Xin; Ding, Yucheng; An, Ningli

2014-12-01

A freestanding multilayer ultrathin nano-membrane (FUN-membrane) with a micro-ring array (MRA) is successfully fabricated through the controllable film deposition. Each micro-ring of FUN-membrane is 3 μm in diameter, 2 μm in height and sub-100 nm in sidewall thickness, demonstrating an ultrahigh sidewall aspect ratio of 20:1. In our strategy, a silica layer (200 nm in thickness), a chromium transition layer (5 nm-thick) and a gold layer (40 nm-thick), were in sequence deposited on patterned photoresist. After removal of the photoresist by lift-off process, a FUN-membrane with MRA was peeled off from the substrate, where the gold layer acted as a protecting layer to prevent the MRA from fracture. The FUN-membrane was then transferred to a flexible polycarbonate (PC) sheet coated with indium tin oxide (ITO) layer, which was then used as a flexible and lightweight cathode. Remarkably, the field emission effect of the fabricated FUN-membrane cathode performs a high field-enhancement factor of 1.2 × 104 and a low turn-on voltage of 2 V/μm, indicating the advantages of the sharp metal edge of MRA. Due to the rational design and material versatility, the FUN-membrane thus could be transferred to either rigid or flexible substrate, even curved surface, such as the skin of bio-robot's arm or leg. Additionally, the FUN-membrane composed of MRA with extremely high aspect ratio of insulator-metal sidewall, also provides potential applications in optical devices, lightweight and flexible display devices, and electronic eye imagers.

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

Effects of interfacial stability between electron transporting layer and cathode on the degradation process of organic light-emitting diodes

NASA Astrophysics Data System (ADS)

Chu, Ta-Ya; Lee, Yong-Han; Song, Ok-Keun

2007-11-01

The authors have demonstrated that the increase of electron injection barrier height between tris(8-hydroxyquinoline)aluminum (Alq3) and LiF /Al cathode is one of the most critical parameters to determine the reliability of organic light-emitting diode with the typical structure of indium tin oxide/N ,N'-bis(naphthalen-1-yl)-N ,N'-bis(phenyl) benzidine/Alq3/LiF /Al. The electrical properties of several devices (hole only, electron only, and integrated double-layered devices) have been measured in the function of operating time to analyze the bulk and interface property changes. Bulk properties of trap energy and mobility in an organic layer have been estimated by using trap-charge-limited currents and transient electroluminescence measurements.

Method for synthesizing thin film electrodes

DOEpatents

Boyle, Timothy J [Albuquerque, NM

2007-03-13

A method for making a thin-film electrode, either an anode or a cathode, by preparing a precursor solution using an alkoxide reactant, depositing multiple thin film layers with each layer approximately 500 1000 .ANG. in thickness, and heating the layers to above 600.degree. C. to achieve a material with electrochemical properties suitable for use in a thin film battery. The preparation of the anode precursor solution uses Sn(OCH.sub.2C(CH.sub.3).sub.3).sub.2 dissolved in a solvent in the presence of HO.sub.2CCH.sub.3 and the cathode precursor solution is formed by dissolving a mixture of (Li(OCH.sub.2C(CH.sub.3).sub.3)).sub.8 and Co(O.sub.2CCH.sub.3).H.sub.2O in at least one polar solvent.

Experimental visualization of the cathode layer in AC surface dielectric barrier discharge

NASA Astrophysics Data System (ADS)

Kim, Sang-You; Lho, Taihyeop; Chung, Kyu-Sun

2018-06-01

A narrow etched polyimide line at the bottom edge of a biased electrode (BE) and a non-etched dielectric surface near the biased electrode were observed in an atmospheric AC flexible surface dielectric barrier discharge of polyimide dielectric. These findings are attributed to the bombardment of positive oxygen ions on the bottom edge of the BE and the electron breakdown trajectory not contacting the polyimide surface following the electric field lines formed between the BE edge and the surface charge layer on the dielectric. The length of the non-etched dielectric surface during the first micro-discharge was observed as 22 μm. This occurred, regardless of three different operating durations, which is in good agreement with the length of the cathode layer according to Paschen's law.

Structural and electrochemical characterization and surface modification of layered solid solution oxide cathodes of lithium ion batteries

NASA Astrophysics Data System (ADS)

Wu, Yan

Lithium ion batteries are widely used to power portable electronic devices such as cell phones and laptop computers due to their high energy density. However, the currently used layered LiCoO2 cathode could deliver only 50 % of its theoretical capacity in practical lithium ion cells (140 mAh/g) due to the chemical and structural instabilities at deep charge with (1-x) < 0.5 in Li1-xCoO2. Also, cobalt is relatively expensive and toxic. These difficulties have generated enormous interest in alternative cathode hosts. In this regard, solid solutions between layered Li[Li1/3Mn2/3]O2 (commonly designated as Li2MnO3) and LiMO2 (M = Mn, Ni, Co)) have become appealing as some of them exhibit much higher capacity (˜ 250 mAh/g on charging to 4.8 V) with lower cost and better safety compared to LiCoO 2. This dissertation investigates the (1-z) Li[Li1/3Mn 2/3]O2 - (z) Li[Mn0.5-yNi0.5-yCo 2y]O2 (y = 1/12, 1/6 and 1/3 and 0.25 = z = 0.75) layered oxide cathodes, which belong to a solid solution series between layered Li[Li 1/3Mn2/3]O2 and Li[Mn0.5-yNi0.5-y Co2y]O2, with an aim to develop a better understanding of the charge-discharge mechanisms and optimize the electrochemical performance of these materials. To accomplish this, the structural and electrochemical characterization of the (1- z) Li[Li1/3Mn2/3]O2 - (z) Li[Mn 0.5-yNi0.5-yCo2y]O2 cathodes is carried out. It is found that the amount of oxygen loss is related to the lithium content in the transition metal layer, and the Co and Mn4+ contents play a role in influencing the electrochemical behavior. In addition, the chemically delithiated samples are found to transform to O1 or P3 structure with a vanishing of the superlattice reflections arising from cationic ordering in the transition metal layer due to the incorporation of protons from the chemical delithiation medium, while the electrochemically charged samples retain the initial O3 structure. These layered solid solution oxides exhibit high irreversible capacity (IRC) loss (difference between first charge and discharge capacity) values (up to 100 mAh/g), which have been reduced significantly by modifying the cathode surface with other materials like Al2O3, AlPO 4, and F-. For example, compared to an IRC of 75 mAh/g and a first discharge capacity of 253 mAh/g for the pristine Li[Li0.2 Mn0.54Ni0.13Co0.13]O2 (y = 1/6 and z = 0.4), the 3 wt. % Al2O3 modified sample exhibits a lower IRC of 41 mAh/g and a higher first discharge capacity of 285 mAh/g, which is two times higher than that achieved with the LiCoO 2 cathode. A careful and systematic analysis of the experimentally observed capacity and IRC values suggest that part of the oxide ion vacancies created during first charge is retained in the layered lattice in contrast to the idealized model (elimination of all oxide ion vacancies) proposed in the literature. The surface modification helps to retain even more number of oxide ion vacancies in the lattice, which leads to a lower IRC and higher discharge capacity values. Additionally, bulk cationic and anionic substitutions of Al3+ and F- in Li[Li0.17Mn0.58Ni0.25 ]O2 (y = 0 and z = 0.5) are found to sensitively decrease the amount of oxygen loss from the lattice.

Effect of sputtered lanthanum hexaboride film thickness on field emission from metallic knife edge cathodes

NASA Astrophysics Data System (ADS)

Kirley, M. P.; Novakovic, B.; Sule, N.; Weber, M. J.; Knezevic, I.; Booske, J. H.

2012-03-01

We report experiments and analysis of field emission from metallic knife-edge cathodes, which are sputter-coated with thin films of lanthanum hexaboride (LaB6), a low-work function material. The emission current is found to depend sensitively on the thickness of the LaB6 layer. We find that films thinner than 10 nm greatly enhance the emitted current. However, cathodes coated with a thicker layer of LaB6 are observed to emit less current than the uncoated metallic cathode. This result is unexpected due to the higher work function of the bare metal cathode. We show, based on numerical calculation of the electrostatic potential throughout the structure, that the external (LaB6/vacuum) barrier is reduced with respect to uncoated samples for both thin and thick coatings. However, this behavior is not exhibited at the internal (metal/LaB6) barrier. In thinly coated samples, electrons tunnel efficiently through both the internal and external barrier, resulting in current enhancement with respect to the uncoated case. In contrast, the thick internal barrier in thickly coated samples suppresses current below the value for uncoated samples in spite of the lowered external barrier. We argue that this coating thickness variation stems from a relatively low (no higher than 1018 cm-3) free carrier density in the sputtered polycrystalline LaB6.

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

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

Li, Wangda; Dolocan, Andrei; Oh, Pilgun

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

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

DOE PAGES

Li, Wangda; Dolocan, Andrei; Oh, Pilgun; ...

2017-04-26

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

Recent progress on RE2O3-Mo/W emission materials.

