Thermionic gas switch

DOEpatents

Hatch, G.L.; Brummond, W.A.; Barrus, D.M.

1984-04-05

The present invention is directed to an improved temperature responsive thermionic gas switch utilizing a hollow cathode and a folded emitter surface area. The folded emitter surface area of the thermionic switch substantially increases the on/off ratio by changing the conduction surface area involved in the two modes thereof. The improved switch of this invention provides an on/off ratio of 450:1 compared to the 10:1 ratio of the prior known thermionic switch, while providing for adjusting the on current. In the improved switch of this invention the conduction area is made small in the off mode, while in the on mode the conduction area is made large. This is achieved by utilizing a folded hollow cathode configuration and utilizing a folded emitter surface area, and by making the dimensions of the folds small enough so that a space charge will develop in the convolutions of the folds and suppress unignited current, thus limiting the current carrying surface in the off mode.

Mesoscale Elucidation of Surface Passivation in the Li-Sulfur Battery Cathode.

PubMed

Liu, Zhixiao; Mukherjee, Partha P

2017-02-15

The cathode surface passivation caused by Li 2 S precipitation adversely affects the performance of lithium-sulfur (Li-S) batteries. Li 2 S precipitation is a complicated mesoscale process involving adsorption, desorption and diffusion kinetics, which are affected profoundly by the reactant concentration and operating temperature. In this work, a mesoscale interfacial model is presented to study the growth of Li 2 S film on carbon cathode surface. Li 2 S film growth experiences nucleation, isolated Li 2 S island growth and island coalescence. The slow adsorption rate at small S 2- concentration inhibits the formation of nucleation seeds and the lateral growth of Li 2 S islands, which deters surface passivation. An appropriate operating temperature, especially in the medium-to-high temperature range, can also defer surface passivation. Fewer Li 2 S nucleation seeds form in such an operating temperature range, thereby facilitating heterogeneous growth and potentially inhibiting the lateral growth of the Li 2 S film, which may ultimately result in reduced surface passivation. The high specific surface area of the cathode microstructure is expected to mitigate the surface passivation.

The Reduction of Sulfuryl Chloride at Teflon-Bonded Carbon Cathodes

DTIC Science & Technology

1980-07-01

titrated mulating cathodes, along with their BET surface potentiometrically with standardized silver nitrate areas. Shawinigan black possesses the...assembly steps when individually dissolved can be titrated through were accomplished in the glove box. iodimetry or iodometry, respectively (7). If

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

Pulsed electromagnetic gas acceleration. [magnetohydrodynamics, plasma power sources and plasma propulsion

NASA Technical Reports Server (NTRS)

Jahn, R. G.; Vonjaskowsky, W. F.; Clark, K. E.

1975-01-01

Terminal voltage measurements with various cathodes and anodes in a high power, quasi-steady magnetoplasmadynamic (MPD) are discussed. The magnitude of the current at the onset of voltage fluctuations is shown to be an increasing function of cathode area and a weaker decreasing function of anode area. Tests with a fluted cathode indicated that the fluctuations originate in the plasma adjacent to the cathode rather than at the cathode surface. Measurements of radiative output from an optical cavity aligned to examine the current-carrying portion of a two-dimensional, 56 kA magnetoplasmadynamic discharge reveal no lasing in that region, consistent with calculations of electron excitation and resonance radiation trapping. A voltage-swept double probe technique allows single-shot determination of electron temperature and electron number density in the recombining MPD exhaust flow. Current distributions within the cavity of MPD hollow cathodes for various static prefills with no injected mass flow are examined.

The effects of hydrogen embrittlement by cathodic protection on the CTOD of buried natural gas pipeline

NASA Astrophysics Data System (ADS)

Kim, Cheol-man; Kim, Woo-sik; Kho, Young-tai

2002-04-01

For the corrosion protection of natural gas transmission pipelines, two methods are used, cathodic protection and a coating technique. In the case of cathodic protection, defects are embrittled by hydrogen occurring at crack tips or surfaces of materials. It is, however, very important to evaluate whether cracks in the embrittled area can grow or not, especially in weld metal. In this work, on the basis of elastic plastic fracture mechanics, we performed CTOD testing under various test conditions, such as potential and current density. The CTOD of the base steel and weld metal showed a strong dependence on the test conditions. The CTOD decreased with increasing cathodic potential and current density. The morphology of the fracture surface showed quasi-cleavage. Cathodic overprotection results in hydrogen embrittlement at the crack tip.

Effect of sintering temperature on the electrolysis of TiO2

NASA Astrophysics Data System (ADS)

Li, Ze-quan; Ru, Li-yue; Bai, Cheng-guang; Zhang, Na; Wang, Hai-hua

2012-07-01

The effects of sintering temperature on the microstructure and the conductivity of TiO2 cathodes were studied by examining the phase composition, microstructure, and element contents of the sintered cathodes and the cathodic products using X-ray diffraction and scanning electronic microscopy-energy dispersive spectrometry. The oxygen vacancy, conductivity, average pore diameter, and specific surface area of the sintered cathodes were detected by X-ray photoelectron spectroscopy, four-point probe, and ASPA 2010. The results showed that TiO2 phase transformations occurred, and oxygen vacancies formed with the increase of sintering temperature. The cathodic conductivity improved, but the average pore diameter and the effective response area of the TiO2 cathode were reduced when the sintering temperature increased. These phenomena could weaken the contact between reaction ions and electrons and also had the same effect on the cathodes and the molten salt. Moreover, they were disadvantageous to ion migration, so a lower sintering temperature was favorable for the microstructure of electrolysis. Consequently, the cathodic conductivity may be improved, but the microstructure became compact with the increase of sintering temperature. The cathodic products at different temperatures indicated that the cathodic conductivity was more important for electrolysis.

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.

Mesoscale Elucidation of Surface Passivation in the Li–Sulfur Battery Cathode

DOE PAGES

Liu, Zhixiao; Mukherjee, Partha P.

2017-01-23

We report the cathode surface passivation caused by Li 2S precipitation adversely affects the performance of lithium-sulfur (Li-S) batteries. Li 2S precipitation is a complicated mesoscale process involving adsorption, desorption and diffusion kinetics, which are affected profoundly by the reactant concentration and operating temperature. In this work, a mesoscale interfacial model is presented to study the growth of Li 2S film on carbon cathode surface. Li 2S film growth experiences nucleation, isolated Li 2S island growth and island coalescence. The slow adsorption rate at small S 2- concentration inhibits the formation of nucleation seeds and the lateral growth of Limore » 2S islands, which deters surface passivation. An appropriate operating temperature, especially in the medium-to-high temperature range, can also defer surface passivation. Fewer Li 2S nucleation seeds form in such an operating temperature range, which facilitates heterogeneous growth and thereby inhibits the lateral growth of the Li 2S film, which may also result in reduced surface passivation. Finally, the high specific surface area of the cathode microstructure is expected to mitigate the surface passivation.« less

Neutron streak camera

DOEpatents

Wang, C.L.

1981-05-14

Apparatus for improved sensitivity and time resolution of a neutron measurement. The detector is provided with an electrode assembly having a neutron sensitive cathode which emits relatively low energy secondary electrons. The neutron sensitive cathode has a large surface area which provides increased sensitivity by intercepting a greater number of neutrons. The cathode is also curved to compensate for differences in transit time of the neutrons emanating from the point source. The slower speeds of the secondary electrons emitted from a certain portion of the cathode are matched to the transit times of the neutrons impinging thereupon.

Neutron streak camera

DOEpatents

Wang, Ching L.

1983-09-13

Apparatus for improved sensitivity and time resolution of a neutron measurement. The detector is provided with an electrode assembly having a neutron sensitive cathode which emits relatively low energy secondary electrons. The neutron sensitive cathode has a large surface area which provides increased sensitivity by intercepting a greater number of neutrons. The cathode is also curved to compensate for differences in transit time of the neutrons emanating from the point source. The slower speeds of the secondary electrons emitted from a certain portion of the cathode are matched to the transit times of the neutrons impinging thereupon.

Investigation on the Plasma-Induced Emission Properties of Large Area Carbon Nanotube Array Cathodes with Different Morphologies

PubMed Central

2011-01-01

Large area well-aligned carbon nanotube (CNT) arrays with different morphologies were synthesized by using a chemical vapor deposition. The plasma-induced emission properties of CNT array cathodes with different morphologies were investigated. The ratio of CNT height to CNT-to-CNT distance has considerable effects on their plasma-induced emission properties. As the ratio increases, emission currents of CNT array cathodes decrease due to screening effects. Under the pulse electric field of about 6 V/μm, high-intensity electron beams of 170–180 A/cm2 were emitted from the surface plasma. The production mechanism of the high-intensity electron beams emitted from the CNT arrays was plasma-induced emission. Moreover, the distribution of the electron beams was in situ characterized by the light emission from the surface plasma. PMID:27502662

Investigation on the Plasma-Induced Emission Properties of Large Area Carbon Nanotube Array Cathodes with Different Morphologies.

PubMed

Liao, Qingliang; Qin, Zi; Zhang, Zheng; Qi, Junjie; Zhang, Yue; Huang, Yunhua; Liu, Liang

2011-12-01

Large area well-aligned carbon nanotube (CNT) arrays with different morphologies were synthesized by using a chemical vapor deposition. The plasma-induced emission properties of CNT array cathodes with different morphologies were investigated. The ratio of CNT height to CNT-to-CNT distance has considerable effects on their plasma-induced emission properties. As the ratio increases, emission currents of CNT array cathodes decrease due to screening effects. Under the pulse electric field of about 6 V/μm, high-intensity electron beams of 170-180 A/cm(2) were emitted from the surface plasma. The production mechanism of the high-intensity electron beams emitted from the CNT arrays was plasma-induced emission. Moreover, the distribution of the electron beams was in situ characterized by the light emission from the surface plasma.

Fair performance comparison of different carbon blacks in lithium-sulfur batteries with practical mass loadings - Simple design competes with complex cathode architecture

NASA Astrophysics Data System (ADS)

Jozwiuk, Anna; Sommer, Heino; Janek, Jürgen; Brezesinski, Torsten

2015-11-01

The lithium-sulfur system is one of the most promising next generation battery systems, as elemental sulfur is cheap, abundant and has a high theoretical specific capacity. Although much research is conducted on complex sulfur/carbon composites and architectures, it is difficult to compare the performance of the cathodes to one another. Factors, such as different electrolyte composition and cell components strongly affect the cyclability of the battery. Here, we show the importance of optimizing ;standard; conditions to allow for fair performance comparison of different carbon blacks. Our optimal electrolyte-to-sulfur ratio is 11 μL mgsulfur-1 and high concentrations of LiNO3 (>0.6 M) are needed because nitrate is consumed continuously during cycling. Utilizing these standard conditions, we tested the cycling behavior of four types of cathodes with individual carbon blacks having different specific surface areas, namely Printex-A, Super C65, Printex XE-2 and Ketjenblack EC-600JD. Both the specific capacity and polysulfide adsorption capability clearly correlate with the surface area of the carbon being used. High specific capacities (>1000 mAh gsulfur-1 at C/5) are achieved with high surface area carbons. We also demonstrate that a simple cathode using Ketjenblack EC-600JD as the conductive matrix material can well compete with those having complex architectures or additives.

3D Analysis of Fuel Cell Electrocatalyst Degradation on Alternate Carbon Supports.

PubMed

Sneed, Brian T; Cullen, David A; Reeves, Kimberly S; Dyck, Ondrej E; Langlois, David A; Mukundan, Rangachary; Borup, Rodney L; More, Karren L

2017-09-06

Understanding the mechanisms associated with Pt/C electrocatalyst degradation in proton exchange membrane fuel cell (PEMFC) cathodes is critical for the future development of higher-performing materials; however, there is a lack of information regarding Pt coarsening under PEMFC operating conditions within the cathode catalyst layer. We report a direct and quantitative 3D study of Pt dispersions on carbon supports (high surface area carbon (HSAC), Vulcan XC-72, and graphitized carbon) with varied surface areas, graphitic character, and Pt loadings ranging from 5 to 40 wt %. This is accomplished both before and after catalyst-cycling accelerated stress tests (ASTs) through observations of the cathode catalyst layer of membrane electrode assemblies. Electron tomography results show Pt nanoparticle agglomeration occurs predominantly at junctions and edges of aggregated graphitized carbon particles, leading to poor Pt dispersion in the as-prepared catalysts and increased coalescence during ASTs. Tomographic reconstructions of Pt/HSAC show much better initial Pt dispersions, less agglomeration, and less coarsening during ASTs in the cathode. However, a large loss of the electrochemically active surface area (ECSA) is still observed and is attributed to accelerated Pt dissolution and nanoparticle coalescence. Furthermore, a strong correlation between Pt particle/agglomerate size and measured ECSA is established and is proposed as a more useful metric than average crystallite size in predicting degradation behavior across different catalyst systems.

3D Analysis of Fuel Cell Electrocatalyst Degradation on Alternate Carbon Supports

DOE PAGES

Sneed, Brian T.; Cullen, David A.; Reeves, Kimberly S.; ...

2017-08-15

Understanding the mechanisms associated with Pt/C electrocatalyst degradation in proton exchange membrane fuel cell (PEMFC) cathodes is critical for the future development of higher-performing materials; however, there is a lack of information regarding Pt coarsening under PEMFC operating conditions within the cathode catalyst layer. We report a direct and quantitative 3D study of Pt dispersions on carbon supports (high surface area carbon (HSAC), Vulcan XC-72, and graphitized carbon) with varied surface areas, graphitic character, and Pt loadings ranging from 5 to 40 wt %. This is accomplished both before and after catalyst-cycling accelerated stress tests (ASTs) through observations of themore » cathode catalyst layer of membrane electrode assemblies. Electron tomography results show Pt nanoparticle agglomeration occurs predominantly at junctions and edges of aggregated graphitized carbon particles, leading to poor Pt dispersion in the as-prepared catalysts and increased coalescence during ASTs. Tomographic reconstructions of Pt/HSAC show much better initial Pt dispersions, less agglomeration, and less coarsening during ASTs in the cathode. However, a large loss of the electrochemically active surface area (ECSA) is still observed and is attributed to accelerated Pt dissolution and nanoparticle coalescence. Moreover, a strong correlation between Pt particle/agglomerate size and measured ECSA is established and is proposed as a more useful metric than average crystallite size in predicting degradation behavior across different catalyst systems.« less

3D Analysis of Fuel Cell Electrocatalyst Degradation on Alternate Carbon Supports

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

Sneed, Brian T.; Cullen, David A.; Reeves, Kimberly S.

Understanding the mechanisms associated with Pt/C electrocatalyst degradation in proton exchange membrane fuel cell (PEMFC) cathodes is critical for the future development of higher-performing materials; however, there is a lack of information regarding Pt coarsening under PEMFC operating conditions within the cathode catalyst layer. We report a direct and quantitative 3D study of Pt dispersions on carbon supports (high surface area carbon (HSAC), Vulcan XC-72, and graphitized carbon) with varied surface areas, graphitic character, and Pt loadings ranging from 5 to 40 wt %. This is accomplished both before and after catalyst-cycling accelerated stress tests (ASTs) through observations of themore » cathode catalyst layer of membrane electrode assemblies. Electron tomography results show Pt nanoparticle agglomeration occurs predominantly at junctions and edges of aggregated graphitized carbon particles, leading to poor Pt dispersion in the as-prepared catalysts and increased coalescence during ASTs. Tomographic reconstructions of Pt/HSAC show much better initial Pt dispersions, less agglomeration, and less coarsening during ASTs in the cathode. However, a large loss of the electrochemically active surface area (ECSA) is still observed and is attributed to accelerated Pt dissolution and nanoparticle coalescence. Moreover, a strong correlation between Pt particle/agglomerate size and measured ECSA is established and is proposed as a more useful metric than average crystallite size in predicting degradation behavior across different catalyst systems.« less

Quantification of the internal resistance distribution of microbial fuel cells.

PubMed

Fan, Yanzhen; Sharbrough, Evan; Liu, Hong

2008-11-01

Identifying the limiting factors in a microbial fuel cell (MFC) system requires qualifying the contribution of each component of an MFC to internal resistance. In this study, a new method was developed to calculate the internal resistance distribution of an MFC. Experiments were conducted to identify the limiting factors in single-chamber MFCs by varying the anode surface areas, cathode surface areas, and phosphate buffer concentrations. For the MFCs with equally sized electrodes (7 cm2) and 200 mM phosphate buffer, the anode contributed just 5.4% of the internal resistance, while the cathode and the electrolyte each contributed 47.3%, indicating that the anode was not the limiting factor in power generation. The limitation of the cathode was further revealed by the 780% higher area-specific resistance (284.4 omega cm2) than the 32.3 omega cm2 of the anode. The electrolyte limitation was also evidenced by the greatly increased contribution of electrolyte in internal resistance from 47.3 to 78.2% when the concentration of phosphate buffer was decreased from 200 to 50 mM. An anodic power density of 6860 mW/m2 was achieved at a current density of 2.62 mA/cm2 using the MFCs with an anode/cathode area ratio of 1/14 and 200 mM phosphate buffer. The method was also successfully applied to analyze the internal resistance distribution of the two chamber MFCs from a previously reported study. The comparison of the internal resistances of the two air cathode systems indicates that the much lower resistances, including anode, cathode, and membrane resistances, contributed to the much better performance of the single-chamber MFCs than the two-chamber system.

Pulsed electromagnetic gas acceleration

NASA Technical Reports Server (NTRS)

Jahn, R. G.; Vonjaskowsky, W. F.; Clark, K. E.

1975-01-01

Terminal voltage measurements with long cathodes in a high power, quasi-steady MPD discharge show that the critical current for the onset of voltage fluctuations, which was previously shown to be a function of cathode area, approaches an asymptote for cathodes of very large surface area. Floating potential measurements and photographs of the discharge luminosity indicate that the fluctuations are confined to the vicinity of the cathode and hence reflect a cathode emission process rather than a fundamental limit on MPD performance. Photoelectric measurements of particular argon neutral and ion transitions show that the higher electronic states are populated more heavily than would be calculated on the basis of Saha-Boltzmann equilibrium at the local electron temperature and number density. Preliminary optical depth measurements show that for a current of 4 kA and an argon mass flow of 12 g/sec, a population inversion exists between the upper and lower states of the 4880 A argon ion transition.

In situ atomic force microscopy analysis of morphology and particle size changes in lithium iron phosphate cathode during discharge.

PubMed

Demirocak, Dervis Emre; Bhushan, Bharat

2014-06-01

Li-ion batteries offer great promise for future plug-in hybrid electric vehicles (PHEVs) and pure electric vehicles (EVs). One of the challenges is to improve the cycle life of Li-ion batteries which requires detailed understanding of the aging phenomenon. In situ techniques are especially valuable to understand aging since it allows monitoring the physical and chemical changes in real time. In this study, in situ atomic force microscopy (AFM) is utilized to study the changes in morphology and particle size of LiFePO4 cathode during discharge. The guidelines for in situ AFM cell design for accurate and reliable measurements based on different designs are presented. The effect of working electrode to counter electrode surface area ratio on cycling data of an in situ cell is also discussed. Analysis of the surface area change in LiFePO4 particles when the cell was cycled between 100% and 70% state of charge is presented. Among four particles analyzed, surface area increase of particles during Li intercalation of LiFePO4 spanned from 1.8% to 14.3% indicating the inhomogeneous nature of the cathode surface. Copyright © 2014 Elsevier Inc. All rights reserved.

Neutron streak camera

DOEpatents

Wang, C.L.

1983-09-13

Disclosed is an apparatus for improved sensitivity and time resolution of a neutron measurement. The detector is provided with an electrode assembly having a neutron sensitive cathode which emits relatively low energy secondary electrons. The neutron sensitive cathode has a large surface area which provides increased sensitivity by intercepting a greater number of neutrons. The cathode is also curved to compensate for differences in transit time of the neutrons emanating from the point source. The slower speeds of the secondary electrons emitted from a certain portion of the cathode are matched to the transit times of the neutrons impinging thereupon. 4 figs.

Electron emission and plasma generation in a modulator electron gun using ferroelectric cathode

NASA Astrophysics Data System (ADS)

Chen, Shutao; Zheng, Shuxin; Zhu, Ziqiu; Dong, Xianlin; Tang, Chuanxiang

2006-10-01

Strong electron emission and dense plasma generation have been observed in a modulator electron gun with a Ba 0.67Sr 0.33TiO 3 ferroelectric cathode. Parameter of the modulator electron gun and lifetime of the ferroelectric cathode were investigated. It was shown that electron emission from Ba 0.67Sr 0.33TiO 3 cathode with a positive triggering pulse is a sort of plasma emission. Electrons were emitted by the co-effect of surface plasma and non-compensated negative polarization charges at the surface of the ferroelectric. The element analyses of the graphite collector after emission process was performed to show the ingredient of the plasma consist of Ba, Ti and Cu heavy cations of the ceramic compound and electrode. It was demonstrated the validity of the Child-Langmuir law by introducing the decrease of vacuum gap and increase of emission area caused by the expansion of the surface plasma.

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

NASA Astrophysics Data System (ADS)

Serra, José M.; Buchkremer, Hans-Peter

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

A Fully-Sealed Carbon-Nanotube Cold-Cathode Terahertz Gyrotron

PubMed Central

Yuan, Xuesong; Zhu, Weiwei; Zhang, Yu; Xu, Ningsheng; Yan, Yang; Wu, Jianqiang; Shen, Yan; Chen, Jun; She, Juncong; Deng, Shaozhi

2016-01-01

Gigahertz to terahertz radiation sources based on cold-cathode vacuum electron technology are pursued, because its unique characteristics of instant switch-on and power saving are important to military and space applications. Gigahertz gyrotron was reported using carbon nanotube (CNT) cold-cathode. It is reported here in first time that a fully-sealed CNT cold-cathode 0.22 THz-gyrotron is realized, typically with output power of 500 mW. To achieve this, we have studied mechanisms responsible for CNTs growth on curved shape metal surface, field emission from the sidewall of a CNT, and crystallized interface junction between CNT and substrate material. We have obtained uniform growth of CNTs on and direct growth from cone-cylinder stainless-steel electrode surface, and field emission from both tips and sidewalls of CNTs. It is essential for the success of a CNT terahertz gyrotron to have such high quality, high emitting performance CNTs. Also, we have developed a magnetic injection electron gun using CNT cold-cathode to exploit the advantages of such a conventional gun design, so that a large area emitting surface is utilized to deliver large current for electron beam. The results indicate that higher output power and higher radiation frequency terahertz gyrotron may be made using CNT cold-cathode electron gun. PMID:27609247

A Fully-Sealed Carbon-Nanotube Cold-Cathode Terahertz Gyrotron.

PubMed

Yuan, Xuesong; Zhu, Weiwei; Zhang, Yu; Xu, Ningsheng; Yan, Yang; Wu, Jianqiang; Shen, Yan; Chen, Jun; She, Juncong; Deng, Shaozhi

2016-09-09

Gigahertz to terahertz radiation sources based on cold-cathode vacuum electron technology are pursued, because its unique characteristics of instant switch-on and power saving are important to military and space applications. Gigahertz gyrotron was reported using carbon nanotube (CNT) cold-cathode. It is reported here in first time that a fully-sealed CNT cold-cathode 0.22 THz-gyrotron is realized, typically with output power of 500 mW. To achieve this, we have studied mechanisms responsible for CNTs growth on curved shape metal surface, field emission from the sidewall of a CNT, and crystallized interface junction between CNT and substrate material. We have obtained uniform growth of CNTs on and direct growth from cone-cylinder stainless-steel electrode surface, and field emission from both tips and sidewalls of CNTs. It is essential for the success of a CNT terahertz gyrotron to have such high quality, high emitting performance CNTs. Also, we have developed a magnetic injection electron gun using CNT cold-cathode to exploit the advantages of such a conventional gun design, so that a large area emitting surface is utilized to deliver large current for electron beam. The results indicate that higher output power and higher radiation frequency terahertz gyrotron may be made using CNT cold-cathode electron gun.

Non-encapsulation approach for high-performance Li–S batteries through controlled nucleation and growth

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

Pan, Huilin; Chen, Junzheng; Cao, Ruiguo

Sulfur encapsulation in high surface area, nanoporous carbon is currently the most widely studied approach to improve the cycling stability of Li-S batteries. However, the relatively large amount of high surface area carbon decreases the overall volumetric energy density in the system and makes it difficult to compete with other battery chemistries. In this paper, we report a new approach that does not depend on sulfur encapsulation and high surface area carbon. We investigate the nucleation and deposition of sulfur using low surface area carbon in the cathode (surface area 17 m2 g-1). Optimization of the solvent properties and themore » deposition condition produce large spherical porous agglomerated particles rather than thin films. A solution mediated nucleation and growth mechanism is identified to form the large porous polysulfide particles. This new mechanism leads to close to 100% sulfur utilization, almost no capacity fading, over 99% coulombic efficacy, and high energy density (2350 Wh kg-1 and 2600 Wh L-1 based on overall mass/volume of cathode). This study may open a fundamentally new approach of using a low surface area carbon host for designing high energy Li-S battery by controlling the nucleation/growth pathway and morphology of sulfur species.« less

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.

Revealing Anisotropic Spinel Formation on Pristine Li- and Mn-Rich Layered Oxide Surface and Its Impact on Cathode Performance

DOE PAGES

Kuppan, Saravanan; Shukla, Alpesh Khushalchand; Membreno, Daniel; ...

2017-01-06

Surface properties of cathode particles play important roles in the transport of ions and electrons and they may ultimately dominate cathode's performance and stability in lithium-ion batteries. Through the use of carefully prepared Li 1.2Ni 0.13Mn 0.54Co 0.13O 2 crystal samples with six distinct morphologies, surface transition-metal redox activities and crystal structural transformation are investigated as a function of surface area and surface crystalline orientation. Complementary depth-profiled core-level spectroscopy, namely, X-ray absorption spectroscopy, electron energy loss spectroscopy, and atomic-resolution scanning transmission electron microscopy, are applied in the study, presenting a fine example of combining advanced diagnostic techniques with a well-definedmore » model system of battery materials. Here, we report the following findings: (1) a thin layer of defective spinel with reduced transition metals, similar to what is reported on cycled conventional secondary particles in the literature, is found on pristine oxide surface even before cycling, and (2) surface crystal structure and chemical composition of both pristine and cycled particles are facet dependent. Oxide structural and cycling stabilities improve with maximum expression of surface facets stable against transition-metal reduction. Finally, the intricate relationships among morphology, surface reactivity and structural transformation, electrochemical performance, and stability of the cathode materials are revealed.« less

Pulsed electromagnetic gas acceleration

NASA Technical Reports Server (NTRS)

Jahn, R. G.; Vonjaskowsky, W. F.; Clark, K. E.

1974-01-01

Detailed measurements of the axial velocity profile and electromagnetic structure of a high power, quasi-steady MPD discharge are used to formulate a gasdynamic model of the acceleration process. Conceptually dividing the accelerated plasma into an inner flow and an outer flow, it is found that more than two-thirds of the total power in the plasma is deposited in the inner flow, accelerating it to an exhaust velocity of 12.5 km/sec. The outer flow, which is accelerated to a velocity of only 6.2 km/sec, appears to provide a current conduction path between the inner flow and the anode. Related cathode studies have shown that the critical current for the onset of terminal voltage fluctuations, which was recently shown to be a function of the cathode area, appears to reach an asymptote for cathodes of very large surface area. Detailed floating potential measurements show that the fluctuations are confined to the vicinity of the cathode and hence reflect a cathode emission process rather than a fundamental limit on MPD performance.

Thin film passivation of laser generated 3D micro patterns in lithium manganese oxide cathodes

NASA Astrophysics Data System (ADS)

Pröll, J.; Kohler, R.; Bruns, M.; Oberst, V.; Weidler, P. G.; Heißler, S.; Kübel, C.; Scherer, T.; Prang, R.; Seifert, H. J.; Pfleging, W.

2013-03-01

The increasing need for long-life lithium-ion batteries requires the further development of electrode materials. Especially on the cathode side new materials or material composites are needed to increase the cycle lifetime. On the one hand, spinel-type lithium manganese oxide is a promising candidate to be used as cathode material due to its non-toxicity, low cost and good thermal stability. On the other hand, the spinel structure suffers from change in the oxidation state of manganese during cycling which is also accompanied by loss of active material into the liquid electrolyte. The general trend is to enhance the active surface area of the cathode in order to increase lithium-ion mobility through the electrode/electrolyte interface, while an enhanced surface area will also promote chemical degradation. In this work, laser microstructuring of lithium manganese oxide thin films was applied in a first step to increase the active surface area. This was done by using 248 nm excimer laser radiation and chromium/quartz mask imaging techniques. In a second step, high power diode laser-annealing operating at a wavelength of 940 nm was used for forming a cubic spinel-like battery phase. This was verified by means of Raman spectroscopy and cyclic voltammetric measurements. In a last step, the laser patterned thin films were coated with indium tin oxide (ITO) layers with a thickness of 10 nm to 50 nm. The influence of the 3D surface topography as well as the ITO thickness on the electrochemical performance was studied by cyclic voltammetry. Post-mortem studies were carried out by using scanning electron microscopy and focused ion beam analysis.

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

Liu, Zhixiao; Mukherjee, Partha P.

We report the cathode surface passivation caused by Li 2S precipitation adversely affects the performance of lithium-sulfur (Li-S) batteries. Li 2S precipitation is a complicated mesoscale process involving adsorption, desorption and diffusion kinetics, which are affected profoundly by the reactant concentration and operating temperature. In this work, a mesoscale interfacial model is presented to study the growth of Li 2S film on carbon cathode surface. Li 2S film growth experiences nucleation, isolated Li 2S island growth and island coalescence. The slow adsorption rate at small S 2- concentration inhibits the formation of nucleation seeds and the lateral growth of Limore » 2S islands, which deters surface passivation. An appropriate operating temperature, especially in the medium-to-high temperature range, can also defer surface passivation. Fewer Li 2S nucleation seeds form in such an operating temperature range, which facilitates heterogeneous growth and thereby inhibits the lateral growth of the Li 2S film, which may also result in reduced surface passivation. Finally, the high specific surface area of the cathode microstructure is expected to mitigate the surface passivation.« 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.

Ab initio investigation of the surface properties of dispenser B-type and scandate thermionic emission cathodes

NASA Astrophysics Data System (ADS)

Vlahos, Vasilios; Lee, Yueh-Lin; Booske, John H.; Morgan, Dane; Turek, Ladislav; Kirshner, Mark; Kowalczyk, Richard; Wilsen, Craig

2009-05-01

Scandate cathodes (BaxScyOz on W) are important thermionic electron emission materials whose emission mechanism remains unclear. Ab initio modeling is used to investigate the surface properties of both scandate and traditional B-type (Ba-O on W) cathodes. We demonstrate that the Ba-O dipole surface structure believed to be present in active B-type cathodes is not thermodynamically stable, suggesting that a nonequilibrium steady state dominates the active cathode's surface structure. We identify a stable, low work function BaxScyOz surface structure, which may be responsible for some scandate cathode properties and demonstrate that multicomponent surface coatings can lower cathode work functions.

Soft-contact conductive carbon enabling depolarization of LiFePO4 cathodes to enhance both capacity and rate performances of lithium ion batteries

NASA Astrophysics Data System (ADS)

Ren, Wenju; Wang, Kai; Yang, Jinlong; Tan, Rui; Hu, Jiangtao; Guo, Hua; Duan, Yandong; Zheng, Jiaxin; Lin, Yuan; Pan, Feng

2016-11-01

Conductive nanocarbons generally are used as the electronic conductive additives to contact with active materials to generate conductive network for electrodes of commercial Li-ion batteries (LIBs). A typical of LiFePO4 (LFP), which has been widely used as cathode material for LIBs with low electronic conductivity, needs higher quantity of conductive nanocarbons to enhance the performance for cathode electrodes. In this work, we systematically studied three types of conductive nanocarbons and related performances in the LFP electrodes, and classify them as hard/soft-contact conductive carbon (named as H/SCC), respectively, according to their crystallite size, surface graphite-defect, specific surface area and porous structure, in which SCC can generate much larger contact area with active nano-particles of cathode materials than that of HCC. It is found that LFP nanocrystals wrapped in SCC networks perform significantly enhanced both capacity and rate performance than that in HCC. Combined experiments with multiphysics simulation, the mechanism is that LFP nanoparticles embedded in SCC with large contact area enable to generate higher depolarized effects with a relatively uniform current density vector (is) and lithium flux vector (NLi) than that in HCC. This discovery will guide us to how to design LIBs by selective using conductive carbon for high-performance LIBs.

An experimental investigation of cathode erosion in high current magnetoplasmadynamic arc discharges

NASA Astrophysics Data System (ADS)

Codron, Douglas A.

Since the early to mid 1960's, laboratory studies have demonstrated the unique ability of magnetoplasmadynamic (MPD) thrusters to deliver an exceptionally high level of specific impulse and thrust at large power processing densities. These intrinsic advantages are why MPD thrusters have been identified as a prime candidate for future long duration space missions, including piloted Mars, Mars cargo, lunar cargo, and other missions beyond low Earth orbit (LEO). The large total impulse requirements inherent of the long duration space missions demand the thruster to operate for a significant fraction of the mission burn time while requiring the cathodes to operate at 50 to 10,000 kW for 2,000 to 10,000 hours. The high current levels lead to high operational temperatures and a corresponding steady depletion of the cathode material by evaporation. This mechanism has been identified as the life-limiting component of MPD thrusters. In this research, utilizing subscale geometries, time dependent cathode axial temperature profiles under varying current levels (20 to 60 A) and argon gas mass flow rates (450 to 640 sccm) for both pure and thoriated solid tungsten cathodes were measured by means of both optical pyrometry and charged-coupled (CCD) camera imaging. Thoriated tungsten cathode axial temperature profiles were compared against those of pure tungsten to demonstrate the large temperature reducing effect lowered work function imparts by encouraging increased thermionic electron emission from the cathode surface. Also, Langmuir probing was employed to measure the electron temperature, electron density, and plasma potential near the "active zone" (the surface area of the cathode responsible for approximately 70% of the emitted current) in order to characterize the plasma environment and verify future model predictions. The time changing surface microstructure and elemental composition of the thoriated tungsten cathodes were analyzed using a scanning electron microscope (SEM) in conjunction with energy-dispersive X-ray spectroscopy (EDS). Such studies have provided a qualitative understanding of the typical pathways in which thorium diffuses and how it is normally redistributed along the cathode surface. Lastly, the erosion rates of both pure and thoriated tungsten cathodes were measured after various run times by use of an analytical scale. These measurements have revealed the ability of thoriated tungsten cathodes to run as long as that of pure tungsten but with significantly less material erosion.

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.

Electromigration Failure Mechanism in Sn-Cu Solder Alloys with OSP Cu Surface Finish

NASA Astrophysics Data System (ADS)

Chu, Ming-Hui; Liang, S. W.; Chen, Chih; Huang, Annie T.

2012-09-01

Organic solderable preservative (OSP) has been adopted as the Cu substrate surface finish in flip-chip solder joints for many years. In this study, the electromigration behavior of lead-free Sn-Cu solder alloys with thin-film under bump metallization and OSP surface finish was investigated. The results showed that severe damage occurred on the substrate side (cathode side), whereas the damage on the chip side (cathode side) was not severe. The damage on the substrate side included void formation, copper dissolution, and formation of intermetallic compounds (IMCs). The OSP Cu interface on the substrate side became the weakest point in the solder joint even when thin-film metallization was used on the chip side. Three-dimensional simulations were employed to investigate the current density distribution in the area between the OSP Cu surface finish and the solder. The results indicated that the current density was higher along the periphery of the bonding area between the solder and the Cu pad, consistent with the area of IMC and void formation in our experimental results.

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.

Aluminum reduction cell electrode

DOEpatents

Payne, J.R.

1983-09-20

The invention is directed to an anode-cathode structure for an electrolytic cell for the reduction of alumina wherein the structure is comprised of a carbon anode assembly which straddles a wedge-shaped refractory hard metal cathode assembly having steeply sloped cathodic surfaces, each cathodic surface being paired in essentially parallel planar relationship with an anode surface. The anode-cathode structure not only takes into account the structural weakness of refractory hard metal materials but also permits the changing of the RHM assembly during operation of the cell. Further, the anode-cathode structure enhances the removal of anode gas from the interpolar gap between the anode and cathode surfaces. 10 figs.