PubMed

Wang, Jinshu; Zhang, Xizhu; Liu, Wei; Cui, Yuntao; Wang, Yiman; Zhou, Meiling

2012-08-01

RE2O3-Mo/W cathodes were prepared by powder metallurgy method. La2O3-Y2O3-Mo cermet cathodes prepared by traditional sintering method and spark plasma sintering (SPS) exhibit different secondary emission properties. The La2O3-Y2O3-Mo cermet cathode prepared by SPS method has smaller grain size and exhibits better secondary emission performance. Monte carlo calculation results indicate that the secondary electron emission way of the cathode correlates with the grain size. Decreasing the grain size can decrease the positive charging effect of RE2O3 and thus is favorable for the escaping of secondary electrons to vacuum. The Scandia doped tungsten matrix dispenser cathode with a sub-micrometer microstructure of matrix with uniformly distributed nanometer-particles of Scandia has good thermionic emission property. Over 100 A/cm2 full space charge limited current density can be obtained at 950Cb. The cathode surface is covered by a Ba-Sc-O active surface layer with nano-particles distributing mainly on growth steps of W grains, leads to the conspicuous emission property of the cathode.

A pillar-layered metal-organic framework as luminescent sensor for selective and reversible response of chloroform

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

Wang, Kun; Li, Shuni; Jiang, Yucheng

A new 3D metal-organic framework, namely, (Zn{sub 4}(H{sub 2}BPTC){sub 2}(HCOO){sub 4}){sub n} (SNNU-1, H{sub 4}BPTC=biphenyl-3,3',5,5'-tetracarboxylic acid, SNNU=Shaanxi Normal University) has been solvothermal synthesized. Four independent tetrahedral Zn atoms are connected by organic ligands to form a 2D Zn-H{sub 2}BPTC layer, which is further bridged by in-situ generated HCOO{sup -} to give the 3D pillar-layered framework of SNNU-1. Unique Zn and H{sub 2}BPTC all act as 4-connected nodes leading to a new 4,4,4-connected topological net with point symbol of (4·5·6{sup 2}·8{sup 2})(4·5{sup 2}·6{sup 2}·8)(5{sup 2}·6{sup 3}·7). Notably, intense blue emission band is observed for SNNU-1, which exhibits solvent-dependent effect. Compared tomore » other common organic solvents, chloroform can specially improve the photoluminescent intensity of SNNU-1. Further repeated response and release experiments clearly showed that SNNU-1 can act as luminescent sensor for selective and reversible detection of chloroform. - Graphical abstract: Zn{sup 2+} ions are bridged by aromatic tetracarboxylate ligands and inorganic formate anions to give a microporous pillar layered open-framework, which exhibits not only strong photoluminescence but also selective and reversible luminescent sensing for chloroform. - Highlights: • Novel Zn-tetracarboxylate-formate microporous pillar layered open-framework. • New 4,4,4-connected topology and rod-packing net. • Solvent-dependent photoluminescent intensity. • Selective and reversible response for chloroform.« less

Hydrothermal vanadium manganese oxides: Anode and cathode materials for lithium-ion batteries

NASA Astrophysics Data System (ADS)

Simões, Mário; Surace, Yuri; Yoon, Songhak; Battaglia, Corsin; Pokrant, Simone; Weidenkaff, Anke

2015-09-01

Vanadium manganese oxides with Mn content up to 33 at% were synthesized by a low temperature hydrothermal route allowing for the preparation of both anodic and cathodic materials for Li-ion batteries. Low amounts of manganese (below 13 at%) lead to the formation of elongated particles of layered hydrated vanadium oxides with manganese and water intercalated between the V2O5 slabs, while for higher Mn content of 33 at%, monoclinic MnV2O6 is formed. Former materials are suitable for high energy cathodes while the latter one is an anodic compound. The material containing 10 at% Mn has the composition Mn0.2V2O5·0.9H2O and shows the best cathodic activity with 20% capacity improvement over V2O5·0.5H2O. Lithiated MnV2O6 with Li5MnV2O6 composition prepared electrochemically was evaluated for the first time as anode in a full-cell against Mn0.2V2O5·0.9H2O cathode. An initial capacity ca. 300 A h kg-1 was measured with this battery corresponding to more than 500 Wh kg-1. These results confirm the prospect of using Li5MnV2O6 anodes in lithium-ion batteries as well as high-capacity layered hydrated vanadium oxides cathodes such as V2O5·0.5H2O and Mn0.2V2O5·0.9H2O.

Control of electrochemical properties of nickel-rich layered cathode materials for lithium ion batteries by variation of the manganese to cobalt ratio

NASA Astrophysics Data System (ADS)

Sun, Ho-Hyun; Choi, Wonchang; Lee, Joong Kee; Oh, In-Hwan; Jung, Hun-Gi

2015-02-01

Various Ni-rich layered oxide cathodes (above 0.80 Ni content), such as LiNi1-y-zCoyAlzO2 (NCA), are used in electric vehicles (EVs) due to their high capacity (∼200 mAh g-1 for NCA). However, to improve cycle performance and thermal stability and to ensure longer and safer usage, numerous studies have investigated surface modification, coating, and doping of cathode materials. In this study, we have investigated the characteristics of Li[Ni0.85CoxMn0.15-x]O2 with various Mn to Co ratios (x = 0-0.15) synthesized by a coprecipitation method. The discharge capacities of the Li[Ni0.85CoxMn0.15-x]O2 cathodes are similar at around 206 mAh g-1 at room temperature and 213.8 mAh g-1 at 55 °C between 2.7 and 4.3 V at a 0.2C rate, while the cyclability, thermal stability, and rate capability of all samples differ according to the Mn and Co ratio. The Li[Ni0.85Co0.05Mn0.10]O2 cathode shows the most promising electrochemical properties under different conditions among the various cathodes evaluated; it displays a high rate capacity (approximately 163 mAh g-1 at 5C rate) at 25 °C and good thermal stability (main exothermic temperature of 233.7 °C and relatively low heat evolution of 857.3 J g-1).

Surface modification of cathode material 0.5Li2MnO3·0.5LiMn1/3Ni1/3Co1/3O2 by alumina for lithium-ion batteries

NASA Astrophysics Data System (ADS)

Li, Yonghu; Chang, Xingping; Xu, Qunjie; Lai, Chunyan; Liu, Xinnuan; Yuan, Xiaolei; Liu, Haimei; Min, Yulin

2018-02-01

In an attempt to overcome the irreversible capacity loss occurred during the first cycle and stabilize the surface structure, an alumina coating layer has been triumphantly prepared on the surface of 0.5Li2MnO3·0.5LiMn1/3Ni1/3Co1/3O2 cathode material with different amounts (1, 2, and 3 wt%) through a simple hydrolysis reaction, followed by an annealing process. The results reveal that the coated materials have a higher crystallinity and the particles are evenly distributed. As a cathode material for lithium-ion batteries, the 2-wt% coated sample delivers initial discharge specific capacity of 211.7 mAh g-1 at a rate of 1 C between 2.0 and 4.8 V with an initial columbic efficiency of 73.2%. Meanwhile, it exhibits the highest discharge specific capacity of 206.2 mAh g-1 with 97.4% capacity retention after 100 cycles at and much elevated rate capability compared to uncoated material. The excellent cycling stability and more superior rate property can be ascribed to alumina coating layer, which has a surface stabilization effect on these cathode materials, lessening the dissolution of metal ions. The electrochemical impedance and cyclic voltammetry studies indicate that coated by alumina improved the kinetic performance for lithium-rich layered materials, showing a prospect for practical lithium battery application.

Investigation into key interfacial reactions within lithium-ion batteries

NASA Astrophysics Data System (ADS)

Vissers, Daniel Richard

Given the concern of global climate change and the understanding that carbon dioxide emissions are driving this change, much effort has been invested into lowering carbon dioxide emissions. One approach to reduce carbon dioxide emissions is to curtail the carbon dioxide emissions from vehicles through the introduction of hybrid electric vehicles, plug-in hybrid electric vehicles, and electric vehicles. Today, lithium cobalt oxide materials are widely used in consumer electronic applications, yet these materials are cost prohibitive for larger scale vehicle applications. As a result, alternative materials with higher energy densities and lower costs are being investigated. One key alternative to cobalt that has received much attention is manganese. Manganese is of interest for its lower cost and favorable environmental friendliness. The use of manganese has led to numerous cathode materials such as Li 1-deltaMn2O4 (4V spinel), Li1-deltaMn 1.5Ni0.25O4 (5V spinel), Li1-(Mn 1-x-yNiyCox)O2 (layered), Li2MnO 3-Li1-delta(Mn1-x-yNiyCox)O 2 (layered-layered), and Li2MnO3-Li1-delta (Mn1-x-yNiyCox)1O2 -Li1-deltaMn2O4 (layered-layered-spinel). The work disclosed in the dissertation focuses on two topics associated with these manganese based cathodes. The first topic is the exceptional cyclic-ability of a high power, high energy density, 5V spinel cathode material (Li 1-deltaMn1.5Ni0.25O4) with a core-shell architecture, and the second is the severe capacity fade associated with manganese dissolution from cathodes at elevated operating temperatures. Both topics are of interest to the Li-ion battery industry. For instance, a 5V spinel cathode represents a viable path to increase both the power and energy density of Li-ion batteries. As its name implies, the 5V spinel operates at 5V that is higher than the conventional 4V lithium ion batteries. Since power and energy are directly proportional to the potential, moving from an operating potential of 4V to 5V represents an increase in both power and energy densities of 25%. When the 5V spinel cathode is coupled with a graphite anode, an energy density of up to 240 Wh kg-1 is possible [2]. Secondly, the severe capacity fade associated with the manganese dissolution generally leads to a design with oversized battery packs, like those for the General Motors Chevy Volt, to meet warranty requirements. The result of this work led to deeper understandings of the underlying mechanisms for the exceptional cyclic-ability of the core-shell 5V spinel and for the severe capacity fade associated with manganese dissolution from the cathode and to a rational approach to resolve the severe capacity fade associated with manganese dissolution.