Aluminum reduction cell electrode

DOEpatents

Payne, John R.

1983-09-20

The invention is directed to an anode-cathode structure for an electrolytic cell for the reduction of alumina wherein the structure is comprised of a carbon anode assembly which straddles a wedge-shaped refractory hard metal cathode assembly having steeply sloped cathodic surfaces, each cathodic surface being paired in essentially parallel planar relationship with an anode surface. The anode-cathode structure not only takes into account the structural weakness of refractory hard metal materials but also permits the changing of the RHM assembly during operation of the cell. Further, the anode-cathode structure enhances the removal of anode gas from the interpolar gap between the anode and cathode surfaces.

Modification of W surfaces by exposure to hollow cathode plasmas

NASA Astrophysics Data System (ADS)

Stancu, C.; Stokker-Cheregi, F.; Moldovan, A.; Dinescu, M.; Grisolia, C.; Dinescu, G.

2017-10-01

In this work, we assess the surface modifications induced on W samples following exposure to He and He/H2 radiofrequency plasmas in hollow cathode discharge configuration. Our study addresses issues that relate to the use of W in next-generation fusion reactors and, therefore, the investigation of W surface degradation following exposure and heating by plasmas to temperatures above 1000 °C is of practical importance. For these experiments, we used commercially available tungsten samples having areas of 30 × 15 mm and 0.1 mm thickness. The hollow cathode plasma was produced using a radiofrequency (RF) generator (13.56 MHz) between parallel plate electrodes. The W samples were mounted as one of the electrodes. The He and He/H2 plasma discharges had a combined effect of heating and bombardment of the W surfaces. The surface modifications were studied for discharge powers between 200 and 300 W, which resulted in the heating of the samples to temperatures between 950 and 1230 °C, respectively. The samples were weighed prior and after plasma exposure, and loss of mass was measured following plasma exposure times up to 90 min. The analysis of changes in surface morphology was carried out by optical microscopy, scanning electron microscopy and atomic force microscopy. Additionally, optical emission spectra of the respective plasmas were recorded from the region localized inside the hollow cathode gap. We discuss the influence of experimental parameters on the changes in surface morphology.

Long Life Na/NiCl2 Cells

NASA Technical Reports Server (NTRS)

Bugga, Ratnakumar V. (Inventor); Surampudi, Subbarao (Inventor); Halpert, Gerald (Inventor)

1996-01-01

The premature capacity failure of Na/NiCl2 secondary cells due to agglomeration of nickel particles on the surface of the NiCl2 cathode is prevented by addition of a minor amount such as 10 percent by weight of a transition metal such as Co, Fe or Mn to the cathode. The chlorides of the transition metals have lower potentials than nickel chloride and chlorinate during charge. A uniform dispersion of the transition metals in the cathodes prevents agglomeration of nickel, maintains morphology of the electrode, maintains the electrochemical area of the electrode and thus maintains capacity of the electrode. The additives do not effect sintering. The addition of sulfur to the liquid catholyte is expected to further reduce agglomeration of nickel in the cathode.

Nucleation and Growth of Lithium Peroxide in the Li-O2 Battery.

PubMed

Lau, Sampson; Archer, Lynden A

2015-09-09

We study the relationship between Li2O2 morphology and the electrochemical performance of the Li-O2 battery using a combination of experiment and theory. Experimental Li-O2 battery discharge curves are accurately captured by a theoretical model in which electrode performance is limited by the nucleation and growth of discrete Li2O2 nanostructures in the cathode. We further show that the characteristic sharp voltage drop widely reported at the end of discharge results from the decrease in electrochemical surface area as Li2O2 covers the cathode surface. Preventing surface nucleation is highlighted as a core strategy for increasing Li-O2 battery capacity.

Research on effect of emission uniformity on X-band relativistic backward oscillator using conformal PIC code

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

Chen, Zaigao

2016-07-15

Explosive emission cathodes (EECs) are adopted in relativistic backward wave oscillators (RBWOs) to generate intense relativistic electron beam. The emission uniformity of the EEC can render saturation of the power generation unstable and the output mode impure. However, the direct measurement of the plasma parameters on the cathode surface is quite difficult and there are very few related numerical study reports about this issue. In this paper, a self-developed three-dimensional conformal fully electromagnetic particle in cell code is used to study the effect of emission uniformity on the X-band RBWO; the electron explosive emission model and the field emission modelmore » are both implemented in the same cathode surface, and the local field enhancement factor is also considered in the field emission model. The RBWO with a random nonuniform EEC is thoroughly studied using this code; the simulation results reveal that when the area ratio of cathode surface for electron explosive emission is 80%, the output power is unstable and the output mode is impure. When the annular EEC does not emit electron in the angle range of 30°, the RBWO can also operate normally.« less

Evaluation of La0.6Sr0.4Co0.2Fe0.8O3-Gd0.1Ce0.9O1.95 composite cathode with three dimensional microstructure reconstruction

NASA Astrophysics Data System (ADS)

Kim, Y. T.; Jiao, Z.; Shikazono, N.

2017-02-01

In the present study, the polarization characteristics of La0.6Sr0.4Co0.2Fe0.8O3 (LSCF) - Gd0.1Ce0.9O1.95 (GDC) composite cathodes with different volume ratios were investigated. Samples with volume ratios of 20:80, 30:70, 50:50, 70:30 and 100:0 vol % were tested. The electrochemical impedance spectroscopy tests and current voltage curve measurements were carried out for the current densities from 0 to 0.2 Acm-2 with an interval of 0.05 Acm-2. The results showed that a volume ratio of LSCF:GDC = 30:70 composite cathode led to the lowest overpotential, and the overpotential increased in the order of 30:70, 50:50, 70:30, 100:0, 20:80 vol %. Three dimensional microstructures of composite cathodes were reconstructed and quantified by dual beam focused ion beam-scanning electron microscope (FIB-SEM). The results showed that neither LSCF surface area nor triple phase boundary (TPB) alone could explain the dependence of polarization characteristics on volume ratios. Current and electrochemical potential distributions were simulated by the Lattice Boltzmann method, in which both surface and TPB reactions were considered. Prediction considering both surface and TPB reactions could predict qualitatively the dependence of overpotentials on LSCF - GDC cathode composition.

Ab initio study of perovskite type oxide materials for solid oxide fuel cells

NASA Astrophysics Data System (ADS)

Lee, Yueh-Lin

2011-12-01

Perovskite type oxides form a family of materials of significant interest for cathodes and electrolytes of solid oxide fuel cells (SOFCs). These perovskites not only are active catalysts for surface oxygen reduction (OR) reactions but also allow incorporating the spilt oxygen monomers into their bulk, an unusual and poorly understood catalytic mechanism that couples surface and bulk properties. The OR mechanisms can be influenced strongly by defects in perovskite oxides, composition, and surface defect structures. This thesis work initiates a first step in developing a general strategy based on first-principles calculations for detailed control of oxygen vacancy content, transport rates of surface and bulk oxygen species, and surface/interfacial reaction kinetics. Ab initio density functional theory methods are used to model properties relevant for the OR reactions on SOFC cathodes. Three main research thrusts, which focus on bulk defect chemistry, surface defect structures and surface energetics, and surface catalytic properties, are carried to investigate different level of material chemistry for improved understanding of key physics/factors that govern SOFC cathode OR activity. In the study of bulk defect chemistry, an ab initio based defect model is developed for modeling defect chemistry of LaMnO 3 under SOFC conditions. The model suggests an important role for defect interactions, which are typically excluded in previous defect models. In the study of surface defect structures and surface energetics, it is shown that defect energies change dramatically (1˜2 eV lower) from bulk values near surfaces. Based on the existing bulk defect model with the calculated ab initio surface defect energetics, we predict the (001) MnO 2 surface oxygen vacancy concentration of (La0.9Sr0.1 )MnO3 is about 5˜6 order magnitude higher than that of the bulk under typical SOFC conditions. Finally, for surface catalytic properties, we show that area specific resistance, oxygen exchange rates, and key OR energetics of the SOFC cathode perovskites, can be described by a single descriptor, either the bulk O p-band or the bulk oxygen vacancy formation energy. These simple descriptors will further enable first-principles optimization/design of new SOFC cathodes.

Preparation and surface characteristics of Re3W matrix scandate cathode: An experimental and theoretical study

NASA Astrophysics Data System (ADS)

Lai, Chen; Wang, Jinshu; Zhou, Fan; Liu, Wei; Hu, Peng; Wang, Changhao; Wang, Ruzhi; Miao, Naihua

2018-05-01

The Scandia doped thermionic cathodes have received great attention owing to their high electron emission density in past two decades. Here, Scandia doped Re3W matrix scandate (RS) cathodes are fabricated by using Sc2O3 doped Re3W powders that prepared by spray drying method. The micromorphology, surface composition and chemical states of RS cathode are investigated with various modern technologies. It reveals that the reduction temperature of RS powders is dramatically increased by Sc2O3. On the surface of RS cathode, a certain amount of Sc2O3 nanoparticles and barium salt submicron particles are observed. According to the in situ Auger electron spectroscopy analysis, the concentration ratio of Ba:Sc:O is determined to be 2.9:1.1:2.7. The X-ray photoelectron spectroscopy data indicates that low oxidation state of Sc is clearly observed in scandate cathodes. The high atomic ratio of Ba on RS cathode surface is suggested due to the high adsorption of Re3W to Ba. Moreover, RS cathode shows better adsorption to Sc by comparison with conventional tungsten matrix scandate cathode. For RS cathode, the main depletion of Sc is suggested to -OSc desorbing from RS cathode surface. RS cathode is expected to be an impressive thermionic cathode with good emission properties and ion anti-bombarding insensitivity.

Effects of pore formers on microstructure and performance of cathode membranes for solid oxide fuel cells

NASA Astrophysics Data System (ADS)

Nie, Lifang; Liu, Juncheng; Zhang, Yujun; Liu, Meilin

La 0.6Sr 0.4Co 0.2Fe 0.8O 3- δ (LSCF) is the most widely used cathode material for intermediate temperature solid oxide fuel cells. In the present communication, porous LSCF cathodes are fabricated by tape casting, a low-cost and reproducible fabrication process. The effects of four different pore formers, namely, graphite, carbon black, rice starch, and corn starch, on the microstructure and electrochemical performance of the LSCF cathode are investigated. Examination of the microstructures reveals that the shape of the pores, the pore size, and the pore distribution in the final ceramic are related to the type of pore formers. Impedance analysis and cell testing show that the best performance is obtained from the cathode using graphite as the pore former. The microstructure indicates that graphite results in a porous LSCF cathode with a large surface area and high porosity, which can offer a considerably long triple phase boundary for catalytic reactions as well as channels for gas phase transport.

Nano Copper Oxide-Modified Carbon Cloth as Cathode for a Two-Chamber Microbial Fuel Cell

PubMed Central

Dong, Feng; Zhang, Peng; Li, Kexun; Liu, Xianhua; Zhang, Pingping

2016-01-01

In this work, Cu2O nanoparticles were deposited on a carbon cloth cathode using a facile electrochemical method. The morphology of the modified cathode, which was characterized by scanning electron microscopy (SEM) and Brunauer-Emmett-Teller (BET) tests, showed that the porosity and specific surface area of the cathode improved with longer deposition times. X-ray photoelectron spectroscopy (XPS) and cyclic voltammetry (CV) results showed that cupric oxide and cuprous oxide coexisted on the carbon cloth, which improved the electrochemical activity of cathode. The cathode with a deposition time of 100 s showed the best performance, with a power density twice that of bare carbon cloth. Linear sweep voltammetry (LSV) and electrochemical impedance spectroscopy (EIS) results revealed that moderate deposition of nano copper oxide on carbon cloth could dramatically reduce the charge transfer resistance, which contributed to the enhanced electrochemical performance. The mediation mechanism of copper oxide nanocatalyst was illustrated by the fact that the recycled conversion between cupric oxide and cuprous oxide accelerated the electron transfer efficiency on the cathode. PMID:28335366

Nano Copper Oxide-Modified Carbon Cloth as Cathode for a Two-Chamber Microbial Fuel Cell.

PubMed

Dong, Feng; Zhang, Peng; Li, Kexun; Liu, Xianhua; Zhang, Pingping

2016-12-09

In this work, Cu₂O nanoparticles were deposited on a carbon cloth cathode using a facile electrochemical method. The morphology of the modified cathode, which was characterized by scanning electron microscopy (SEM) and Brunauer-Emmett-Teller (BET) tests, showed that the porosity and specific surface area of the cathode improved with longer deposition times. X-ray photoelectron spectroscopy (XPS) and cyclic voltammetry (CV) results showed that cupric oxide and cuprous oxide coexisted on the carbon cloth, which improved the electrochemical activity of cathode. The cathode with a deposition time of 100 s showed the best performance, with a power density twice that of bare carbon cloth. Linear sweep voltammetry (LSV) and electrochemical impedance spectroscopy (EIS) results revealed that moderate deposition of nano copper oxide on carbon cloth could dramatically reduce the charge transfer resistance, which contributed to the enhanced electrochemical performance. The mediation mechanism of copper oxide nanocatalyst was illustrated by the fact that the recycled conversion between cupric oxide and cuprous oxide accelerated the electron transfer efficiency on the cathode.

Alkaline fuel cell performance investigation

NASA Technical Reports Server (NTRS)

Martin, R. E.; Manzo, M. A.

1988-01-01

An exploratory experimental fuel cell test program was conducted to investigate the performance characteristics of alkaline laboratory research electrodes. The objective of this work was to establish the effect of temperature, pressure, and concentration upon performance and evaluate candidate cathode configurations having the potential for improved performance. The performance characterization tests provided data to empirically establish the effect of temperature, pressure, and concentration upon performance for cell temperatures up to 300 F and reactant pressures up to 200 psia. Evaluation of five gold alloy cathode catalysts revealed that three doped gold alloys had more that two times the surface areas of reference cathodes and therefore offered the best potential for improved performance.

Alkaline fuel cell performance investigation

NASA Technical Reports Server (NTRS)

Martin, R. E.; Manzo, M. A.

1988-01-01

An exploratory experimental fuel cell test program was conducted to investigate the performance characteristics of alkaline laboratory research electrodes. The objective of this work was to establish the effect of temperature, pressure, and concentration upon performance and evaluate candidate cathode configurations having the potential for improved performance. The performance characterization tests provided data to empirically establish the effect of temperature, pressure, and concentration upon performance for cell temperatures up to 300 F and reactant pressures up to 200 psia. Evaluation of five gold alloy cathode catalysts revealed that three doped gold alloys had more than two times the surface areas of reference cathodes and therefore offered the best potential for improved performance.

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.

Fibrinogen adsorption onto 316L stainless steel under polarized conditions.

PubMed

Gettens, Robert T T; Gilbert, Jeremy L

2008-04-01

Adsorption of the plasma protein fibrinogen onto electrically polarized 316L stainless steel was observed and quantified using both in situ and ex situ atomic force microscopy (AFM) techniques. Significant differences in fibrinogen adsorption were observed across voltages. Ex situ studies showed significantly lower area coverage (theta) and height of adsorbed Fb on cathodically polarized surfaces when compared to anodically polarized surfaces. Conformational differences in the protein may explain the distinctions in Fb surface area coverage (theta) and height between the anodic and cathodic cases. In situ studies showed significantly slower kinetics of Fb adsorption onto surfaces below -100 mV (vs. Ag/AgCl) compared to surfaces polarized above -100 mV. Electrochemical current density data showed large charge transfer processes (approximately 1 x 10(-5) to 1 x 10(-4) A/cm(2)) taking place on the 316L SS surfaces at voltages below -100 mV (vs. Ag/AgCl). These relatively large current densities point to flux of ionic species away from the surface as a major source of the reduction in adsorption kinetics rather than just hydrophilic or electrostatic effects. Copyright 2007 Wiley Periodicals, Inc.

Effect of CO on the field emission properties of tetrapod zinc oxide cathode.

PubMed

Wang, Jinchan; Zhang, Xiaobing; Lei, Wei; Mao, Fuming; Cui, Yunkang; Xiao, Mei

2012-08-01

Tetrapod zinc oxide (T-ZnO), being a kind of nano-material, has large specific surface area and surface binding energy, which will make it sensitive to the ambient gas condition. So the field emission properties will be influenced by the gas adsorption when being applied as the cathode materials of field emission devices. Carbon monoxide is the main residual gas in T-ZnO field emission devices. In this paper, carbon monoxide was introduced into a field emission device with T-ZnO emitters. The field emission currents of tetrapod ZnO were compared before and after exposure to CO.

Study on structural refinement and electrochemical behaviour of Ba0.5Sr0.5Co0.8Fe0.2O3-δ as cathode materials for intermediate temperature solid oxide fuel cells (IT-SOFC)

NASA Astrophysics Data System (ADS)

Kautkar, Pranay R.; Shirbhate, Shraddha C.; Acharya, Smita A.

2018-05-01

Ba0.5Sr0.5Co0.8Fe0.2O3-δ (BSCF) was prepared by ethylene glycol-citrate combined sol-gel combustion route and calcined at optimized temperature 1050°C. The X-ray Diffraction (XRD) data revealing the crystal purity of BSCF cathode was refined by the Cubic-type structure having the space group Pm-3m by Rietveld analysis. Refined lattice parameter of BSCF cathode is a = 3.9759 Å and unit cell volume is 62.85 (4) Å3, Co/Fe-O bond length from VESTA program figured out to be 1.987 (3) Å. Electron density distribution (EDD) of the unit cell of BSCF cathode shows the bonding feature with oxygen ions, this could represent oxygen vacancies are present in the lattice. These results reflected in electrochemical impedance spectra measurement of symmetric cell. Area of specific resistance (ASR) of the BSCF cathode was found to be 0.17 Ω.cm2 at 700°C and respective activation energy (Ea) 1.15 eV. It shows surface exchange at cathode interface, surface diffusion and self-diffusion happened through Ce0.85Sd0.15O1.95 (SDC15) electrolyte.

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.

Fundamental understanding of oxygen reduction and reaction behavior and developing high performance and stable hetero-structured cathodes

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

Liu, Xingbo

2016-11-14

New unique hetero-structured cathode has been developed in this project. La 2NiO 4+δ (LNO) as a surface catalyst with interstitial oxygen defects was introduced onto the state-of-the-art (La 0.6Sr 0.4) 0.95Co 0.2Fe 0.8O 3-δ (LSCF) cathode to enhance the surface-limited ORR kinetics on SOFC cathode. Furthermore, the hetero-structured cathode surface maintains high activity under electrode polarization with much less negative effects from surface cation segregation of Sr, which is known to cause degradation issues for conventional LSCF and LSC cathodes, thus improving the cathode long-term stability. The interface chemistry distribution and oxygen transport properties have been studied to prove themore » enhancement of power out and stability of LNO-infiltrated LSCF cathode. The further investigation demonstrates that CeO 2 & La 2-xNiO 4+δ (x=0-0.2) co-infiltration is a simple and cost-effective method to improve both performance and stability of LSCF cathode by limiting nano-particles growth/delamination and further improve the surface stability. For the first time, a physical model is proposed to illustrate how unique interstitial species on hetero-structured cathode surface work to regulate the exchange rate of the incorporation reaction. Meanwhile, fundamental investigation of the surface oxygen exchange and bulk oxygen transport properties under over-potential conditions across cathode materials have been carried out in this project, which were discussed and compared to the Nernst equation that is generally applied to treat any oxide electrodes under equilibrium.« less

Nanotechnology Enabled Hybrid Power System Suitable for Portable Telecommunications and Sensor Applications

DTIC Science & Technology

2010-12-01

and conventional Li-ion cells is the cathode material. Lithium iron phosphate ( LiFePO4 ) is a cathode material with many desirable characteristics: low... LiFePO4 , coated with conductive materials. The high surface area of the nanoparticles allows excellent interpenetration of the conductive materials...above--the A123 LiFePO4 -based nanoenabled battery, the Ioxus nanoenabled supercapacitor, and our custom-designed control circuit--were assembled into a

Cathodic Stripping Analysis Complicated by Adsorption Processes: Determination of 2-Thiouracil at a Rotating Silver Disk Electrode,

DTIC Science & Technology

1983-01-01

concentration, poten- tial sweep rate, rotation speed, deposition potential and other parameters -on the shape and height of the stripping peaks have...concentration, potential sweep rate, rotation speed, deposition potential and other parameters on the shape and height of the stripping peaks have been...of the greater surface area of a solid electrode compared to a dropping mercury electrode. Cathodic stripping voltametry at a rotating silver disk

N-type Cu2O doped activated carbon as catalyst for improving power generation of air cathode microbial fuel cells.

PubMed

Zhang, Xi; Li, Kexun; Yan, Pengyu; Liu, Ziqi; Pu, Liangtao

2015-01-01

A novel n-type Cu2O doped activated carbon (AC) air cathode (Cu/AC) was developed as an alternative to Pt electrode for oxygen reduction in microbial fuel cells (MFCs). The maximum power density of MFCs using this novel air cathode was as high as 1390±76mWm(-2), almost 59% higher than the bare AC air cathode. Specifically, the resistance including total resistance and charge transfer resistance significantly decreased comparing to the control. Tafel curve also showed the faster electro-transfer kinetics of Cu/AC with exchange current density of 1.03×10(-3)Acm(-2), which was 69% higher than the control. Ribbon-like Cu2O was deposited on the surface of AC with the mesopore surface area increasing. Cubic Cu2O crystals exclusively expose (111) planes with the interplanar crystal spacing of 2.48Å, which was the dominate active sites for oxygen reduction reaction (ORR). N-type Cu2O with oxygen vacancies played crucial roles in electrochemical catalytic activity. Copyright © 2015 Elsevier Ltd. All rights reserved.

Synthetic process for preparation of high surface area electroactive compounds for battery applications

DOEpatents

Evenson, Carl; Mackay, Richard

2013-07-23

A process is disclosed for the preparation of electroactive cathode compounds useful in lithium-ion batteries, comprising exothermic mixing of low-cost precursors and calcination under appropriate conditions. The exothermic step may be a spontaneous flameless combustion reaction. The disclosed process can be used to prepare any lithium metal phosphate or lithium mixed metal phosphate as a high surface area single phase compound.

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.

Mesoporous Li1.2Mn0.54Ni0.13Co0.13O2 nanotubes for high-performance cathodes in Li-ion batteries

NASA Astrophysics Data System (ADS)

Ma, Dingtao; Li, Yongliang; Zhang, Peixin; Cooper, Adam J.; Abdelkader, Amr M.; Ren, Xiangzhong; Deng, Libo

2016-04-01

One-dimensional nanotubes constructed from interconnected Li1.2Mn0.54Ni0.13Co0.13O2 secondary particles of diameters measuring ca. 40 nm, were synthesized by a one-pot electrospinning method. Novel electrodes were constructed from (a) nanoparticles only, and (b) hollow nanofibres, and employed as cathodes in Li-ion batteries. The nanotube cathode exhibited impressive specific charge capacity, good cycling stability, and excellent rate capability. A discharge capacity of 140 mAh g-1 with capacity retention of 89% at 3 C was achieved after 300 cycles. The significant improvement of electrochemical performance is attributed to the high surface area of the nanotubes, well-guided charge transfer kinetics with short ionic diffusion pathways, and large effective contact area with the electrolyte during the cycling process.

Pluronic F127 as auxiliary template for preparing nitrogen and oxygen dual doped mesoporous carbon cathode of lithium-oxygen batteries

NASA Astrophysics Data System (ADS)

Wu, Junwei; Liu, Yanchen; Cui, Yanhui; Ouyang, Jue; Baker, Andrew P.; Li, Zuohua; Zhang, Huayu

2018-02-01

Two mesoporous carbon foam (MCF) with nitrogen and oxygen dual doped are fabricated through facile templated hydrothermal process. One using fumed silica as single template is named S-MCF, and another using fumed silica and Pluronic F127 as double templates is named D-MCF. When using Pluronic F127 as an auxiliary template, the D-MCF shows different porous architecture and surface chemical nature from S-MCF, thus they behave differently as cathode materials in Li-O2 batteries. The D-MCF electrode exhibits a slight lower discharge capacity and an increased overpotential than that of S-SCF due to the decreased surface area and oxygen content. However, a better cycle stability was proved for the D-MCF electrode because of its higher nitrogen and lower oxygen content. When further composited with RuO2 nanoparticles, the RuO2/D-MCF cathode can operate 160 cycles with capacity cutoff of 500 mAh g-1, and this prolonged cycle life, compared to the 102 cycles of S-MCF cathode, verifies the superior electrochemical stability of D-MCF further and illuminates the crucial role of carbon substrate in the cathodes of Li-O2 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.

Characterization and performance of high power iron(VI) ferrate batteries

NASA Astrophysics Data System (ADS)

Walz, Kenneth A.; Suyama, Amy N.; Suyama, Wendy E.; Sene, Jeosadaque J.; Zeltner, Walter A.; Armacanqui, Edgar M.; Roszkowski, Andrew J.; Anderson, Marc A.

In this paper we report on the high power discharge performance and impedance characteristics of potassium ferrate (K 2FeO 4) and barium ferrate (BaFeO 4) cathodes in zinc alkaline dry cells. The results show that if ferrate materials can be packaged to maximize the cathode surface area, they may offer superior performance over electrolytic manganese dioxide at operating voltages exceeding 1.6 V and currents as high as 100 mA/g of active material.

Novel hierarchically porous carbon materials obtained from natural biopolymer as host matrixes for lithium-sulfur battery applications.

PubMed

Zhang, Bin; Xiao, Min; Wang, Shuanjin; Han, Dongmei; Song, Shuqin; Chen, Guohua; Meng, Yuezhong

2014-08-13

Novel hierarchically porous carbon materials with very high surface areas, large pore volumes and high electron conductivities were prepared from silk cocoon by carbonization with KOH activation. The prepared novel porous carbon-encapsulated sulfur composites were fabricated by a simple melting process and used as cathodes for lithium sulfur batteries. Because of the large surface area and hierarchically porous structure of the carbon material, soluble polysulfide intermediates can be trapped within the cathode and the volume expansion can be alleviated effectively. Moreover, the electron transport properties of the carbon materials can provide an electron conductive network and promote the utilization rate of sulfur in cathode. The prepared carbon-sulfur composite exhibited a high specific capacity and excellent cycle stability. The results show a high initial discharge capacity of 1443 mAh g(-1) and retain 804 mAh g(-1) after 80 discharge/charge cycles at a rate of 0.5 C. A Coulombic efficiency retained up to 92% after 80 cycles. The prepared hierarchically porous carbon materials were proven to be an effective host matrix for sulfur encapsulation to improve the sulfur utilization rate and restrain the dissolution of polysulfides into lithium-sulfur battery electrolytes.

The influence of cathode material on electrochemical degradation of trichloroethylene in aqueous solution.

PubMed

Rajic, Ljiljana; Fallahpour, Noushin; Podlaha, Elizabeth; Alshawabkeh, Akram

2016-03-01

In this study, different cathode materials were evaluated for electrochemical degradation of aqueous phase trichloroethylene (TCE). A cathode followed by an anode electrode sequence was used to support reduction of TCE at the cathode via hydrodechlorination (HDC). The performance of iron (Fe), copper (Cu), nickel (Ni), aluminum (Al) and carbon (C) foam cathodes was evaluated. We tested commercially available foam materials, which provide large electrode surface area and important properties for field application of the technology. Ni foam cathode produced the highest TCE removal (68.4%) due to its high electrocatalytic activity for hydrogen generation and promotion of HDC. Different performances of the cathode materials originate from differences in the bond strength between atomic hydrogen and the material. With a higher electrocatalytic activity than Ni, Pd catalyst (used as cathode coating) increased TCE removal from 43.5% to 99.8% for Fe, from 56.2% to 79.6% for Cu, from 68.4% to 78.4% for Ni, from 42.0% to 63.6% for Al and from 64.9% to 86.2% for C cathode. The performance of the palladized Fe foam cathode was tested for degradation of TCE in the presence of nitrates, as another commonly found groundwater species. TCE removal decreased from 99% to 41.2% in presence of 100 mg L(-1) of nitrates due to the competition with TCE for HDC at the cathode. The results indicate that the cathode material affects TCE removal rate while the Pd catalyst significantly enhances cathode activity to degrade TCE via HDC. Copyright © 2015 Elsevier Ltd. All rights reserved.

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.

Ab initio investigation of barium-scandium-oxygen coatings on tungsten for electron emitting cathodes

NASA Astrophysics Data System (ADS)

Vlahos, Vasilios; Booske, John H.; Morgan, Dane

2010-02-01

Microwave, x-ray, and radio-frequency radiation sources require a cathode emitting electrons into vacuum. Thermionic B-type dispenser cathodes consist of BaxOz coatings on tungsten (W), where the surface coatings lower the W work function and enhance electron emission. The new and promising class of scandate cathodes modifies the B-type surface through inclusion of Sc, and their superior emissive properties are also believed to stem from the formation of a low work function surface alloy. In order to better understand these cathode systems, density-functional theory (DFT)-based ab initio modeling is used to explore the stability and work function of BaxScyOz on W(001) monolayer-type surface structures. It is demonstrated how surface depolarization effects can be calculated easily using ab initio calculations and fitted to an analytic depolarization equation. This approach enables the rapid extraction of the complete depolarization curve (work function versus coverage relation) from relatively few DFT calculations, useful for understanding and characterizing the emitting properties of novel cathode materials. It is generally believed that the B-type cathode has some concentration of Ba-O dimers on the W surface, although their structure is not known. Calculations suggest that tilted Ba-O dimers are the stable dimer surface configuration and can explain the observed work function reduction corresponding to various dimer coverages. Tilted Ba-O dimers represent a new surface coating structure not previously proposed for the activated B-type cathode. The thermodynamically stable phase of Ba and O on the W surface was identified to be the Ba0.25O configuration, possessing a significantly lower Φ value than any of the Ba-O dimer configurations investigated. The identification of a more stable Ba0.25O phase implies that if Ba-O dimers cover the surface of emitting B-type cathodes, then a nonequilibrium steady state must dominate the emitting surface. The identification of a stable and low work function Ba0.25Sc0.25O structure suggests that addition of Sc to the B-type cathode surface could form this alloy structure under operating conditions, leading to improved cathode performance and stability. Detailed comparison to previous experimental results of BaxScyOz on W surface coatings are made to both validate the modeling and aid in interpretation of experimental data. The studies presented here demonstrate that ab initio methods are powerful for understanding the fundamental physics of electron emitting materials systems and can potentially aid in the development of improved cathodes.

Substantial Humic Acid Adsorption to Activated Carbon Air Cathodes Produces a Small Reduction in Catalytic Activity.

PubMed

Yang, Wulin; Watson, Valerie J; Logan, Bruce E

2016-08-16

Long-term operation of microbial fuel cells (MFCs) can result in substantial degradation of activated carbon (AC) air-cathode performance. To examine a possible role in fouling from organic matter in water, cathodes were exposed to high concentrations of humic acids (HA). Cathodes treated with 100 mg L(-1) HA exhibited no significant change in performance. Exposure to 1000 mg L(-1) HA decreased the maximum power density by 14% (from 1310 ± 30 mW m(-2) to 1130 ± 30 mW m(-2)). Pore blocking was the main mechanism as the total surface area of the AC decreased by 12%. Minimization of external mass transfer resistances using a rotating disk electrode exhibited only a 5% reduction in current, indicating about half the impact of HA adsorption was associated with external mass transfer resistance and the remainder was due to internal resistances. Rinsing the cathodes with deionized water did not restore cathode performance. These results demonstrated that HA could contribute to cathode fouling, but the extent of power reduction was relatively small in comparison to large mass of humics adsorbed. Other factors, such as biopolymer attachment, or salt precipitation, are therefore likely more important contributors to long-term fouling of MFC cathodes.

A two-stage series diode for intense large-area moderate pulsed X rays production.

PubMed

Lai, Dingguo; Qiu, Mengtong; Xu, Qifu; Su, Zhaofeng; Li, Mo; Ren, Shuqing; Huang, Zhongliang

2017-01-01

This paper presents a method for moderate pulsed X rays produced by a series diode, which can be driven by high voltage pulse to generate intense large-area uniform sub-100-keV X rays. A two stage series diode was designed for Flash-II accelerator and experimentally investigated. A compact support system of floating converter/cathode was invented, the extra cathode is floating electrically and mechanically, by withdrawing three support pins several milliseconds before a diode electrical pulse. A double ring cathode was developed to improve the surface electric field and emission stability. The cathode radii and diode separation gap were optimized to enhance the uniformity of X rays and coincidence of the two diode voltages based on the simulation and theoretical calculation. The experimental results show that the two stage series diode can work stably under 700 kV and 300 kA, the average energy of X rays is 86 keV, and the dose is about 296 rad(Si) over 615 cm 2 area with uniformity 2:1 at 5 cm from the last converter. Compared with the single diode, the average X rays' energy reduces from 132 keV to 88 keV, and the proportion of sub-100-keV photons increases from 39% to 69%.

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

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

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

2015-08-11

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

In-situ synthesis of 3D GA on titanium wire as a binder- free electrode for electro-Fenton removing of EDTA-Ni.

PubMed

Wen, Shulong; Niu, Zhuyu; Zhang, Zhen; Li, Lianghao; Chen, Yuancai

2018-01-05

Ethylenediaminetetraacetic acid (EDTA) could form stable complexes with toxic metals such as nickel due to its strong chelation. The three-dimensional (3D) macroporous graphene aerogels (GA), which was in-situ assembled by reduced graphene oxide (rGO) sheets on titanium wire as binder-free electrode, was presented as cathode for the degradation of EDTA-Ni in Electro-Fenton process. The X-ray diffraction (XRD), Scanning Electron Microscopy (SEM), Transmission Electron Microscope (TEM) and Brunauer-Emmett-Teller (BET) results indicated 3D GA formed three dimensional architecture with large and homogenous macropore structure and surface area. Cyclic Voltammetry (CV), Linear Sweep Voltammetry (LSV) and Rotating Ring-disk Electrode (RRDE) results showed that the 3D GA cathode at pH 3 displayed the highest current density and electrochemical active surface area (ECSA), and better two-electron selectivity for ORR than other pH value, confirming the 3D-GA cathode at pH 3 has the highest electrocatalytic activity and generates more H 2 O 2 . The factors such as pH, applied current density, concentration of Fe 2+ , Na 2 SO 4, and aeration rates of air were also investigated. Under the optimum conditions, 73.5% of EDTA-Ni was degraded after reaction for 2h. Mechanism analysis indicated that the production of OH on the 3D GA cathode played an important role in the removal of EDTA-Ni in the 3D GA-EF process, where the direct regeneration of Fe 2+ on the cathode would greatly reduce the consumption of H 2 O 2 . Therefore, it is of great promise for 3D-GA catalyst to be developed as highly efficient, cost-effective and durable cathode for the removal of EDTA-Ni. Copyright © 2017 Elsevier B.V. All rights reserved.

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.

Microbiologically Influenced Corrosion

DTIC Science & Technology

2009-01-01

related directly to the biomineralized deposits on the surface. Ennoble- ment in marine waters has been attributed to depolarization of the oxygen... abiotic ally oxi- dized metal precipitates, and still others that derive energy by oxidizing metals. Manganese. Manganese oxidation is coupled to cell...circumstances, pitting involves the conventional features of differential aeration, a large cathode: anode surface area, and the development of

Real-time thermal imaging of solid oxide fuel cell cathode activity in working condition.

PubMed

Montanini, Roberto; Quattrocchi, Antonino; Piccolo, Sebastiano A; Amato, Alessandra; Trocino, Stefano; Zignani, Sabrina C; Faro, Massimiliano Lo; Squadrito, Gaetano

2016-09-01

Electrochemical methods such as voltammetry and electrochemical impedance spectroscopy are effective for quantifying solid oxide fuel cell (SOFC) operational performance, but not for identifying and monitoring the chemical processes that occur on the electrodes' surface, which are thought to be strictly related to the SOFCs' efficiency. Because of their high operating temperature, mechanical failure or cathode delamination is a common shortcoming of SOFCs that severely affects their reliability. Infrared thermography may provide a powerful tool for probing in situ SOFC electrode processes and the materials' structural integrity, but, due to the typical design of pellet-type cells, a complete optical access to the electrode surface is usually prevented. In this paper, a specially designed SOFC is introduced, which allows temperature distribution to be measured over all the cathode area while still preserving the electrochemical performance of the device. Infrared images recorded under different working conditions are then processed by means of a dedicated image processing algorithm for quantitative data analysis. Results reported in the paper highlight the effectiveness of infrared thermal imaging in detecting the onset of cell failure during normal operation and in monitoring cathode activity when the cell is fed with different types of fuels.

Electrowinning of U-Pu onto inert solid cathode in LiCl-KCl eutectic melts containing UCl3 and PuCl3

NASA Astrophysics Data System (ADS)

Sakamura, Yoshiharu; Murakami, Tsuyoshi; Tada, Kohei; Kitawaki, Shinichi

2018-04-01

Electrowinning process was investigated for extracting actinides from molten salts used for the pyrochemical reprocessing of spent nuclear fuels. The separation of actinides from lanthanides is expected to be enhanced by employing inert solid cathodes due to larger potential differences on these cathodes. In this study, the co-deposition behavior of Pu and U metals onto an inert solid cathode made of tungsten was examined in LiCl-KCl eutectic melts containing UCl3 and PuCl3 at 773 K. The standard potential of U3+/U is 0.31 V more positive than that of Pu3+/Pu. The U3+ concentration was varied in the range of 0.11-0.66 wt%, while the Pu3+ concentration was maintained at approximately 2.9 wt%. When the U3+ concentration was not sufficiently low, the deposited U metal readily grew outward from the electrode surface and the electrode surface area rapidly increased, which facilitated only the deposition of U metal. It was estimated that metallic Pu can be efficiently collected along with U at U3+ concentrations lower than ∼0.2 wt%.

Amorphous layer formation in Al86.0Co7.6Ce6.4 glass-forming alloy by large-area electron beam irradiation

NASA Astrophysics Data System (ADS)

Li, C. L.; Murray, J. W.; Voisey, K. T.; Clare, A. T.; McCartney, D. G.

2013-09-01

Amorphous Al-Co-Ce alloys are of interest because of their resistance to corrosion, but high cooling rates are generally required to suppress the formation of crystalline phases. In this study, the surface of a bulk crystalline Al-Co-Ce alloy of a glass-forming composition was treated using large area electron beam (LAEB) irradiation. Scanning electron microscopy shows that, compared to the microstructure of the original crystalline material, the treated surface exhibits greatly improved microstructural and compositional uniformity. Glancing angle X-ray diffraction conducted on the surface of treated samples indicates the formation of the amorphous phase following 25 and 50 pulses at 35 kV cathode voltage. However, when the samples are treated with 100 and 150 pulses at 35 kV cathode voltage of electron beam irradiation, the treated layer comprises localised crystalline regions in an amorphous matrix. In addition, the formation of cracks in the treated layer is found to be localised around the Al8Co2Ce phase in the bulk material. Overall, crack length per unit area had no clear change with an increase in the number of pulses.

Electrolytic Cell For Production Of Aluminum Employing Planar Anodes.

DOEpatents

Barnett, Robert J.; Mezner, Michael B.; Bradford, Donald R

2004-10-05

A method of producing aluminum in an electrolytic cell containing alumina dissolved in an electrolyte, the method comprising providing a molten salt electrolyte having alumina dissolved therein in an electrolytic cell. A plurality of anodes and cathodes having planar surfaces are disposed in a generally vertical orientation in the electrolyte, the anodes and cathodes arranged in alternating or interleaving relationship to provide anode planar surfaces disposed opposite cathode planar surfaces, the anode comprised of carbon. Electric current is passed through anodes and through the electrolyte to the cathodes depositing aluminum at the cathodes and forming carbon containing gas at the anodes.

Sintered wire cathode

DOEpatents

Falce, Louis R [San Jose, CA; Ives, R Lawrence [Saratoga, CA

2009-06-09

A porous cathode structure is fabricated from a plurality of wires which are placed in proximity to each other in elevated temperature and pressure for a sintering time. The sintering process produces the porous cathode structure which may be divided into a plurality of individual porous cathodes, one of which may be placed into a dispenser cathode support which includes a cavity for containing a work function reduction material such as BaO, CaO, and Al.sub.2O.sub.3. The work function reduction material migrates through the pores of the porous cathode from a work replenishment surface adjacent to the cavity of the dispenser cathode support to an emitting cathode surface, thereby providing a dispenser cathode which has a uniform work function and therefore a uniform electron emission.

Long-term performance of activated carbon air cathodes with different diffusion layer porosities in microbial fuel cells.

PubMed

Zhang, Fang; Pant, Deepak; Logan, Bruce E

2011-12-15

Activated carbon (AC) air-cathodes are inexpensive and useful alternatives to Pt-catalyzed electrodes in microbial fuel cells (MFCs), but information is needed on their long-term stability for oxygen reduction. AC cathodes were constructed with diffusion layers (DLs) with two different porosities (30% and 70%) to evaluate the effects of increased oxygen transfer on power. The 70% DL cathode initially produced a maximum power density of 1214±123 mW/m(2) (cathode projected surface area; 35±4 W/m(3) based on liquid volume), but it decreased by 40% after 1 year to 734±18 mW/m(2). The 30% DL cathode initially produced less power than the 70% DL cathode, but it only decreased by 22% after 1 year (from 1014±2 mW/m(2) to 789±68 mW/m(2)). Electrochemical tests were used to examine the reasons for the degraded performance. Diffusion resistance in the cathode was found to be the primary component of the internal resistance, and it increased over time. Replacing the cathode after 1 year completely restored the original power densities. These results suggest that the degradation in cathode performance was due to clogging of the AC micropores. These findings show that AC is a cost-effective material for oxygen reduction that can still produce ~750 mW/m(2) after 1 year. Copyright © 2011 Elsevier B.V. All rights reserved.

Silver Vanadium Phosphorous Oxide, Ag(2)VO(2)PO(4): Chimie Douce Preparation and Resulting Lithium Cell Electrochemistry.

PubMed

Kim, Young Jin; Marschilok, Amy C; Takeuchi, Kenneth J; Takeuchi, Esther S

2011-08-15

Recently, we have shown silver vanadium phosphorous oxide (Ag(2)VO(2)PO(4), SVPO) to be a promising cathode material for lithium based batteries. Whereas the first reported preparation of SVPO employed an elevated pressure, hydrothermal approach, we report herein a novel ambient pressure synthesis method to prepare SVPO, where our chimie douce preparation is readily scalable and provides material with a smaller, more consistent particle size and higher surface area relative to SVPO prepared via the hydrothermal method. Lithium electrochemical cells utilizing SVPO cathodes made by our new process show improved power capability under constant current and pulse conditions over cells containing cathode from SVPO prepared via the hydrothermal method.

Advanced oxidation of biorefractory organics in aqueous solution together with bioelectricity generation by microbial fuel cells with composite FO/GPEs

NASA Astrophysics Data System (ADS)

Fu, Bao-rong; Shen, Chao; Ren, Jing; Chen, Jia-yi; Zhao, Lin

2018-03-01

In this study, ferric oxide loading graphite particle electrodes (FO/GPEs) were prepared as cathode of a three-dimensional electrode MFC-Fenton system. The properties of the composite cathode were examined with higher surface area and more mesopores. FO/GPEs could work as both cathode and Fenton iron reagents, contributing to high oxidation activity and better performance of electricity generation. The application of FO/GPEs MFC-Fenton system on degrading p-nitrophenol presented high catalytic efficiency in a wide range of pH value. The removal of p-nitrophenol and TOC attained to about 85 % within 8 and 64 h at neutral pH, respectively. A neutral FO/GPEs MFC-Fenton oxidation mechanism was also proposed. Specifically, both the surface iron sites and dissolved iron ions catalyzed the decomposition of H2O2. As results, the generated hydroxyl radicals were used for p-nitrophenol degradation and the iron oxide was recycled.

Surface studies of thermionic cathodes and the mechanism of operation of an impregnated tungsten cathode

NASA Technical Reports Server (NTRS)

Forman, R.

1976-01-01

The surface properties of conventional impregnated cathodes were investigated by the use of Auger spectroscopy and work function measurements, and these were compared with a synthesized barium or barium oxide coated tungsten surface. The barium and barium oxide coated surfaces were prepared by evaporating barium onto a tungsten surface that can be heated to elevated temperatures. Multilayer or monolayer coverages can be investigated using this technique. The results of this study show that the surface of an impregnated tungsten cathode is identical to that observed for a synthesized monolayer or partial monolayer of barium on partially oxidized tungsten, using the criteria of identical Auger patterns and work functions. Desorption measurements of barium from a tungsten surface were also made. These results in conjunction with Auger and work function data were interpreted to show that throughout most of its life an impregnated cathode operating in the range of 1100 C has a partial monolayer rather than a monolayer of barium on its surface.

Fuel cell plates with skewed process channels for uniform distribution of stack compression load

DOEpatents

Granata, Jr., Samuel J.; Woodle, Boyd M.

1989-01-01

An electrochemical fuel cell includes an anode electrode, a cathode electrode, an electrolyte matrix sandwiched between electrodes, and a pair of plates above and below the electrodes. The plate above the electrodes has a lower surface with a first group of process gas flow channels formed thereon and the plate below the electrodes has an upper surface with a second group of process gas flow channels formed thereon. The channels of each group extend generally parallel to one another. The improvement comprises the process gas flow channels on the lower surface of the plate above the anode electrode and the process gas flow channels on the upper surface of the plate below the cathode electrode being skewed in opposite directions such that contact areas of the surfaces of the plates through the electrodes are formed in crisscross arrangements. Also, the plates have at least one groove in areas of the surfaces thereof where the channels are absent for holding process gas and increasing electrochemical activity of the fuel cell. The groove in each plate surface intersects with the process channels therein. Also, the opposite surfaces of a bipolar plate for a fuel cell contain first and second arrangements of process gas flow channels in the respective surfaces which are skewed the same amount in opposite directions relative to the longitudinal centerline of the plate.

Electromagnetic radiation detector

DOEpatents

Benson, Jay L.; Hansen, Gordon J.

1976-01-01

An electromagnetic radiation detector including a collimating window, a cathode member having a photoelectric emissive material surface angularly disposed to said window whereby radiation is impinged thereon at acute angles, an anode, separated from the cathode member by an evacuated space, for collecting photoelectrons emitted from the emissive cathode surface, and a negatively biased, high transmissive grid disposed between the cathode member and anode.

Microanalysis of extended-test xenon hollow cathodes

NASA Technical Reports Server (NTRS)

Verhey, Timothy R.; Patterson, Michael J.

1991-01-01

Four hollow cathode electron sources were analyzed via boroscopy, scanning electron microscopy, energy dispersive x ray analysis, and x ray diffraction analysis. These techniques were used to develop a preliminary understanding of the chemistry of the devices that arise from contamination due to inadequate feed-system integrity and improper insert activation. Two hollow cathodes were operated in an ion thruster simulator at an emission current of 23.0 A for approximately 500 hrs. The two tests differed in propellant-feed systems, discharge power supplies, and activation procedures. Tungsten deposition and barium tungstate formation on the internal cathode surfaces occurred during the first test, which were believed to result from oxygen contamination of the propellant feed-system. Consequently, the test facility was upgraded to reduce contamination, and the test was repeated. The second hollow cathode was found to have experienced significantly less tungsten deposition. A second pair of cathodes examined were the discharge and the neutralizer hollow cathodes used in a life-test of a 30-cm ring-cusp ion thruster at a 5.5 kW power level. The cathodes' test history was documented and the post-test microanalyses are described. The most significant change resulting from the life-test was substantial tungsten deposition on the internal cathode surfaces, as well as removal of material from the insert surface. In addition, barium tungstate and molybdate were found on insert surfaces. As a result of the cathode examinations, procedures and approaches were proposed for improved discharge ignition and cathode longevity.

Laboratory Studies and Preliminary Evaluation of Destructive Technologies for the Removal of RDX from the Water Waste Stream of Holston Army Ammunition Plan

DTIC Science & Technology

2010-05-01

with electrode plates . ERDC/EL TR-10-4 29 Total Electrode Surface Area = 0.4311 m² Cathodic Surface Area = 0.2156 m² Reactor Volume = 1632 mL 35...27 Figure 15. Continuous flow electrochemical reactor packed with electrode plates . .......................... 28 Figure...Environmental Compliance (TDEC) is in the process of establishing a total maximum daily load (TMDL) that will regulate the mass of hexahydro- 1,3,5

Simulation of cathode spot crater formation and development on CuCr alloy in vacuum arc

NASA Astrophysics Data System (ADS)

Wang, Lijun; Zhang, Xiao; Wang, Yuan; Yang, Ze; Jia, Shenli

2018-04-01

The two-dimensional (2D) rotary axisymmetric model is used to describe the formation and development of a cathode spot on a copper-chromium alloy (CuCr) in a vacuum arc. The model includes hydrodynamic equations and the heat transfer equation. Parameters used in this model come from experiments and other researchers' work. The influence of parameters is analyzed, and the simulation results are compared with pure metal simulation results. In simulation, the depth of the cathode crater is from 0.5 μm to 1.1 μm, the radius of the cathode crater is from 1.6 μm to 2.6 μm, the maximum velocity of the droplet is from 200 m/s to 600 m/s, and the maximum temperature is from 3500 K to 5000 K which is located in the area with a radius of 0.5-1.5 μm. The simulation results show that a smooth cathode surface is advantageous for reducing ablation, the ablation on the CuCr alloy is smaller than that on the pure metal cathode electrode, and the cathode spot appears on the chromium grain only on CuCr. The simulation results are in good agreement with the experiment.

Image intensifier gain uniformity improvements in sealed tubes by selective scrubbing

DOEpatents

Thomas, S.W.

1995-04-18

The gain uniformity of sealed microchannel plate image intensifiers (MCPIs) is improved by selectively scrubbing the high gain sections with a controlled bright light source. Using the premise that ions returning to the cathode from the microchannel plate (MCP) damage the cathode and reduce its sensitivity, a HeNe laser beam light source is raster scanned across the cathode of a microchannel plate image intensifier (MCPI) tube. Cathode current is monitored and when it exceeds a preset threshold, the sweep rate is decreased 1000 times, giving 1000 times the exposure to cathode areas with sensitivity greater than the threshold. The threshold is set at the cathode current corresponding to the lowest sensitivity in the active cathode area so that sensitivity of the entire cathode is reduced to this level. This process reduces tube gain by between 10% and 30% in the high gain areas while gain reduction in low gain areas is negligible. 4 figs.

Image intensifier gain uniformity improvements in sealed tubes by selective scrubbing

DOEpatents

Thomas, Stanley W.

1995-01-01

The gain uniformity of sealed microchannel plate image intensifiers (MCPIs) is improved by selectively scrubbing the high gain sections with a controlled bright light source. Using the premise that ions returning to the cathode from the microchannel plate (MCP) damage the cathode and reduce its sensitivity, a HeNe laser beam light source is raster scanned across the cathode of a microchannel plate image intensifier (MCPI) tube. Cathode current is monitored and when it exceeds a preset threshold, the sweep rate is decreased 1000 times, giving 1000 times the exposure to cathode areas with sensitivity greater than the threshold. The threshold is set at the cathode current corresponding to the lowest sensitivity in the active cathode area so that sensitivity of the entire cathode is reduced to this level. This process reduces tube gain by between 10% and 30% in the high gain areas while gain reduction in low gain areas is negligible.

Cathodic current enhancement via manganese and oxygen related reactions in marine biofilms

NASA Astrophysics Data System (ADS)

Strom, Matthew James

Corrosion is a threat that has economic, and environmental impacts worldwide. Many types of corrosive attack are the subject of ongoing research. One of these areas of research is microbiologically influenced corrosion, which is the enhancement and/or initiation of corrosion events caused by microorganisms. It is well known that colonies of microorganisms can enhance cathodic currents through biofilm formation. The aim of the present work was to elucidate the role of manganese in enhancing cathodic currents in the presence of biofilms. Repeated polarizations conducted in Delaware Bay waters, on biofilm coated Cr identified potentially sustainable reduction reactions. The reduction of MnO2 and the enhancement of the oxygen reduction reaction (ORR) were proven to be factors that influence cathodic current enhancement. The removal of ambient oxygen during polarizations resulted in a shutdown of cathodic current enhancement. These field data led to an exploration of the synergistic relationship between MnO2 and the ORR. Laboratory studies of the catalysis of peroxide disproportionation by MnO2 were monitored using a hanging mercury drop electrode. Experiments were run at an ambient sweater pH of 8 and pH 9, which simulated the near-surface conditions typical of cathodes immersed in seawater. Rapid reoxidation at the more basic pH was shown to allow manganese to behave as a persistent catalyst under the typical electrochemical surface conditions of a cathode. As a result a mechanism for ORR enhancement by manganese was proposed as a unique mechanism for cathodic current enhancement in biofilms. A separate field study of Delaware biofilms on stainless steel coupled to a sacrificial Al anode was carried out to identify the ORR enhancement mechanism and sustainable redox reactions at the cathode. Chemical treatments of glutaraldehyde and formaldoxime were applied to cathodes with biofilms to distinguish between enzymatic and MnO2 related ORR enhancement. The results ruled out the enzymatic catalysis of ORR and supported the catalysis by MnO2. Sustainable redox reactions at the cathode were evaluated by monitoring the cathodic current of biofilm coated stainless steel for a year under different polarization intensities. The results showed that sustainable cathodic reactions were present in marine biofilms but their influence on the cathodic current was negligible until a potential was reached where the ORR could take place. Additionally seasonal variability was observed in the enhanced cathodic current in Delaware Bay biofilms. This was attributed to the seasonal variability of manganese in the water column.

Polyaniline/β-MnO2 nanocomposites as cathode electrocatalyst for oxygen reduction reaction in microbial fuel cells.

PubMed

Zhou, Xinxing; Xu, Yunzhi; Mei, Xiaojie; Du, Ningjie; Jv, Rongmao; Hu, Zhaoxia; Chen, Shouwen

2018-05-01

An efficient and inexpensive catalyst for oxygen reduction reaction (ORR), polyaniline (PANI) and β-MnO 2 nanocomposites (PANI/β-MnO 2 ), was developed for air-cathode microbial fuel cells (MFCs). The PANI/β-MnO 2 , β-MnO 2 , PANI and β-MnO 2 mixture modified graphite felt electrodes were fabricated as air-cathodes in double-chambered MFCs and their cell performances were compared. At a dosage of 6 mg cm -2 , the maximum power densities of MFCs with PANI/β-MnO 2 , β-MnO 2 , PANI and β-MnO 2 mixture cathodes reached 248, 183 and 204 mW m -2 , respectively, while the cathode resistances were 38.4, 45.5 and 42.3 Ω, respectively, according to impedance analysis. Weak interaction existed between the rod-like β-MnO 2 and surficial growth granular PANI, this together with the larger specific surface area and PANI electric conducting nature enhanced the electrochemical activity for ORR and improved the power generation. The PANI/β-MnO 2 nanocomposites are a promising cathode catalyst for practical application of MFCs. Copyright © 2018. Published by Elsevier Ltd.

Enhanced Hydrogen Evolution Reactions on Nanostructured Cu2ZnSnS4 (CZTS) Electrocatalyst

NASA Astrophysics Data System (ADS)

Digraskar, Renuka V.; Mulik, Balaji B.; Walke, Pravin S.; Ghule, Anil V.; Sathe, Bhaskar R.

2017-08-01

A novel and facile one-step sonochemical method is used to synthesize Cu2ZnSnS4 (CZTS) nanoparticles (2.6 ± 0.4 nm) as cathode electrocatalyst for hydrogen evolution reactions. The detailed morphology, crystal and surface structure, and composition of the CZTS nanostructures were characterized by high resolution transmission electron microscopy (HR-TEM), Selected area electron diffraction (SAED), X-ray diffraction, Raman spectroscopy, FTIR analysis, Brunauer-Emmett-Teller (BET) surface area measurements, Electron dispersive analysis, X-ray photoelectron spectroscopy respectively. Electrocatalytic abilities of the nanoparticles toward Hydrogen Evolution Reactions (HER) were verified through cyclic voltammograms (CV) and Linear sweep voltammetry (LSV), electrochemical impedance spectroscopy (EIS), and Tafel polarization measurements. It reveals enhanced activity at lower onset potential 300 mV v/s RHE, achieved at exceptionally high current density -130 mA/cm2, which is higher than the existing non-nobel metal based cathodes. Further result exhibits Tafel slope of 85 mV/dec, exchange current density of 882 mA/cm2, excellent stability (> 500 cycles) and lower charge transfer resistance. This sonochemically fabricated CZTSs nanoparticles are leading to significantly reduce cell cost and simplification of preparation process over existing high efficiency Pt and other nobel metal-free cathode electrocatalyst.

Electrorefining cell with parallel electrode/concentric cylinder cathode

DOEpatents

Gay, Eddie C.; Miller, William E.; Laidler, James J.

1997-01-01

A cathode-anode arrangement for use in an electrolytic cell is adapted for electrochemically refining spent nuclear fuel from a nuclear reactor and recovering purified uranium for further treatment and possible recycling as a fresh blanket or core fuel in a nuclear reactor. The arrangement includes a plurality of inner anodic dissolution baskets that are each attached to a respective support rod, are submerged in a molten lithium halide salt, and are rotationally displaced. An inner hollow cylindrical-shaped cathode is concentrically disposed about the inner anodic dissolution baskets. Concentrically disposed about the inner cathode in a spaced manner are a plurality of outer anodic dissolution baskets, while an outer hollow cylindrical-shaped is disposed about the outer anodic dissolution baskets. Uranium is transported from the anode baskets and deposited in a uniform cylindrical shape on the inner and outer cathode cylinders by rotating the anode baskets within the molten lithium halide salt. Scrapers located on each anode basket abrade and remove the spent fuel deposits on the surfaces of the inner and outer cathode cylinders, with the spent fuel falling to the bottom of the cell for removal. Cell resistance is reduced and uranium deposition rate enhanced by increasing the electrode area and reducing the anode-cathode spacing. Collection efficiency is enhanced by trapping and recovery of uranium dendrites scrapped off of the cylindrical cathodes which may be greater in number than two.

Electrorefining cell with parallel electrode/concentric cylinder cathode

DOEpatents

Gay, E.C.; Miller, W.E.; Laidler, J.J.

1997-07-22

A cathode-anode arrangement for use in an electrolytic cell is adapted for electrochemically refining spent nuclear fuel from a nuclear reactor and recovering purified uranium for further treatment and possible recycling as a fresh blanket or core fuel in a nuclear reactor. The arrangement includes a plurality of inner anodic dissolution baskets that are each attached to a respective support rod, are submerged in a molten lithium halide salt, and are rotationally displaced. An inner hollow cylindrical-shaped cathode is concentrically disposed about the inner anodic dissolution baskets. Concentrically disposed about the inner cathode in a spaced manner are a plurality of outer anodic dissolution baskets, while an outer hollow cylindrical-shaped is disposed about the outer anodic dissolution baskets. Uranium is transported from the anode baskets and deposited in a uniform cylindrical shape on the inner and outer cathode cylinders by rotating the anode baskets within the molten lithium halide salt. Scrapers located on each anode basket abrade and remove the spent fuel deposits on the surfaces of the inner and outer cathode cylinders, with the spent fuel falling to the bottom of the cell for removal. Cell resistance is reduced and uranium deposition rate enhanced by increasing the electrode area and reducing the anode-cathode spacing. Collection efficiency is enhanced by trapping and recovery of uranium dendrites scrapped off of the cylindrical cathodes which may be greater in number than two. 12 figs.

Microstructure control of SOFC cathode material: The role of dispersing agent

NASA Astrophysics Data System (ADS)

Ismail, Ismariza; Jani, Abdul Mutalib Md; Osman, Nafisah

2017-09-01

In the present works, La0.6Sr0.4Co0.2Fe0.8O3-δ (LSCF) cathode powders were synthesized by a sol-gel method with the aid of ethylene glycol which served as the dispersing agent. The phase formation and morphology of the powders were examined by X-Ray diffractometer (XRD) and field emission scanning electron microscopy (FESEM), respectively. The electrochemical properties of the synthesized cathode were obtained using an electrochemical impedance spectroscopy (EIS). The characteristic peaks for LSCF phase appears in the X-ray diffractogram after calcined at 500 °C and complete formation of LSCF single phase was attained at 700 °C. FESEM micrographs showed the presence of spherical particles of the powders with approximate particle size between 10 to 60 nm along with agglomerate morphologies. Well dispersed particles and fewer aggregates were observed for samples prepared with addition of ethylene glycol as the synthesizing aid. The surface area obtained for powder sample prepared with the aid of dispersing agent is 12.0 m2g-1. The EIS measurement results depicts a lower area specific resistance (ASR) obtained for sample prepared with addition of the ethylene glycol as compared to the pristine sample. The present results encourage the optimization of the cathode particle design in order to further improve the cathode performance.

Nanosized LiFePO4-decorated emulsion-templated carbon foam for 3D micro batteries: a study of structure and electrochemical performance

NASA Astrophysics Data System (ADS)

Asfaw, Habtom D.; Roberts, Matthew R.; Tai, Cheuk-Wai; Younesi, Reza; Valvo, Mario; Nyholm, Leif; Edström, Kristina

2014-07-01

In this article, we report a novel 3D composite cathode fabricated from LiFePO4 nanoparticles deposited conformally on emulsion-templated carbon foam by a sol-gel method. The carbon foam is synthesized via a facile and scalable method which involves the carbonization of a high internal phase emulsion (polyHIPE) polymer template. Various techniques (XRD, SEM, TEM and electrochemical methods) are used to fully characterize the porous electrode and confirm the distribution and morphology of the cathode active material. The major benefits of the carbon foam used in our work are closely connected with its high surface area and the plenty of space suitable for sequential coating with battery components. After coating with a cathode material (LiFePO4 nanoparticles), the 3D electrode presents a hierarchically structured electrode in which a porous layer of the cathode material is deposited on the rigid and bicontinuous carbon foam. The composite electrodes exhibit impressive cyclability and rate performance at different current densities affirming their importance as viable power sources in miniature devices. Footprint area capacities of 1.72 mA h cm-2 at 0.1 mA cm-2 (lowest rate) and 1.1 mA h cm-2 at 6 mA cm-2 (highest rate) are obtained when the cells are cycled in the range 2.8 to 4.0 V vs. lithium.In this article, we report a novel 3D composite cathode fabricated from LiFePO4 nanoparticles deposited conformally on emulsion-templated carbon foam by a sol-gel method. The carbon foam is synthesized via a facile and scalable method which involves the carbonization of a high internal phase emulsion (polyHIPE) polymer template. Various techniques (XRD, SEM, TEM and electrochemical methods) are used to fully characterize the porous electrode and confirm the distribution and morphology of the cathode active material. The major benefits of the carbon foam used in our work are closely connected with its high surface area and the plenty of space suitable for sequential coating with battery components. After coating with a cathode material (LiFePO4 nanoparticles), the 3D electrode presents a hierarchically structured electrode in which a porous layer of the cathode material is deposited on the rigid and bicontinuous carbon foam. The composite electrodes exhibit impressive cyclability and rate performance at different current densities affirming their importance as viable power sources in miniature devices. Footprint area capacities of 1.72 mA h cm-2 at 0.1 mA cm-2 (lowest rate) and 1.1 mA h cm-2 at 6 mA cm-2 (highest rate) are obtained when the cells are cycled in the range 2.8 to 4.0 V vs. lithium. Electronic supplementary information (ESI) available. See DOI: 10.1039/c4nr01682c

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

Linking Initial Microstructure to ORR Related Property Degradation in SOFC Cathode: A Phase Field Simulation

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

Lei, Y.; Cheng, T. -L.; Wen, Y. H.

Microstructure evolution driven by thermal coarsening is an important factor for the loss of oxygen reduction reaction rates in SOFC cathode. In this work, the effect of an initial microstructure on the microstructure evolution in SOFC cathode is investigated using a recently developed phase field model. Specifically, we tune the phase fraction, the average grain size, the standard deviation of the grain size and the grain shape in the initial microstructure, and explore their effect on the evolution of the grain size, the density of triple phase boundary, the specific surface area and the effective conductivity in LSM-YSZ cathodes. Itmore » is found that the degradation rate of TPB density and SSA of LSM is lower with less LSM phase fraction (with constant porosity assumed) and greater average grain size, while the degradation rate of effective conductivity can also be tuned by adjusting the standard deviation of grain size distribution and grain aspect ratio. The implication of this study on the designing of an optimal initial microstructure of SOFC cathodes is discussed.« less

Linking Initial Microstructure to ORR Related Property Degradation in SOFC Cathode: A Phase Field Simulation

DOE PAGES

Lei, Y.; Cheng, T. -L.; Wen, Y. H.

2017-07-05

Microstructure evolution driven by thermal coarsening is an important factor for the loss of oxygen reduction reaction rates in SOFC cathode. In this work, the effect of an initial microstructure on the microstructure evolution in SOFC cathode is investigated using a recently developed phase field model. Specifically, we tune the phase fraction, the average grain size, the standard deviation of the grain size and the grain shape in the initial microstructure, and explore their effect on the evolution of the grain size, the density of triple phase boundary, the specific surface area and the effective conductivity in LSM-YSZ cathodes. Itmore » is found that the degradation rate of TPB density and SSA of LSM is lower with less LSM phase fraction (with constant porosity assumed) and greater average grain size, while the degradation rate of effective conductivity can also be tuned by adjusting the standard deviation of grain size distribution and grain aspect ratio. The implication of this study on the designing of an optimal initial microstructure of SOFC cathodes is discussed.« less

A niobium and tantalum co-doped perovskite cathode for solid oxide fuel cells operating below 500 °C

PubMed Central

Li, Mengran; Zhao, Mingwen; Li, Feng; Zhou, Wei; Peterson, Vanessa K.; Xu, Xiaoyong; Shao, Zongping; Gentle, Ian; Zhu, Zhonghua

2017-01-01

The slow activity of cathode materials is one of the most significant barriers to realizing the operation of solid oxide fuel cells below 500 °C. Here we report a niobium and tantalum co-substituted perovskite SrCo0.8Nb0.1Ta0.1O3−δ as a cathode, which exhibits high electroactivity. This cathode has an area-specific polarization resistance as low as ∼0.16 and ∼0.68 Ω cm2 in a symmetrical cell and peak power densities of 1.2 and 0.7 W cm−2 in a Gd0.1Ce0.9O1.95-based anode-supported fuel cell at 500 and 450 °C, respectively. The high performance is attributed to an optimal balance of oxygen vacancies, ionic mobility and surface electron transfer as promoted by the synergistic effects of the niobium and tantalum. This work also points to an effective strategy in the design of cathodes for low-temperature solid oxide fuel cells. PMID:28045088

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.

Oxygen transport in the internal xenon plasma of a dispenser hollow cathode

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

Capece, Angela M., E-mail: acapece@pppl.gov; Shepherd, Joseph E.; Polk, James E.

2014-04-21

Reactive gases such as oxygen and water vapor modify the surface morphology of BaO dispenser cathodes and degrade the electron emission properties. For vacuum cathodes operating at fixed temperature, the emission current drops rapidly when oxygen adsorbs on top of the low work function surface. Previous experiments have shown that plasma cathodes are more resistant to oxygen poisoning and can operate with O{sub 2} partial pressures one to two orders of magnitude higher than vacuum cathodes before the onset of poisoning occurs. Plasma cathodes used for electric thrusters are typically operated with xenon; however, gas phase barium, oxygen, and tungstenmore » species may be found in small concentrations. The densities of these minor species are small compared with the plasma density, and thus, their presence in the discharge does not significantly alter the xenon plasma parameters. It is important, however, to consider the transport of these minor species as they may deposit on the emitter surface and affect the electron emission properties. In this work, we present the results of a material transport model used to predict oxygen fluxes to the cathode surface by solving the species conservation equations in a cathode with a 2.25 mm diameter orifice operated at a discharge current of 15 A, a Xe flow rate of 3.7 sccm, and 100 ppm of O{sub 2}. The dominant ionization process for O{sub 2} is resonant charge exchange with xenon ions. Ba is effectively recycled in the plasma; however, BaO and O{sub 2} are not. The model shows that the oxygen flux to the surface is not diffusion-limited; therefore, the high resistance to oxygen poisoning observed in plasma cathodes likely results from surface processes not considered here.« less

Insights into the role of wettability in cathode catalyst layer of proton exchange membrane fuel cell; pore scale immiscible flow and transport processes

NASA Astrophysics Data System (ADS)

Fathi, H.; Raoof, A.; Mansouri, S. H.

2017-05-01

The production of liquid water in cathode catalyst layer, CCL, is a significant barrier to increase the efficiency of proton exchange membrane fuel cell. Here we present, for the first time, a direct three-dimensional pore-scale modelling to look at the complex immiscible two-phase flow in CCL. After production of the liquid water at the surface of CCL agglomerates due to the electrochemical reactions, water spatial distribution affects transport of oxygen through the CCL as well as the rate of reaction at the agglomerate surfaces. To explore the wettability effects, we apply hydrophilic and hydrophobic properties using different surface contact angles. Effective diffusivity is calculated under several water saturation levels. Results indicate larger diffusive transport values for hydrophilic domain compared to the hydrophobic media where the liquid water preferentially floods the larger pores. However, hydrophobic domain showed more available surface area and higher oxygen consumption rate at the reaction sites under various saturation levels, which is explained by the effect of wettability on pore-scale distribution of water. Hydrophobic domain, with a contact angle of 150, reveals efficient water removal where only 28% of the pore space stays saturated. This condition contributes to the enhanced available reaction surface area and oxygen diffusivity.

Novel Approach to Strengthening Ceramic Cathode Contact and Validation in a Generic Stack Test Fixture

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

Chou, Yeong-Shyung; Bonnett, Jeff F.; Stevenson, Jeffry W.

The ceramic contact material at the cathode side has been identified as the weakest mechanical link in solid oxide fuel cells, due to poor sintering at low stack fabrication temperatures. In this work, a novel approach of mechanical interlocking with an engineered surface was proposed to strengthen LSM-type contacts. The engineered cathode surface was made by depositing large LSM20 granules onto a wet cathode print, followed by sintering. Granules of three sizes were tested (mesh #35, #60, and #100). Small coupons of anode-supported YSZ electrolyte with LSM cathode were joined at 850 and 950oC for 2h with LSM contact usingmore » either the engineered surface or plain surfaces. The results of contact strength measurements showed about 14 times increase with engineered surface compared to plain surfaces. Validation with a 2”x2” LSM-based cell in a generic stack fixture showed good thermal cycle stability with minimal change in ohmic impedance over ten cycles.« less

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.

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

Planar fuel cell utilizing nail current collectors for increased active surface area

DOEpatents

George, Thomas J.; Meacham, G. B. Kirby

2002-03-26

A plurality of nail current collector members are useful in the gas flow passages of an electrochemical device to optimize the active surfaces of the device and to provide structural support. In addition, the thicknesses of cathode and anode layers within the electrochemical device are varied according to current flow through the device to reduce resistance and increase operating efficiency.

Planar fuel cell utilizing nail current collectors for increased active surface area

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

George, Thomas J.; Meacham, G.B. Kirby

1999-11-26

A plurality of nail current collector members are useful in the gas flow passages of an electrochemical device to optimize the active surfaces of the device and to provide structural support. In addition, the thicknesses of cathode and anode layers within the electrochemical device are varied according to current flow through the device to reduce resistance and increase operating efficiency.

Fabrication and electrochemical properties of hemisphere structured 3D Li(Li0.2Mn0.54Co0.13Ni0.13)O2 cathode thin film for all-solid-state lithium battery.

PubMed

Yim, H; Kong, W Y; Yoon, S J; Kim, Y C; Choi, J W

2013-05-01

The Li[Li0.2Mn0.54Ni0.13Co0.13]O2 cathode thin films were deposited on planar, hemisphere, linked hemisphere, and isolated hemisphere structured Pt current collector thin films to investigate the effect of 3-dimensional (3-D) structure for the electrochemical properties of active cathode thin films. The films of linked hemisphere structure shows the highest initial discharge capacity of 140 microA h/cm2-microm which is better than those of planar (62 microA h/cm2-microm), hemisphere (94.6 microA h/cm2-microm), and isolated hemisphere (135 microA h/cm2-microm) films due to increase of surface area for cathode thin films. Linked hemisphere shows the biggest capacity and the best retention rate because 6 nanobridges of each hemisphere bring strong connection.