Highly CO2-Tolerant Cathode for Intermediate-Temperature Solid Oxide Fuel Cells: Samarium-Doped Ceria-Protected SrCo0.85Ta0.15O3-δ Hybrid.

PubMed

Li, Mengran; Zhou, Wei; Zhu, Zhonghua

2017-01-25

Susceptibility to CO 2 is one of the major challenges for the long-term stability of the alkaline-earth-containing cathodes for intermediate-temperature solid oxide fuel cells. To alleviate the adverse effects from CO 2 , we incorporated samarium-stabilized ceria (SDC) into a SrCo 0.85 Ta 0.15 O 3-δ (SCT15) cathode by either mechanical mixing or a wet impregnation method and evaluated their cathode performance stability in the presence of a gas mixture of 10% CO 2 , 21% O 2 , and 69% N 2 . We observed that the CO 2 tolerance of the hybrid cathode outperforms the pure SCT15 cathode by over 5 times at 550 °C. This significant enhancement is likely attributable to the low CO 2 adsorption and reactivity of the SDC protective layer, which are demonstrated through thermogravimetric analysis, energy-dispersive spectroscopy, and electrical conductivity study.

RHETT/EPDM Flight Hollow Cathode

NASA Technical Reports Server (NTRS)

Manzella, David; Patterson, Michael; Pastel, Michael

1997-01-01

Under the sponsorship of the BMDO Russian Hall Electric Thruster Technology program two xenon hollow cathodes, a flight unit and a flight spare were fabricated, acceptance tested and delivered to the Naval Research Laboratory for use on the Electric Propulsion Demonstration Module. These hollow cathodes, based on the International Space Station plasma contactor design, were fabricated at the NASA Lewis Research Center for use with a D-55 anode layer thruster in the first on-orbit operational application of this technology. The 2.2 Ampere nominal emission current of this device was obtained with a xenon flow rate of 0.6 mg/s. Ignition of the cathode discharge was accomplished through preheating the active electron emitter with a resistive heating element before application of a 650 volt ignition pulse between the emitter and an external starting electrode. The successful acceptance testing of the Electric Propulsion Demonstration Module utilizing these cathodes demonstrated the suitability of cathodes based on barium impregnated inserts in an enclosed keeper configuration for use with Hall thruster propulsion systems.

Role of Cr 3+ /Cr 6+ redox in chromium-substituted Li 2 MnO 3 ·LiNi 1/2 Mn 1/2 O 2 layered composite cathodes: electrochemistry and voltage fade

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

Lee, Eungje; Park, Joong Sun; Wu, Tianpin

2015-01-01

The substitution of chromium into the composite Li 2MnO 3·LiNi 1/2Mn 1/2O 2cathode dramatically affects the initial electrochemical activation process; however the voltage fade process during cycling persists.

Cathode luminescence light source for broadband applications in the visible spectrum

NASA Technical Reports Server (NTRS)

Foster, John E. (Inventor)

2007-01-01

A device and method for generating cathode luminescence is provided. The device and method generate broad spectrum electromagnetic radiation in the visible. A layer of particles, such as quartz or alumina powder, is exposed to electrons in a plasma discharge. Surface excitation of these particles or the generations/excitation of F-center sites give rise to luminescence.

Amorphous and Crystalline Vanadium Oxides as High-Energy and High-Power Cathodes for Three-Dimensional Thin-Film Lithium Ion Batteries.

PubMed

Mattelaer, Felix; Geryl, Kobe; Rampelberg, Geert; Dendooven, Jolien; Detavernier, Christophe

2017-04-19

Flexible wearable electronics and on-chip energy storage for wireless sensors drive rechargeable batteries toward thin-film lithium ion batteries. To enable more charge storage on a given surface, higher energy density materials are required, while faster energy storage and release can be obtained by going to thinner films. Vanadium oxides have been examined as cathodes in classical and thin-film lithium ion batteries for decades, but amorphous vanadium oxide thin films have been mostly discarded. Here, we investigate the use of atomic layer deposition, which enables electrode deposition on complex three-dimensional (3D) battery architectures, to obtain both amorphous and crystalline VO 2 and V 2 O 5 , and we evaluate their thin-film cathode performance. Very high volumetric capacities are found, alongside excellent kinetics and good cycling stability. Better kinetics and higher volumetric capacities were observed for the amorphous vanadium oxides compared to their crystalline counterparts. The conformal deposition of these vanadium oxides on silicon micropillar structures is demonstrated. This study shows the promising potential of these atomic layer deposited vanadium oxides as cathodes for 3D all-solid-state thin-film lithium ion batteries.

Nickel foam-supported polyaniline cathode prepared with electrophoresis for improvement of rechargeable Zn battery performance

NASA Astrophysics Data System (ADS)

Xia, Yang; Zhu, Derong; Si, Shihui; Li, Degeng; Wu, Sen

2015-06-01

Porous nickel foam is used as a substrate for the development of rechargeable zinc//polyaniline battery, and the cathode electrophoresis of PANI microparticles in non-aqueous solution is applied to the fabrication of Ni foam supported PANI electrode, in which the corrosion of the nickel foam substrate is prohibited. The Ni foam supported PANI cathode with high loading is prepared by PANI electrophoretic deposition, and followed by PANI slurry casting under vacuum filtration. The electrochemical charge storage performance for PANI material is significantly improved by using nickel foam substrate via the electrophoretic interlayer. The specific capacity of the nickel foam-PANI electrode with the electrophoretic layer is higher than the composite electrode without the electrophoretic layer, and the specific capacity of PANI supported by Ni foam reaches up to 183.28 mAh g-1 at the working current of 2.5 mA cm-2. The present electrophoresis deposition method plays the facile procedure for the immobilization of PANI microparticles onto the surface of non-platinum metals, and it becomes feasible to the use of the Ni foam supported PANI composite cathode for the Zn/PANI battery in weak acidic electrolyte.

First-charge instabilities of layered-layered lithium-ion-battery materials

DOE PAGES

Croy, Jason R.; Iddir, Hakim; Gallagher, Kevin; ...

2015-09-03

Dynamical simulation at 1000 K shows the migration of oxygen ions in delithiated Li 7/6-xNi 1/4Mn 7/12O 2(withx= 1) from oxygen layers (lower panel, att= 0) to form O–O pairs (upper panel att= 35 ps) thereby lowering the energy of charged cathode material.

Lithium-sulfur batteries: electrochemistry, materials, and prospects.

PubMed

Yin, Ya-Xia; Xin, Sen; Guo, Yu-Guo; Wan, Li-Jun

2013-12-09

With the increasing demand for efficient and economic energy storage, Li-S batteries have become attractive candidates for the next-generation high-energy rechargeable Li batteries because of their high theoretical energy density and cost effectiveness. Starting from a brief history of Li-S batteries, this Review introduces the electrochemistry of Li-S batteries, and discusses issues resulting from the electrochemistry, such as the electroactivity and the polysulfide dissolution. To address these critical issues, recent advances in Li-S batteries are summarized, including the S cathode, Li anode, electrolyte, and new designs of Li-S batteries with a metallic Li-free anode. Constructing S molecules confined in the conductive microporous carbon materials to improve the cyclability of Li-S batteries serves as a prospective strategy for the industry in the future. Copyright © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Monitoring the solid-state electrochemistry of Cu(2,7-AQDC) (AQDC = anthraquinone dicarboxylate) in a lithium battery: coexistence of metal and ligand redox activities in a metal-organic framework.

PubMed

Zhang, Zhongyue; Yoshikawa, Hirofumi; Awaga, Kunio

2014-11-19

By adopting a facile synthetic strategy, we obtained a microporous redox-active metal-organic framework (MOF), namely, Cu(2,7-AQDC) (2,7-H2AQDC = 2,7-anthraquinonedicarboxylic acid) (1), and utilized it as a cathode active material in lithium batteries. With a voltage window of 4.0-1.7 V, both metal clusters and anthraquinone groups in the ligands exhibited reversible redox activity. The valence change of copper cations was clearly evidenced by in situ XANES analysis. By controlling the voltage window of operation, extremely high recyclability of batteries was achieved, suggesting the framework was robust. This MOF is the first example of a porous material showing independent redox activity on both metal cluster nodes and ligand sites.