Performance and Structural Evolution of Nano-Scale Infiltrated Solid Oxide Fuel Cell Cathodes

NASA Astrophysics Data System (ADS)

Call, Ann Virginia

Nano-structured mixed ionic and electronic conducting (MIEC) materials have garnered intense interest in electrode development for solid oxide fuel cells due to their high surface areas which allow for effective catalytic activity and low polarization resistances. In particular, composite solid oxide fuel cell (SOFC) cathodes consisting of ionic conducting scaffolds infiltrated with MIEC nanoparticles have exhibited some of the lowest reported polarization resistances. In order for cells utilizing nanostructured moRPhologies to be viable for commercial implementation, more information on their initial performance and long term stability is necessary. In this study, symmetric cell cathodes were prepared via wet infiltration of Sr0.5Sm 0.5CoO3 (SSC) nano-particles via a nitrate process into porous Ce0.9Gd0.1O1.95 (GDC) scaffolds to be used as a model system to investigate performance and structural evolution. Detailed analysis of the cells and cathodes was carried out using electrochemical impedance spectroscopy (EIS). Initial polarization resistances (RP) as low as 0.11 O cm2 at 600ºC were obtained for these SSC-GDC cathodes, making them an ideal candidate for studying high performance nano-structured electrodes. The present results show that the infiltrated cathode microstructure has a direct impact on the initial performance of the cell. Small initial particle sizes and high infiltration loadings (up to 30 vol% SSC) improved initial RP. A simple microstructure-based electrochemical model successfully explained these trends in RP. Further understanding of electrode performance was gleaned from fitting EIS data gathered under varying temperatures and oxygen partial pressures to equivalent circuit models. Both RQ and Gerischer impedance elements provided good fits to the main response in the EIS data, which was associated with the combination of oxygen surface exchange and oxygen diffusion in the electrode. A gas diffusion response was also observed at relatively low pO2. The cells were subjected to life testing at temperatures between 650°C and 800°C for as long as 1500 h. EIS measurements, carried out periodically during the life tests, were done in air at 600°C, a typical expected intermediate-temperature SOFC operating temperature. These were accelerated tests because the aging temperatures > 600ºC should accelerate most degradation processes such as nano-particle coarsening. Long-term RP versus time data was fitted to a combined surface resistance and coarsening kinetics model, and a t0.25 power law coarsening model was found to provide the best fits to the data, suggesting that surface diffusion is the dominant mass transport pathway in SSC-GDC infiltrated cathodes. That is, cathode degradation was due primarily to the coarsening-induced decrease in active SSC surface area. Scanning electron microscopy (SEM) performed after electrochemical life testing confirmed the extent of coarsening of the SSC nanoparticles. The model is used to make predictions regarding long-term stability of infiltrated SSC electrodes, and is also compared with prior results on a similar perovskite MIEC electrode, LSCF. An important new finding is that increasing infiltration loadings yields a marked decrease in the long term degradation rate. Predictions based on accelerated life tests found the lowest possible operating temperature while achieving a degradation rate of 0.5% per kh is 595°C, corresponding to an initial particle size of 40 nm.

Effect of paraelectrode processes on contraction of space charge in periodic-pulse lasers

NASA Astrophysics Data System (ADS)

Arytyunyan, R. V.; Baranov, V. Yu.; Borisov, V. M.; Vinokhodov, A. Yu.; Kiryukhin, Yu. B.

1986-05-01

A characteristic feature of periodic-pulse electric-discharge CO2-lasers and excimer lasers is contraction of the space charge as the pulse repetition rate increases. The emission energy per pulse decreases as a consequence, with the average laser power first ceasing to increase linearly beyond a certain corner repetition rate and then decreasing beyond a certain critical repetition rate. A study of this phenomenon was made, for the purpose of separating the effect of paracathode processes from the effect of gas dynamics and then evaluating the effect of the former alone. Paraelectrode perturbations were simulated by focusing the radiation from the an XeCl-laser on the cathode surface in an atmosphere of nonabsorbing gases. Laser pulses of up to approximately 0.5 J energy and of approximately 50 ns duration were focused within a spot of 1 mm(2) area on a cathode inside a discharge chamber, with the power density of incident radiation regulated by means of an attenuator. A space charge within a volume of 2.5x4.5x9 cm(3) was generated between this specially shaped cathode and a mesh anode with an approximately 50% optical transmission coefficient. The space charge in helium and in neon was photographed, and the time lag of a discharge pulse behind a contracting laser pulse was measured as a function of the laser pulse energy for these two gases, as well as for a He+C12 gas mixture. The general trend was found to be the same in each case, the time lag increasing with increasing energy first at a slower rate up to a critical energy level and then faster. It has been established that plasma does not build up on the cathode before the laser pulse energy reaches 30 mJ (for a 3 mm(2) surface area), while plasma glow begins as the laser pulse energy reaches 150 mJ. A contracted channel begins to form within the laser-cathode interaction space, with an attendant fast increase of the time lag owing to evaporation of the cathode metal.

Initial Plasma Testing of the Ion Proportional Surface Emission Cathode

DTIC Science & Technology

2008-07-15

REPRINT 3. DATES COVERED (From - To) 4. TITLE AND SUBTITLE Initial Plasma Testing of the Ion Proportional Surface Emission Cathode 5a. CONTRACT NUMBER...substrate and an adjacent metal cathode element. The substrate potential is held positive of the cathode with gate elements. In plasma , the gate is...eliminated due to ambient ion flux which maintains the substrate potential near plasma ground. Prototype devices have been tested using a laboratory plasma

Amplified cathodic electrochemiluminescence of luminol based on Pd and Pt nanoparticles and glucose oxidase decorated graphene as trace label for ultrasensitive detection of protein.

PubMed

Cao, Yaling; Yuan, Ruo; Chai, Yaqin; Liu, Huijing; Liao, Yuhong; Zhuo, Ying

2013-09-15

An ultrasensitive electrochemiluminescence (ECL) immunosensor was constructed for ultrasensitive detection of carcinoembryonic antigen (CEA) based on an amplified cathodic ECL of luminol at low potential. Firstly, Au nanoparticles (AuNPs) were electrodeposited onto single walled carbon nanotube-graphene composites (CNTs-Gra) coated glass carbon electrode (GCE) with enhanced surface area and good biocompatibility to capture primary antibody (Ab1) and then bind the antigen analytes. Secondly, Pd and Pt nanoparticles (Pd&PtNPs) decorated reduced graphene oxide (Pd&PtNPs@rGO) and glucose oxidase (GOD) labeled secondary antibody (Pd&PtNPs@ rGO-GOD-Ab2) could be captured onto the electrode surface by a sandwich immunoassay protocol to generate amplified cathodic ECL signals of luminol in the presence of glucose. The Pd&PtNPs@rGO composites and loaded GOD promoted luminol cathodic ECL response by efficiently catalyzing glucose to in-situ produce amount of hydrogen peroxide (H2O2) working as a coreactant of luminol. Then in turn Pd&PtNPs catalyzed H2O2 to generate various reactive oxygen species (ROSs), which accelerated the cathodic ECL reaction of luminol, enhanced the cathodic ECL intensity of luminol and improved the sensitivity of the immunosensor. The as-proposed ECL immunosensor exhibited sensitive response on the detection of CEA ranging from 0.0001 ng mL(-1) to 160 ng mL(-1) with a detection limit of 0.03 pg mL(-1) (S/N=3). Moreover, the stability, specificity, lifetime and reproducibility tests demonstrated the feasibility of the developed immunoassay, which can be further extended to the detection of other disease biomarkers. Copyright © 2013 Elsevier B.V. All rights reserved.

Understanding local degradation of cycled Ni-rich cathode materials at high operating temperature for Li-ion batteries

NASA Astrophysics Data System (ADS)

Hwang, Sooyeon; Kim, Dong Hyun; Chung, Kyung Yoon; Chang, Wonyoung

2014-09-01

We utilize transmission electron microscopy in conjunction with electron energy loss spectroscopy to investigate local degradation that occurs in LixNi0.8Co0.15Al0.05O2 cathode materials (NCA) after 30 cycles with cutoff voltages of 4.3 V and 4.8 V at 55 °C. NCA has a homogeneous crystallographic structure before electrochemical reactions; however, we observed that 30 cycles of charge/discharge reactions induced inhomogeneity in the crystallographic and electronic structures and also introduced porosity particularly at surface area. These changes were more noticeable in samples cycled with higher cutoff voltage of 4.8 V. Effect of operating temperature was further examined by comparing electronic structures of oxygen of the NCA particles cycled at both room temperature and 55 °C. The working temperature has a greater impact on the NCA cathode materials at a cutoff voltage of 4.3 V that is the practical the upper limit voltage in most applications, while a cutoff voltage of 4.8 V is high enough to cause surface degradation even at room temperature.

Thin film rechargeable electrodes based on conductive blends of nanostructured olivine LiFePO4 and sucrose derived nanocarbons for lithium ion batteries.

PubMed

Praveen, P; Jyothsna, U; Nair, Priya; Ravi, Soumya; Balakrishnan, A; Subramanian, K R V; Nair, A Sreekumaran; Nair, V Shantikumar; Sivakumar, N

2013-08-01

The present study provides the first reports of a novel approach of electrophoretic co-deposition technique by which titanium foils are coated with LiFePO4-carbon nanocomposites synthesized by sol gel route and processed into high-surface area cathodes for lithium ion batteries. The study elucidates how sucrose additions as carbon source can affect the surface morphology and the redox reaction behaviors underlying these cathodes and thereby enhance the battery performance. The phase and morphological analysis were done using XRD and XPS where the LiFePO4 formed was confirmed to be a high purity orthorhombic system. From the analysis of the relevant electrochemical parameters using cyclic voltammetry and electrochemical impedance spectroscopy, a 20% increment and 90% decrement in capacity and impedance values were observed respectively. The composite electrodes also exhibited a specific capacity of 130 mA h/g. It has been shown that cathodes based on such composite systems can allow significant room for improvement in the cycling performance at the electrode/electrolyte interface.

Fluorinated reduced graphene oxide as a protective layer on the metallic lithium for application in the high energy batteries.

PubMed

Bobnar, Jernej; Lozinšek, Matic; Kapun, Gregor; Njel, Christian; Dedryvère, Rémi; Genorio, Boštjan; Dominko, Robert

2018-04-11

Metallic lithium is considered to be one of the most promising anode materials since it offers high volumetric and gravimetric energy densities when combined with high-voltage or high-capacity cathodes. However, the main impediment to the practical applications of metallic lithium is its unstable solid electrolyte interface (SEI), which results in constant lithium consumption for the formation of fresh SEI, together with lithium dendritic growth during electrochemical cycling. Here we present the electrochemical performance of a fluorinated reduced graphene oxide interlayer (FGI) on the metallic lithium surface, tested in lithium symmetrical cells and in combination with two different cathode materials. The FGI on the metallic lithium exhibit two roles, firstly it acts as a Li-ion conductive layer and electronic insulator and secondly, it effectively suppresses the formation of high surface area lithium (HSAL). An enhanced electrochemical performance of the full cell battery system with two different types of cathodes was shown in the carbonate or in the ether based electrolytes. The presented results indicate a potential application in future secondary Li-metal batteries.

Advanced cathode materials for polymer electrolyte fuel cells based on pt/ metal oxides: from model electrodes to catalyst systems.

PubMed

Fabbri, Emiliana; Pătru, Alexandra; Rabis, Annett; Kötz, Rüdiger; Schmidt, Thomas J

2014-01-01

The development of stable catalyst systems for application at the cathode side of polymer electrolyte fuel cells (PEFCs) requires the substitution of the state-of-the-art carbon supports with materials showing high corrosion resistance in a strongly oxidizing environment. Metal oxides in their highest oxidation state can represent viable support materials for the next generation PEFC cathodes. In the present work a multilevel approach has been adopted to investigate the kinetics and the activity of Pt nanoparticles supported on SnO2-based metal oxides. Particularly, model electrodes made of SnO2 thin films supporting Pt nanoparticles, and porous catalyst systems made of Pt nanoparticles supported on Sb-doped SnO2 high surface area powders have been investigated. The present results indicate that SnO2-based supports do not modify the oxygen reduction reaction mechanism on the Pt nanoparticle surface, but rather lead to catalysts with enhanced specific activity compared to Pt/carbon systems. Different reasons for the enhancement in the specific activity are considered and discussed.

Co-Flow Hollow Cathode Technology

NASA Technical Reports Server (NTRS)

Hofer, Richard R.; Goebel, Dan M.

2011-01-01

Hall thrusters utilize identical hollow cathode technology as ion thrusters, yet must operate at much higher mass flow rates in order to efficiently couple to the bulk plasma discharge. Higher flow rates are necessary in order to provide enough neutral collisions to transport electrons across magnetic fields so that they can reach the discharge. This higher flow rate, however, has potential life-limiting implications for the operation of the cathode. A solution to the problem involves splitting the mass flow into the hollow cathode into two streams, the internal and external flows. The internal flow is fixed and set such that the neutral pressure in the cathode allows for a high utilization of the emitter surface area. The external flow is variable depending on the flow rate through the anode of the Hall thruster, but also has a minimum in order to suppress high-energy ion generation. In the co-flow hollow cathode, the cathode assembly is mounted on thruster centerline, inside the inner magnetic core of the thruster. An annular gas plenum is placed at the base of the cathode and propellant is fed throughout to produce an azimuthally symmetric flow of gas that evenly expands around the cathode keeper. This configuration maximizes propellant utilization and is not subject to erosion processes. External gas feeds have been considered in the past for ion thruster applications, but usually in the context of eliminating high energy ion production. This approach is adapted specifically for the Hall thruster and exploits the geometry of a Hall thruster to feed and focus the external flow without introducing significant new complexity to the thruster design.

Surface studies of barium and barium oxide on tungsten and its application to understanding the mechanism of operation of an impregnated tungsten cathode

NASA Technical Reports Server (NTRS)

Forman, R.

1976-01-01

Surface studies have been made of multilayer and monolayer films of barium and barium oxide on a tungsten substrate. The purpose of the investigation was to synthesize the surface conditions that exist on an activated impregnated tungsten cathode and obtain a better understanding of the mechanism of operation of such cathodes. The techniques employed in these measurements were Auger spectroscopy and work-function measurements. The results of this study show that the surface of an impregnated cathode is identical to that observed for a synthesized monolayer or partial monolayer of barium on oxidized tungsten by evaluating Auger spectra and work-function measurements. Data obtained from desorption studies of barium monolayers on a tungsten substrate in conjunction with Auger and work-function results have been interpreted to show that throughout most of its life an impreganated cathode has a partial monolayer, rather than a monolayer, of barium on its surface.

The effect of surface-bulk potential difference on the kinetics of intercalation in core-shell active cathode particles

NASA Astrophysics Data System (ADS)

Kazemiabnavi, Saeed; Malik, Rahul; Orvananos, Bernardo; Abdellahi, Aziz; Ceder, Gerbrand; Thornton, Katsuyo

2018-04-01

Surface modification of active cathode particles is commonly observed in battery research as either a surface phase evolving during the cycling process, or intentionally engineered to improve capacity retention, rate capability, and/or thermal stability of the cathode material. Here, a continuum-scale model is developed to simulate the galvanostatic charge/discharge of a cathode particle with core-shell heterostructure. The particle is assumed to be comprised of a core material encapsulated by a thin layer of a second phase that has a different open-circuit voltage. The effect of the potential difference between the surface and bulk phases (Ω) on the kinetics of lithium intercalation and the galvanostatic charge/discharge profiles is studied at different values of Ω, C-rates, and exchange current densities. The difference between the Li chemical potential in the surface and bulk phases of the cathode particle results in a concentration difference between these two phases. This leads to a charge/discharge asymmetry in the galvanostatic voltage profiles, causing a decrease in the accessible capacity of the particle. These effects are more significant at higher magnitudes of surface-bulk potential difference. The proposed model provides detailed insight into the kinetics and voltage behavior of the intercalation/de-intercalation processes in core-shell heterostructure cathode particles.

In Situ observation of dark current emission in a high gradient rf photocathode gun

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

Shao, Jiahang; Shi, Jiaru; Antipov, Sergey P.

Undesirable electron field emission (also known as dark current) in high gradient rf photocathode guns deteriorates the quality of the photoemission current and limits the operational gradient. To improve the understanding of dark current emission, a high-resolution (~100 μm) dark current imaging experiment has been performed in an L-band photocathode gun operating at ~100 MV/m of surface gradient. Scattered strong emission areas with high current have been observed on the cathode. The field enhancement factor β of selected regions on the cathode has been measured. Finally, the postexaminations with scanning electron microscopy and white light interferometry reveal the origins ofmore » ~75% strong emission areas overlap with the spots where rf breakdown has occurred.« less

In Situ observation of dark current emission in a high gradient rf photocathode gun

DOE PAGES

Shao, Jiahang; Shi, Jiaru; Antipov, Sergey P.; ...

2016-08-15

Undesirable electron field emission (also known as dark current) in high gradient rf photocathode guns deteriorates the quality of the photoemission current and limits the operational gradient. To improve the understanding of dark current emission, a high-resolution (~100 μm) dark current imaging experiment has been performed in an L-band photocathode gun operating at ~100 MV/m of surface gradient. Scattered strong emission areas with high current have been observed on the cathode. The field enhancement factor β of selected regions on the cathode has been measured. Finally, the postexaminations with scanning electron microscopy and white light interferometry reveal the origins ofmore » ~75% strong emission areas overlap with the spots where rf breakdown has occurred.« less

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

PubMed

Jadhav, G S; Ghangrekar, M M

2008-12-01

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

Controllable embedding of sulfur in high surface area nitrogen doped three dimensional reduced graphene oxide by solution drop impregnation method for high performance lithium-sulfur batteries

NASA Astrophysics Data System (ADS)

Zegeye, Tilahun Awoke; Tsai, Meng-Che; Cheng, Ju-Hsiang; Lin, Ming-Hsien; Chen, Hung-Ming; Rick, John; Su, Wei-Nien; Kuo, Chung-Feng Jeffrey; Hwang, Bing-Joe

2017-06-01

High capacity lithium-sulfur batteries with stable cycle performance and sulfur loadings greater than 70 wt% are regarded as promising candidates for energy storage devices. However, it has been challenged to achieving practical application of sulfur cathode because of low loading of active sulfur and poor cycle performance. Herein, we design novel nanocomposite cathode materials consist of sulfur (80 wt%) embedded within nitrogen doped three-dimensional reduced graphene oxide (N-3D-rGO) by controllable sulfur-impregnation method. Nitrogen doping helps increase the surface area by ten times from pristine graphene, and pore volume by seven times. These structural features allow the cathode to hold more sulfur. It also adsorbs polysulfides and prevents their detachment from the host materials; thereby achieving stable cycle performance. The solution drop sulfur-impregnation method provides uniform distribution of nano-sulfur in controlled manner. The material delivers a high initial discharge capacity of 1042 mAhg-1 and 916 mAhg-1 with excellent capacity retention of 94.8% and 81.9% at 0.2 C and 0.5 C respectively after 100 cycles. Thus, the combination of solution drop and nitrogen doping opens a new chapter for resolving capacity fading as well as long cycling problems and creates a new strategy to increase sulfur loading in controlled mechanism.

Modelling potential/current distribution in microbial electrochemical systems shows how the optimal bioanode architecture depends on electrolyte conductivity.

PubMed

Lacroix, Rémy; Da Silva, Serge; Gaig, Monica Viaplana; Rousseau, Raphael; Délia, Marie-Line; Bergel, Alain

2014-11-07

The theoretical bases for modelling the distribution of the electrostatic potential in microbial electrochemical systems are described. The secondary potential distribution (i.e. without mass transport limitation of the substrate) is shown to be sufficient to validly address microbial electrolysis cells (MECs). MECs are modelled with two different ionic conductivities of the solution (1 and 5.3 S m(-1)) and two bioanode kinetics (jmax = 5.8 or 34 A m(-2)). A conventional reactor configuration, with the anode and the cathode face to face, is compared with a configuration where the bioanode perpendicular to the cathode implements the electrochemical reaction on its two sides. The low solution conductivity is shown to have a crucial impact, which cancels out the advantages obtained by setting the bioanode perpendicular to the cathode. For the same reason, when the surface area of the anode is increased by multiplying the number of plates, care must be taken not to create too dense anode architecture. Actually, the advantages of increasing the surface area by multiplying the number of plates can be lost through worsening of the electrochemical conditions in the multi-layered anode, because of the increase of the electrostatic potential of the solution inside the anode structure. The model gives the first theoretical bases for scaling up MECs in a rather simple but rigorous way.

Porous nitrogen-doped carbon nanosheet on graphene as metal-free catalyst for oxygen reduction reaction in air-cathode microbial fuel cells.

PubMed

Wen, Qing; Wang, Shaoyun; Yan, Jun; Cong, Lijie; Chen, Ye; Xi, Hongyuan

2014-02-01

Porous nitrogen-doped carbon nanosheet on graphene (PNCN) was used as an alternative cathode catalyst for oxygen reduction reaction (ORR) in air-cathode microbial fuel cells (MFCs). Here we report a novel, low-cost, scalable, synthetic method for preparation of PNCN via the carbonization of graphite oxide-polyaniline hybrid (GO-PANI), subsequently followed by KOH activation treatment. Due to its high concentration of nitrogen and high specific surface area, PNCN exhibited an excellent catalytic activity for ORR. As a result, the maximum power density of 1159.34mWm(-2) obtained with PNCN catalyst was higher than that of Pt/C catalyst (858.49mWm(-2)) in a MFC. Therefore, porous nitrogen-doped carbon nanosheet could be a good alternative to Pt catalyst in MFCs. © 2013.

High-energy detector

DOEpatents

Bolotnikov, Aleksey E [South Setauket, NY; Camarda, Giuseppe [Farmingville, NY; Cui, Yonggang [Upton, NY; James, Ralph B [Ridge, NY

2011-11-22

The preferred embodiments are directed to a high-energy detector that is electrically shielded using an anode, a cathode, and a conducting shield to substantially reduce or eliminate electrically unshielded area. The anode and the cathode are disposed at opposite ends of the detector and the conducting shield substantially surrounds at least a portion of the longitudinal surface of the detector. The conducting shield extends longitudinally to the anode end of the detector and substantially surrounds at least a portion of the detector. Signals read from one or more of the anode, cathode, and conducting shield can be used to determine the number of electrons that are liberated as a result of high-energy particles impinge on the detector. A correction technique can be implemented to correct for liberated electron that become trapped to improve the energy resolution of the high-energy detectors disclosed herein.

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

Influence of propellant choice on MPD arcjet cathode surface current density distribution

NASA Astrophysics Data System (ADS)

Sheshadri, T. S.

1989-10-01

The radial current density on an MPD arcjet cathode surface is theoretically investigated for five propellants. It is found that excessive current concentration at the upstream end of the cathode occurs in the case of hydrogen. This undesirable effect is traced to the higher electrical conductivity of hydrogen plasma.

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.

Multifunctional Composite Nanofibers for Smart Structures

DTIC Science & Technology

2011-10-13

low cost. It is coated onto the surface of CNF to use as a supercapacitor cathode. The high porosity and surface area of nanofiber composite...SiNP fusion, pulverization, and capacity loss can be minimized during electrochemical cycling. Carbon is also ductile in absorbing the mechanical...b) Figure 2 Core-shell CNF/Si composite with a thin layer of carbon shell coating on SiNP (a) and the capacity of both

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

Highly ordered and ultra-long carbon nanotube arrays as air cathodes for high-energy-efficiency Li-oxygen batteries

NASA Astrophysics Data System (ADS)

Yu, Ruimin; Fan, Wugang; Guo, Xiangxin; Dong, Shaoming

2016-02-01

Carbonaceous air cathodes with rational architecture are vital for the nonaqueous Li-O2 batteries to achieve large energy density, high energy efficiency and long cycle life. In this work, we report the cathodes made of highly ordered and vertically aligned carbon nanotubes grown on permeable Ta foil substrates (VACNTs-Ta) via thermal chemical vapour deposition. The VACNTs-Ta, composed of uniform carbon nanotubes with approximately 240 μm in superficial height, has the super large surface area. Meanwhile, the oriented carbon nanotubes provide extremely outstanding passageways for Li ions and oxygen species. Electrochemistry tests of VACNTs-Ta air cathodes show enhancement in discharge capacity and cycle life compared to those made from short-range oriented and disordered carbon nanotubes. By further combining with the LiI redox mediator that is dissolved in the tetraethylene dimethyl glycol based electrolytes, the batteries exhibit more than 200 cycles at the current density of 200 mA g-1 with a cut-off discharge capacity of 1000 mAh g-1, and their energy efficiencies increase from 50% to 82%. The results here demonstrate the importance of cathode construction for high-energy-efficiency and long-life Li-O2 batteries.

Turning Waste Chemicals into Wealth-A New Approach To Synthesize Efficient Cathode Material for an Li-O2 Battery.

PubMed

Yao, Ying; Wu, Feng

2017-09-20

An Li-O 2 battery requires the oxygen-breathing cathode to be highly electronically conductive, rapidly oxygen diffusive, structurally stable, and often times electrocatalytically active. Catalyst-decorated porous carbonaceous materials are the chosen air cathode in this regard. Alternatively, biomass-derived carbonaceous materials possess great ability to remove heavy and toxic metal ions from waste, forming a metal-adsorbed porous carbonaceous material. The similar structure between the air cathode and the metal-adsorbed biomass-derived carbon nicely bridges these two irrelevant areas. In this study, we investigated the electrochemical activity of a biochar material Ag-ESB directly synthesized from ethanol sludge residue in a rechargeable aprotic Li-O 2 battery. Ag ions were adsorbed from sewage and became Ag nanoparticles with uniform coverage on the biochar surface. The as-prepared material exhibits good electrochemical behavior in battery testing, especially toward the battery efficiency and cyclability. This study provides the possibility of synthetically efficient cathode material by reusing "waste" such as biofuel sludge residue. It is an economically and environmentally friendly approach both for an energy-storage system and for waste recycling.

Turning Waste Chemicals into Wealth—A New Approach To Synthesize Efficient Cathode Material for an Li–O 2 Battery

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

Yao, Ying; Wu, Feng

An Li–O 2 battery requires the oxygen-breathing cathode to be highly electronically conductive, rapidly oxygen diffusive, structurally stable, and often times electrocatalytically active. Catalyst-decorated porous carbonaceous materials are the chosen air cathode in this regard. Alternatively, biomass-derived carbonaceous materials possess great ability to remove heavy and toxic metal ions from waste, forming a metal-adsorbed porous carbonaceous material. The similar structure between the air cathode and the metal-adsorbed biomass-derived carbon nicely bridges these two irrelevant areas. In this study, we investigated the electrochemical activity of a biochar material Ag-ESB directly synthesized from ethanol sludge residue in a rechargeable aprotic Li–O 2more » battery. Ag ions were adsorbed from sewage and became Ag nanoparticles with uniform coverage on the biochar surface. The as-prepared material exhibits good electrochemical behavior in battery testing, especially toward the battery efficiency and cyclability. This study provides the possibility of synthetically efficient cathode material by reusing “waste” such as biofuel sludge residue. It is an economically and environmentally friendly approach both for an energy-storage system and for waste recycling.« 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

Anode initiated surface flashover switch

DOEpatents

Brainard, John P.; Koss, Robert J.

2003-04-29

A high voltage surface flashover switch has a pair of electrodes spaced by an insulator. A high voltage is applied to an anode, which is smaller than the opposing, grounded, cathode. When a controllable source of electrons near the cathode is energized, the electrons are attracted to the anode where they reflect to the insulator and initiate anode to cathode breakdown.

Structure and hemocompatibility of nanocrystalline titanium nitride produced under glow-discharge conditions

NASA Astrophysics Data System (ADS)

Sowińska, Agnieszka; Czarnowska, Elżbieta; Tarnowski, Michał; Witkowska, Justyna; Wierzchoń, Tadeusz

2018-04-01

Significant efforts are being made towards developing novel antithrombotic materials. The purpose of the presented study was to characterize two variants of nitrided surface layers produced on alloy Ti-6Al-4V in different areas of low-temperature plasma - at the plasma potential (TiNp) or at the cathode potential (TiNc). The layers were characterized in terms of their microstructure, surface topography and wettability, and platelet response to the environment of different pH. The produced layers were of the TiN + Ti2N + αTiN-type, but the layer produced at the plasma potential was thinner, smoother and had lower surface free energy compared with that produced at the cathode potential. Biological evaluation demonstrated more fibrinogen buildup, less platelet adhesion and aggregation, and fewer strongly activated platelets on the TiNp surface compared with those parameters on the TiNc surface and on the titanium alloy in its initial state. Interestingly, both surface types were significantly resistant to fibrinogen adsorption and platelet adhesion in the environment of lower pH. In conclusion, the nitrided surface layer produced at the plasma potential is a promising material and this basic information is critical for further development of hemocompatible materials.

Diagnostics of cathode material loss in cutting plasma torch

NASA Astrophysics Data System (ADS)

Gruber, J.; Šonský, J.; Hlína, J.

2014-07-01

A cutting plasma torch was observed in several ways by a high-speed camera with a focus on the cathode area. In the first experiment, the plasma arc between the nozzle tip and anode was recorded in a series of duty cycles ranging from new unworn cathodes to cathode failure due to wear and material loss. In the second experiment, we used a specially modified nozzle to observe the inside area between the cathode and the nozzle exit through a fused silica window. Finally, using tilted view, we observed a pool of molten hafnium at the cathode tip during the plasma torch operation. The process of cathode material melting, droplet formation, their expulsion and rate of cathode material loss was examined.

Nano-scale investigations of electric-dipole-layer enhanced field and thermionic emission from high current density cathodes

NASA Astrophysics Data System (ADS)

Vlahos, Vasilios

Cesium iodide coated graphitic fibers and scandate cathodes are two important electron emission technologies. The coated fibers are utilized as field emitters for high power microwave sources. The scandate cathodes are promising thermionic cathode materials for pulsed power vacuum electron devices. This work attempts to understand the fundamental physical and chemical relationships between the atomic structure of the emitting cathode surfaces and the superior emission characteristics of these cathodes. Ab initio computational modeling in conjunction with experimental investigations was performed on coated fiber cathodes to understand the origin of their very low turn on electric field, which can be reduced by as much as ten-fold compared to uncoated fibers. Copious amounts of cesium and oxygen were found co-localized on the fiber, but no iodine was detected on the surface. Additional ab initio studies confirmed that cesium oxide dimers could lower the work function significantly. Surface cesium oxide dipoles are therefore proposed as the source of the observed reduction in the turn on electric field. It is also proposed that emission may be further enhanced by secondary electrons from cesium oxide during operation. Thermal conditioning of the coated cathode may be a mechanism by which surface cesium iodide is converted into cesium oxide, promoting the depletion of iodine by formation of volatile gas. Ab initio modeling was also utilized to investigate the stability and work functions of scandate structures. The work demonstrated that monolayer barium-scandium-oxygen surface structures on tungsten can dramatically lower the work function of the underlying tungsten substrate from 4.6 eV down to 1.16 eV, by the formation of multiple surface dipoles. On the basis of this work, we conclude that high temperature kinetics force conventional dispenser cathodes (barium-oxygen monolayers on tungsten) to operate in a non-equilibrium compositional steady state with higher than optimal work functions of ˜2 eV. We hypothesize that scandium enables the barium-oxygen surface monolayer kinetics to access a more thermodynamically stable phase with reported work functions as low as ˜1.3 eV.

Electricity generation from real industrial wastewater using a single-chamber air cathode microbial fuel cell with an activated carbon anode.

PubMed

Mohamed, Hend Omar; Obaid, M; Sayed, Enas Taha; Liu, Yang; Lee, Jinpyo; Park, Mira; Barakat, Nasser A M; Kim, Hak Yong

2017-08-01

This study introduces activated carbon (AC) as an effective anode for microbial fuel cells (MFCs) using real industrial wastewater without treatment or addition of external microorganism mediators. Inexpensive activated carbon is introduced as a proper electrode alternative to carbon cloth and carbon paper materials, which are considered too expensive for the large-scale application of MFCs. AC has a porous interconnected structure with a high bio-available surface area. The large surface area, in addition to the high macro porosity, facilitates the high performance by reducing electron transfer resistance. Extensive characterization, including surface morphology, material chemistry, surface area, mechanical strength and biofilm adhesion, was conducted to confirm the effectiveness of the AC material as an anode in MFCs. The electrochemical performance of AC was also compared to other anodes, i.e., Teflon-treated carbon cloth (CCT), Teflon-treated carbon paper (CPT), untreated carbon cloth (CC) and untreated carbon paper (CP). Initial tests of a single air-cathode MFC display a current density of 1792 mAm -2 , which is approximately four times greater than the maximum value of the other anode materials. COD analyses and Coulombic efficiency (CE) measurements for AC-MFC show the greatest removal of organic compounds and the highest CE efficiency (60 and 71%, respectively). Overall, this study shows a new economical technique for power generation from real industrial wastewater with no treatment and using inexpensive electrode materials.

Durable electrocatalytic-activity of Pt-Au/C cathode in PEMFCs.

PubMed

Selvaganesh, S Vinod; Selvarani, G; Sridhar, P; Pitchumani, S; Shukla, A K

2011-07-21

Longevity remains as one of the central issues in the successful commercialization of polymer electrolyte membrane fuel cells (PEMFCs) and primarily hinges on the durability of the cathode. Incorporation of gold (Au) to platinum (Pt) is known to ameliorate both the electrocatalytic activity and stability of cathode in relation to pristine Pt-cathodes that are currently being used in PEMFCs. In this study, an accelerated stress test (AST) is conducted to simulate prolonged fuel-cell operating conditions by potential cycling the carbon-supported Pt-Au (Pt-Au/C) cathode. The loss in performance of PEMFC with Pt-Au/C cathode is found to be ∼10% after 7000 accelerated potential-cycles as against ∼60% for Pt/C cathode under similar conditions. These data are in conformity with the electrochemical surface-area values. PEMFC with Pt-Au/C cathode can withstand >10,000 potential cycles with very little effect on its performance. X-ray diffraction and transmission electron microscopy studies on the catalyst before and after AST suggest that incorporating Au with Pt helps mitigate aggregation of Pt particles during prolonged fuel-cell operations while X-ray photoelectron spectroscopy reflects that the metallic nature of Pt is retained in the Pt-Au catalyst during AST in comparison to Pt/C that shows a major portion of Pt to be present as oxidic platinum. Field-emission scanning electron microscopy conducted on the membrane electrode assembly before and after AST suggests that incorporating Au with Pt helps mitigating deformations in the catalyst layer. This journal is © the Owner Societies 2011

An electrochemical impedance spectroscopy study of polymer electrolyte membrane fuel cells electrocatalyst single wall carbon nanohorns-supported.

PubMed

Brandão, Lúcia; Boaventura, Marta; Passeira, Carolina; Gattia, Daniele Mirabile; Marazzi, Renzo; Antisari, Marco Vittori; Mendes, Adélio

2011-10-01

Electrochemical impedance spectroscopy (EIS) was used to study the polymer electrolyte membrane fuel cells (PEMFC) performance when using single wall carbon nanohorns (SWNH) to support Pt nanoparticles. Additionally, as-prepared and oxidized SWNH Pt-supports were compared with conventional carbon black. Two different oxidizing treatments were considered: oxygen flow at 500 degrees C and reflux in an acid solution at 85 degrees C. Both oxidizing treatments increased SWNH surface area; oxygen treatment increased surface area 4 times while acid treatment increased 2.6 times. The increase in surface area should be related to the opening access to the inner tube of SWNH. Acid treatment of SWNH increased chemical fragility and decreased electrocatalyst load in comparison with as-prepared SWNH. On the other hand, the oxygen treated SWNH sample allowed to obtain the highest electrocatalyst load. The use of as-prepared and oxygen treated SWNH showed in both cases catalytic activities 60% higher than using conventional carbon black as electrocatalyst support in PEMFC. Moreover, EIS analysis indicated that the major improvement in performance is related to the cathode kinetics in the as-prepared SWNH sample, while concerning the oxidized SWNH sample, the improvements are related to the electrokinetics in both anode and cathode electrodes. These improvements should be related with differences in the hydrophobic character between SWNH and carbon black.

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.

Electrorefiner

DOEpatents

Miller, W.E.; Tomczuk, Z.

1995-08-22

An apparatus is disclosed capable of functioning as a solid cathode and for removing crystalline structure from the upper surface of a liquid cathode, includes a metallic support vertically disposed with respect to an electrically insulating container capable of holding a liquid metal cathode. A piston of electrically insulating material mounted on the drive tube, surrounding the current lead, for vertical and rotational movement with respect thereto including a downwardly extending collar portion surrounding the metallic current lead. At least one portion of the piston remote from the metallic current lead being removed. Mechanism for lowering the piston to the surface of the liquid cathode and raising the piston from the surface along with mechanism for rotating the piston around its longitudinal axis. 5 figs.

Electrorefiner

DOEpatents

Miller, William E.; Tomczuk, Zygmunt

1995-01-01

An apparatus capable of functioning as a solid cathode and for removing crystalline structure from the upper surface of a liquid cathode, includes a metallic support vertically disposed with respect to an electrically insulating container capable of holding a liquid metal cathode. A piston of electrically insulating material mounted on the drive tube, surrounding the current lead, for vertical and rotational movement with respect thereto including a downwardly extending collar portion surrounding the metallic current lead. At least one portion of the piston remote from the metallic current lead being removed. Mechanism for lowering the piston to the surface of the liquid cathode and raising the piston from the surface along with mechanism for rotating the piston around its longitudinal axis.

Microstructure Evolution and Failure Analysis of an Aluminum-Copper Cathode Conductive Head Produced by Explosive Welding

NASA Astrophysics Data System (ADS)

Wei, Yanni; Luo, Yongguang; Qu, Hongtao; Zou, Juntao; Liang, Shuhua

2017-12-01

In this paper, microstructure evolution and failure analysis of the aluminum-copper interface of cathode conductive heads during their use were studied. The interface morphologies, compositions, conductivity and mechanical properties were investigated and analyzed. Obvious corrosion was found on the surface of the contact interface, which was more prevalent on an Al matrix. The crack increased sharply in the local metallurgical bonding areas on the interface, with the compound volume having no significant change. The phase transformation occurred on the interface during use, which was investigated using the elemental composition and x-ray diffraction pattern. The microhardness near the interface increased accordingly. An obvious electrical conductivity decrease appeared on the Al/Cu interface of the cathode conductive head after use over a specific time interval. Therefore, the deterioration of the microstructures and corrosion are the primary factors that affect the electrical conductivity and effective bonding, which will lead to eventual failure.

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.

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.

Electrochemical Deburring

NASA Technical Reports Server (NTRS)

Burley, R. K.

1983-01-01

Electrochemical deburring removes burrs from assembled injector tubes. Since process uses liquid anodic dissolution in liquid electrolyte to proide deburring action, smoothes surfaces and edges in otherwise inaccessible areas. Tool consists of sleeve that contains metallic ring cathode. Sleeve is placed over tube, and electrolytic solution is forced to flow between tube and sleeve. The workpiece serves an anode.

Novel Architectures for Achieving Direct Electron Transfer in Enzymatic Biofuel Cells

NASA Astrophysics Data System (ADS)

Blaik, Rita A.

Enzymatic biofuel cells are a promising source of alternative energy for small device applications, but still face the challenge of achieving direct electron transfer with high enzyme concentrations in a simple system. In this dissertation, methods of constructing electrodes consisting of enzymes attached to nanoparticle-enhanced substrates that serve as high surface area templates are evaluated. In the first method described, glucose oxidase is covalently attached to gold nanoparticles that are assembled onto genetically engineered M13 bacteriophage. The resulting anodes achieve a high peak current per area and a significant improvement in enzyme surface coverage. In the second system, fructose dehydrogenase, a membrane-bound enzyme that has the natural ability to achieve direct electron transfer, is immobilized into a matrix consisting of binders and carbon nanotubes to extend the lifetime of the anode. For the cathode, bilirubin oxidase is immobilized in a carbon nanotube and sol-gel matrix to achieve direct electron transfer. Finally, a full fuel cell consisting of both an anode and cathode is constructed and evaluated with each system described.

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

PubMed

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

2015-11-14

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

Co-Pt core-shell nanostructured catalyst prepared by selective chemical vapor pulse deposition of Pt on Co as a cathode in polymer electrolyte fuel cells

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

Seo, Sang-Joon; Chung, Ho-Kyoon; Yoo, Ji-Beom

2014-01-15

A new type of PtCo/C catalyst for use as a cathode in polymer electrolyte fuel cells was prepared by selective chemical vapor pulse deposition (CVPD) of Pt on the surface of Co. The activity of the prepared catalyst for oxygen reduction was higher than that of a catalyst prepared by sequential impregnation (IMP) with the two metallic components. This catalytic activity difference occurs because the former catalyst has smaller Pt crystallites that produce stronger Pt-Co interactions and have a larger Pt surface area. Consequently, the CVPD catalyst has a great number of Co particles that are in close contact withmore » the added Pt. The Pt surface was also electronically modified by interactions with Co, which were stronger in the CVPD catalyst than in the IMP catalyst, as indicated by X-ray diffraction, X-ray photoemission spectroscopy, and cyclic voltammetry measurements of the catalysts.« less

Surface-Selective Preferential Production of Reactive Oxygen Species on Piezoelectric Ceramics for Bacterial Killing.

PubMed

Tan, Guoxin; Wang, Shuangying; Zhu, Ye; Zhou, Lei; Yu, Peng; Wang, Xiaolan; He, Tianrui; Chen, Junqi; Mao, Chuanbin; Ning, Chengyun

2016-09-21

Reactive oxygen species (ROS) can be used to kill bacterial cells, and thus the selective generation of ROS from material surfaces is an emerging direction in antibacterial material discovery. We found the polarization of piezoelectric ceramic causes the two sides of the disk to become positively and negatively charged, which translate into cathode and anode surfaces in an aqueous solution. Because of the microelectrolysis of water, ROS are preferentially formed on the cathode surface. Consequently, the bacteria are selectively killed on the cathode surface. However, the cell experiment suggested that the level of ROS is safe for normal mammalian cells.

Regenerable Nickel-Functionalized Activated Carbon Cathodes Enhanced by Metal Adsorption to Improve Hydrogen Production in Microbial Electrolysis Cells.

PubMed

Kim, Kyoung-Yeol; Yang, Wulin; Logan, Bruce E

2018-06-07

While nickel is a good alternative to platinum as a catalyst for the hydrogen evolution reaction, it is desirable to reduce the amount of nickel needed for cathodes in microbial electrolysis cells (MECs). Activated carbon (AC) was investigated as a cathode base structure for Ni as it is inexpensive and an excellent adsorbent for Ni, and it has a high specific surface area. AC nickel-functionalized electrodes (AC-Ni) were prepared by incorporating Ni salts into AC by adsorption, followed by cathode fabrication using a phase inversion process using a poly(vinylidene fluoride) (PVDF) binder. The AC-Ni cathodes had significantly higher (∼50%) hydrogen production rates than controls (plain AC) in smaller MECs (static flow conditions) over 30 days of operation, with no performance decrease over time. In larger MECs with catholyte recirculation, the AC-Ni cathode produced a slightly higher hydrogen production rate (1.1 ± 0.1 L-H 2 /L reactor /day) than MECs with Ni foam (1.0 ± 0.1 L-H 2 /L reactor /day). Ni dissolution tests showed that negligible amounts of Ni were lost into the electrolyte at pHs of 7 or 12, and the catalytic activity was restored by simple readsorption using a Ni salt solution when Ni was partially removed by an acid wash.

Free-Standing Air Cathodes Based on 3D Hierarchically Porous Carbon Membranes: Kinetic Overpotential of Continuous Macropores in Li-O2 Batteries.

PubMed

Xu, Shu-Mao; Liang, Xiao; Ren, Zhi-Chu; Wang, Kai-Xue; Chen, Jie-Sheng

2018-06-04

Free-standing macroporous air electrodes with enhanced interfacial contact, rapid mass transport, and tailored deposition space for large amounts of Li 2 O 2 are essential for improving the rate performance of Li-O 2 batteries. An ordered mesoporous carbon membrane with continuous macroporous channels was prepared by inversely topological transformation from ZnO nanorod array. Utilized as a free-standing air cathode for Li-O 2 battery, the hierarchically porous carbon membrane shows superior rate performance. However, the increased cross-sectional area of the continuous macropores on the cathode surface leads to a kinetic overpotential with large voltage hysteresis and linear voltage variation against Butler-Volmer behavior. The kinetics were investigated based on the rate-determining step of second electron transfer accompanied by migration of Li + in solid or quasi-solid intermediates. These discoveries shed light on the design of the air cathode for Li-O 2 batteries with high-rate performance. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

CuCr2O4@rGO Nanocomposites as High-Performance Cathode Catalyst for Rechargeable Lithium-Oxygen Batteries

NASA Astrophysics Data System (ADS)

Liu, Jiandi; Zhao, Yanyan; Li, Xin; Wang, Chunge; Zeng, Yaping; Yue, Guanghui; Chen, Qiang

2018-06-01

Rechargeable lithium-oxygen batteries have been considered as a promising energy storage technology because of their ultra-high theoretical energy densities which are comparable to gasoline. In order to improve the electrochemical properties of lithium-oxygen batteries (LOBs), especially the cycling performance, a high-efficiency cathode catalyst is the most important component. Hence, we aim to demonstrate that CuCr2O4@rGO (CCO@rGO) nanocomposites, which are synthesized using a facile hydrothermal method and followed by a series of calcination processes, are an effective cathode catalyst. The obtained CCO@rGO nanocomposites which served as the cathode catalyst of the LOBs exhibited an outstanding cycling performance for over 100 cycles with a fixed capacity of 1000 mAh g-1 at a current density of 200 mA g-1. The enhanced properties were attributed to the synergistic effect between the high catalytic efficiency of the spinel-structured CCO nanoparticles, the high specific surface area, and high conductivity of the rGO.[Figure not available: see fulltext.

The Effect of Potassium Impurities Deliberately Introduced into Activated Carbon Cathodes on the Performance of Lithium-Oxygen Batteries

DOE PAGES

Zhai, Dengyun; Lau, Kah Chun; Wang, Hsien-Hau; ...

2015-12-02

Rechargeable lithium-air (Li-O 2) batteries have drawn much interest owing to their high energy density. We report on the effect of deliberately introducing potassium impurities into the cathode material on the electrochemical performance of a Li-O 2 battery. Small amounts of potassium introduced into the activated carbon (AC) cathode material in the synthesis process are found to have a dramatic effect on the performance of the Li-O 2 cell. An increased amount of potassium significantly increases capacity, cycle life, and round-trip efficiency. This improved performance is probably due to a larger amount of LiO 2 in the discharge product, whichmore » is a mixture of LiO 2 and Li 2O 2, resulting from the increase in the amount of potassium present. No substantial correlation with porosity or surface area in an AC cathode is found. Lastly, experimental and computational studies indicate that potassium can act as an oxygen reduction catalyst, which can account for the dependence of performance on the amount of potassium.« less

Kinetics of oxygen reduction in perovskite cathodes for solid oxide fuel cells: A combined modeling and experimental approach

NASA Astrophysics Data System (ADS)

Miara, Lincoln James

Solid oxide fuel cells (SOFCs) have the potential to replace conventional stationary power generation technologies; however, there are major obstacles to commercialization, the most problematic of which is poor cathode performance. Commercialization of SOFCs will follow when the mechanisms occurring at the cathode are more thoroughly understood and adapted for market use. The catalytic reduction of oxygen occurring in SOFC cathodes consists of many elementary steps such as gas phase diffusion, chemical and/or electrochemical reactions which lead to the adsorption and dissociation of molecular oxygen onto the cathode surface, mass transport of oxygen species along the surface and/or through the bulk of the cathode, and full reduction and incorporation of the oxygen at the cathode/electrolyte two or three phase boundary. Electrochemical impedance spectroscopy (EIS) is the main technique used to identify the occurrence of these different processes, but when this technique is used without an explicit model describing the kinetics it is difficult to unravel the interdependence of each of these processes. The purpose of this dissertation is to identify the heterogeneous reactions occurring at the cathode of an SOFC by combining experimental EIS results with mathematical models describing the time dependent behavior of the system. This analysis is performed on two different systems. In the first case, experimental EIS results from patterned half cells composed of Ca-doped lanthanum manganite (LCM)| yttria-doped ZrO2 (YSZ) are modeled to investigate the temperature and partial pressure of oxygen, pO2, dependence of oxygen adsorption/dissociation onto the LCM surface, surface diffusion of atomic oxygen, and electrochemical reduction and incorporation of the oxygen into the electrolyte in the vicinity of the triple phase boundary (TPB). This model determines the time-independent state-space equations from which the Faradaic admittance transfer function is obtained. The unknown rate constants (kad, k des, k1, k1¯ ), and parameters (Ds, Q°, n) arising from the governing equations are estimated from a combination of experiments, mathematical analysis, and numerical data analysis. In the second system, dense patterned films of cathode with composition: La0.6Sr0.4Co0.2Fe0.8O3-delta (LSCF-6428) were fabricated on Ga-doped CeO2 coated YSZ substrates. These samples were analyzed by EIS over a temperature and pO 2 range of 600--800 °C and 10-3--1.00 atm, respectively. To understand the EIS results, a 2-dimensional model was developed which accounted for surface oxygen exchange, and both surface and bulk transport of oxygen to the electrolyte interface. The results were obtained by numerically solving a stationary partial differential equation describing the oxygen vacancy distribution in the cathode. From these results, the model impedance was derived and then fitted to the experimental EIS results. From the fitting results the contributions to the impedance from each of the processes were estimated. Also, the surface exchange rate was estimated over the experimental operating conditions. Finally, the results suggest that the surface diffusion occurred by an interstitial type mechanism in this material. The cathode surface is intimately involved in most of the oxygen reduction processes; however, the surface structure and chemistry is typically treated as an extension of the bulk without consideration of the actual surface properties. Recent evidence suggests that significant changes occur to the surface during operation which in turn leads to changes in electrochemical performance. To investigate these phenomena, well-oriented thin films (250 nm in thickness) of Sr-doped lanthanum manginite (LSM) films were grown on single crystals of YSZ (111). Films which were cathodically biased with a -1 V applied dc potential were compared to control samples. The cathodic bias results in both an enhancement in electrochemical performance and a change in surface chemistry. The changes in electrochemical performance were monitored by ES, while the surface changes were tracked with a combination of soft x-ray techniques such as x-ray photoemission spectroscopy and x-ray absorption spectroscopy. The soft x-ray results indicated that the removal of surface passivating phases (i.e., SrO and MnO) are correlated with improved performance. This work demonstrates the success of estimating fundamental parameters, such as diffusivity and surface coverage, from experimental EIS results using a physically realistic model without, as is commonly done, assuming a specific rate limiting step or using an ambiguous equivalent circuit. This allows researchers to fabricate designer cathodes by selecting materials with optimal kinetic properties such as rapid oxygen dissociation and rapid oxygen transport in (or on) the cathode, independent of geometry.

Electrochemical CO2 Reduction via Gas-Phase Catholyte

NASA Astrophysics Data System (ADS)

Carter, Brittany E.; Nesbitt, Nathan T.; D'Imperio, Luke A.; Naughton, Jeffrey R.; Courtney, Dave T.; Shepard, Steve; Burns, Michael J.; Vermaas, David A.; Smith, Wilson A.; Naughton, Michael J.

Reducing CO2 to CO through electrolysis, for the eventual conversion to hydrocarbons, provides a path towards utility-scale seasonal storage of renewable energy. Electrochemical reduction of CO2 has previously been achieved using a two chamber system. The chambers are typically separated by a semipermeable Nafion membrane, with an oxygen evolution catalyst anode on one side, a gold cathode on the other, and a solution containing CO2 on both sides. If instead, CO2 gas was in the second chamber, the reaction should yield more CO formed from CO2 at a given overpotential; this would result from the increased concentration of CO2 at the cathode surface and more facile mass transport of the CO and CO2. With liquid in one chamber and gas in the other, electrolysis is performed by integrating the cathode onto the semipermeable Nafion membrane. This membrane electrode assembly is fabricated via nanoimprint lithography (NIL), simultaneously achieving high active surface area and permeability. Challenges to the Nafion NIL process, and the performance of the system in CO2 reduction, will be presented. This material is based upon work supported by the National Science Foundation Graduate Research Fellowship under Grant No. (DGE-1258923).

Effort towards symmetric removal and surface smoothening of 1.3-GHz niobium single-cell cavity in vertical electropolishing using a unique cathode

NASA Astrophysics Data System (ADS)

Chouhan, Vijay; Kato, Shigeki; Nii, Keisuke; Yamaguchi, Takanori; Sawabe, Motoaki; Hayano, Hitoshi; Ida, Yoshiaki

2017-08-01

A detailed study on vertical electropolishing (VEP) of a 1.3-GHz single-cell niobium coupon cavity, which contains six coupons and four viewports at different positions, is reported. The cavity was vertically electropolished using a conventional rod and three types of unique cathodes named as Ninja cathodes, which were designed to have four retractable blades made of either an insulator or a metal or a combination of both. This study reveals the effect of the cathodes and their rotation speed on uniformity in removal thickness and surface morphology at different positions inside the cavity. Removal thickness was measured at several positions of the cavity using an ultrasonic thickness gauge and the surface features of the coupons were examined by an optical microscope and a surface profiler. The Ninja cathode with partial metallic blades was found to be effective not only in reducing asymmetric removal, which is one of the major problems in VEP and might be caused by the accumulation of hydrogen (H2 ) gas bubbles on the top iris of the cavity, but also in yielding a smooth surface of the entire cavity. A higher rotation speed of the Ninja cathode prevents bubble accumulation on the upper iris, and might result in a viscous layer of similar thickness in the cavity cell. Moreover, a higher electric field at the equator owing to the proximity of partial metallic blades to the equator surface resulted in a smooth surface. The effects of H2 gas bubbles and stirring were also observed in lab EP experiments.

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

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.

Magnetic-cusp, cathodic-arc source

DOEpatents

Falabella, S.

1995-11-21

A magnetic-cusp for a cathodic-arc source wherein the arc is confined to the desired cathode surface, provides a current path for electrons from the cathode to the anode, and utilizes electric and magnetic fields to guide ions from the cathode to a point of use, such as substrates to be coated. The magnetic-cusp insures arc stability by an easy magnetic path from anode to cathode, while the straight-through arrangement leads to high ion transmission. 3 figs.

Corrosion-resistant catalyst supports for phosphoric acid fuel cells

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

Kosek, J.A.; Cropley, C.C.; LaConti, A.B.

High-surface-area carbon blacks such as Vulcan XC-72 (Cabot Corp.) and graphitized carbon blacks such as 2700{degree}C heat-treated Black Pearls 2000 (HTBP) (Cabot Corp.) have found widespread applications as catalyst supports in phosphoric acid fuel cells (PAFCs). However, due to the operating temperatures and pressures being utilized in PAFCs currently under development, the carbon-based cathode catalyst supports suffer from corrosion, which decreases the performance and life span of a PAFC stack. The feasibility of using alternative, low-cost, corrosion-resistant catalyst support (CRCS) materials as replacements for the cathode carbon support materials was investigated. The objectives of the program were to prepare high-surface-areamore » alternative supports and to evaluate the physical characteristics and the electrochemical stability of these materials. The O{sub 2} reduction activity of the platinized CRCS materials was also evaluated. 2 refs., 3 figs.« less

Temporal response of a surface flashover on a velvet cathode in a relativistic diode

DOE PAGES

Coleman, J. E.; Moir, D. C.; Crawford, M. T.; ...

2015-03-11

Surface flashover of a carbon fiber velvet cathode generates a discharge from which electrons are relativistically accelerated to γ ranging from 4.9 to 8.8 through a 17.8 cm diode. This discharge is assumed to be a hydrocarbon mixture. Our objective is to quantify the dynamics over the ~100 ns pulse of the plasma discharge generated on the surface of the velvet cathode and across the anode-cathode (A-K) gap. We present a qualitative comparison of calculated and measured results, which includes time resolved measurements with a photomultiplier tube and charge-coupled device images. Additionally, initial visible spectroscopy measurements will also be presentedmore » confirming the ion species are dominated by hydrogen.« less

Electrochemical Activation of Diamond Microelectrodes: Implications for the In Vitro Measurement of Serotonin in the Bowel

PubMed Central

Duran, Boris; Brocenschi, Ricardo F.; France, Marion; Galligan, James J.; Swain, Greg M.

2014-01-01

The electrochemical pretreatment of diamond microelectrodes was investigated for the purpose of learning how an anodic, cathodic or a combined anodic + cathodic polarization affects the charge-transfer kinetics for two surface-sensitive redox systems: ferri/ferrocyanide and serotonin (5-hydroxytryptamine, 5-HT). The pretreatments were performed in 0.5 mol L−1 H2SO4. The anodic pretreatment was performed galvanically for 30 s at 250 mA cm−2. The 10 cathodic pretreatment was performed for 180 s at −250 mA cm−2. The combined pretreatment involved application of the anodic step first followed by the cathodic step. The results clearly demonstrate that the best performance for both redox systems is obtained after the cathodic polarization, which presumably activates the electrode by cleaning the surface and removing site-blocking surface carbon-oxygen functionalities. The cathodic pretreatment was found to be effective at activating a fouled microelectrode in situ. This observation has important implication for the measurement of 5-HT in the bowel. PMID:24802953

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.

Surface area loss mechanisms of Pt3Co nanocatalysts in proton exchange membrane fuel cells

NASA Astrophysics Data System (ADS)

Rasouli, S.; Ortiz Godoy, R. A.; Yang, Z.; Gummalla, M.; Ball, S. C.; Myers, D.; Ferreira, P. J.

2017-03-01

Pt3Co catalyst nanoparticles of 4.9 nm size present on the cathode side of a PEMFC membrane-electrode assembly (MEA) were analyzed by transmission electron microscopy after 10 K voltage cycles under different operating conditions. The operating conditions include baseline (0.4-0.95 V, 80° C, 100% Relative Humidity (RH)), high potential (0.4-1.05 V, 80° C, 100% RH), high temperature (0.4-0.95 V, 90° C, 100% RH), and low humidity (0.4-0.95 V, 80° C, 30% RH). Particle growth and particle loss to the membrane is more severe in the high potential sample than in the high temperature and baseline MEAs, while no significant particle growth and particle precipitation in the membrane can be observed in the low humidity sample. Particles with different morphologies were seen in the cathode including: 1-Spherical individual particles resulting from modified electro-chemical Ostwald ripening and 2-aggregated and coalesced particles resulting from either necking of two or more particles or preferential deposition of Pt between particles with consequent bridging. The difference in the composition of these morphologies results in composition variations through the cathode from cathode/diffusion media (DM) to the cathode/membrane interface.

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.

Fundamental Investigations and Rational Design of Durable High-Performance SOFC Cathodes

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

Chen, Yu; Ding, Dong; Wei, Tao

The main objective of this project is to unravel the degradation mechanism of LSCF cathodes under realistic operating conditions with different types of contaminants, aiming towards the rational design of cathodes with high-performance and enhanced durability by combining a porous backbone (such as LSCF) with a thin catalyst coating. The mechanistic understanding will help us to optimize the composition and morphology of the catalyst layer and microstructure of the LSCF backbone for better performance and durability. More specifically, the technical objectives include: (1) to unravel the degradation mechanism of LSCF cathodes under realistic operating conditions with different types of contaminantsmore » using in situ and ex situ measurements performed on specially-designed cathodes; (2) to examine the microstructural and compositional evolution of LSCF cathodes as well as the cathode/electrolyte interfaces under realistic operating conditions; (3) to correlate the fuel cell performance instability and degradation with the microstructural and morphological evolution and surface chemistry change of the cathode under realistic operating conditions; (4) to explore new catalyst materials and electrode structures to enhance the stability of the LSCF cathode under realistic operating conditions; and (5) to validate the long term stability of the modified LSCF cathode in commercially available cells under realistic operating conditions. We have systematically evaluated LSCF cathodes in symmetrical cells and anode supported cells under realistic conditions with different types of contaminants such as humidity, CO 2, and Cr. Electrochemical models for the design of test cells and understanding of mechanisms have been developed for the exploration of fundamental properties of electrode materials. It is demonstrated that the activity and stability of LSCF cathodes can be degraded by the introduction of contaminants. The microstructural and compositional evolution of LSCF cathodes as well as the cathode/electrolyte interfaces under realistic operating conditions has been studied. It is found that SrO readily segregated/enriched on the LSCF surface. More severe contamination conditions cause more SrO on surface. Novel catalyst coatings through particle depositions (PrOx) or continuous thin films (PNM) were successfully developed to improve the activity and stability of LSCF cathodes. Finally, we have demonstrated enhanced activity and stability of LSCF cathodes over longer periods of time in homemade and commercially available cells by an optimized PNM (dense film and particles) infiltration process, under clean air and realistic operating conditions (3% H 2O, 5% CO 2 and direct Crofer contact). Both performance and durability of single cells with PNM coating has been enhanced compared with those without coating. Raman analysis of cathodes surface indicated that the intensity of SrCrO 4 was significantly decreased.« less

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.

Mechanisms of LiCoO2 Cathode Degradation by Reaction with HF and Protection by Thin Oxide Coatings.

PubMed

Tebbe, Jonathon L; Holder, Aaron M; Musgrave, Charles B

2015-11-04

Reactions of HF with uncoated and Al and Zn oxide-coated surfaces of LiCoO2 cathodes were studied using density functional theory. Cathode degradation caused by reaction of HF with the hydroxylated (101̅4) LiCoO2 surface is dominated by formation of H2O and a LiF precipitate via a barrierless reaction that is exothermic by 1.53 eV. We present a detailed mechanism where HF reacts at the alumina coating to create a partially fluorinated alumina surface rather than forming AlF3 and H2O and thus alumina films reduce cathode degradation by scavenging HF and avoiding H2O formation. In contrast, we find that HF etches monolayer zinc oxide coatings, which thus fail to prevent capacity fading. However, thicker zinc oxide films mitigate capacity loss by reacting with HF to form a partially fluorinated zinc oxide surface. Metal oxide coatings that react with HF to form hydroxyl groups over H2O, like the alumina monolayer, will significantly reduce cathode degradation.

Materials Characteristics and Surface Morphology of a Cesium Iodide Coated Carbon Velvet Cathode (POSTPRINT)

DTIC Science & Technology

2009-03-31

cathodes consist of an array of carbon fibers pyrolytically bonded to a carbon substrate. The fibers then receive a CsI coating using either a...the oil side of the vacuum interface along the cathode shank. Current transformers provide current measurements of the cathode current, again

Thrust and Performance Study of Micro Pulsed Plasma Thrusters

DTIC Science & Technology

2010-03-01

Due to the high- voltage potential, numerous electrons are able to collect in a small area. As the collection of the electrons grows, the ...quasi- neutral plasma removes the need to have a second emitter of free electrons to neutralize the plasma like in the Hall thrusters. PPTs and µPPTs...surface of the cathode. The micro-protrusions

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.

Anisotropic etching of platinum electrodes at the onset of cathodic corrosion

PubMed Central

Hersbach, Thomas J. P.; Yanson, Alexei I.; Koper, Marc T. M.

2016-01-01

Cathodic corrosion is a process that etches metal electrodes under cathodic polarization. This process is presumed to occur through anionic metallic reaction intermediates, but the exact nature of these intermediates and the onset potential of their formation is unknown. Here we determine the onset potential of cathodic corrosion on platinum electrodes. Electrodes are characterized electrochemically before and after cathodic polarization in 10 M sodium hydroxide, revealing that changes in the electrode surface start at an electrode potential of −1.3 V versus the normal hydrogen electrode. The value of this onset potential rules out previous hypotheses regarding the nature of cathodic corrosion. Scanning electron microscopy shows the formation of well-defined etch pits with a specific orientation, which match the voltammetric data and indicate a remarkable anisotropy in the cathodic etching process, favouring the creation of (100) sites. Such anisotropy is hypothesized to be due to surface charge-induced adsorption of electrolyte cations. PMID:27554398

Effect of anodic treatment on the electrocatalytic activity of superficial Raney nickel catalyst in cathodic hydrogen

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

Korovin, N.V.; Kozlova, N.I.; Kumenko, M.V.

This work is concerned with the effect of oxidation on the activity of Raney nickel catalyst in cathodic hydrogen evolution. The superficial Raney nickel catalyst (nickel SRC) was prepared by a previously described procedure. The surface of the nickel SRC was oxidized by applying an anodic sweep over the potential range from 0.25 to 1.00 V with a potential sweep rate of 1 mV/sec. The rate of cathodic hydrogen evolution increases after pretreatment of the surface of nickel SRC by application of an anodic pulse. A significant increase in the reaction rate most probably is due to oxygen adsorption onmore » the nickel SRC surface. The largest increase in the amount of weakly bound hydrogen corresponds to the most active electrode. Oxidation of the nickel surface by an anodic pulse causes both an acceleration and a retardation of the cathodic hydrogen evolution reaction.« less

Influence of Pr6O11 on oxygen electroreduction kinetics and electrochemical performance of Sr2Fe1.5Mo0.5O6-δ based cathode

NASA Astrophysics Data System (ADS)

Osinkin, D. A.; Beresnev, S. M.; Bogdanovich, N. M.

2018-07-01

Oxygen electroreduction kinetics and electrochemical performance of the Pr6O11-impregnated Sr2Fe1.5Mo0.5O6-δ - Ce0.8Sm0.2O1.9 (SFM-SDC) cathode have been first studied. By means of distribution of relaxation times and non-linear least squares analysis of impedance spectra were shown that the addition of Pr6O11 into the cathode leads to the increase in the rate of the low-frequency step. It is suggested that the observed phenomenon is associated with the increase in the rate of surface oxygen exchange. It is shown that the introduction of praseodymium oxide into the cathode results in a decrease in the area specific polarization resistances of the cathode at equilibrium potentials from 0.23 to 0.06 Ω cm2 at 800 °C in air. The maximum power density of symmetrical solid oxide fuel cell (SOFC) with impregnated SFM-SDC electrodes and supporting 760 μm La0.85Sr0.15Ga0.85Mg0.15O3-δ electrolyte without buffer/barrier and collector layers under air/wet hydrogen (dry CH4) condition was about 0.5 (0.26) W cm-2 at 800 °C. The overvoltage of the cathode was higher than that of the anode under air/wet hydrogen and vice versa when methane was supplied to the anode. The obtained results elucidate that the impregnated SFM-SDC is a promising cathode for SOFC application.

Synthesis of hierarchical porous δ-MnO2 nanoboxes as an efficient catalyst for rechargeable Li-O2 batteries

NASA Astrophysics Data System (ADS)

Zhang, Jian; Luan, Yanping; Lyu, Zhiyang; Wang, Liangjun; Xu, Leilei; Yuan, Kaidi; Pan, Feng; Lai, Min; Liu, Zhaolin; Chen, Wei

2015-09-01

A rechargeable lithium-oxygen (Li-O2) battery with a remarkably high theoretical energy storage capacity has attracted enormous research attention. However, the poor oxygen reduction and oxygen evolution reaction (ORR and OER) activities in discharge and charge processes cause low energy efficiency, poor electrolyte stability and short cycle life. This requires the development of efficient cathode catalysts to dramatically improve the Li-O2 battery performances. MnO2-based materials are recognized as efficient and low-cost catalysts for a Li-O2 battery cathode. Here, we report a controllable approach to synthesize hierarchical porous δ-MnO2 nanoboxes by using Prussian blue analogues as the precursors. The obtained products possess hierarchical pore size and an extremely large surface area (249.3 m2 g-1), which would favour oxygen transportation and provide more catalytically active sites to promote ORR and OER as the Li-O2 battery cathode. The battery shows enhanced discharge capacity (4368 mA h g-1@0.08 mA cm-2), reduced overpotential (270 mV), improved rate performance and excellent cycle stability (248 cycles@500 mA h g-1 and 112 cycles@1000 mA h g-1), in comparison with the battery with a VX-72 carbon cathode. The superb performance of the hierarchical porous δ-MnO2 nanoboxes, together with a convenient fabrication method, presents an alternative to develop advanced cathode catalysts for the Li-O2 battery.A rechargeable lithium-oxygen (Li-O2) battery with a remarkably high theoretical energy storage capacity has attracted enormous research attention. However, the poor oxygen reduction and oxygen evolution reaction (ORR and OER) activities in discharge and charge processes cause low energy efficiency, poor electrolyte stability and short cycle life. This requires the development of efficient cathode catalysts to dramatically improve the Li-O2 battery performances. MnO2-based materials are recognized as efficient and low-cost catalysts for a Li-O2 battery cathode. Here, we report a controllable approach to synthesize hierarchical porous δ-MnO2 nanoboxes by using Prussian blue analogues as the precursors. The obtained products possess hierarchical pore size and an extremely large surface area (249.3 m2 g-1), which would favour oxygen transportation and provide more catalytically active sites to promote ORR and OER as the Li-O2 battery cathode. The battery shows enhanced discharge capacity (4368 mA h g-1@0.08 mA cm-2), reduced overpotential (270 mV), improved rate performance and excellent cycle stability (248 cycles@500 mA h g-1 and 112 cycles@1000 mA h g-1), in comparison with the battery with a VX-72 carbon cathode. The superb performance of the hierarchical porous δ-MnO2 nanoboxes, together with a convenient fabrication method, presents an alternative to develop advanced cathode catalysts for the Li-O2 battery. Electronic supplementary information (ESI) available. See DOI: 10.1039/c5nr02983j

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

Detailed numerical simulation of cathode spots in vacuum arcs: Interplay of different mechanisms and ejection of droplets

NASA Astrophysics Data System (ADS)

Kaufmann, H. T. C.; Cunha, M. D.; Benilov, M. S.; Hartmann, W.; Wenzel, N.

2017-10-01

A model of cathode spots in high-current vacuum arcs is developed with account of all the potentially relevant mechanisms: the bombardment of the cathode surface by ions coming from a pre-existing plasma cloud; vaporization of the cathode material in the spot, its ionization, and the interaction of the produced plasma with the cathode; the Joule heat generation in the cathode body; melting of the cathode material and motion of the melt under the effect of the plasma pressure and the Lorentz force and related phenomena. After the spot has been ignited by the action of the cloud (which takes a few nanoseconds), the metal in the spot is melted and accelerated toward the periphery of the spot, with the main driving force being the pressure due to incident ions. Electron emission cooling and convective heat transfer are dominant mechanisms of cooling in the spot, limiting the maximum temperature of the cathode to approximately 4700-4800 K. A crater is formed on the cathode surface in this way. After the plasma cloud has been extinguished, a liquid-metal jet is formed and a droplet is ejected. No explosions have been observed. The modeling results conform to estimates of different mechanisms of cathode erosion derived from the experimental data on the net and ion erosion of copper cathodes.

The Li-ion rechargeable battery: a perspective.

PubMed

Goodenough, John B; Park, Kyu-Sung

2013-01-30

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

Temporal response of a surface flashover on a velvet cathode in a relativistic diode

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

Coleman, J. E.; Moir, D. C.; Crawford, M. T.

2015-03-15

Surface flashover of a carbon fiber velvet cathode generates a discharge from which electrons are relativistically accelerated to γ ranging from 4.9 to 8.8 through a 17.8 cm diode. This discharge is assumed to be a hydrocarbon mixture. The principal objective of these experiments is to quantify the dynamics over the ∼100 ns pulse of the plasma discharge generated on the surface of the velvet cathode and across the anode-cathode (A-K) gap. A qualitative comparison of calculated and measured results is presented, which includes time resolved measurements with a photomultiplier tube and charge-coupled device images. In addition, initial visible spectroscopy measurements willmore » also be presented confirming the ion species are dominated by hydrogen.« less

Graphene-coated carbon fiber cloth for flexible electrodes of glucose fuel cells

NASA Astrophysics Data System (ADS)

Hoshi, Kazuki; Muramatsu, Kazuo; Sumi, Hisato; Nishioka, Yasushiro

2016-02-01

In this work, we fabricated flexible electrodes for a miniaturized, simple structured, and flexible glucose biofuel cell (BFC) using a graphene-coated carbon fiber cloth (GCFC). The areas of the anode and cathode electrodes were 3 × 10 mm2. The anode area was coated with the enzyme glucose oxidase, and the cathode area was coated with the enzyme bilirubin oxidase. No ion-exchange film was needed because glucose oxidase selectively oxidizes glucose and bilirubin oxidase selectively reduces oxygen. The power density of the BFC with GCFC electrodes in a phosphate buffer solution of 200 mM glucose solution at room temperature was 34.3 µW/cm2 at 0.43 V. The power density of a BFC using carbon fiber cloth (CFC) without graphene modification was 18.5 µW/cm2 at 0.13 V. The BFC with the GCFC electrode continued to function longer than 24 h with a power density higher than 5 µW/cm2. These effects were attributed to the much larger effective surface areas of the GCFC electrodes that maintain more enzymes than those of the CFC electrodes.