Performance of High Layer Thickness in Selective Laser Melting of Ti6Al4V

PubMed Central

Shi, Xuezhi; Ma, Shuyuan; Liu, Changmeng; Chen, Cheng; Wu, Qianru; Chen, Xianping; Lu, Jiping

2016-01-01

To increase building rate and save cost, the selective laser melting (SLM) of Ti6Al4V with a high layer thickness (200 μm) and low cost coarse powders (53 μm–106 μm) at a laser power of 400 W is investigated in this preliminary study. A relatively large laser beam with a diameter of 200 μm is utilized to produce a stable melt pool at high layer thickness, and the appropriate scanning track, which has a smooth surface with a shallow contact angle, can be obtained at the scanning speeds from 40 mm/s to 80 mm/s. By adjusting the hatch spacings, the density of multi-layer samples can be up to 99.99%, which is much higher than that achieved in previous studies about high layer thickness selective laser melting. Meanwhile, the building rate can be up to 7.2 mm3/s, which is about 2 times–9 times that of the commercial equipment. Besides, two kinds of defects are observed: the large un-melted defects and the small spherical micropores. The formation of the un-melted defects is mainly attributed to the inappropriate overlap rates and the unstable scanning tracks, which can be eliminated by adjusting the processing parameters. Nevertheless, the micropores cannot be completely eliminated. It is worth noting that the high layer thickness plays a key role on surface roughness rather than tensile properties during the SLM process. Although a sample with a relatively coarse surface is generated, the average values of yield strength, ultimate tensile strength, and elongation are 1050 MPa, 1140 MPa, and 7.03%, respectively, which are not obviously different than those with the thin layer thickness used in previous research; this is due to the similar metallurgical bonding and microstructure. PMID:28774097

A pre-lithiation method for sulfur cathode used for future lithium metal free full battery

NASA Astrophysics Data System (ADS)

Wu, Yunwen; Yokoshima, Tokihiko; Nara, Hiroki; Momma, Toshiyuki; Osaka, Tetsuya

2017-02-01

Lithium metal free sulfur battery paired by lithium sulfide (Li2S) is a hot point in recent years because of its potential for relatively high capacity and its safety advantage. Due to the insulating nature and high sensitivity to moisture of Li2S, it calls for new way to introduce Li ion into S cathode besides the method of directly using the Li2S powder for the battery pre-lithiation. Herein, we proposed a pre-lithiation method to lithiate the polypyrrole (PPy)/S/Ketjenblack (KB) electrode into PPy/Li2S/KB cathode at room temperature. By this process, the fully lithiated PPy/Li2S/KB cathode showed facilitated charge transfer than the original PPy/S/KB cathode, leading to better cycling performance at high C-rates and disappearance of over potential phenomenon. In this work, the ion-selective PPy layer has been introduced on the cathode surface by an electrodeposition method, which can suppress the polysulfide dissolution from the cathode source. The lithium metal free full battery coupled by the prepared Li2S/KB cathode and graphite anode exhibited excellent cycling performance. Hence, we believe this comprehensive fabrication approach of Li2S cathode will pave a way for the application of new type lithium metal free secondary battery.

Method of preparing graphene-sulfur nanocomposites for rechargeable lithium-sulfur battery electrodes

DOEpatents

Liu, Jun; Lemmon, John P; Yang, Zhenguo; Cao, Yuliang; Li, Xiaolin

2015-04-07

A method of preparing a graphene-sulfur nanocomposite for a cathode in a rechargeable lithium-sulfur battery comprising thermally expanding graphite oxide to yield graphene layers, mixing the graphene layers with a first solution comprising sulfur and carbon disulfide, evaporating the carbon disulfide to yield a solid nanocomposite, and grinding the solid nanocomposite to yield the graphene-sulfur nanocomposite. Rechargeable-lithium-sulfur batteries having a cathode that includes a graphene-sulfur nanocomposite can exhibit improved characteristics. The graphene-sulfur nanocomposite can be characterized by graphene sheets with particles of sulfur adsorbed to the graphene sheets. The sulfur particles have an average diameter of less than 50 nm.

The role of AlF3 coatings in improving electrochemical cycling of Li-enriched nickel-manganese oxide electrodes for Li-ion batteries.

PubMed

Sun, Yang-Kook; Lee, Min-Joon; Yoon, Chong S; Hassoun, Jusef; Amine, Khalil; Scrosati, Bruno

2012-03-02

A Li[Li(0.19)Ni(0.16)Co(0.08)Mn(0.57)]O(2) cathode was coated with AlF(3) on the surface. The AlF(3)-coating enhanced the overall electrochemical characteristics of the electrode while overcoming the typical shortcomings of lithium-enriched cathodes. This improvement was attributed to the transformation of the initial electrode layer to a spinel phase, induced by the Li chemical leaching effect of the AlF(3) coating layer. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Measurement of the through thickness compression of a battery separator

NASA Astrophysics Data System (ADS)

Yan, Shutian; Huang, Xiaosong; Xiao, Xinran

2018-04-01

The mechanical integrity of the separator is critical to the reliable operation of a battery. Due to its minimal thickness, compression experiments with a single/a few layers of separator are difficult to perform. In this work, a capacitance based displacement set-up has been developed for the measurement of the through thickness direction (TTD) compression stress-strain behavior of the separator and the investigation of its interaction with the electrode. The experiments were performed for a stack of two layers of Celgard 2400 separator, NMC cathode, and separator/NMC cathode/separator stack in both dry and wet (i.e. submersed in dimethyl carbonate DMC) conditions. The experimental results reveal that the separator compression modulus can be significantly affected by the presence of DMC. The iso-stress based rule of mixtures was used to compute the compressive stress-strain curve for the stack from that of the separator and NMC layer. The computed curve agreed with the experimental curve reasonably well up to about 0.16 strain but deviated significantly to a softer response at higher strains. The results suggest that, in the stack, the TTD compressive deformation of the separator is influenced by the NMC cathode.

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

NASA Astrophysics Data System (ADS)

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

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

Raman microscopy of lithium-manganese-rich transition metal oxide cathodes

DOE PAGES

Ruther, Rose E.; Callender, Andrew F.; Zhou, Hui; ...

2014-11-15

Lithium-rich and manganese-rich (LMR) layered transition metal (TM) oxide composites with general formula xLi 2MnO 3·(1-x)LiMO 2 (M = Ni, Co, Mn) are promising cathode candidates for high energy density lithium ion batteries. Lithium-manganese-rich TM oxides crystallize as a nanocomposite layered phase whose structure further evolves with electrochemical cycling. Raman spectroscopy is a powerful tool to monitor the crystal chemistry and correlate phase changes with electrochemical behavior. While several groups have reported Raman spectra of lithium rich TM oxides, the data show considerable variability in terms of both the vibrational features observed and their interpretation. In this paper, Raman microscopymore » is used to investigate lithium-rich and manganese-rich TM cathodes as a function of voltage and electrochemical cycling at various temperatures. No growth of a spinel phase is observed within the cycling conditions. However, analysis of the Raman spectra does indicate the structure of LMR-NMC deviates significantly from an ideal layered phase. Finally, the results also highlight the importance of using low laser power and large sample sizes to obtain consistent data sets.« less

Study of a contracted glow in low-frequency plasma-jet discharges operating with argon

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

Minotti, F.; Giuliani, L.; Xaubet, M.

2015-11-15

In this work, we present an experimental and theoretical study of a low frequency, atmospheric plasma-jet discharge in argon. The discharge has the characteristics of a contracted glow with a current channel of submillimeter diameter and a relatively high voltage cathode layer. In order to interpret the measurements, we consider the separate modeling of each region of the discharge: main channel and cathode layer, which must then be properly matched together. The main current channel was modeled, extending a previous work, as similar to an arc in which joule heating is balanced by lateral heat conduction, without thermal equilibrium betweenmore » electrons and heavy species. The cathode layer model, on the other hand, includes the emission of secondary electrons by ion impact and by additional mechanisms, of which we considered emission due to collision of atoms excited at metastable levels, and field-enhanced thermionic emission (Schottky effect). The comparison of model and experiment indicates that the discharge can be effectively sustained in its contracted form by the secondary electrons emitted by collision of excited argon atoms, whereas thermionic emission is by far insufficient to provide the necessary electrons.« less

High-Rate Charging Induced Intermediate Phases and Structural Changes of Layer-Structured Cathode for Lithium-Ion Batteries

DOE PAGES

Zhou, Yong-Ning; Yue, Ji-Li; Hu, Enyuan; ...

2016-08-08

Using fast time-resolved in situ X-ray diffraction, charge-rate dependent phase transition processes of layer structured cathode material LiNi 1/3Mn 1/3Co 1/3O 2 for lithium-ion batteries are studied. During first charge, intermediate phases emerge at high rates of 10C, 30C, and 60C, but not at low rates of 0.1C and 1C. These intermediate phases can be continuously observed during relaxation after the charging current is switched off. After half-way charging at high rate, sample studied by scanning transmission electron microscopy shows Li-rich and Li-poor phases' coexistence with tetrahedral occupation of Li in Li-poor phase. Also, the high rate induced overpotential ismore » thought to be the driving force for the formation of this intermediate Li-poor phase. The in situ quick X-ray absorption results show that the oxidation of Ni accelerates with increasing charging rate and the Ni 4+ state can be reached at the end of charge with 30C rate. Finally, these results give new insights in the understanding of the layered cathodes during high-rate charging.« less

High-Thermal- and Air-Stability Cathode Material with Concentration-Gradient Buffer for Li-Ion Batteries.

PubMed

Shi, Ji-Lei; Qi, Ran; Zhang, Xu-Dong; Wang, Peng-Fei; Fu, Wei-Gui; Yin, Ya-Xia; Xu, Jian; Wan, Li-Jun; Guo, Yu-Guo

2017-12-13

Delivery of high capacity with high thermal and air stability is a great challenge in the development of Ni-rich layered cathodes for commercialized Li-ion batteries (LIBs). Herein we present a surface concentration-gradient spherical particle with varying elemental composition from the outer end LiNi 1/3 Co 1/3 Mn 1/3 O 2 (NCM) to the inner end LiNi 0.8 Co 0.15 Al 0.05 O 2 (NCA). This cathode material with the merit of NCM concentration-gradient protective buffer and the inner NCA core shows high capacity retention of 99.8% after 200 cycles at 0.5 C. Furthermore, this cathode material exhibits much improved thermal and air stability compared with bare NCA. These results provide new insights into the structural design of high-performance cathodes with high energy density, long life span, and storage stability materials for LIBs in the future.

Magnetron sputtered zinc oxide nanorods as thickness-insensitive cathode interlayer for perovskite planar-heterojunction solar cells.

PubMed

Liang, Lusheng; Huang, Zhifeng; Cai, Longhua; Chen, Weizhong; Wang, Baozeng; Chen, Kaiwu; Bai, Hua; Tian, Qingyong; Fan, Bin

2014-12-10

Suitable electrode interfacial layers are essential to the high performance of perovskite planar heterojunction solar cells. In this letter, we report magnetron sputtered zinc oxide (ZnO) film as the cathode interlayer for methylammonium lead iodide (CH3NH3PbI3) perovskite solar cell. Scanning electron microscopy and X-ray diffraction analysis demonstrate that the sputtered ZnO films consist of c-axis aligned nanorods. The solar cells based on this ZnO cathode interlayer showed high short circuit current and power conversion efficiency. Besides, the performance of the device is insensitive to the thickness of ZnO cathode interlayer. Considering the high reliability and maturity of sputtering technique both in lab and industry, we believe that the sputtered ZnO films are promising cathode interlayers for perovskite solar cells, especially in large-scale production.

Verification of high efficient broad beam cold cathode ion source

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

Abdel Reheem, A. M., E-mail: amreheem2009@yahoo.com; Radiation Physics Department, National Center for Radiation Research and Technology; Ahmed, M. M.

2016-08-15

An improved form of cold cathode ion source has been designed and constructed. It consists of stainless steel hollow cylinder anode and stainless steel cathode disc, which are separated by a Teflon flange. The electrical discharge and output characteristics have been measured at different pressures using argon, nitrogen, and oxygen gases. The ion exit aperture shape and optimum distance between ion collector plate and cathode disc are studied. The stable discharge current and maximum output ion beam current have been obtained using grid exit aperture. It was found that the optimum distance between ion collector plate and ion exit aperturemore » is equal to 6.25 cm. The cold cathode ion source is used to deposit aluminum coating layer on AZ31 magnesium alloy using argon ion beam current which equals 600 μA. Scanning electron microscope and X-ray diffraction techniques used for characterizing samples before and after aluminum deposition.« less

Neutron and gamma detector using an ionization chamber with an integrated body and moderator

DOEpatents

Ianakiev, Kiril D.; Swinhoe, Martyn T.; Lestone, John Paul

2006-07-18

A detector for detecting neutrons and gamma radiation includes a cathode that defines an interior surface and an interior volume. A conductive neutron-capturing layer is disposed on the interior surface of the cathode and a plastic housing surrounds the cathode. A plastic lid is attached to the housing and encloses the interior volume of the cathode forming an ionization chamber, into the center of which an anode extends from the plastic lid. A working gas is disposed within the ionization chamber and a high biasing voltage is connected to the cathode. Processing electronics are coupled to the anode and process current pulses which are converted into Gaussian pulses, which are either counted as neutrons or integrated as gammas, in response to whether pulse amplitude crosses a neutron threshold. The detector according to the invention may be readily fabricated into single or multilayer detector arrays.

Electromagnetic micropores: fabrication and operation.

PubMed

Basore, Joseph R; Lavrik, Nickolay V; Baker, Lane A

2010-12-21

We describe the fabrication and characterization of electromagnetic micropores. These devices consist of a micropore encompassed by a microelectromagnetic trap. Fabrication of the device involves multiple photolithographic steps, combined with deep reactive ion etching and subsequent insulation steps. When immersed in an electrolyte solution, application of a constant potential across the micropore results in an ionic current. Energizing the electromagnetic trap surrounding the micropore produces regions of high magnetic field gradients in the vicinity of the micropore that can direct motion of a ferrofluid onto or off of the micropore. This results in dynamic gating of the ion current through the micropore structure. In this report, we detail fabrication and characterize the electrical and ionic properties of the prepared electromagnetic micropores.

High performance planar p-i-n perovskite solar cells with crown-ether functionalized fullerene and LiF as double cathode buffer layers

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

Liu, Xiaodong; Zhou, Yi, E-mail: yizhou@suda.edu.cn, E-mail: songbo@suda.edu.cn, E-mail: liyf@iccas.ac.cn; Song, Bo, E-mail: yizhou@suda.edu.cn, E-mail: songbo@suda.edu.cn, E-mail: liyf@iccas.ac.cn

2015-08-10

Double cathode buffer layers (CBLs) composed of fullerene derivative functionalized with a crown-ether end group in its side chain (denoted as PCBC) and a LiF layer were introduced between the PCBM acceptor layer and the top cathode in planar p-i-n perovskite solar cells (pero-SCs) based on CH{sub 3}NH{sub 3}PbI{sub 3−X}Cl{sub X}. The devices with the PCBC/LiF double CBLs showed significant improvements in power conversion efficiency (PCE) and long-term stability when compared to the device with LiF single CBL. Through optimizing the spin-coating speed of PCBC, a maximum PCE of 15.53% has been achieved, which is approximately 15% higher than thatmore » of the device with single LiF CBL. The remarkable improvement in PCE can be attributed to the formation of a better ohmic contact in the CBL between PCBC and LiF/Al electrode arising from the dipole moment of PCBC, leading to the enhanced fill factor and short-circuit current density (J{sub sc}). Besides the PCE, the long-term stability of the devices with PCBC interlayer is also superior to that of the device with LiF single CBL, which is due to the more effective protection for the perovskite/PCBM interface.« less

Permselective SPEEK/Nafion Composite-Coated Separator as a Potential Polysulfide Crossover Barrier Layer for Li-S Batteries.

PubMed

Babu, Dasari Bosu; Giribabu, Krishnan; Ramesha, Kannadka

2018-06-13

Minimizing the shuttle effect by constraining polysulfides to the cathode compartment and activating the passive layer between cathode and separator are highly important for improving the Li-S cell performance, Coulombic efficiency, and cycle life. Here, we report a submicron thin coating of permselective sulfonated poly(ether ether ketone) (SPEEK) composite layer on the separator that would reduce polysulfide crossover, imparting a significant improvement in cycle life. It is observed that SPEEK increases the stability, and adding Nafion improves the capacity value. Among different ratios of Nafion and SPEEK (25:75, 50:50, and 75:25), the composite with a SPEEK/Nafion ratio of 50:50 showed a controlled shuttle effect with a stable cell capacity of 600 mA h g -1 up to 300 cycles. This modified separator with permselective coatings not only reduces the polysulfide shuttle but also improves the wettability and interfacial contact, which results in an improvement in average cell potential and lithium diffusivity. It is demonstrated here that the combination of functional (ionomer coating on separator) and nonfunctional (extra cathode layer) physical barriers effectively suppresses the polysulfide crossover and improves the electrochemical performance of Li-S batteries. The cell shows an initial capacity of 1300 mA h g -1 and a capacity retention of 650 mA h g -1 over 500 cycles with a 6 mg/cm 2 sulfur loading.

Oxygen Release Induced Chemomechanical Breakdown of Layered Cathode Materials

DOE PAGES

Mu, Linqin; Lin, Ruoqian; Xu, Rong; ...