Evaluation of Cathode Heater Assembly for 42 GHz, 200 kW Gyrotron

NASA Astrophysics Data System (ADS)

Sharma, S. K.; Singh, Narendra Kumar; Singh, Udaybir; Khatun, Hasina; Kumar, Nitin; Alaria, M. K.; Raju, R. S.; Jain, P. K.; Sinha, A. K.

2014-09-01

In this paper, the evaluation of cathode-heater assembly of magnetron injection gun (MIG) for 42 GHz, 200 kW gyrotron is presented. The cathode-heater assembly is purchased from M/S SEMICON.The cathode-heater assembly is experimentally studied in three different conditions; in a belljar system, during vacuum processing of MIG and during MIG testing to ensure the required rise of cathode surface temperature for pre-set heater power.

Selective Deposition of SiO2 on Ion Conductive Area of Soda-lime Glass Surface

PubMed Central

Sakai, Daisuke; Harada, Kenji; Hara, Yuichiro; Ikeda, Hiroshi; Funatsu, Shiro; Uraji, Keiichiro; Suzuki, Toshio; Yamamoto, Yuichi; Yamamoto, Kiyoshi; Ikutame, Naoki; Kawaguchi, Keiga; Kaiju, Hideo; Nishii, Junji

2016-01-01

Selective deposition of SiO2 nanoparticles was demonstrated on a soda-lime glass surface with a periodic sodium deficient pattern formed using the electrical nanoimprint. Positively charged SiO2 particles generated using corona discharge in a cyclic siloxane vapor, were selectively deposited depending on the sodium pattern. For such phenomena to occur, the sodium ion migration to the cathode side was indispensable to the electrical charge compensation on the glass surface. Therefore, the deposition proceeded preferentially outside the alkali-deficient area. Periodic SiO2 structures with 424 nm and 180 nm heights were obtained using one-dimensional (6 μm period) and two-dimensional (500 nm period) imprinted patterns. PMID:27291796

In-situ sputtering apparatus

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

Erickson, Mark R.; Poole, Henry J.; Custer, III, Arthur W.

A sputtering apparatus that includes at least a target presented as an inner surface of a confinement structure, the inner surface of the confinement structure is preferably an internal wall of a circular tube. A cathode is disposed adjacent the internal wall of the circular tube. The cathode preferably provides a hollow core, within which a magnetron is disposed. Preferably, an actuator is attached to the magnetron, wherein a position of the magnetron within the hollow core is altered upon activation of the actuator. Additionally, a carriage supporting the cathode and communicating with the target is preferably provided, and amore » cable bundle interacting with the cathode and linked to a cable bundle take up mechanism provided power and coolant to the cathode, magnetron, actuator and an anode of the sputtering apparatus.« less

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.

Nanosized LiFePO4-decorated emulsion-templated carbon foam for 3D micro batteries: a study of structure and electrochemical performance.

PubMed

Asfaw, Habtom D; Roberts, Matthew R; Tai, Cheuk-Wai; Younesi, Reza; Valvo, Mario; Nyholm, Leif; Edström, Kristina

2014-08-07

In this article, we report a novel 3D composite cathode fabricated from LiFePO4 nanoparticles deposited conformally on emulsion-templated carbon foam by a sol-gel method. The carbon foam is synthesized via a facile and scalable method which involves the carbonization of a high internal phase emulsion (polyHIPE) polymer template. Various techniques (XRD, SEM, TEM and electrochemical methods) are used to fully characterize the porous electrode and confirm the distribution and morphology of the cathode active material. The major benefits of the carbon foam used in our work are closely connected with its high surface area and the plenty of space suitable for sequential coating with battery components. After coating with a cathode material (LiFePO4 nanoparticles), the 3D electrode presents a hierarchically structured electrode in which a porous layer of the cathode material is deposited on the rigid and bicontinuous carbon foam. The composite electrodes exhibit impressive cyclability and rate performance at different current densities affirming their importance as viable power sources in miniature devices. Footprint area capacities of 1.72 mA h cm(-2) at 0.1 mA cm(-2) (lowest rate) and 1.1 mA h cm(-2) at 6 mA cm(-2) (highest rate) are obtained when the cells are cycled in the range 2.8 to 4.0 V vs. lithium.

Axis-1 diode simulations I: standard 2-inch cathode

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

Ekdahl, Carl

2011-01-11

The standard configuration of the DARHT Axis-I diode features a 5.08-cm diameter velvet emitter mounted in the flat surface of the cathode shroud. The surface of the velvet is slightly recessed {approx}2.5 mm. This configuration produces a 1.75 kA beam when a 3.8-MV pulse is applied to the anode-cathode (AK) gap. This note addresses some of the physics of this diode through the use of finite-element simulations.

Surface breakdown igniter for mercury arc devices

DOEpatents

Bayless, John R.

1977-01-01

Surface breakdown igniter comprises a semiconductor of medium resistivity which has the arc device cathode as one electrode and has an igniter anode electrode so that when voltage is applied between the electrodes a spark is generated when electrical breakdown occurs over the surface of the semiconductor. The geometry of the igniter anode and cathode electrodes causes the igniter discharge to be forced away from the semiconductor surface.

From Coating to Dopant: How the Transition Metal Composition Affects Alumina Coatings on Ni-Rich Cathodes

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

Han, Binghong; Key, Baris; Lapidus, Saul H.

Surface alumina coatings have been shown to be an effective way to improve the stability and cyclability of cathode materials. However, a detailed understanding of the relationship between the surface coatings and the bulk layered oxides is needed to better define the critical cathode–electrolyte interface. In this work, we systematically studied the effect of the composition of Ni-rich LiNi xMn yCo 1–x–yO 2 (NMC) on the surface alumina coatings. Changing cathode composition from LiNi 0.5Mn 0.3Co 0.2O 2 (NMC532) to LiNi 0.6Mn 0.2Co 0.2O 2 (NMC622) and LiNi 0.8Mn 0.1Co 0.1O 2 (NMC811) was found to facilitate the diffusion ofmore » surface alumina into the bulk after high-temperature annealing. By use of a variety of spectroscopic techniques, Al was seen to have a high bulk compatibility with higher Ni/Co content, and low bulk compatibility was associated with Mn in the transition metal layer. It was also noted that the cathode composition affected the observed morphology and surface chemistry of the coated material, which has an effect on electrochemical cycling. The presence of a high surface Li concentration and strong alumina diffusion into the bulk led to a smoother surface coating on NMC811 with no excess alumina aggregated on the surface. Structural characterization of pristine NMC particles also suggests surface Co segregation, which may act to mediate the diffusion of the Al from the surface to the bulk. The diffusion of Al into the bulk was found to be detrimental to the protection function of surface coatings leading to poor overall cyclability, indicating the importance of compatibility between surface coatings and bulk oxides on the electrochemical performance of coated cathode materials.In conclusion, these results are important in developing a better coating method for synthesis of next-generation cathode materials for lithium-ion batteries.« less

From Coating to Dopant: How the Transition Metal Composition Affects Alumina Coatings on Ni-Rich Cathodes

DOE PAGES

Han, Binghong; Key, Baris; Lapidus, Saul H.; ...

2017-11-01

Surface alumina coatings have been shown to be an effective way to improve the stability and cyclability of cathode materials. However, a detailed understanding of the relationship between the surface coatings and the bulk layered oxides is needed to better define the critical cathode–electrolyte interface. In this work, we systematically studied the effect of the composition of Ni-rich LiNi xMn yCo 1–x–yO 2 (NMC) on the surface alumina coatings. Changing cathode composition from LiNi 0.5Mn 0.3Co 0.2O 2 (NMC532) to LiNi 0.6Mn 0.2Co 0.2O 2 (NMC622) and LiNi 0.8Mn 0.1Co 0.1O 2 (NMC811) was found to facilitate the diffusion ofmore » surface alumina into the bulk after high-temperature annealing. By use of a variety of spectroscopic techniques, Al was seen to have a high bulk compatibility with higher Ni/Co content, and low bulk compatibility was associated with Mn in the transition metal layer. It was also noted that the cathode composition affected the observed morphology and surface chemistry of the coated material, which has an effect on electrochemical cycling. The presence of a high surface Li concentration and strong alumina diffusion into the bulk led to a smoother surface coating on NMC811 with no excess alumina aggregated on the surface. Structural characterization of pristine NMC particles also suggests surface Co segregation, which may act to mediate the diffusion of the Al from the surface to the bulk. The diffusion of Al into the bulk was found to be detrimental to the protection function of surface coatings leading to poor overall cyclability, indicating the importance of compatibility between surface coatings and bulk oxides on the electrochemical performance of coated cathode materials.In conclusion, these results are important in developing a better coating method for synthesis of next-generation cathode materials for lithium-ion batteries.« less

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

DOE PAGES

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

2016-07-19

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

Superior lithium-ion insertion/extraction properties of a novel LiFePO4/C/graphene material used as a cathode in aqueous solution.

PubMed

Duan, Wenyuan; Zhao, Mingshu; Shen, Junfang; Zhao, Suixin; Song, Xiaoping

2017-09-28

Herein, olivine LiFePO 4 covered with graphene and carbon layers is prepared via a sol-gel method, followed by calcination, and the resultant composite is used as a cathode material in aqueous rechargeable lithium-ion batteries (ARLBs). The phase structure and morphology of the composite are characterized via X-ray diffraction (XRD), transmission electron microscopy (TEM), high-resolution transmission electron microscopy (HRTEM) and specific surface area analysis (BET). The ARLB system is fabricated using LiFePO 4 /C/graphene as the cathode and a zinc anode in 1 mol L -1 ZnSO 4 ·7H 2 O and saturated LiNO 3 aqueous solution without dissolved oxygen, which delivers a capacity of 153 mA h g -1 at 0.5C rate. Even at a 50C rate, it maintains a capacity of 95 mA h g -1 after 200 cycles. The excellent rate capabilities show that this cathode material exhibits good electrochemical performance and this novel ARLB has great potential in the fields of energy storage and high power sources.

Carbon-Free CoO Mesoporous Nanowire Array Cathode for High-Performance Aprotic Li-O2 Batteries.

PubMed

Wu, Baoshan; Zhang, Hongzhang; Zhou, Wei; Wang, Meiri; Li, Xianfeng; Zhang, Huamin

2015-10-21

Although various kinds of catalysts have been developed for aprotic Li-O2 battery application, the carbon-based cathodes are still vulnerable to attacks from the discharge intermediates or products, as well as the accompanying electrolyte decomposition. To ameliorate this problem, the free-standing and carbon-free CoO nanowire array cathode was purposely designed for Li-O2 batteries. The single CoO nanowire formed as a special mesoporous structure, owing even comparable specific surface area and pore volume to the typical Super-P carbon particles. In addition to the highly selective oxygen reduction/evolution reactions catalytic activity of CoO cathodes, both excellent discharge specific capacity and cycling efficiency of Li-O2 batteries were obtained, with 4888 mAh gCoO(-1) and 50 cycles during 500 h period. Owing to the synergistic effect between elaborate porous structure and selective intermediate absorption on CoO crystal, a unique bimodal growth phenomenon of discharge products was occasionally observed, which further offers a novel mechanism to control the formation/decomposition morphology of discharge products in nanoscale. This research work is believed to shed light on the future development of high-performance aprotic Li-O2 batteries.

Improvement of water management in a vapor feed direct methanol fuel cell

NASA Astrophysics Data System (ADS)

Masdar, M. Shahbudin; Tsujiguchi, Takuya; Nakagawa, Nobuyoshi

Water transport in a vapor feed direct methanol fuel cell was improved by fixing a hydrophobic air filter (HAF) at the cathode. Effects of the HAF properties and the fixed positions, i.e., just on the cathode surface or by providing a certain space from the surface, of the HAF on the water transport as well as the power generation performance were investigated. The water transport was evaluated by measuring the partial pressure of water, PH2O , and methanol, PCH3OH , at the anode gas layer using in situ mass spectrometry with a capillary probe and also the water and methanol fluxes across the electrode structure using a conventional method. The HAF with the highest hydrophobicity and the highest flow resistance had the strongest effect on increasing the water back diffusion from the cathode to the anode through the membrane and increasing the current density. It was noted that the HAF fixation by providing a space from the cathode surface was more effective in increasing JWCO and the current density than that of the direct placement on the cathode surface. There was an optimum distance for the HAF placement depending on the humidity of the outside air.

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.

Characterization and Performance of a High-Current-Density Ion Implanter with Magnetized Hollow-Cathode Plasma Source

NASA Astrophysics Data System (ADS)

Falkenstein, Zoran; Rej, Donald; Gavrilov, Nikolai

1998-10-01

In a collaboration between the Institute of Electrophysics (IEP) and the Los Alamos National Laboratory (LANL), the IEP has developed an industrial scalable, high-power, large-area ion source for the surface modification of materials. The plasma source of the ion beam source can be described as a pulsed glow discharge with a cold, hollow-cathode in a weak magnetic field. Extraction and focusing of positive ions by an acceleration and ion-optical plate system renders the generation of a homogeneous, large-area ion beam with an averaged total ion current of up to 50 mA at acceleration voltages of up to 50 kV. The principle set-up of the ion beam source as well as some electrical characteristics (gas discharge current and the extracted ion beam current) are presented for a lab-scale prototype. Measurements of the radial ion current density profiles within the ion beam for various discharge parameters, as well as results on surface modification by ion implantation of nitrogen into aluminum and chromium are presented. Finally, a comparison of the applied ion dose with the retained ion doses is given.

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.

Nanoporous LiMn2O4 spinel prepared at low temperature as cathode material for aqueous supercapacitors

NASA Astrophysics Data System (ADS)

Wang, F. X.; Xiao, S. Y.; Gao, X. W.; Zhu, Y. S.; Zhang, H. P.; Wu, Y. P.; Holze, R.

2013-11-01

LiMn2O4 spinel was prepared by a hydrothermal method using α-MnO2 nanotubes as precursor at 180 °C, a temperature much lower than that in previously reported methods. It is nanoporous with a pore size of about 40-50 nm and a BET surface area of 9.76 m2 g-1. It exhibits a high specific capacitance of 189 F g-1 at 0.3 A g-1 as a cathode for an aqueous supercapacitor. Even at 12 A g-1, it still has a capacitance of 166 F g-1. After 1500 cycles, there is no evident capacity fading. The LiMn2O4 cathode can deliver an energy density of 31.9 Wh kg-1 at 3480 W kg-1 and even maintain 19.4 Wh kg-1 at about 5100 W kg-1 based on the mass of LiMn2O4.

Toward Stabilizing Co 3O 4 Nanoparticles as an Oxygen Reduction Reaction Catalyst for Intermediate-Temperature SOFCs

DOE PAGES

Ren, Yaoyu; Cheng, Yuan; Gorte, Raymond J.; ...

2017-04-05

The oxygen reduction reaction (ORR) activity of a series of composite cathodes consisting of a porous Gd 0.20Ce 0.80O 2-δ (GDC) scaffold infiltrated with Sr-, Co-, and Y-nitrate solutions has been systematically investigated in this study. The results show that such infiltrated cathodes if calcined at low temperatures such as 350°C exhibit low polarization resistance (RP) in the temperature range of 450–700°C, even though XRD analysis reveals that the calcined product is virtually a mixture of Co 3O 4 and SrCO 3. A further study by design-of-experiment suggests that the true ORR-active species is Co 3O 4, whereas SrCO 3more » serves as a sintering inhibitor to preserve the high surface area of Co 3O 4. The findings and understanding in this study present a new strategy for future development of active cathodes for intermediate-temperature solid oxide fuel cells (SOFCs).« less

Powerful glow discharge excilamp

DOEpatents

Tarasenko, Victor F.; Panchenko, Aleksey N.; Skakun, Victor S.; Sosnin, Edward A.; Wang, Francis T.; Myers, Booth R.; Adamson, Martyn G.

2002-01-01

A powerful glow discharge lamp comprising two coaxial tubes, the outer tube being optically transparent, with a cathode and anode placed at opposite ends of the tubes, the space between the tubes being filled with working gas. The electrodes are made as cylindrical tumblers placed in line to one other in such a way that one end of the cathode is inserted into the inner tube, one end of the anode coaxially covers the end of the outer tube, the inner tube penetrating and extending through the anode. The increased electrodes' surface area increases glow discharge electron current and, correspondingly, average radiation power of discharge plasma. The inner tube contains at least one cooling liquid tube placed along the axis of the inner tube along the entire lamp length to provide cathode cooling. The anode has a circumferential heat extracting radiator which removes heat from the anode. The invention is related to lighting engineering and can be applied for realization of photostimulated processes under the action of powerful radiation in required spectral range.

Erythrocyte-like hollow carbon capsules and their application in proton exchange membrane fuel cells.

PubMed

Kim, Jung Ho; Yu, Jong-Sung

2010-12-14

Hierarchical nanostructured erythrocyte-like hollow carbon (EHC) with a hollow hemispherical macroporous core of ca. 230 nm in diameter and 30-40 nm thick mesoporous shell was synthesized and explored as a cathode catalyst support in a proton exchange membrane fuel cell (PEMFC). The morphology control of EHC was successfully achieved using solid core/mesoporous shell (SCMS) silica template and different styrene/furfuryl alcohol mixture compositions by a nanocasting method. The EHC-supported Pt (20 wt%) cathodes prepared have demonstrated markedly enhanced catalytic activity towards oxygen reduction reactions (ORRs) and greatly improved PEMFC polarization performance compared to carbon black Vulcan XC-72 (VC)-supported ones, probably due to the superb structural characteristics of the EHC such as uniform size, well-developed porosity, large specific surface area and pore volume. In particular, Pt/EHC cathodes exhibited ca. 30-60% higher ORR activity than a commercial Johnson Matthey Pt catalyst at a low catalyst loading of 0.2 mg Pt cm(-2).

Toward Stabilizing Co 3O 4 Nanoparticles as an Oxygen Reduction Reaction Catalyst for Intermediate-Temperature SOFCs

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

Ren, Yaoyu; Cheng, Yuan; Gorte, Raymond J.

The oxygen reduction reaction (ORR) activity of a series of composite cathodes consisting of a porous Gd 0.20Ce 0.80O 2-δ (GDC) scaffold infiltrated with Sr-, Co-, and Y-nitrate solutions has been systematically investigated in this study. The results show that such infiltrated cathodes if calcined at low temperatures such as 350°C exhibit low polarization resistance (RP) in the temperature range of 450–700°C, even though XRD analysis reveals that the calcined product is virtually a mixture of Co 3O 4 and SrCO 3. A further study by design-of-experiment suggests that the true ORR-active species is Co 3O 4, whereas SrCO 3more » serves as a sintering inhibitor to preserve the high surface area of Co 3O 4. The findings and understanding in this study present a new strategy for future development of active cathodes for intermediate-temperature solid oxide fuel cells (SOFCs).« less

Optical Plasma Control During ARC Carbon Nanotube Growth

NASA Technical Reports Server (NTRS)

Hinkov, I.; Farhat, S.; DeLaChapelle, M. Lamy; Fan, S. S.; Han, H. X.; Li, G. H.; Scott, C. D.

2001-01-01

To improve nanotube production, we developed a novel optical control technique, based on the shape of the visible plasma zone created between the anode and the cathode in the direct current (DC) arc process. For a given inert gas, we adjust the anode to cathode distance (ACD) in order to obtain strong visible vortices around the cathode. This enhance anode vaporization, which improve nanotubes formation. In light of our experimental results, we focus our discussion on the relationship between plasma parameters and nanotube growth. Plasma temperature control during arc process is achieved using argon, helium, and their mixtures as a buffer gases. The variation of the gas mixture from pure argon to pure helium changes plasma temperature. As a consequence, the microscopic characteristics of nanotubes as diameter distribution is changed moving from smaller values for argon to higher diameters for helium. We also observe a dependence of the macroscopic characteristics of the final products as Brunauer-Emmett-Teller (BET) surface area.

Pulsed Electron Source with Grid Plasma Cathode and Longitudinal Magnetic Field for Modification of Material and Product Surfaces

NASA Astrophysics Data System (ADS)

Devyatkov, V. N.; Koval, N. N.

2018-01-01

The description and the main characteristics of the pulsed electron source "SOLO" developed on the basis of the plasma cathode with grid stabilization of the emission plasma boundary are presented. The emission plasma is generated by a low-pressure arc discharge, and that allows to form the dense low-energy electron beam with a wide range of independently adjustable parameters of beam current pulses (pulse duration of 20-250 μs, pulse repetition rate of 1-10 s-1, amplitude of beam current pulses of 20-300 A, and energy of beam electrons of 5-25 keV). The special features of generation of emission plasma by constricted low-pressure arc discharge in the grid plasma cathode partially dipped into a non-uniform magnetic field and of formation and transportation of the electron beam in a longitudinal magnetic field are considered. The application area of the electron source and technologies realized with its help are specified.

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

PubMed

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

2016-02-14

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

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.

Surface-enhanced redox chemistry of polysulphides on a metallic and polar host for lithium-sulphur batteries.

PubMed

Pang, Quan; Kundu, Dipan; Cuisinier, Marine; Nazar, L F

2014-08-26

The lithium-sulphur battery relies on the reversible conversion between sulphur and Li2S and is highly appealing for energy storage owing to its low cost and high energy density. Porous carbons are typically used as sulfur hosts, but they do not adsorb the hydrophilic polysulphide intermediates or adhere well to Li2S, resulting in pronounced capacity fading. Here we report a different strategy based on an inherently polar, high surface area metallic oxide cathode host and show that it mitigates polysulphide dissolution by forming an excellent interface with Li2S. Complementary physical and electrochemical probes demonstrate strong polysulphide/Li2S binding with this 'sulphiphilic' host and provide experimental evidence for surface-mediated redox chemistry. In a lithium-sulphur cell, Ti4O7/S cathodes provide a discharge capacity of 1,070 mAh g(-1) at intermediate rates and a doubling in capacity retention with respect to a typical conductive carbon electrode, at practical sulphur mass fractions up to 70 wt%. Stable cycling performance is demonstrated at high rates over 500 cycles.

Three-Dimensionally Hierarchical Graphene Based Aerogel Encapsulated Sulfur as Cathode for Lithium/Sulfur Batteries

PubMed Central

Li, Haipeng; Sun, Liancheng; Wang, Zhuo; Zhang, Yongguang; Tan, Taizhe; Wang, Gongkai

2018-01-01

A simple and effective method was developed to obtain the electrode for lithium/sulfur (Li/S) batteries with high specific capacity and cycling durability via adopting an interconnected sulfur/activated carbon/graphene (reduced graphene oxide) aerogel (S/AC/GA) cathode architecture. The AC/GA composite with a well-defined interconnected conductive network was prepared by a reduction-induced self-assembly process, which allows for obtaining compact and porous structures. During this process, reduced graphene oxide (RGO) was formed, and due to the presence of oxygen-containing functional groups on its surface, it not only improves the electronic conductivity of the cathode but also effectively inhibits the polysulfides dissolution and shuttle. The introduced activated carbon allowed for lateral and vertical connection between individual graphene sheets, completing the formation of a stable three-dimensionally (3D) interconnected graphene framework. Moreover, a high specific surface area and 3D interconnected porous structure efficiently hosts a higher amount of active sulfur material, about 65 wt %. The designed S/AC/GA composite electrodes deliver an initial capacity of 1159 mAh g−1 at 0.1 C and can retain a capacity of 765 mAh g−1 after 100 cycles in potential range from 1 V to 3 V. PMID:29373525

A polymerized C60 coating enhancing interfacial stability at three-dimensional LiCoO2 in high-potential regime

NASA Astrophysics Data System (ADS)

Hudaya, Chairul; Halim, Martin; Pröll, Johannes; Besser, Heino; Choi, Wonchang; Pfleging, Wilhelm; Seifert, Hans Jürgen; Lee, Joong Kee

2015-12-01

The interfacial instabilities, including side reactions due to electrolyte decompositions and Cobalt (Co) dissolutions, are the main detrimental processes at LiCoO2 cathode when a high-voltage window (>4.2 V) is applied. Nevertheless, cycling the cathode with a voltage above 4.2 V would deliver an increased gravimetric capacity, which is desired for high power battery operation. To address these drawbacks, we demonstrate a synergistic approach by manufacturing the three-dimensional high-temperature LiCoO2 electrodes (3D HT-LCO) using laser-microstructuring, laser-annealing and subsequent coating with polymerized C60 thin films (C60@3D HT-LCO) by plasma-assisted thermal evaporation. The C60@3D HT-LCO cathode delivers higher initial discharge capacity compared to its theoretical value, i.e. 175 mA h g-1 at 0.1 C with cut-off voltage of 3.0-4.5 V. This cathode combines the advantages of the 3D electrode architecture and an advanced C60 coating/passivation concept leading to an improved electrochemical performance, due to an increased active surface area, a decreased charge transfer resistance, a prevented Co dissolution into the electrolyte and a suppressed side reaction and electrolyte decomposition. This work provides a novel solution for other cathode materials having similar concerns in high potential regimes for application in lithium-ion microbatteries.

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

PubMed Central

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

2016-01-01

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

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

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

PubMed

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

2016-02-04

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

Study on Dy0.45Ba0.05Sr0.5Co0.8Fe0.2O3-δ-Ce0.85Gd0.15O1.95 composite cathode material for intermediate temperature solid oxide fuel cell

NASA Astrophysics Data System (ADS)

Kautkar, Pranay R.; Acharya, Smita A.

2018-05-01

xDy0.45Ba0.05Sr0.5Co0.8Fe0.2O3-δ - xCe0.85Gd0.15O1.95 (x = 50 %) composite cathode supported on Ce0.85Gd0.15O1.95 (GDC15) electrolyte are studied for applications in IT-SOFCs. Results attribute that Dy0.45Ba0.05Sr0.5Co0.8Fe0.2O3-δ material is chemically compatible with Ce0.85Gd0.15O1.95 (GDC15). Rietveld refined X-ray diffraction patterns notify orthorhombic (space group:Pbnm) symmetry for Dy0.45 Ba0.05Sr0.5Co0.8Fe0.2O3-δ and fluorite type structure (space group: Fm-3m) symmetry for GDC15. The polarization resistance (Rp) of composite cathode reduces to the minimum value of 1.35 Ω cm2 at 650 °C in air. Area specific resistance (ASR) of composite cathode has found 0.67 Ω.cm2 at 650°C respectively. Result shows that the surface diffusion of the dissociative adsorbed oxygen at electrode/electrolyte interface on the composite cathode.

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

NASA Astrophysics Data System (ADS)

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

2016-02-01

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

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

NASA Astrophysics Data System (ADS)

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

2017-09-01

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

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.

Solid oxide fuel cells having porous cathodes infiltrated with oxygen-reducing catalysts

DOEpatents

Liu, Meilin; Liu, Ze; Liu, Mingfei; Nie, Lifang; Mebane, David Spencer; Wilson, Lane Curtis; Surdoval, Wayne

2014-08-12

Solid-oxide fuel cells include an electrolyte and an anode electrically coupled to a first surface of the electrolyte. A cathode is provided, which is electrically coupled to a second surface of the electrolyte. The cathode includes a porous backbone having a porosity in a range from about 20% to about 70%. The porous backbone contains a mixed ionic-electronic conductor (MIEC) of a first material infiltrated with an oxygen-reducing catalyst of a second material different from the first material.

Evaluation of advanced high rate Li-SOCl2 cells

NASA Technical Reports Server (NTRS)

Deligiannis, F.; Ang, V.; Dawson, S.; Frank, H.; Subbarao, S.

1986-01-01

Under NASA sponsorship, JPL is developing advanced, high rate Li-SOCl2 cells for future space missions. As part of this effort, Li-SOCl2 cells of various designs were examined for performance and safety. The cells differed from one another in several aspects, such as: nature of carbon cathode, catalysts, cell configuration, case polarity, and safety devices. Performance evaluation included constant-current discharge over a range of currents and temperatures. Abuse-testing consisted of shortcircuiting, charging, and over-discharge. Energy densities greater than 300 Wh/Kg at the C/2 rate were found for some designs. A cell design featuring a high-surface-area carbon cathode was found to deliver nearly 500 Wh/Kg at moderate discharge rates. Temperature influenced the performance significantly.

Spinel lithium manganese oxide nanoparticles: unique molten salt synthesis strategy and excellent electrochemical performances.

PubMed

Wang, Xiong; Zhu, Juanjuan; Liu, Yingjie

2009-11-01

As a promising candidate cathode material, spinel lithium manganese oxide nanoparticles were successfully synthesized through a novel molten salt synthesis route at relatively low temperature, using manganese dioxide nanowires as precursor. A variety of techniques were applied to characterize the spinel nanomaterial, including X-ray diffraction, transmission electron microscopy, field-emission scanning electron microscopy, and X-ray photoelectron spectroscopy. The average particle size of the resulting spinel nanoparticles was about 80 nm with narrow distribution. As cathode material for rechargeable lithium ion battery, the electrochemical properties were investigated. All the results show that the electrochemical performances of the homogeneous spinel nanoparticles were improved, which might be ascribed to large specific surface area, fairly narrow size distribution, and the unique synthesis strategy.

Lithium ion batteries with titania/graphene anodes

DOEpatents

Liu, Jun; Choi, Daiwon; Yang, Zhenguo; Wang, Donghai; Graff, Gordon L; Nie, Zimin; Viswanathan, Vilayanur V; Zhang, Jason; Xu, Wu; Kim, Jin Yong

2013-05-28

Lithium ion batteries having an anode comprising at least one graphene layer in electrical communication with titania to form a nanocomposite material, a cathode comprising a lithium olivine structure, and an electrolyte. The graphene layer has a carbon to oxygen ratio of between 15 to 1 and 500 to 1 and a surface area of between 400 and 2630 m.sup.2/g. The nanocomposite material has a specific capacity at least twice that of a titania material without graphene material at a charge/discharge rate greater than about 10 C. The olivine structure of the cathode of the lithium ion battery of the present invention is LiMPO.sub.4 where M is selected from the group consisting of Fe, Mn, Co, Ni and combinations thereof.

Vacuum encapsulated, high temperature diamond amplified cathode capsule and method for making same

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

Rao, Triveni; Walsh, Josh; Gangone, Elizabeth

2015-12-29

A vacuum encapsulated, hermetically sealed cathode capsule for generating an electron beam of secondary electrons, which generally includes a cathode element having a primary emission surface adapted to emit primary electrons, an annular insulating spacer, a diamond window element comprising a diamond material and having a secondary emission surface adapted to emit secondary electrons in response to primary electrons impinging on the diamond window element, a first high-temperature solder weld disposed between the diamond window element and the annular insulating spacer and a second high-temperature solder weld disposed between the annular insulating spacer and the cathode element. The cathode capsulemore » is formed by a high temperature weld process under vacuum such that the first solder weld forms a hermetical seal between the diamond window element and the annular insulating spacer and the second solder weld forms a hermetical seal between the annular spacer and the cathode element whereby a vacuum encapsulated chamber is formed within the capsule.« less

Vacuum encapsulated hermetically sealed diamond amplified cathode capsule and method for making same

DOEpatents

Rao, Triveni; Walsh, John; Gangone, Elizabeth

2014-12-30

A vacuum encapsulated, hermetically sealed cathode capsule for generating an electron beam of secondary electrons, which generally includes a cathode element having a primary emission surface adapted to emit primary electrons, an annular insulating spacer, a diamond window element comprising a diamond material and having a secondary emission surface adapted to emit secondary electrons in response to primary electrons impinging on the diamond window element, a first cold-weld ring disposed between the cathode element and the annular insulating spacer and a second cold-weld ring disposed between the annular insulating spacer and the diamond window element. The cathode capsule is formed by a vacuum cold-weld process such that the first cold-weld ring forms a hermetical seal between the cathode element and the annular insulating spacer and the second cold-weld ring forms a hermetical seal between the annular spacer and the diamond window element whereby a vacuum encapsulated chamber is formed within the capsule.

Non-linear macro evolution of a dc driven micro atmospheric glow discharge

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

Xu, S. F.; Zhong, X. X., E-mail: xxzhong@sjtu.edu.cn

2015-10-15

We studied the macro evolution of the micro atmospheric glow discharge generated between a micro argon jet into ambient air and static water. The micro discharge behaves similarly to a complex ecosystem. Non-linear behaviors are found for the micro discharge when the water acts as a cathode, different from the discharge when water behaves as an anode. Groups of snapshots of the micro discharge formed at different discharge currents are captured by an intensified charge-coupled device with controlled exposure time, and each group consisted of 256 images taken in succession. Edge detection methods are used to identify the water surfacemore » and then the total brightness is defined by adding up the signal counts over the area of the micro discharge. Motions of the water surface at different discharge currents show that the water surface lowers increasingly rapidly when the water acts as a cathode. In contrast, the water surface lowers at a constant speed when the water behaves as an anode. The light curves are similar to logistic growth curves, suggesting that a self-inhibition process occurs in the micro discharge. Meanwhile, the total brightness increases linearly during the same time when the water acts as an anode. Discharge-water interactions cause the micro discharge to evolve. The charged particle bomb process is probably responsible for the different behaviors of the micro discharges when the water acts as cathode and anode.« less

Electron gun for a multiple beam klystron with magnetic compression of the electron beams

DOEpatents

Ives, R. Lawrence; Tran, Hien T; Bui, Thuc; Attarian, Adam; Tallis, William; David, John; Forstall, Virginia; Andujar, Cynthia; Blach, Noah T; Brown, David B; Gadson, Sean E; Kiley, Erin M; Read, Michael

2013-10-01

A multi-beam electron gun provides a plurality N of cathode assemblies comprising a cathode, anode, and focus electrode, each cathode assembly having a local cathode axis and also a central cathode point defined by the intersection of the local cathode axis with the emitting surface of the cathode. Each cathode is arranged with its central point positioned in a plane orthogonal to a device central axis, with each cathode central point an equal distance from the device axis and with an included angle of 360/N between each cathode central point. The local axis of each cathode has a cathode divergence angle with respect to the central axis which is set such that the diverging magnetic field from a solenoidal coil is less than 5 degrees with respect to the projection of the local cathode axis onto a cathode reference plane formed by the device axis and the central cathode point, and the local axis of each cathode is also set such that the angle formed between the cathode reference plane and the local cathode axis results in minimum spiraling in the path of the electron beams in a homogenous magnetic field region of the solenoidal field generator.

Cathode surface effects and H.F.-behaviour of vacuum arcs

NASA Astrophysics Data System (ADS)

Fu, Yan Hong

To gain a better understanding of the essential processes occurring during a vacuum arc interruption for the further development of the vacuum arc circuit breaker, cathode spot behavior, current interruption, dielectrical recovery and overvoltage generation are investigated. An experimental study on cathode spot behavior of the DC vacuum arc in relation to cathode surface roughness and a qualitative physical model to interpret the results are reported. An experimental investigation on the High Frequency (HF) current interruption, multiple recognitions and voltage escalation phenomena is reported. A calculation program to predict the level of overvoltages generated by the operation of a vacuum breaker in a realistic single phase circuit is developed. Detailed results are summarized.

Surface-reconstructed graphite nanofibers as a support for cathode catalysts of fuel cells.

PubMed

Gan, Lin; Du, Hongda; Li, Baohua; Kang, Feiyu

2011-04-07

Graphite nanofibers (GNFs), on which surface graphite edges were reconstructed into nano-loops, were explored as a cathode catalyst support for fuel cells. The high degree of graphitization, as well as the surface-reconstructed nano-loops that possess topological defects for uniform metal deposition, resulted in an improved performance of the GNF-supported Pt catalyst.

High speed electrostatic photomultiplier tube for the 1.06 micrometer wavelength. Cup and slat dynode chain combined with flat cathode and coax output produces 0.25 nsec rise time

NASA Technical Reports Server (NTRS)

Sparks, S. D.

1973-01-01

The Varian cup and slat dynode chain was modified to have a flat cathode. These modifications were incorporated in an all-electrostatic photomultiplier tube having a rise time of 0.25 n sec. The tube delivered under the contract had a flat S-20 opaque cathode with a useful diameter of 5 mm. The design of the tube is such that a III to V cathode support is mounted in place of the existing cathode substrate. This cathode support is designed to accept a transferred III to V cathode and maintain the cathode surface in the same position as the S-20 photocathode.