2018-04-18

Chemical and mechanical properties interplay on the nanometric scale and collectively govern the functionalities of battery materials. Understanding the relationship between the two can inform the design of battery materials with optimal chemomechanical properties for long-life lithium batteries. Herein, we report a mechanism of nanoscale mechanical breakdown in layered oxide cathode materials, originating from oxygen release at high states of charge under thermal abuse conditions. Here, we observe that the mechanical breakdown of charged Li 1-xNi 0.4Mn 0.4Co 0.2O 2 materials proceeds via a two-step pathway involving intergranular and intragranular crack formation. Owing to the oxygen release, sporadic phase transformationsmore » from the layered structure to the spinel and/or rocksalt structures introduce local stress, which initiates microcracks along grain boundaries and ultimately leads to the detachment of primary particles; i.e., intergranular crack formation. Furthermore, intragranular cracks (pores and exfoliations) form, likely due to the accumulation of oxygen vacancies and continuous phase transformations at the surfaces of primary particles. Finally, finite element modeling confirms our experimental observation that the crack formation is attributable to formation of oxygen vacancies, oxygen release, and phase transformations. This study is designed to directly observe the chemomechanical behavior of layered oxide cathode materials and provides a chemical basis for strengthening primary and secondary particles by stabilizing the oxygen anions in the lattice.« less

Oxygen Release Induced Chemomechanical Breakdown of Layered Cathode Materials

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

Mu, Linqin; Lin, Ruoqian; Xu, Rong

Chemical and mechanical properties interplay on the nanometric scale and collectively govern the functionalities of battery materials. Understanding the relationship between the two can inform the design of battery materials with optimal chemomechanical properties for long-life lithium batteries. Herein, we report a mechanism of nanoscale mechanical breakdown in layered oxide cathode materials, originating from oxygen release at high states of charge under thermal abuse conditions. Here, we observe that the mechanical breakdown of charged Li 1-xNi 0.4Mn 0.4Co 0.2O 2 materials proceeds via a two-step pathway involving intergranular and intragranular crack formation. Owing to the oxygen release, sporadic phase transformationsmore » from the layered structure to the spinel and/or rocksalt structures introduce local stress, which initiates microcracks along grain boundaries and ultimately leads to the detachment of primary particles; i.e., intergranular crack formation. Furthermore, intragranular cracks (pores and exfoliations) form, likely due to the accumulation of oxygen vacancies and continuous phase transformations at the surfaces of primary particles. Finally, finite element modeling confirms our experimental observation that the crack formation is attributable to formation of oxygen vacancies, oxygen release, and phase transformations. This study is designed to directly observe the chemomechanical behavior of layered oxide cathode materials and provides a chemical basis for strengthening primary and secondary particles by stabilizing the oxygen anions in the lattice.« less

Sputtering graphite coating to improve the elevated-temperature cycling ability of the LiMn2O4 electrode.

PubMed

Wang, Jiexi; Zhang, Qiaobao; Li, Xinhai; Wang, Zhixing; Guo, Huajun; Xu, Daguo; Zhang, Kaili

2014-08-14

To improve the cycle performance of LiMn2O4 at elevated temperature, a graphite layer is introduced to directly cover the surface of a commercial LiMn2O4-based electrode via room-temperature DC magnetron sputtering. The as-modified cathodes display improved capacity retention as compared to the bare LiMn2O4 cathode (BLMO) at 55 °C. When sputtering graphite for 30 min, the sample shows the best cycling performance at 55 °C, maintaining 96.2% capacity retention after 200 cycles. Reasons with respect to the graphite layer for improving the elevated-temperature performance of LiMn2O4 are systematically investigated via the methods of cyclic voltammetry, electrochemical impedance spectroscopy, X-ray photoelectron spectrometry, scanning and transmission electron microscopy, X-ray diffraction and inductively coupled plasma-atomic emission spectrometry. The results demonstrate that the graphite coated LiMn2O4 cathode has much less increased electrode polarization and electrochemical impedance than BLMO during the elevated-temperature cycling process. Furthermore, the graphite layer is able to alleviate the severe dissolution of manganese ions into the electrolyte and mitigate the morphological and structural degradation of LiMn2O4 during cycling. A model for the electrochemical kinetics process is also suggested for explaining the roles of the graphite layer in suppressing the Mn dissolution.

LOW TEMPERATURE CATHODE SUPPORTED ELECTROLYTES

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

Harlan U. Anderson; Fatih Dogan; Vladimir Petrovsky

2002-03-31

This project has three main goals: Thin Films Studies, Preparation of Graded Porous Substrates and Basic Electrical Characterization and testing of Planar Single Cells. This period has continued to address the problem of making dense 1/2 to 5 {micro}m thick dense layers on porous substrates (the cathode LSM). Our current status is that we are making structures of 2-5 cm{sup 2} in area, which consist of either dense YSZ or CGO infiltrated into a 2-5 {micro}m thick 50% porous layer made of either nanoncrystalline CGO or YSZ powder. This composite structure coats a macroporous cathode or anode; which serves asmore » the structural element of the bi-layer structure. These structures are being tested as SOFC elements. A number of structures have been evaluated both as symmetrical and as button cell configuration. Results of this testing indicates that the cathodes contribute the most to cell losses for temperatures below 750 C. In this investigation different cathode materials were studied using impedance spectroscopy of symmetric cells and IV characteristics of anode supported fuel cells. Cathode materials studied included La{sub 0.8}Sr{sub 0.2}Co{sub 0.2}Fe{sub 0.8}O{sub 3} (LSCF), La{sub 0.7}Sr{sub 0.2}MnO{sub 3} (LSM), Pr{sub 0.8}Sr{sub 0.2}Fe{sub 0.8}O{sub 3} (PSCF), Sm{sub 0.8}Sr{sub 0.2}Co{sub 0.2}Fe{sub 0.8}O{sub 3} (SSCF), and Yb{sub .8}Sr{sub 0.2}Co{sub 0.2}Fe{sub 0.8}O{sub 3} (SSCF). A new technique for filtering the Fourier transform of impedance data was used to increase the sensitivity of impedance analysis. By creating a filter specifically for impedance spectroscopy the resolution was increased. The filter was tailored to look for specific circuit elements like R//C, Warburg, or constant phase elements. As many as four peaks can be resolved using the filtering technique on symmetric cells. It may be possible to relate the different peaks to material parameters, like the oxygen exchange coefficient. The cathode grouped in order from lowest to highest ASR is LSCF < PSCF < SSCF < YSCF < LSM. The button cell results agree with this ordering indicating that this is an important tool for use in developing our understanding of electrode behavior in fuel cells.« less

Tunnel barrier schottky

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

Chu, Rongming; Cao, Yu; Li, Zijian

2018-02-20

A diode includes: a semiconductor substrate; a cathode metal layer contacting a bottom of the substrate; a semiconductor drift layer on the substrate; a graded aluminum gallium nitride (AlGaN) semiconductor barrier layer on the drift layer and having a larger bandgap than the drift layer, the barrier layer having a top surface and a bottom surface between the drift layer and the top surface, the barrier layer having an increasing aluminum composition from the bottom surface to the top surface; and an anode metal layer directly contacting the top surface of the barrier layer.

DE-FG02-08ER64658 (OASIS) - Final Technical Report

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

Sharman, Jonathan

Project OASIS (Operation of Advanced Structures, Interfaces and Sub-components for MEAs) was a 12 month project that ran from 1st September 2008 to 31st August 2009, and was managed by the Department of Energy Office of Science, Chicago Office, as Award No DE-FG02-08ER64658, with Johnson Matthey Fuel Cells Inc. as the sole contractor. The project was completed on schedule, with technical successes (details below) and payment of the full grant award made by DOE. The aim of the project was the development of membrane electrode assemblies (MEAs) for H2/air polymer electrolyte membrane (PEM) fuel cells that would give higher performancemore » under hot/dry and dry operating conditions, ideally with no loss of performance under wet conditions. Reducing or eliminating the need for humidifying the incoming gases will allow significant system cost and size reduction for many fuel cell applications including automotive, stationary and back-up power, and portable systems. Portable systems are also of particular interest in military markets. In previous work Johnson Matthey Fuel Cells had developed very stable, corrosion-resistant catalysts suitable for resisting degradation by carbon corrosion in particular. These materials were applied within the OASIS project as they are considered necessary for systems such as automotive where multiple start-stop events are experienced. These catalysts were contrasted with more conventional materials in the design of catalyst layers and novel microporous layers (MPLs) and gas diffusion layer (GDL) combinations were also explored. Early on in the work it was shown how much more aggressive high temperature operation is than dry operation. At the same humidity, tests at 110?C caused much more dehydration than tests at 80?C and the high temperature condition was much more revealing of improvements made to MEA design. Alloy catalysts were introduced and compared with Pt catalysts with a range of particle sizes. It was apparent that the larger particle sizes of the alloy catalysts led to a reduction in performance that offset much of their kinetic advantage. The Pt-only materials clearly showed that small particles are beneficial to good performance under hot/dry conditions, because of their higher surface area, although they are known to be less stable to cyclic operation. An ex-situ water vapour sorption technique was developed that showed a very clear correlation with in-cell performance: catalyst powders that absorbed more water gave better performance in-cell. It was shown that alloy catalysts could give a 25 mV advantage over Pt-only at 1 Acm-2. GDL design was also shown to influence performance and more permeable GDLs on the anode allowed better membrane hydration and therefore conductivity. A very impermeable GDL on the cathode caused cathode flooding even under dry conditions, but a novel cathode MPL incorporating ionomer and operating at 110?C, 33/17% RH showed a 150 mV gain at 800 mAcm-2 over the conventional MPL. This project has increased the understanding of the factors that influence performance loss under dry conditions, including the development of an insightful ex-situ characterisation technique (Dynamic Vapour Sorption). All the approaches investigated can be readily implemented in state-of the-art MEAs, although optimisation would be needed to integrate the new designs with existing MEA types and to tune to the exact range of operating conditions. The work is thus expected to benefit the public by feeding through more condition-tolerant production MEAs to a range of applications and thereby accelerate the commercialisation of fuel cell technology. In summary, a number of specific catalyst, catalyst layer, MPL and GDL improvements were made during this project. Often the best designs under dry conditions translated to some performance loss under wet conditions, but compromise situations were also found where dry performance was improved with no loss of wet performance.« less

Structure for implementation of back-illuminated CMOS or CCD imagers

NASA Technical Reports Server (NTRS)

Pain, Bedabrata (Inventor); Cunningham, Thomas J. (Inventor)

2009-01-01

A structure for implementation of back-illuminated CMOS or CCD imagers. An epitaxial silicon layer is connected with a passivation layer, acting as a junction anode. The epitaxial silicon layer converts light passing through the passivation layer and collected by the imaging structure to photoelectrons. A semiconductor well is also provided, located opposite the passivation layer with respect to the epitaxial silicon layer, acting as a junction cathode. Prior to detection, light does not pass through a dielectric separating interconnection metal layers.

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

Li + Defects in a Solid-State Li Ion Battery: Theoretical Insights with a Li 3 OCl Electrolyte

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

Stegmaier, Saskia; Voss, Johannes; Reuter, Karsten

In a solid-state Li ion battery, the solid-state electrolyte exits principally in regions of high externally applied potentials, and this varies rapidly at the interfaces with electrodes due to the formation of electrochemical double layers. Here, we investigate the implications of these for a model solid-state Li ion battery Li|Li 3OCl|C, where C is simply a metallic intercalation cathode. We use DFT to calculate the potential dependence of the formation energies of the Li + charge carriers in superionic Li 3OCl. We find that Li+ vacancies are the dominant species at the cathode while Li+ interstitials dominate at the anode.more » With typical Mg aliovalent doping of Li 3OCl, Li + vacancies dominate the bulk of the electrolyte as well, with freely mobile vacancies only ~ 10 -4 of the Mg doping density at room temperature. We study the repulsive interaction between Li+ vacancies and find that this is extremely short range, typically only one lattice constant due to local structural relaxation around the vacancy and this is significantly shorter than pure electrostatic screening. We model a Li 3OCl- cathode interface by treating the cathode as a nearly ideal metal using a polarizable continuum model with an ε r = 1000. There is a large interface segregation free energy of ~ - 1 eV per Li + vacancy. Combined with the short range for repulsive interactions of the vacancies, this means that very large vacancy concentrations will build up in a single layer of Li 3OCl at the cathode interface to form a compact double layer. The calculated potential drop across the interface is ~ 3 V for a nearly full concentration of vacancies at the surface. This suggests that nearly all the cathode potential drop in Li 3OCl occurs at the Helmholtz plane rather than in a diffuse space-charge region. We suggest that the conclusions found here will be general to other superionic conductors as well.« less

Li + Defects in a Solid-State Li Ion Battery: Theoretical Insights with a Li 3 OCl Electrolyte

DOE PAGES

Stegmaier, Saskia; Voss, Johannes; Reuter, Karsten; ...

2017-04-26

In a solid-state Li ion battery, the solid-state electrolyte exits principally in regions of high externally applied potentials, and this varies rapidly at the interfaces with electrodes due to the formation of electrochemical double layers. Here, we investigate the implications of these for a model solid-state Li ion battery Li|Li 3OCl|C, where C is simply a metallic intercalation cathode. We use DFT to calculate the potential dependence of the formation energies of the Li + charge carriers in superionic Li 3OCl. We find that Li+ vacancies are the dominant species at the cathode while Li+ interstitials dominate at the anode.more » With typical Mg aliovalent doping of Li 3OCl, Li + vacancies dominate the bulk of the electrolyte as well, with freely mobile vacancies only ~ 10 -4 of the Mg doping density at room temperature. We study the repulsive interaction between Li+ vacancies and find that this is extremely short range, typically only one lattice constant due to local structural relaxation around the vacancy and this is significantly shorter than pure electrostatic screening. We model a Li 3OCl- cathode interface by treating the cathode as a nearly ideal metal using a polarizable continuum model with an ε r = 1000. There is a large interface segregation free energy of ~ - 1 eV per Li + vacancy. Combined with the short range for repulsive interactions of the vacancies, this means that very large vacancy concentrations will build up in a single layer of Li 3OCl at the cathode interface to form a compact double layer. The calculated potential drop across the interface is ~ 3 V for a nearly full concentration of vacancies at the surface. This suggests that nearly all the cathode potential drop in Li 3OCl occurs at the Helmholtz plane rather than in a diffuse space-charge region. We suggest that the conclusions found here will be general to other superionic conductors as well.« less

Hydrogen determination in chemically delithiated lithium ion battery cathodes by prompt gamma activation analysis

NASA Astrophysics Data System (ADS)

Alvarez, Emilio, II

2007-12-01

Lithium ion batteries, due to their relatively high energy density, are now widely used as the power source for portable electronics. Commercial lithium ion cells currently employ layered LiCoO2 as a cathode but only 50% of its theoretical capacity can be utilized. The factors that cause the limitation are not fully established in the literature. With this perspective, prompt gamma-ray activation analysis (PGAA) has been employed to determine the hydrogen content in various oxide cathodes that have undergone chemical extraction of lithium (delithiation). The PGAA data is complemented by data obtained from atomic absorption spectroscopy (AAS), redox titration, thermogravimetric analysis (TGA), and mass spectroscopy to better understand the capacity limitations and failure mechanisms of lithium ion battery cathodes. As part of this work, the PGAA facility has been redesigned and reconstructed. The neutron and gamma-ray backgrounds have been reduced by more than an order of magnitude. Detection limits for elements have also been improved. Special attention was given to the experimental setup including potential sources of error and system calibration for the detection of hydrogen. Spectral interference with hydrogen arising from cobalt was identified and corrected for. Limits of detection as a function of cobalt mass present in a given sample are also discussed. The data indicates that while delithiated layered Li1- xCoO2, Li1-xNi 1/3Mn1/3Co1/3O2, and Li1- xNi0.5Mn0.5O2 take significant amounts of hydrogen into the lattice during deep extraction, orthorhombic Li 1-xMnO2, spinel Li1- xMn2O4, and olivine Li1- xFePO4 do not. Layered LiCoO2, LiNi 0.5Mn0.5O2, and LiNi1/3Mn1/3Co 1/3O2 have been further analyzed to assess their relative chemical instabilities while undergoing stepped chemical delithiation. Each system takes increasing amounts of protons at lower lithium contents. The differences are attributed to the relative chemical instabilities of the various cathodes that could be related to the position of the transition metal band and the top of the O2-:2p band. Chemically delithiated layered Li[Li0.17Mn0.33Co 0.5-yNiy]O 2 cathodes have also been characterized. The first charge and discharge capacities decrease with increasing nickel content. The decrease in the capacity with increasing nickel content is due to a decrease in the lithium content present in the transition metal layer and a consequent decrease in the amount of oxygen irreversibly lost during the first charge.

Study on corrosion migrations within catalyst-coated membranes of proton exchange membrane electrolyzer cells

DOE PAGES

Mo, Jingke; Steen, Stuart; Kang, Zhenye; ...

2017-10-09

The corrosion of low-cost, easily manufactured metallic components inside the electrochemical environment of proton exchange membrane electrolyzer cells (PEMECs) has a significant effect on their performance and durability. Here, 316 stainless steel (SS) mesh was used as a model liquid/gas diffusion layer material to investigate the migration of corrosion products in the catalyst-coated membrane of a PEMEC. Iron and nickel cation particles were found distributed throughout the anode catalyst layer, proton exchange membrane, and cathode catalyst layer, as revealed by scanning transmission electron microscopy and energy dispersive X-ray spectroscopy. Our results indicate the corrosion products of 316 SS are transportedmore » from anode to cathode through the nanochannels of the Nafion membrane, resulting in impeded proton transport and overall PEMEC performance loss.« less

Study on corrosion migrations within catalyst-coated membranes of proton exchange membrane electrolyzer cells

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

Mo, Jingke; Steen, Stuart; Kang, Zhenye

The corrosion of low-cost, easily manufactured metallic components inside the electrochemical environment of proton exchange membrane electrolyzer cells (PEMECs) has a significant effect on their performance and durability. Here, 316 stainless steel (SS) mesh was used as a model liquid/gas diffusion layer material to investigate the migration of corrosion products in the catalyst-coated membrane of a PEMEC. Iron and nickel cation particles were found distributed throughout the anode catalyst layer, proton exchange membrane, and cathode catalyst layer, as revealed by scanning transmission electron microscopy and energy dispersive X-ray spectroscopy. Our results indicate the corrosion products of 316 SS are transportedmore » from anode to cathode through the nanochannels of the Nafion membrane, resulting in impeded proton transport and overall PEMEC performance loss.« less

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.