INTENSE ENERGETIC GAS DISCHARGE

DOEpatents

Luce, J.S.

1960-03-01

A method and apparatus for initiating and sustaining an energetic gas arc discharge are described. A hollow cathode and a hollow anode are provided. By regulating the rate of gas flow into the interior of the cathode, the arc discharge is caused to run from the inner surface of the cathode with the result that adequate space-charge neutralization is provided inside the cathode but not in the main arc volume. Thus, the gas fed to the cathode is substantially completely ionized before it leaves the cathode, with the result that an energetic arc discharge can be maintained at lower operating pressures.

Characterization of the NEXT Hollow Cathode Inserts After Long-Duration Testing

NASA Technical Reports Server (NTRS)

Mackey, J.; Shastry, R.; Soulas, G.

2017-01-01

Hollow dispenser cathode inserts are a critical element of electric propulsion systems, and should therefore be well understood during long term operation to ensure reliable system performance. This work destructively investigated cathode inserts from the NEXT long-duration test which demonstrated 51,184 hours of high-voltage operation, 918 kg of propellant throughput, and 35.5 MN-s of total impulse. The characterization methods used include scanning electron microscopy with energy dispersive spectroscopy and X-ray diffraction. Microscopy analysis has been performed on fractured surfaces, emission surfaces, and metallographically polished cross-sections of post-test inserts and unused inserts. Impregnate distribution, etch region thickness, impregnate chemical content, emission surface topography, and emission surface phase identification are the primary factors investigated.

Locally Resolved Electron Emission Area and Unified View of Field Emission from Ultrananocrystalline Diamond Films

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

Chubenko, Oksana; Baturin, Stanislav S.; Kovi, Kiran K.

One of the common problems in case of field emission from polycrystalline diamond films, which typically have uniform surface morphology, is uncertainty in determining exact location of electron emission sites across the surface. Although several studies have suggested that grain boundaries are the main electron emission source, it is not particularly clear what makes some sites emit more than the others. It is also practically unclear how one could quantify the actual electron emission area and therefore field emission current per unit area. In this paper we study the effect of actual, locally resolved, field emission (FE) area on electronmore » emission characteristics of uniform planar highly conductive nitrogen-incorporated ultrananocrystalline diamond ((N)UNCD) field emitters. It was routinely found that field emission from as-grown planar (N)UNCD films is always confined to a counted number of discrete emitting centers across the surface which varied in size and electron emissivity. It was established that the actual FE area critically depends on the applied electric field, as well as that the actual FE area and the overall electron emissivity improve with sp2 fraction present in the film irrespectively of the original substrate roughness and morphology. To quantify the actual FE area and its dependence on the applied electric field, imaging experiments were carried out in a vacuum system in a parallel-plate configuration with a specialty anode phosphor screen. Electron emission micrographs were taken concurrently with I-V characteristics measurements. In addition, a novel automated image processing algorithm was developed to process extensive imaging datasets and calculate emission area per image. By doing so, it was determined that the emitting area was always significantly smaller than the FE cathode surface area. Namely, the actual FE area would change from 5×10-3 % to 1.5 % of the total cathode area with the applied electric field increased. Finally and most importantly, it was shown that when I-E curves as measured in the experiment were normalized by the field-dependent emission area, the resulting j-E curves demonstrated a strong kink and significant deviation from Fowler-Nordheim (FN) law, and eventually saturated at a current density of ~100 mA/cm2 . This value was nearly identical for all (N)UNCD films measured in this study, regardless of the substrate.« less

Application of electron beam equipment based on a plasma cathode gun in additive technology

NASA Astrophysics Data System (ADS)

Galchenko, N. K.; Kolesnikova, K. A.; Semenov, G. V.; Rau, A. G.; Raskoshniy, S. Y.; Bezzubko, A. V.; Dampilon, B. V.; Sorokova, S. N.

2016-11-01

The paper discusses the application of electron beam equipment based on a plasma cathode gun for three-dimensional surface modification of metals and alloys. The effect of substrate surface preparation on the adhesion strength of gas thermal coatings has been investigated.

Proposal for Research on High-Brightness Cathodes for High-Power Free-Electron Lasers (FEL)

DTIC Science & Technology

2013-05-09

recent experiments involving single crystal diamond amplifier cathodes (DAC) at Brookhaven National Laboratory ( BNL ). While the emission surface of our...diamond grain in the entire structure, both surface and interior, is passivated with hydrogen. The aforementioned studies at BNL found that

Electrochemical Cathodic Polarization, a Simplified Method That Can Modified and Increase the Biological Activity of Titanium Surfaces: A Systematic Review

PubMed Central

2016-01-01

Background The cathodic polarization seems to be an electrochemical method capable of modifying and coat biomolecules on titanium surfaces, improving the surface activity and promoting better biological responses. Objective The aim of the systematic review is to assess the scientific literature to evaluate the cellular response produced by treatment of titanium surfaces by applying the cathodic polarization technique. Data, Sources, and Selection The literature search was performed in several databases including PubMed, Web of Science, Scopus, Science Direct, Scielo and EBSCO Host, until June 2016, with no limits used. Eligibility criteria were used and quality assessment was performed following slightly modified ARRIVE and SYRCLE guidelines for cellular studies and animal research. Results Thirteen studies accomplished the inclusion criteria and were considered in the review. The quality of reporting studies in animal models was low and for the in vitro studies it was high. The in vitro and in vivo results reported that the use of cathodic polarization promoted hydride surfaces, effective deposition, and adhesion of the coated biomolecules. In the experimental groups that used the electrochemical method, cellular viability, proliferation, adhesion, differentiation, or bone growth were better or comparable with the control groups. Conclusions The use of the cathodic polarization method to modify titanium surfaces seems to be an interesting method that could produce active layers and consequently enhance cellular response, in vitro and in vivo animal model studies. PMID:27441840

Electrochemical surface modification of titanium in dentistry.

PubMed

Kim, Kyo-Han; Ramaswamy, Narayanan

2009-01-01

Titanium and its alloys have good biocompatibility with body cells and tissues and are widely used for implant applications. However, clinical procedures place more stringent and tough requirements on the titanium surface necessitating artificial surface treatments. Among the many methods of titanium surface modification, electrochemical techniques are simple and cheap. Anodic oxidation is the anodic electrochemical technique while electrophoretic and cathodic depositions are the cathodic electrochemical techniques. By anodic oxidation it is possible to obtain desired roughness, porosity and chemical composition of the oxide. Anodic oxidation at high voltages can improve the crystallinity of the oxide. The chief advantage of this technique is doping of the coating of the bath constituents and incorporation of these elements improves the properties of the oxide. Electrophoretic deposition uses hydroxyapatite (HA) powders dispersed in a suitable solvent at a particular pH. Under these operating conditions these particles acquire positive charge and coatings are obtained on the cathodic titanium by applying an external electric field. These coatings require a post-sintering treatment to improve the coating properties. Cathodic deposition is another type of electrochemical method where HA is formed in situ from an electrolyte containing calcium and phosphate ions. It is also possible to alter structure and/or chemistry of the obtained deposit. Nano-grained HA has higher surface energy and greater biological activity and therefore emphasis is being laid to produce these coatings by cathodic deposition.

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

Shao, Jiahang; Antipov, Sergey P.; Baryshev, Sergey V.

Field emission from a solid metal surface has been continuously studied for a century over macroscopic to atomic scales. It is general knowledge that, other than the surface properties, the emitted current is governed solely by the applied electric field. A pin cathode has been used to study the dependence of field emission on stored energy in an L-band rf gun. The stored energy was changed by adjusting the axial position (distance between the cathode base and the gun back surface) of the cathode while the applied electric field on the cathode tip is kept constant. Avery strong correlation ofmore » the field-emission current with the stored energy has been observed. While eliminating all possible interfering sources, an enhancement of the current by a factor of 5 was obtained as the stored energy was increased by a factor of 3. It implies that under certain circumstances a localized field emission may be significantly altered by the global parameters in a system.« less

Direct observation of the oxygenated species during oxygen reduction on a platinum fuel cell cathode

NASA Astrophysics Data System (ADS)

Casalongue, Hernan Sanchez; Kaya, Sarp; Viswanathan, Venkatasubramanian; Miller, Daniel J.; Friebel, Daniel; Hansen, Heine A.; Nørskov, Jens K.; Nilsson, Anders; Ogasawara, Hirohito

2013-12-01

The performance of polymer electrolyte membrane fuel cells is limited by the reduction at the cathode of various oxygenated intermediates in the four-electron pathway of the oxygen reduction reaction. Here we use ambient pressure X-ray photoelectron spectroscopy, and directly probe the correlation between the adsorbed species on the surface and the electrochemical potential. We demonstrate that, during the oxygen reduction reaction, hydroxyl intermediates on the cathode surface occur in several configurations with significantly different structures and reactivities. In particular, we find that near the open-circuit potential, non-hydrated hydroxyl is the dominant surface species. On the basis of density functional theory calculations, we show that the removal of hydration enhances the reactivity of oxygen species. Tuning the hydration of hydroxyl near the triple phase boundary will be crucial for designing more active fuel cell cathodes.

A Semi-Empirical Two Step Carbon Corrosion Reaction Model in PEM Fuel Cells

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

Young, Alan; Colbow, Vesna; Harvey, David

2013-01-01

The cathode CL of a polymer electrolyte membrane fuel cell (PEMFC) was exposed to high potentials, 1.0 to 1.4 V versus a reversible hydrogen electrode (RHE), that are typically encountered during start up/shut down operation. While both platinum dissolution and carbon corrosion occurred, the carbon corrosion effects were isolated and modeled. The presented model separates the carbon corrosion process into two reaction steps; (1) oxidation of the carbon surface to carbon-oxygen groups, and (2) further corrosion of the oxidized surface to carbon dioxide/monoxide. To oxidize and corrode the cathode catalyst carbon support, the CL was subjected to an accelerated stressmore » test cycled the potential from 0.6 VRHE to an upper potential limit (UPL) ranging from 0.9 to 1.4 VRHE at varying dwell times. The reaction rate constants and specific capacitances of carbon and platinum were fitted by evaluating the double layer capacitance (Cdl) trends. Carbon surface oxidation increased the Cdl due to increased specific capacitance for carbon surfaces with carbon-oxygen groups, while the second corrosion reaction decreased the Cdl due to loss of the overall carbon surface area. The first oxidation step differed between carbon types, while both reaction rate constants were found to have a dependency on UPL, temperature, and gas relative humidity.« less

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

Advanced electrorefiner design

DOEpatents

Miller, W.E.; Gay, E.C.; Tomczuk, Z.

1996-07-02

A combination anode and cathode is described for an electrorefiner which includes a hollow cathode and an anode positioned inside the hollow cathode such that a portion of the anode is near the cathode. A retaining member is positioned at the bottom of the cathode. Mechanism is included for providing relative movement between the anode and the cathode during deposition of metal on the inside surface of the cathode during operation of the electrorefiner to refine spent nuclear fuel. A method is also disclosed which includes electrical power means selectively connectable to the anode and the hollow cathode for providing electrical power to the cell components, electrically transferring uranium values and plutonium values from the anode to the electrolyte, and electrolytically depositing substantially pure uranium on the hollow cathode. Uranium and plutonium are deposited at a liquid cathode together after the PuCl{sub 3} to UCl{sub 3} ratio is greater than 2:1. Slots in the hollow cathode provides close anode access for the liquid pool in the liquid cathode. 6 figs.

Advanced electrorefiner design

DOEpatents

Miller, William E.; Gay, Eddie C.; Tomczuk, Zygmunt

1996-01-01

A combination anode and cathode for an electrorefiner which includes a hollow cathode and an anode positioned inside the hollow cathode such that a portion of the anode is near the cathode. A retaining member is positioned at the bottom of the cathode. Mechanism is included for providing relative movement between the anode and the cathode during deposition of metal on the inside surface of the cathode during operation of the electrorefiner to refine spent nuclear fuel. A method is also disclosed which includes electrical power means selectively connectable to the anode and the hollow cathode for providing electrical power to the cell components, electrically transferring uranium values and plutonium values from the anode to the electrolyte, and electrolytically depositing substantially pure uranium on the hollow cathode. Uranium and plutonium are deposited at a liquid cathode together after the PuCl.sub.3 to UCl.sub.3 ratio is greater than 2:1. Slots in the hollow cathode provides close anode access for the liquid pool in the liquid cathode.

Structural and Morphological Properties of Carbon Supports: Effect of Catalyst degradation, ECS Transactions 33(1), 425 (2010)

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

A. Patel; K. Artyushkova; P. Atanassov

The object of this work was to identify correlations between performance losses of Pt electrocatalysts on carbon support materials and the chemical and morphological parameters that describe them. Accelerated stress testing, with an upper potential of 1.2 V, was used to monitor changes to cathode properties, including kinetic performance and effective platinum surface area losses. The structure and chemical compositions were studied using X-ray Photoelectron Spectroscopy and Scanning Electron Microscopy coupled with Digital Image Processing. As this is an ongoing study, it is difficult to draw firm conclusions, though a trend between support surface area overall performance loss was foundmore » to exist.« less

Structural and Morphological Properties of Carbon Supports: Effect on Catalyst Degradation

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

Patel, Anant; Artyushkova, Kateryna; Atanassov, Plamen

2010-07-01

The object of this work was to identify correlations between performance losses of Pt electrocatalysts on carbon support materials and the chemical and morphological parameters that describe them. Accelerated stress testing, with an upper potential of 1.2 V, was used to monitor changes to cathode properties, including kinetic performance and effective platinum surface area losses. The structure and chemical compositions were studied using X-ray Photoelectron Spectroscopy and Scanning Electron Microscopy coupled with Digital Image Processing. As this is an ongoing study, it is difficult to draw firm conclusions, though a trend between support surface area overall performance loss was foundmore » to exist.« less

Scanning Electron Microscopy with Samples in an Electric Field

PubMed Central

Frank, Ludĕk; Hovorka, Miloš; Mikmeková, Šárka; Mikmeková, Eliška; Müllerová, Ilona; Pokorná, Zuzana

2012-01-01

The high negative bias of a sample in a scanning electron microscope constitutes the “cathode lens” with a strong electric field just above the sample surface. This mode offers a convenient tool for controlling the landing energy of electrons down to units or even fractions of electronvolts with only slight readjustments of the column. Moreover, the field accelerates and collimates the signal electrons to earthed detectors above and below the sample, thereby assuring high collection efficiency and high amplification of the image signal. One important feature is the ability to acquire the complete emission of the backscattered electrons, including those emitted at high angles with respect to the surface normal. The cathode lens aberrations are proportional to the landing energy of electrons so the spot size becomes nearly constant throughout the full energy scale. At low energies and with their complete angular distribution acquired, the backscattered electron images offer enhanced information about crystalline and electronic structures thanks to contrast mechanisms that are otherwise unavailable. Examples from various areas of materials science are presented.

Enhanced Performance of non-PGM Catalysts in Air Operated PEM-Fuel Cells

DOE PAGES

Barkholtz, Heather M.; Chong, Lina; Kaiser, Zachary Brian; ...

2016-10-13

Here a non-platinum group metal (non-PGM) oxygen reduction catalyst was prepared from “support-free” zeolitic imidazolate framework (ZIF) precursor and tested in the proton exchange membrane fuel cell with air as the cathode feed. The iron nitrogen and carbon composite (FeeNeC) based catalyst has high specific surface area decorated uniformly with active sites, which redefines the triple phase boundary (TPB) and requires re-optimization of the cathodic membrane electrode fabrication to ensure efficient mass and charge transports to the catalyst surface. This study reports an effort in optimizing catalytic ink formulation for the membrane electrode preparation and its impact to the fuelmore » cell performance under air. Through optimization, the fuel cell areal current density as high as 115.2 mA/cm 2 at 0.8 V or 147.6 mA/cm 2 at 0.8 V iR-free has been achieved under one bar air. We also investigated impacts on fuel cell internal impedance and the water formation.« less

Influence of laser pulse duration on the electrochemical performance of laser structured LiFePO4 composite electrodes

NASA Astrophysics Data System (ADS)

Mangang, M.; Seifert, H. J.; Pfleging, W.

2016-02-01

Lithium iron phosphate is a promising cathode material for lithium-ion batteries, despite its low electrical conductivity and lithium-ion diffusion kinetic. To overcome the reduced rate performance, three dimensional (3D) architectures were generated in composite cathode layers. By using ultrashort laser radiation with pulse durations in the femtosecond regime the ablation depth per pulse is three times higher compared to nanosecond laser pulses. Due to the 3D structuring, the surface area of the active material which is in direct contact with liquid electrolyte, i.e. the active surface, is increased. As a result the capacity retention and the cycle stability were significantly improved, especially for high charging/discharging currents. Furthermore, a 3D structure leads to higher currents during cyclic voltammetry. Thus, the lithium-ion diffusion kinetic in the cell was improved. In addition, using ultrashort laser pulses results in a high aspect ratio and further improvement of the cell kinetic was achieved.

Electron beam extraction on plasma cathode electron sources system

NASA Astrophysics Data System (ADS)

Purwadi, Agus; Taufik, M., Lely Susita R.; Suprapto, Saefurrochman, H., Anjar A.; Wibowo, Kurnia; Aziz, Ihwanul; Siswanto, Bambang

2017-03-01

ELECTRON BEAM EXTRACTION ON PLASMA CATHODE ELECTRON SOURCES SYSTEM. The electron beam extraction through window of Plasma Generator Chamber (PGC) for Pulsed Electron Irradiator (PEI) device and simulation of plasma potential has been studied. Plasma electron beam is extracted to acceleration region for enlarging their power by the external accelerating high voltage (Vext) and then it is passed foil window of the PEI for being irradiated to any target (atmospheric pressure). Electron beam extraction from plasma surface must be able to overcome potential barrier at the extraction window region which is shown by estimate simulation (Opera program) based on data of plasma surface potential of 150 V with Ueks values are varied by 150 kV, 175 kV and 200 kV respectively. PGC is made of 304 stainless steel with cylindrical shape in 30 cm of diameter, 90 cm length, electrons extraction window as many as 975 holes on the area of (15 × 65) cm2 with extraction hole cell in 0.3 mm of radius each other, an cylindrical shape IEP chamber is made of 304 stainless steel in 70 cm diameter and 30 cm length. The research result shown that the acquisition of electron beam extraction current depends on plasma parameters (electron density ne, temperature Te), accelerating high voltage Vext, the value of discharge parameter G, anode area Sa, electron extraction window area Se and extraction efficiency value α.

Mosaic-shaped cathode for highly durable solid oxide fuel cell under thermal stress

NASA Astrophysics Data System (ADS)

Joo, Jong Hoon; Jeong, Jaewon; Kim, Se Young; Yoo, Chung-Yul; Jung, Doh Won; Park, Hee Jung; Kwak, Chan; Yu, Ji Haeng

2014-02-01

In this study, we propose a novel "mosaic structure" for a SOFC (solid oxide fuel cell) cathode with high thermal expansion to improve the stability against thermal stress. Self-organizing mosaic-shaped cathode has been successfully achieved by controlling the amount of binder in the dip-coating solution. The anode-supported cell with mosaic-shaped cathode shows itself to be highly durable performance for rapid thermal cycles, however, the performance of the cell with a non-mosaic cathode exhibits severe deterioration originated from the delamination at the cathode/electrolyte interface after 7 thermal cycles. The thermal stability of an SOFC cathode can be evidently improved by controlling the surface morphology. In view of the importance of the thermal expansion properties of the cathode, the effects of cathode morphology on the thermal stress stability are discussed.

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.

Gated Field-Emission Cathode Radio-Frequency (RF) Gun

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

Fermi Research Alliance, Fermi Alliance

The goal of this CRADA was to procure the carbon nanotube cathode from Radiabeam, install it in HBESL and make current measurements as a function of the gun gradient. The gun was operated at 1.3 GHz. After testing, send the cathode back to RadiaBeam for surface analysis.

Electron diffusion through the baffle aperture of a hollow cathode thruster

NASA Technical Reports Server (NTRS)

Brophy, J. R.; Wilbur, P. J.

1979-01-01

The use of a hollow cathode in place of an oxide cathode to increase thruster operating lifetimes requires, among other things, the addition of a baffle to restrict the flow of electrons from the hollow cathode. A theoretical model is developed which relates the baffle aperture area of a hollow-cathode thruster to the magnetic flux density and plasma properties in the aperture region, with the result that this model could be used as an aid in thruster design. Extensive Langmuir probing is undertaken to verify the validity of the model and demonstrate its capability. It is shown that the model can be used to calculate the aperture area required to effect discharge operation at a specified discharge voltage and arc current.

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.

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

Beilis, I. I.

A model was developed of vacuum arc cathode spot motion in a magnetic field that obliquely intercepts the cathode surface. The model takes into account a force under an electric field caused by retrograde spot motion across the normal component of the magnetic field, producing a drift velocity component in the direction of the acute angle between the magnetic field and the cathode surface. The relationship between velocity of the retrograde direction and drift velocity of the cathode spot motion to the acute angle was developed. The dependencies of the drift angle θ on the acute angle φ, magnetic fieldmore » strength B, and arc current I were calculated. It was found that the calculated θ increased with φ, B, and I in accordance with Robson's measurements.« less

Improved Direct Methanol Fuel Cell Stack

DOEpatents

Wilson, Mahlon S.; Ramsey, John C.

2005-03-08

A stack of direct methanol fuel cells exhibiting a circular footprint. A cathode and anode manifold, tie-bolt penetrations and tie-bolts are located within the circular footprint. Each fuel cell uses two graphite-based plates. One plate includes a cathode active area that is defined by serpentine channels connecting the inlet and outlet cathode manifold. The other plate includes an anode active area defined by serpentine channels connecting the inlet and outlet of the anode manifold, where the serpentine channels of the anode are orthogonal to the serpentine channels of the cathode. Located between the two plates is the fuel cell active region.

Rotating cathode device for molten salt bath

NASA Astrophysics Data System (ADS)

1983-11-01

The invention relates to a rotating cathode device for molten salt baths used to prepare metallic titanium or aluminum and the like by electrolysis of molten salts. The rotating cathode device is described. It is a cyclindrical cathode mounted on a rotating spindle, made of a lightweight material and mounted in such a way as to avoid thermal strain between the rotational shaft and the cylindrical cathode. At least one of the upper and lower ends of the cylindrical cathode are closed by a cap and a seal consisting of an inorganic fiber composite in the area between the cap and the cathode.

Roles of surface chemistry on safety and electrochemistry in lithium ion batteries.

PubMed

Lee, Kyu Tae; Jeong, Sookyung; Cho, Jaephil

2013-05-21

Motivated by new applications including electric vehicles and the smart grid, interest in advanced lithium ion batteries has increased significantly over the past decade. Therefore, research in this field has intensified to produce safer devices with better electrochemical performance. Most research has focused on the development of new electrode materials through the optimization of bulk properties such as crystal structure, ionic diffusivity, and electric conductivity. More recently, researchers have also considered the surface properties of electrodes as critical factors for optimizing performance. In particular, the electrolyte decomposition at the electrode surface relates to both a lithium ion battery's electrochemical performance and safety. In this Account, we give an overview of the major developments in the area of surface chemistry for lithium ion batteries. These ideas will provide the basis for the design of advanced electrode materials. Initially, we present a brief background to lithium ion batteries such as major chemical components and reactions that occur in lithium ion batteries. Then, we highlight the role of surface chemistry in the safety of lithium ion batteries. We examine the thermal stability of cathode materials: For example, we discuss the oxygen generation from cathode materials and describe how cells can swell and heat up in response to specific conditions. We also demonstrate how coating the surfaces of electrodes can improve safety. The surface chemistry can also affect the electrochemistry of lithium ion batteries. The surface coating strategy improved the energy density and cycle performance for layered LiCoO2, xLi2MnO3·(1 - x)LiMO2 (M = Mn, Ni, Co, and their combinations), and LiMn2O4 spinel materials, and we describe a working mechanism for these enhancements. Although coating the surfaces of cathodes with inorganic materials such as metal oxides and phosphates improves the electrochemical performance and safety properties of batteries, the microstructure of the coating layers and the mechanism of action are not fully understood. Therefore, researchers will need to further investigate the surface coating strategy during the development of new lithium ion batteries.

Structured electron beams from nano-engineered cathodes

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

Lueangaramwong, A.; Mihalcea, D.; Andonian, G.

The ability to engineer cathodes at the nano-scale have open new possibilities such as enhancing quantum eciency via surface-plasmon excitation, forming ultra-low-emittance beams, or producing structured electron beams. In this paper we present numerical investigations of the beam dynamics associated to this class of cathode in the weak- and strong-field regimes.We finally discuss the possible applications of some of the achievable cathode patterns when coupled with other phase space manipulations.

Generation of uniform low-temperature plasma in a pulsed non-self-sustained glow discharge with a large-area hollow cathode

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

Akhmadeev, Yu. H.; Denisov, V. V., E-mail: volodyadenisov@yandex.ru; Koval, N. N.

Generation of plasma in a pulsed non-self-sustained glow discharge with a hollow cathode with an area of ≥2 m{sup 2} at gas pressures of 0.4–1 Pa was studied experimentally. At an auxiliary arc-discharge current of 100 A and a main discharge voltage of 240 V, a pulse-periodic glow discharge with a current amplitude of 370 A, pulse duration of 340 μs, and repetition rate of 1 kHz was obtained. The possibility of creating a uniform gas-discharge plasma with a density of up to 10{sup 12} cm{sup −3} and an electron temperature of 1 eV in a volume of >0.2 m{supmore » 3} was demonstrated. Such plasma can be efficiently used to treat material surfaces and generate pulsed ion beams with a current density of up to 15 mA/cm{sup 2}.« less

Electrodeposition of Copper onto Polypyrrole Films: Application to Proton Reduction

NASA Astrophysics Data System (ADS)

Chikouche, Imene; Sahari, Ali; Zouaoui, Ahmed; Zegadi, Ameur

2016-09-01

In this paper, we have electrodeposited copper on polypyrrole surface. Results show that at high applied cathodic potential (>-1.8V), copper electrodeposition occurs with difficulties. The amount of electrodeposited copper is low (1.32%) and it is limited by the low polypyrrole conductivity. At this potential, poor conductivity is caused by its insulating state. However, at an applied cathodic potential of -1.2V, the polypyrrole exhibits a relatively high conductivity and copper particles are electrodeposited with large amounts (12.44%) on polypyrrole/silicon system. At high applied cathodic potential, the SEM images show clearly dispersed grains of copper, but polypyrrole surface is less occupied. At an applied cathodic potential of -1.2V, the SEM image shows that polypyrrole surface is homogenously more occupied with copper. After copper deposition, the Cu/PPy/Si system is used to catalyze the hydrogen reaction. It was found that, once the deposited copper is present with considerable amounts, the proton reduction occurs easily. As for the polypyrrole conductivity, it was found that electrodeposited copper onto PPy/Si surface affect the total conductivity.

A passive microfluidic hydrogen-air fuel cell with exceptional stability and high performance.

PubMed

Mitrovski, Svetlana M; Nuzzo, Ralph G

2006-03-01

We describe an advanced microfluidic hydrogen-air fuel cell (FC) that exhibits exceptional durability and high performance, most notably yielding stable output power (>100 days) without the use of an anode-cathode separator membrane. This FC embraces an entirely passive device architecture and, unlike conventional microfluidic designs that exploit laminar hydrodynamics, no external pumps are used to sustain or localize the reagent flow fields. The devices incorporate high surface area/porous metal and metal alloy electrodes that are embedded and fully immersed in liquid electrolyte confined in the channels of a poly(dimethylsiloxane) (PDMS)-based microfluidic network. The polymeric network also serves as a self-supporting membrane through which oxygen and hydrogen are supplied to the cathode and alloy anode, respectively, by permeation. The operational stability of the device and its performance is strongly dependent on the nature of the electrolyte used (5 M H2SO4 or 2.5 M NaOH) and composition of the anode material. The latter choice is optimized to decrease the sensitivity of the system to oxygen cross-over while still maintaining high activity towards the hydrogen oxidation reaction (HOR). Three types of high surface area anodes were tested in this work. These include: high-surface area electrodeposited Pt (Pt); high-surface area electrodeposited Pd (Pd); and thin palladium adlayers supported on a "porous" Pt electrode (Pd/Pt). The FCs display their best performance in 5 M H2SO4 using the Pd/Pt anode. This exceptional stability and performance was ascribed to several factors, namely: the high permeabilities of O2, H2, and CO2 in PDMS; the inhibition of the formation of insoluble carbonate species due to the presence of a highly acidic electrolyte; and the selectivity of the Pd/Pt anode toward the HOR. The stability of the device for long-term operation was modeled using a stack of three FCs as a power supply for a portable display that otherwise uses a 3 V battery.

Feasibility of Cathode Surface Coating Technology for High-Energy Lithium-ion and Beyond-Lithium-ion Batteries.

PubMed

Kalluri, Sujith; Yoon, Moonsu; Jo, Minki; Liu, Hua Kun; Dou, Shi Xue; Cho, Jaephil; Guo, Zaiping

2017-12-01

Cathode material degradation during cycling is one of the key obstacles to upgrading lithium-ion and beyond-lithium-ion batteries for high-energy and varied-temperature applications. Herein, we highlight recent progress in material surface-coating as the foremost solution to resist the surface phase-transitions and cracking in cathode particles in mono-valent (Li, Na, K) and multi-valent (Mg, Ca, Al) ion batteries under high-voltage and varied-temperature conditions. Importantly, we shed light on the future of materials surface-coating technology with possible research directions. In this regard, we provide our viewpoint on a novel hybrid surface-coating strategy, which has been successfully evaluated in LiCoO 2 -based-Li-ion cells under adverse conditions with industrial specifications for customer-demanding applications. The proposed coating strategy includes a first surface-coating of the as-prepared cathode powders (by sol-gel) and then an ultra-thin ceramic-oxide coating on their electrodes (by atomic-layer deposition). What makes it appealing for industry applications is that such a coating strategy can effectively maintain the integrity of materials under electro-mechanical stress, at the cathode particle and electrode- levels. Furthermore, it leads to improved energy-density and voltage retention at 4.55 V and 45 °C with highly loaded electrodes (≈24 mg.cm -2 ). Finally, the development of this coating technology for beyond-lithium-ion batteries could be a major research challenge, but one that is viable. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Hot hollow cathode gun assembly

DOEpatents

Zeren, J.D.

1983-11-22

A hot hollow cathode deposition gun assembly includes a hollow body having a cylindrical outer surface and an end plate for holding an adjustable heat sink, the hot hollow cathode gun, two magnets for steering the plasma from the gun into a crucible on the heat sink, and a shutter for selectively covering and uncovering the crucible.

Solar Powered CO.Sub.2 Conversion

NASA Technical Reports Server (NTRS)

Chen, Bin (Inventor)

2016-01-01

Methods and devices for reducing CO.sub.2 to produce hydrocarbons are disclosed. A device comprises a photoanode capable of splitting H.sub.2O into electrons, protons, and oxygen; an electrochemical cell cathode comprising an electro-catalyst capable of reducing CO.sub.2; H.sub.2O in contact with the surface of the photoanode; CO.sub.2 in contact with the surface of the cathode; and a proton-conducting medium positioned between the photoanode and the cathode. Electrical charges associated with the protons and the electrons move from the photoanode to the cathode, driven in part by a chemical potential difference sufficient to drive the electrochemical reduction of CO.sub.2 at the cathode. A light beam is the sole source of energy used to drive chemical reactions. The photoanode can comprise TiO.sub.2 nanowires or nanotubes, and can also include WO.sub.3 nanowires or nanotubes, quantum dots of CdS or PbS, and Ag or Au nanostructures. The cathode can comprise a conductive gas diffusion layer with nanostructures of an electro-catalyst such as Cu or Co.

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

NASA Astrophysics Data System (ADS)

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

2013-03-01

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

Metal-Free Carbon-Based Materials: Promising Electrocatalysts for Oxygen Reduction Reaction in Microbial Fuel Cells

PubMed Central

Sawant, Sandesh Y.; Han, Thi Hiep; Cho, Moo Hwan

2016-01-01

Microbial fuel cells (MFCs) are a promising green approach for wastewater treatment with the simultaneous advantage of energy production. Among the various limiting factors, the cathodic limitation, with respect to performance and cost, is one of the main obstacles to the practical applications of MFCs. Despite the high performance of platinum and other metal-based cathodes, their practical use is limited by their high cost, low stability, and environmental toxicity. Oxygen is the most favorable electron acceptor in the case of MFCs, which reduces to water through a complicated oxygen reduction reaction (ORR). Carbon-based ORR catalysts possessing high surface area and good electrical conductivity improve the ORR kinetics by lowering the cathodic overpotential. Recently, a range of carbon-based materials have attracted attention for their exceptional ORR catalytic activity and high stability. Doping the carbon texture with a heteroatom improved their ORR activity remarkably through the favorable adsorption of oxygen and weaker molecular bonding. This review provides better insight into ORR catalysis for MFCs and the properties, performance, and applicability of various metal-free carbon-based electrocatalysts in MFCs to find the most appropriate cathodic catalyst for the practical applications. The approaches for improvement, key challenges, and future opportunities in this field are also explored. PMID:28029116

Performance of MnO2 Crystallographic Phases in Rechargeable Lithium-Air Oxygen Cathode

NASA Astrophysics Data System (ADS)

Oloniyo, Olubukun; Kumar, Senthil; Scott, Keith

2012-05-01

Manganese dioxide (MnO2) has been shown to be effective for improving the efficiency of cathodes in lithium-air cells. Different crystallographic phases including α-, β-, and γ-MnO2 nanowires, α-MnO2 nanospheres, and α-MnO2 nanowires on carbon ( α-MnO2/C) were synthesized using the hydrothermal method. Their physical properties were examined using x-ray diffraction (XRD), Brunauer-Emmett-Teller (BET) surface area measurements, and scanning electron microscopy (SEM) and found to be in agreement with the literature. Electrochemical properties of the synthesized catalyst particles were investigated by fabricating cathodes and testing them in a lithium-air cell with lithium hexafluorophosphate in propylene carbonate (LiPF6/PC) and tetra(ethylene glycol)dimethyl ether (LiTFSi/TEGDME) electrolytes. α-MnO2 had the highest discharge capacity in the LiTFSi/TEGDME electrolyte (2500 mAh/g), whilst α-MnO2/C in LiPF6/PC showed a significantly higher discharge capacity of 11,000 mAh/g based on total mass of the catalytic cathode. However, the latter showed poor capacity retention compared with γ-MnO2 nanowires, which was stable for up to 30 cycles. The reported discharge capacity is higher than recorded in previous studies on lithium-air cells.

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

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

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

2017-05-19

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

Hierarchical nanostructured hollow spherical carbon with mesoporous shell as a unique cathode catalyst support in proton exchange membrane fuel cell.

PubMed

Fang, Baizeng; Kim, Jung Ho; Kim, Minsik; Kim, Minwoo; Yu, Jong-Sung

2009-03-07

Hierarchical nanostructured spherical carbon with hollow macroporous core in combination with mesoporous shell has been explored to support Pt cathode catalyst with high metal loading in proton exchange membrane fuel cell (PEMFC). The hollow core-mesoporous shell carbon (HCMSC) has unique structural characteristics such as large specific surface area and mesoporous volume, ensuring uniform dispersion of the supported high loading (60 wt%) Pt nanoparticles with small particle size, and well-developed three-dimensionally interconnected hierarchical porosity network, facilitating fast mass transport. The HCMSC-supported Pt(60 wt%) cathode catalyst has demonstrated markedly enhanced catalytic activity toward oxygen reduction and greatly improved PEMFC polarization performance compared with carbon black Vulcan XC-72 (VC)-supported ones. Furthermore, the HCMSC-supported Pt(40 wt%) or Pt(60 wt%) outperforms the HCMSC-supported Pt(20 wt%) even at a low catalyst loading of 0.2 mg Pt cm(-2) in the cathode, which is completely different from the VC-supported Pt catalysts. The capability of supporting high loading Pt is supposed to accelerate the commercialization of PEMFC due to the anticipated significant reduction in the amount of catalyst support required, diffusion layer thickness and fabricating cost of the supported Pt catalyst electrode.

Rational Design of Porous Covalent Triazine-Based Framework Composites as Advanced Organic Lithium-Ion Battery Cathodes.