Synthesis and discharge performances of NiCl2 by surface modification of carbon coating as cathode material of thermal battery

NASA Astrophysics Data System (ADS)

Jin, Chuanyu; Zhou, Lingping; Fu, Licai; Zhu, Jiajun; Li, Deyi

2017-04-01

The high solubility in molten salt and low conductivity of NiCl2, compared with traditional FeS2 and CoS2, have become the restrictions for its extensive application in cathode materials of thermal batteries. In this study, carbon coated NiCl2 cathode is successfully fabricated by the carbonization of stearic acid. The high specific energy of 641 Wh kg-1 at current densities of 0.5 A cm-2 are observed for the carbon coated NiCl2 thermal batteries, which is higher than the pure NiCl2 with 475 Wh kg-1. The high specific energies and high-current discharge ability are attribute to the graphite and amorphous carbon layers on the surface of NiCl2 crystalline, which were detected by TEM after carbonization. The graphite layers can improve the conductivity of NiCl2. Meanwhile the coated carbon structure could reduce the solubility of NiCl2 in molten salt.

Synchrotron X-ray studies of model SOFC cathodes, part II: Porous powder cathodes

DOE PAGES

Chang, Kee-Chul; Ingram, Brian; Ilavsky, Jan; ...

2017-10-28

Infiltrated La 0.6Sr 0.4Co 0.2Fe 0.8O 3-δ (LSCF) sintered porous powder cathodes for solid oxide fuel cells have been investigated by synchrotron ultra-small angle x-ray scattering (USAXS). Here, we demonstrated that atomic layer deposition (ALD) is the method for a uniform coating and liquid-phase infiltration for growing nanoscale particles on the porous LSCF surfaces. The MnO infiltrate, grown by ALD, forms a conformal layer with a uniform thickness throughout the pores evidenced by USAXS thickness fringes. The La 0.6Sr 0.4CoO 3 (LSC) and La 2Zr 2O 7 (LZO) infiltrates, grown by liquid-phase infiltration, were found to form nanoscale particles onmore » the surfaces of LSCF particles resulting in increased surface areas. In conclusion, impedance measurements suggest that the catalytic property of LSC infiltrate, not the increased surface area of LZO, is important for increasing oxygen reduction activities.« less

Synchrotron X-ray studies of model SOFC cathodes, part II: Porous powder cathodes

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

Chang, Kee-Chul; Ingram, Brian; Ilavsky, Jan

Infiltrated La 0.6Sr 0.4Co 0.2Fe 0.8O 3-δ (LSCF) sintered porous powder cathodes for solid oxide fuel cells have been investigated by synchrotron ultra-small angle x-ray scattering (USAXS). Here, we demonstrated that atomic layer deposition (ALD) is the method for a uniform coating and liquid-phase infiltration for growing nanoscale particles on the porous LSCF surfaces. The MnO infiltrate, grown by ALD, forms a conformal layer with a uniform thickness throughout the pores evidenced by USAXS thickness fringes. The La 0.6Sr 0.4CoO 3 (LSC) and La 2Zr 2O 7 (LZO) infiltrates, grown by liquid-phase infiltration, were found to form nanoscale particles onmore » the surfaces of LSCF particles resulting in increased surface areas. In conclusion, impedance measurements suggest that the catalytic property of LSC infiltrate, not the increased surface area of LZO, is important for increasing oxygen reduction activities.« less

Calcium intercalation into layered fluorinated sodium iron phosphate

NASA Astrophysics Data System (ADS)

Lipson, Albert L.; Kim, Soojeong; Pan, Baofei; Liao, Chen; Fister, Timothy T.; Ingram, Brian J.

2017-11-01

The energy density and cost of battery systems, relative to the current state-of-the art, can be improved by developing alternative chemistries utilizing multivalent working ions such as calcium. Many challenges must be overcome, such as the identification of cathode materials with high energy density and an electrolyte with a wide electrochemical stability window that can plate and strip calcium metal, before market implementation. Herein, the feasibility and cycling performance of Ca2+ intercalation into a desodiated layered Na2FePO4F host is described. This is the first demonstration of Ca2+ intercalation into a polyanionic framework, which implies that other polyanionic framework materials may be active for Ca2+ intercalation. Although substantial effort is expected in order to develop a high energy density cathode material, this study demonstrates the feasibility of Ca2+ intercalation into multiple host structures types, thereby extending opportunities for development of Ca insertion host structures, suggesting such a cathode material can be identified and developed.

Electronic structure of BaO/W cathode surfaces

NASA Technical Reports Server (NTRS)

Muller, Wolfgang

1989-01-01

The local electronic structure of the emissive layer of barium dispenser thermionic cathodes is investigated theoretically using the relativistic scattered-wave approach. The interaction of Ba and O with W, Os, and W-Os alloy surfaces is studied with atomic clusters modeling different absorption environments representative of B- and M-type cathodes. Ba is found to be strongly oxidized, while O and the metal substrate are in a reduced chemical state. The presence of O enhances the surface dipole and Ba binding energy relative to Ba on W. Model results for W-Os alloy substrates show only relatively small changes in Ba and O for identical geometries, but very large charge redistributions inside the substrate, which are attributed to the electronegativity difference between Os and W. If Os is present in the surface layer, the charge transfer from Ba to the substrate and the Ba binding energy increase relative to W. Explanations are offered for the improved electron emission from alloy surfaces and the different emission enhancement for different alloy substrates.

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

Durability of nickel-metal hydride (Ni-MH) battery cathode using nickel-aluminum layered double hydroxide/carbon (Ni-Al LDH/C) composite

NASA Astrophysics Data System (ADS)

Béléké, Alexis Bienvenu; Higuchi, Eiji; Inoue, Hiroshi; Mizuhata, Minoru

2014-02-01

We report the durability of the optimized nickel-aluminum layered double hydroxide/carbon (Ni-Al LDH/C) composite prepared by liquid phase deposition (LPD) as cathode active materials in nickel metal hydride (Ni-MH) secondary battery. The positive electrode was used for charge-discharge measurements under two different current: 5 mA for 300 cycles in half-cell conditions, and 5.8 mA for 569 cycles in battery regime, respectively. The optimized Ni-Al LDH/C composite exhibits a good lifespan and stability with the capacity retention above 380 mA h gcomp-1 over 869 cycles. Cyclic voltammetry shows that the α-Ni(OH)2/γ-NiOOH redox reaction is maintained even after 869 cycles, and the higher current regime is beneficial in terms of materials utilization. X-ray diffraction (XRD) patterns of the cathode after charge and discharge confirms that the α-Ni(OH)2/γ-NiOOH redox reaction occurs without any intermediate phase.

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.

Miniature Lightweight Ion Pump

NASA Technical Reports Server (NTRS)

Sinha, Mahadeva P.

2010-01-01

This design offers a larger surface area for pumping of active gases and reduces the mass of the pump by eliminating the additional vacuum enclosure. There are three main components to this ion pump: the cathode and anode pumping elements assembly, the vacuum enclosure (made completely of titanium and used as the cathode and maintained at ground potential) containing the assembly, and the external magnet. These components are generally put in a noble diode (or differential) configuration of the ion pump technology. In the present state of the art, there are two cathodes, one made of titanium and the other of tantalum. The anodes are made up of an array of stainless steel cylinders positioned between the two cathodes. All the elements of the pump are in a vacuum enclosure. After the reduction of pressure in this enclosure to a few microns, a voltage is applied between the cathode and the anode elements. Electrons generated by the ionization are accelerated toward the anodes that are confined in the anode space by the axial magnetic field. For the generation of the axial field along the anode elements, the magnet is designed in a C-configuration and is fabricated from rare earth magnetic materials (Nd-B-Fe or Sm-Co) possessing high energy product values, and the yoke is fabricated from the high permeability material (Hiperco-50A composed of Fe-Co-V). The electrons in this region collide with the gas molecules and generate their positive ions. These ions are accelerated into the cathode and eject cathode material (Ti). The neutral atoms deposit on the anode surfaces. Because of the chemical activity of Ti, the atoms combine with chemically active gas molecules (e.g. N2, O2, etc.) and remove them. New layers of Ti are continually deposited, and the pumping of active gases is thus accomplished. Pumping of the inert gases is accomplished by their burial several atomic layers deep into the cathode. However, they tend to re-emit if the entrapping lattice atoms are sputtered away. For stable pumping of inert gases, one side of the cathode is made of Ta. Impaction on Ta produces energetic, neutral atoms that pump the inert gases on the anode structure at the peripheral areas of the cathodes (between anode rings). For inert gases stability, a post design has been implemented. Here, posts of cathode material (Ti) are mounted on the cathode. These protrude into the initial part of the anode elements. Materials sputtered from the posts condense on the anode assembly and on the cathode plane at higher rates than in the normal diodes due to enhanced sputtering at glancing angles from geometrical considerations. This increases pumping by burial. This post design has enhanced pumping rates for both active and inert gases, compared with conventional designs.