PubMed

Yuan, Ruoxin; Kang, Wenbin; Zhang, Chuhong

2018-06-02

In an effort to explore the use of organic high-performance lithium ion battery cathodes as an alternative to resolve the current bottleneck hampering the development of their inorganic counterparts, a rational strategy focusing on the optimal composition of covalent triazine-based frameworks (CTFs) with carbon-based materials of varied dimensionalities is delineated. Two-dimensional reduced graphene oxide (rGO) with a compatible structural conformation with the layered CTF is the most suitable scaffold for the tailored mesopores in the polymeric framework, providing outstanding energy storage ability. Through facile ionothermal synthesis and structure engineering, the obtained CTF-rGO composite possesses a high specific surface area of 1357.27 m²/g, and when used as a lithium ion battery cathode it delivers a large capacity of 235 mAh/g in 80 cycles at 0.1 A/g along with a stable capacity of 127 mAh/g over 2500 cycles at 5 A/g. The composite with modified pore structure shows drastically improved performance compared to a pristine CTF, especially at large discharge currents. The CTF-rGO composite with excellent capacity, stability, and rate performance shows great promise as an emerging high-performance cathode that could revolutionize the conventional lithium-ion battery industry.

CoxFe1-x oxide coatings on metallic interconnects for solid oxide fuel cells

NASA Astrophysics Data System (ADS)

Shen, Fengyu; Lu, Kathy

2016-10-01

In order to improve the performance of Cr-containing steel as an interconnect material for solid oxide fuel cells, CoFe alloy coatings with Co:Fe ratios of 9:1, 8:2, 7:3, 6:4, and 5:5 are deposited by electrodeposition and then oxidized to CoxFe1-x oxide coatings with a thickness of ∼6 μm as protective layers on the interconnect. The area specific resistance of the coated interconnect increases with the Fe content. Higher Co content oxide coatings are more effective in limiting the growth of the chromia scale while all coatings are effective in inhibiting Cr diffusion and evaporation. With the Co0.8Fe0.2 oxide coated interconnect, the electrochemical performance of the Sm0.5Sr0.5Co0.2Fe0.8O3 cathode is improved. Only 1.54 atomic percentage of Cr is detected on the surface of the Sm0.5Sr0.5Co0.2Fe0.8O3 cathode while no Cr is detected 0.66 μm or more into the cathode. CoxFe1-x oxide coatings are promising candidates for solid oxide fuel cell interconnects with the advantage of using existing cathode species for compatibility and performance enhancement.

Viability of Using Diamond Field Emitter Array Cathodes in Free Electron Lasers

DTIC Science & Technology

2010-06-01

essential component of a field emitter array is the shape of the electric field lines and equipotential lines at the surface of the array. The...BARRIER AND QUANTUM TUNNELING ...........25 B. FIELD ENHANCEMENT AND SURFACE PROTRUSIONS .........26 C. ELECTRIC FIELDS AND ELECTRON TRAVEL...26 Figure 4. Diagram of a protrusion (triangular in shape) from the surface of a cathode. The protrusion is of height h, with a

Mixed ion/electron-conductive protective soft nanomatter-based conformal surface modification of lithium-ion battery cathode materials

NASA Astrophysics Data System (ADS)

Park, Jang-Hoon; Kim, Ju-Myung; Lee, Chang Kee; Lee, Sang-Young

2014-10-01

Understanding and control of interfacial phenomena between electrode material and liquid electrolytes are of major scientific importance for boosting development of high-performance lithium ion batteries with reliable electrochemical/safety attributes. Here, as an innovative surface engineering approach to address the interfacial issues, a new concept of mixed ion/electron-conductive soft nanomatter-based conformal surface modification of the cathode material is presented. The soft nanomatter is comprised of an electron conductive carbonaceous (C) substance embedded in an ion conductive polyimide (PI) nanothin compliant film. In addition to its structural uniqueness, the newly proposed surface modification benefits from a simple fabrication process. The PI/carbon soft nanomatter is directly synthesized on LiCoO2 surface via one-pot thermal treatment of polyamic acid (=PI precursor) and sucrose (=carbon source) mixture, where the LiCoO2 powders are chosen as a model system to explore the feasibility of this surface engineering strategy. The resulting PI/carbon coating layer facilitates electronic conduction and also suppresses unwanted side reactions arising from the cathode material-liquid electrolyte interface. These synergistic coating effects of the multifunctional PI/carbon soft nanomatter significantly improve high-voltage cell performance and also mitigate interfacial exothermic reaction between cathode material and liquid electrolyte.

Nano-patterned superconducting surface for high quantum efficiency cathode

DOEpatents

Hannon, Fay; Musumeci, Pietro

2017-03-07

A method for providing a superconducting surface on a laser-driven niobium cathode in order to increase the effective quantum efficiency. The enhanced surface increases the effective quantum efficiency by improving the laser absorption of the surface and enhancing the local electric field. The surface preparation method makes feasible the construction of superconducting radio frequency injectors with niobium as the photocathode. An array of nano-structures are provided on a flat surface of niobium. The nano-structures are dimensionally tailored to interact with a laser of specific wavelength to thereby increase the electron yield of the surface.

Membrane electrode assembly fabricated with the combination of Pt/C and hollow shell structured-Pt-SiO2@ZrO2 sphere for self-humidifying proton exchange membrane fuel cell

NASA Astrophysics Data System (ADS)

Ko, Y. D.; Yang, H. N.; Züttel, Andreas; Kim, S. D.; Kim, W. J.

2017-11-01

The Pt-supported hollow structured Pt-HZrO2 with the shell thickness of 27 nm is successfully synthesized. The water retention ability of Pt-HZrO2 is significantly enhanced compared with that of SiO2@ZrO2 due to the hydrophilic hollow structured HZrO2with high BET surface area. Pt-C and Pt-HZrO2 are combined with different weight fractions to prepare the double catalyst electrode (DCE). The membrane electrode assembly with the DCE is fabricated and applied to both anode and cathode or anode side only. The water flooding and thus rapid voltage drop is affected by the presence/or absence of the DCE at the cathode side. The cell test and visual experiment suggests that the Pt-HZrO2 layer adsorb the water molecules generated by the oxygen reduction reaction (ORR), preventing the water flooding. The power generation under RH 0% strongly suggests the back-diffusion of water molecules generated by the ORR. The flow rate to the cathode significantly affects the water flooding and cell performance. Higher flow rate to the cathode is advantageous to expel the water generated by the ORR, thus preventing water flooding and enhancing the cell performance. Therefore, the weight fraction of Pt-C to Pt-HZrO2 and the flow rate to the cathode should be well balanced.

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

Report on Carbon Nano Material Workshop: Challenges and Opportunities

DTIC Science & Technology

2013-01-22

trolyte fuel cells ( PEMFCs ) utilize the ability of the catalysts to initiate and maintain the oxygen reduction reaction on the cathode and the fuel...oxidation reaction on the anode. In order to increase the efficiency of the PEMFC catalysts, high-surface-area mesoporous carbons, carbon blacks, carbon...mechanical and thermal properties derived from a three-dimensional intercon- nected nanonetwork structure. The exceptional properties of CAs for PEMFC

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

DOEpatents

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

2016-05-31

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

Facile Synthesis of Bowl-Like LiFePO4/C Composite with High Rate-Performance

NASA Astrophysics Data System (ADS)

Jing, Peng; Yao, Lei; Xiang, Mingwu; Wang, Yan; Wu, Jinhua; Wang, Boya; Zhang, Yun; Wu, Hao; Liu, Heng

2018-07-01

Olivine-structured LiFePO4/C composites with high rate-performance were synthesized via an industrial spray-drying technique using a low cost Fe3O4 as iron source. The as-obtained LiFePO4/C exhibits a unique bowl-like morphology with a particle size of 2-5 μm in diameter. A continuous uniform carbon coating layer on the surface of LiFePO4/C cathodes promotes fast electron transport, whilst it guarantees the favorable electrochemical reaction. Especially the formation of porous structure leads to an average pore volume of 0.127 cm3 g-1 and a high specific surface area of 34.46 m2 g-1, which is conducive to facilitating the penetration of electrolyte and providing the more contact area of electrolyte with LiFePO4/C. As a result, the as-prepared LiFePO4/C cathode material delivers an outstanding discharge capacity of 102.1 mAh g-1, 94.2% of the initial capacity (108.3 mAh g-1), after 1000 cycles at 10 C. Even at an ultrahigh current rate of 50 C, it still shows an initial discharge capacity of 58 mAh g-1.

Facile Synthesis of Bowl-Like LiFePO4/C Composite with High Rate-Performance

NASA Astrophysics Data System (ADS)

Jing, Peng; Yao, Lei; Xiang, Mingwu; Wang, Yan; Wu, Jinhua; Wang, Boya; Zhang, Yun; Wu, Hao; Liu, Heng

2018-03-01

Olivine-structured LiFePO4/C composites with high rate-performance were synthesized via an industrial spray-drying technique using a low cost Fe3O4 as iron source. The as-obtained LiFePO4/C exhibits a unique bowl-like morphology with a particle size of 2-5 μm in diameter. A continuous uniform carbon coating layer on the surface of LiFePO4/C cathodes promotes fast electron transport, whilst it guarantees the favorable electrochemical reaction. Especially the formation of porous structure leads to an average pore volume of 0.127 cm3 g-1 and a high specific surface area of 34.46 m2 g-1, which is conducive to facilitating the penetration of electrolyte and providing the more contact area of electrolyte with LiFePO4/C. As a result, the as-prepared LiFePO4/C cathode material delivers an outstanding discharge capacity of 102.1 mAh g-1, 94.2% of the initial capacity (108.3 mAh g-1), after 1000 cycles at 10 C. Even at an ultrahigh current rate of 50 C, it still shows an initial discharge capacity of 58 mAh g-1.

Mesoporous carbon spheres with controlled porosity for high-performance lithium-sulfur batteries

NASA Astrophysics Data System (ADS)

Wang, Dexian; Fu, Aiping; Li, Hongliang; Wang, Yiqian; Guo, Peizhi; Liu, Jingquan; Zhao, Xiu Song

2015-07-01

Mesoporous carbon (MC) spheres with hierarchical pores, controlled pore volume and high specific surface areas have been prepared by a mass-producible spray drying assisted template method using sodium alginate as carbon precursor and commercial colloidal silica particles as hard template. The resulting MC spheres, possessing hierarchical pores in the range of 3-30 nm, are employed as conductive matrices for the preparation of cathode materials for lithium-sulfur batteries. A high pressure induced one-step impregnation of elemental sulfur into the pore of the MC spheres has been exploited. The electrochemical performances of sulfur-impregnated MC spheres (S-MC) derived from MC spheres with different pore volume and specific surface area but with the same sulfur loading ratio of 60 wt% (S-MC-X-60) have been investigated in details. The S-MC-4-60 composite cathode material displayed a high initial discharge capacity of 1388 mAhg-1 and a good cycling stability of 857 mAhg-1 after 100 cycles at 0.2C, and shows also excellent rate capability of 864 mAhg-1 at 2C. More importantly, the sulfur loading content in MC-4 spheres can reach as high as 80%, and it still can deliver a capacity of 569 mAhg-1 after 100 cycles at 0.2C.

Both anodal and cathodal transcranial direct current stimulation improves semantic processing.

PubMed

Brückner, Sabrina; Kammer, Thomas

2017-02-20

Transcranial direct current stimulation (tDCS) is a common method to modulate cortical activity. Anodal tDCS is usually associated with an enhancement of the stimulated brain area, whereas cathodal tDCS is often described as inhibitory brain stimulation method. Our aim was to investigate whether this canonical assumption derived from the motor system could be transferred to the semantic system. Three groups with 20 healthy subjects each were stimulated at Wernicke's area with either anodal, cathodal or sham tDCS. Subsequently, they performed a simple lexical decision task for a duration of about 25min. Subjects receiving anodal tDCS revealed faster reaction times (RTs) compared to the sham group, although not reaching statistical significance. Surprisingly, in the cathodal group RTs were decreased significantly. All subjects were faster in the second half of the task, but the tDCS-induced improvement lasted for the entire duration of the task. Error rates were not influenced by tDCS, neither were RTs in a choice reaction time task. Thus, both anodal and cathodal tDCS applied to Wernicke's area improved semantic processing. Recently, a meta-analysis revealed that the canonical anodal excitation and cathodal inhibition assumption is observed rarely in cognitive studies. In particular, an inhibitory effect of cathodal tDCS on cognition is rare. Our findings thus support the speculation, that especially language functions could be somewhat 'immune' to cathodal inhibition. Copyright © 2016 The Author(s). Published by Elsevier Ltd.. All rights reserved.

Titanium is not "the most biocompatible metal" under cathodic potential: The relationship between voltage and MC3T3 preosteoblast behavior on electrically polarized cpTi surfaces.

PubMed

Ehrensberger, Mark T; Sivan, Shiril; Gilbert, Jeremy L

2010-06-15

An electrochemically controlled system has been developed which allows for cell culture directly on electrically polarized metal surfaces with simultaneous control and assessment of the electrochemical current, potential, and impedance of the interface. This system was utilized in this study to assess the interactions between electrochemically polarized commercially pure titanium (cpTi) and MC3T3 preosteoblast cells. Cells were cultured on CpTi for 24 h at static potentials between -1000 mV and +1000 mV vs. Ag/AgCl and cell morphology (SEM and cell area) and viability (MTT and Live-Dead assay) were assessed along with the electrochemical current densities and surface oxide impedance properties. The results indicate that cathodic polarization in the range of -600 mV to -1000 mV markedly reduces the spreading and viability of cells cultured directly on cpTi within 24 h, while anodic polarization (-300 mV to +1000 mV) out to 72 h shows no difference in cell behavior as compared to the OCP condition. Analysis of the relationship between the cell outcomes and the electrochemical current densities and impedance indicated the presence of voltage-dependent electrochemical thresholds (cathodic current density, i(c) > 1.0 microA/cm(2), R(p) < 10(5) Omega cm(2)) which may control the biocompatibility of cpTi. In addition, these outcomes have direct clinical significance for modular orthopedic implants whose potential can shift, via fretting corrosion, down into the range of potentials exhibiting poor cell behavior. (c) 2009 Wiley Periodicals, Inc.

Targeted partial surface modification with nano-SiO2@Li2CoPO4F as high-voltage cathode material for LIBs

NASA Astrophysics Data System (ADS)

Chang, Caiyun; Huang, Zhipeng; Tian, Runsai; Jiang, Xinyu; Li, Chunsheng; Feng, Jijun

2017-10-01

Tuning whole/partial surface modification on cathode material with oxide material is a sought-after method to enhance the electrochemical performance in power storage field. Herein, nano-SiO2 targeted partial surface modified high voltage cathode material Li2CoPO4F has been successfully fabricated via a facile self-assembly process in silica dispersion at ambient temperature. With the aid of polar -OH groups attracted on the surface of SiO2 micelles, the nano-SiO2 preferentially nestle up along the borders and boundaries of Li2CoPO4F particles, where protection should be deployed with emphasis against the undesirable interactions between materials and electrolytes. Compared with pristine Li2CoPO4F, the SiO2 selectively modified Li2CoPO4F cathode materials, especially LCPF-3S, exhibit desirable electrochemical performances with higher discharge capacity, more outstanding cycle stability and favorable rate capability without any additional carbon involved. The greatly enhanced electrochemical properties can be attributed to the improved lithium-ion diffusion kinetics and structure tolerance during repeated lithiation/delithiation process. Such findings reveal a great potential of nano-SiO2 modified Li2CoPO4F as high energy cathode material for lithium ion batteries.

Possible Mg intercalation mechanism at the Mo6 S8 cathode surface proposed by first-principles methods

NASA Astrophysics Data System (ADS)

Wan, Liwen; Prendergast, David

2015-03-01

In recent years, great attention has been paid to the development of divalent Mg-ion batteries, which can potentially double the energy density and volumetric capacity compared to monovalent Li-ion batteries. The prototype Mg-ion battery, comprising Mg(anode)/Mg(AlCl2BuEt)2.THF(electrolyte)/Mo6S8(cathode), was established in 2000 by Aurbach et al. Despite the remarkable success of this prototype system, we still lack a clear understanding of the fundamental Mg intercalation/deposition mechanism at the electrolyte/electrode interfaces that perhaps results in the observed sluggish Mg transport process. Our previous work has shown that Mg-ions are strongly coordinated in the bulk electrolyte by a combination of counterion, Cl-, and organic aprotic solvent, THF. In this work, we use first-principles methods to study Mg intercalation behavior at the Mo6S8 cathode surface with the presence of solvent molecules. It is found that the image charge, formed on this metallic cathode surface, can effectively weaken the solvent-surface interactions and facilitate Mg intercalation. A detailed Mg intercalation mechanism is proposed and the unique role of Mo6S8 as the cathode material is emphasized. This work is supported as part of the Joint Center for Energy Storage Research (JCESR), an Energy Innovation Hub funded by the U.S. Department of Energy, Office of Science, Basic Energy Sciences.

Mathematical modeling of the temperature distribution under the cathode spot of the vacuum arc

NASA Astrophysics Data System (ADS)

Kuznetsov, V. G.; Babushkina, E. S.

2016-07-01

We present a solution to the problem of the temperature distribution under the cathode spot of taking into account melting and spare deposits of metal, brought to boiling temperature on the surface of the cathode spot. The process of heat transfer in the metal is described by the unsteady three dimensional heat conduction equation in Cartesian coordinate system. Similarly, we present a solution to the problem of the temperature distribution in the presence of the pores in the surface layer of the metal. To solve this task we used a numerical method to finite differences and variable directions. We present the calculated data on the distribution of temperature under the cathode spot for different values of spot diameters and speeds its movement.

Filtered cathodic arc deposition apparatus and method

DOEpatents

Krauss, Alan R.

1999-01-01

A filtered cathodic arc deposition method and apparatus for the production of highly dense, wear resistant coatings which are free from macro particles. The filtered cathodic arc deposition apparatus includes a cross shaped vacuum chamber which houses a cathode target having an evaporable surface comprised of the coating material, means for generating a stream of plasma, means for generating a transverse magnetic field, and a macro particle deflector. The transverse magnetic field bends the generated stream of plasma in the direction of a substrate. Macro particles are effectively filtered from the stream of plasma by traveling, unaffected by the transverse magnetic field, along the initial path of the plasma stream to a macro particle deflector. The macro particle deflector has a preformed surface which deflects macro particles away from the substrate.

Nickel Hydroxide-Modified Sulfur/Carbon Composite as a High-Performance Cathode Material for Lithium Sulfur Battery.

PubMed

Niu, Xiao-Qing; Wang, Xiu-Li; Xie, Dong; Wang, Dong-Huang; Zhang, Yi-Di; Li, Yi; Yu, Ting; Tu, Jiang-Ping

2015-08-05

Tailored sulfur cathode is vital for the development of a high performance lithium-sulfur (Li-S) battery. A surface modification on the sulfur/carbon composite would be an efficient strategy to enhance the cycling stability. Herein, we report a nickel hydroxide-modified sulfur/conductive carbon black composite (Ni(OH)2@S/CCB) as the cathode material for the Li-S battery through the thermal treatment and chemical precipitation method. In this composite, the sublimed sulfur is stored in the CCB, followed by a surface modification of Ni(OH)2 nanoparticles with size of 1-2 nm. As a cathode for the Li-S battery, the as-prepared Ni(OH)2@S/CCB electrode exhibits better cycle stability and higher rate discharge capacity, compared with the bare S/CCB electrode. The improved performance is largely due to the introduction of Ni(OH)2 surface modification, which can effectively suppress the "shuttle effect" of polysulfides, resulting in enhanced cycling life and higher capacity.

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.

Al13-pillared anatase TiO2 as a cathode for a lithium battery

NASA Astrophysics Data System (ADS)

Sun, X. D.; Ma, C. L.; Wang, Y. D.; Li, H. D.

2004-11-01

Al13-pillared anatase TiO2 is used as a cathode of a lithium battery for the first time. First, a layered titanium dioxide with cationic surfactant ions of cetyltrimethylammonium (CTA+) in the interlayers is synthesized by self-assembly. Then, pillared TiO2 is obtained by exchange of polyoxo cations of aluminium, [Al13O4(OH)24(H2O)12]7+, with CTA+ and subsequent calcination at 300 °C for 1 h in the air. Powder x-ray diffraction (XRD), transmission electron microscopy (TEM) and surface area (BET) methods are used to characterize the layered and pillared forms of titanium dioxide. A lithium battery with the Al13-pillared TiO2 as the cathode and Li metal foil as the anode is studied within the 1-2.2 V voltage range. The specific capacity of the closed button cell (size 2025) that is delivered on the initial discharge reached 191.4 mA h g-1 at the rate of 25 mA g-1. The cell shows good cycling performance over 50 cycles.

A long life 4 V class lithium-ion polymer battery with liquid-free polymer electrolyte

NASA Astrophysics Data System (ADS)

Kobayashi, Yo; Shono, Kumi; Kobayashi, Takeshi; Ohno, Yasutaka; Tabuchi, Masato; Oka, Yoshihiro; Nakamura, Tatsuya; Miyashiro, Hajime

2017-02-01

Ether-based solid polymer electrolyte (SPE) is one of the most well-known lithium ion conductors. Unlike the other inorganic electrolytes, SPE exhibits advantages of flexibility and large-area production, enabling low cost production of large size batteries. However, because the ether group is oxidized at 4 V versus Li/Li+ cathode, and due to its high irreversibility with the carbon anode, ether-based SPE was believed to be inapplicable to 4 V class lithium-ion batteries with carbon anode. Here we report a remarkably stable SPE in combination with a 4 V class cathode and carbon anode achieved by the proper design at the interface. The introduced boron-based lithium salt prohibits further oxidation of SPE at the cathode interface. The surface modification of graphite by the annealing of polyvinyl chloride mostly prohibits the continuous consumption of lithium at the graphite anode. Using above interface design, we achieved 60% capacity retention after 5400 cycles. The proposed battery provides a possible approach for realizing flammable electrolyte-free lithium-ion batteries, which achieve innovative safety improvements of large format battery systems for stationary use.

Comprehensive Enhancement of Nanostructured Lithium-Ion Battery Cathode Materials via Conformal Graphene Dispersion

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

Chen, Kan-Sheng; Xu, Rui; Luu, Norman S.

Efficient energy storage systems based on lithium-ion batteries represent a critical technology across many sectors including consumer electronics, electrified transportation, and a smart grid accommodating intermittent renewable energy sources. Nanostructured electrode materials present compelling opportunities for high-performance lithium-ion batteries, but inherent problems related to the high surface area to volume ratios at the nanometer-scale have impeded their adoption for commercial applications. Here, we demonstrate a materials and processing platform that realizes high-performance nanostructured lithium manganese oxide (nano-LMO) spinel cathodes with conformal graphene coatings as a conductive additive. The resulting nanostructured composite cathodes concurrently resolve multiple problems that have plagued nanoparticle-basedmore » lithium-ion battery electrodes including low packing density, high additive content, and poor cycling stability. Moreover, this strategy enhances the intrinsic advantages of nano-LMO, resulting in extraordinary rate capability and low temperature performance. With 75% capacity retention at a 20C cycling rate at room temperature and nearly full capacity retention at -20 degrees C, this work advances lithium-ion battery technology into unprecedented regimes of operation.« less

Comprehensive Enhancement of Nanostructured Lithium-Ion Battery Cathode Materials via Conformal Graphene Dispersion.

PubMed

Chen, Kan-Sheng; Xu, Rui; Luu, Norman S; Secor, Ethan B; Hamamoto, Koichi; Li, Qianqian; Kim, Soo; Sangwan, Vinod K; Balla, Itamar; Guiney, Linda M; Seo, Jung-Woo T; Yu, Xiankai; Liu, Weiwei; Wu, Jinsong; Wolverton, Chris; Dravid, Vinayak P; Barnett, Scott A; Lu, Jun; Amine, Khalil; Hersam, Mark C

2017-04-12

Efficient energy storage systems based on lithium-ion batteries represent a critical technology across many sectors including consumer electronics, electrified transportation, and a smart grid accommodating intermittent renewable energy sources. Nanostructured electrode materials present compelling opportunities for high-performance lithium-ion batteries, but inherent problems related to the high surface area to volume ratios at the nanometer-scale have impeded their adoption for commercial applications. Here, we demonstrate a materials and processing platform that realizes high-performance nanostructured lithium manganese oxide (nano-LMO) spinel cathodes with conformal graphene coatings as a conductive additive. The resulting nanostructured composite cathodes concurrently resolve multiple problems that have plagued nanoparticle-based lithium-ion battery electrodes including low packing density, high additive content, and poor cycling stability. Moreover, this strategy enhances the intrinsic advantages of nano-LMO, resulting in extraordinary rate capability and low temperature performance. With 75% capacity retention at a 20C cycling rate at room temperature and nearly full capacity retention at -20 °C, this work advances lithium-ion battery technology into unprecedented regimes of operation.

An improved alkaline direct formate paper microfluidic fuel cell.

PubMed

Galvan, Vicente; Domalaon, Kryls; Tang, Catherine; Sotez, Samantha; Mendez, Alex; Jalali-Heravi, Mehdi; Purohit, Krutarth; Pham, Linda; Haan, John; Gomez, Frank A

2016-02-01

Paper-based microfluidic fuel cells (MFCs) are a potential replacement for traditional FCs and batteries due to their low cost, portability, and simplicity to operate. In MFCs, separate solutions of fuel and oxidant migrate through paper due to capillary action and laminar flow and, upon contact with each other and catalyst, produce electricity. In the present work, we describe an improved microfluidic paper-based direct formate FC (DFFC) employing formate and hydrogen peroxide as the anode fuel and cathode oxidant, respectively. The dimensions of the lateral column, current collectors, and cathode were optimized. A maximum power density of 2.53 mW/cm(2) was achieved with a DFFC of surface area 3.0 cm(2) , steel mesh as current collector, 5% carbon to paint mass ratio for cathode electrode and, 30% hydrogen peroxide. The longevity of the MFC's detailed herein is greater than eight hours with continuous flow of streams. In a series configuration, the MFCs generate sufficient energy to power light-emitting diodes and a handheld calculator. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Thermionic energy converters

DOEpatents

Monroe, Jr., James E.

1977-08-09

A thermionic device for converting nuclear energy into electrical energy comprising a tubular anode spaced from and surrounding a cylindrical cathode, the cathode having an outer emitting surface of ruthenium, and nuclear fuel on the inner cylindrical surface. The nuclear fuel is a ceramic composition of fissionable material in a metal matrix. An axial void is provided to collect and contain fission product gases.

Near atomically smooth alkali antimonide photocathode thin films

DOE PAGES

Feng, Jun; Karkare, Siddharth; Nasiatka, James; ...

2017-01-24

Nano-roughness is one of the major factors degrading the emittance of electron beams that can be generated by high efficiency photocathodes, such as the thermally reacted alkali antimonide thin films. In this paper, we demonstrate a co-deposition based method for producing alkali antimonide cathodes that produce near atomic smoothness with high reproducibility. Here, we calculate the effect of the surface roughness on the emittance and show that such smooth cathode surfaces are essential for operation of alkali antimonide cathodes in high field, low emittance radio frequency electron guns and to obtain ultracold electrons for ultrafast electron diffraction applications.

Near atomically smooth alkali antimonide photocathode thin films

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

Feng, Jun; Karkare, Siddharth; Nasiatka, James

Nano-roughness is one of the major factors degrading the emittance of electron beams that can be generated by high efficiency photocathodes, such as the thermally reacted alkali antimonide thin films. In this paper, we demonstrate a co-deposition based method for producing alkali antimonide cathodes that produce near atomic smoothness with high reproducibility. Here, we calculate the effect of the surface roughness on the emittance and show that such smooth cathode surfaces are essential for operation of alkali antimonide cathodes in high field, low emittance radio frequency electron guns and to obtain ultracold electrons for ultrafast electron diffraction applications.

Apparatus for electroplating particles of small dimension

DOEpatents

Yu, C.M.; Illige, J.D.

1980-09-19

The thickness, uniformity, and surface smoothness requirements for surface coatings of glass microspheres for use as targets for laser fusion research are critical. Because of thier minute size, the microspheres are difficult to manipulate and control in electroplating systems. The electroplating apparatus of the present invention addresses these problems by providing a cathode cell having a cell chamber, a cathode and an anode electrically isolated from each other and connected to an electrical power source. During the plating process, the cathode is controllably vibrated along with solution pulse to maintain the particles in random free motion so as to attain the desired properties.

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.

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

NASA Astrophysics Data System (ADS)

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

2017-09-01

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

Stabilizing platinum in phosphoric acid fuel cells

NASA Technical Reports Server (NTRS)

Remick, R. J.

1981-01-01

The cathode of the phosphoric acid fuel cell uses a high surface area platinum catalyst supported on a carbon substrate. During operation, the small platinum crystallites sinter, causing loss in cell performance. A support was developed that stabilizes platinum in the high surface area condition by retarding or preventing the sintering process. The approach is to form etch pits in the carbon by oxidizing the carbon in the presence of a metal oxide catalyst, remove the metal oxide by an acid wash, and then deposit platinum in these pits. Results confirm the formation of etch pits in each of the three supports chosen for investigation: Vulcan XC-72R, Vulcan XC-72 that was graphized at 2500 C, and Shawinigan Acetylene Black.

Sub-2 nm Thick Fluoroalkylsilane Self-Assembled Monolayer-Coated High Voltage Spinel Crystals as Promising Cathode Materials for Lithium Ion Batteries

PubMed Central

Zettsu, Nobuyuki; Kida, Satoru; Uchida, Shuhei; Teshima, Katsuya

2016-01-01

We demonstrate herein that an ultra-thin fluoroalkylsilane self-assembled monolayer coating can be used as a modifying agent at LiNi0.5Mn1.5O4−δcathode/electrolyte interfaces in 5V-class lithium-ion batteries. Bare LiNi0.5Mn1.5O4−δ cathode showed substantial capacity fading, with capacity dropping to 79% of the original capacity after 100 cycles at a rate of 1C, which was entirely due to dissolution of Mn3+ from the spinel lattice via oxidative decomposition of the organic electrolyte. Capacity retention was improved to 97% on coating ultra-thin FAS17-SAM onto the LiNi0.5Mn1.5O4 cathode surface. Such surface protection with highly ordered fluoroalkyl chains insulated the cathode from direct contact with the organic electrolyte and led to increased tolerance to HF. PMID:27553901

Effect of hydrogen on cathodic corrosion of titanium aluminide

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

Gao, K.W.; Jin, J.W.; Qiao, L.J.

1996-01-01

Cathodic corrosion of titanium aluminide (TiAl) during hydrogen charging in various acidic aqueous solutions and in molten salt at 160 C was studied. At constant potential, the rate of cathodic corrosion (V) was much higher than during anodic dissolution, and V increased linearly with increasing current. V was 10 times higher in the acid solution than in the salt solution under the same current. Disruption of the surface film by local hydride formation during cathodic polarization was shown to be the key step.

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.

The enhancement of heavy metal removal from polluted river water treatment by integrated carbon-aluminium electrodes using electrochemical method

NASA Astrophysics Data System (ADS)

Yussuf, N. M.; Embong, Z.; Abdullah, S.; Masirin, M. I. M.; Tajudin, S. A. A.; Ahmad, S.; Sahari, S. K.; Anuar, A. A.; Maxwell, O.

2018-01-01

The heavy metal removal enhancement from polluted river water was investigated using two types of electrodes consist of integrated carbon-aluminium and a conventional aluminium plate electrode at laboratory-scale experiments. In the integrated electrode systems, the aluminium electrode surface was coated with carbon using mixed slurry containing carbon black, polyvinyl acetate and methanol. The electrochemical treatment was conducted on the parameter condition of 90V applied voltage, 3cm of electrode distance and 60 minutes of electrolysis operational time. Surface of both electrodes was investigated for pre and post electrolysis treatment by using SEM-EDX analytical technique. Comparison between both of the electrode configuration exhibits that more metals were accumulated on carbon integrated electrode surfaces for both anode and cathode, and more heavy metals were detected on the cathode. The atomic percentage of metals distributed on the cathode conventional electrode surface consist of Al (94.62%), Zn (1.19%), Mn (0.73%), Fe (2.81%) and Cu (0.64%), while on the anode contained O (12.08%), Al (87.63%) and Zn (0.29%). Meanwhile, cathode surface of integrated electrode was accumulated with more metals; O (75.40%), Al (21.06%), Zn (0.45%), Mn (0.22), Fe (0.29%), Cu (0.84%), Pb (0.47%), Na (0.94%), Cr (0.08%), Ni (0.02%) and Ag (0.22%), while on anode contain Al (3.48%), Fe (0.49 %), C (95.77%), and Pb (0.26%). According to this experiment, it was found that integrated carbon-aluminium electrodes have a great potential to accumulate more heavy metal species from polluted water compare to the conventional aluminium electrode. Here, heavy metal accumulation process obviously very significant on the cathode surface.

Rapid temperature increase near the anode and cathode in the afterglow of a pulsed positive streamer discharge

NASA Astrophysics Data System (ADS)

Ono, Ryo

2018-06-01

The spatiotemporal evolution of the temperature in the afterglow of point-to-plane, pulsed positive streamer discharge was measured near the anode tip and cathode surface using laser-induced predissociation fluorescence of OH radicals. The temperature exhibited a rapid increase and displayed a steep spatial gradient after a discharge pulse. The rate of temperature rise reached 84 K μs‑1 at mm, where z represents the distance from the anode tip. The temperature rise was much faster than in the middle of the gap; it was only 2.8 K μs‑1 at mm. The temperature reached 1700 K near the anode tip at s and 1500 K near the cathode surface at s, where t represents the postdischarge time. The spatial gradient reached 1280 K mm‑1 near the anode tip at s. The mechanism responsible for the rapid temperature increase was discussed, including rapid heating of the gas in the early postdischarge phase (s), and vibration-to-translation energy transfer in the later postdischarge phase (s). The high temperatures near the anode tip and cathode surface are particularly important for the ignition of combustible mixtures and for surface treatments, including solid-surface treatments, water treatments, and plasma medicine using pulsed streamer discharges.

Effect of current ripple on cathode erosion in 30 kWe class arcjets

NASA Technical Reports Server (NTRS)

Harris, William J.; O'Hair, Edgar A.; Hatfield, Lynn L.; Kristiansen, M.; Grimes, Montgomery D.

1991-01-01

An investigation was conducted to study the effect of current ripple on cathode erosion in 30 kWe class arcjets to determine the change in the cathode erosion rate for high (11 percent) and low (4 percent) current ripple. The measurements were conducted using a copper-tungsten cathode material to accelerate the cathode erosion process. It is shown that the high ripple erosion rate was initially higher than the low ripple erosion rate, but decreased asymptotically with time to a level less than half that of the low ripple value. Results suggest that high ripple extends the cathode lifetime for long duration operation, and improves arc stability by increasing the cathode attachment area.

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

Mitigating external and internal cathode fouling using a polymer bonded separator in microbial fuel cells.

PubMed

Yang, Wulin; Rossi, Ruggero; Tian, Yushi; Kim, Kyoung-Yeol; Logan, Bruce E

2018-02-01

Microbial fuel cell (MFC) cathodes rapidly foul when treating domestic wastewater, substantially reducing power production over time. Here a wipe separator was chemically bonded to an activated carbon air cathode using polyvinylidene fluoride (PVDF) to mitigate cathode fouling and extend cathode performance over time. MFCs with separator-bonded cathodes produced a maximum power density of 190 ± 30 mW m -2 after 2 months of operation using domestic wastewater, which was ∼220% higher than controls (60 ± 50 mW m -2 ) with separators that were not chemically bonded to the cathode. Less biomass (protein) was measured on the bonded separator surface than the non-bonded separator, indicating chemical bonding reduced external bio-fouling. Salt precipitation that contributed to internal fouling was also reduced using separator-bonded cathodes. Overall, the separator-bonded cathodes showed better performance over time by mitigating both external bio-fouling and internal salt fouling. Copyright © 2017 Elsevier Ltd. All rights reserved.

Destructive Evaluation of a Xenon Hollow Cathode after a 28,000 Hour Life Test

NASA Technical Reports Server (NTRS)

Sarver-Verhey, Timothy R.

1998-01-01

International Space Station (ISS) plasma contactor system requires a hollow cathode assembly (HCA) with a lifetime of at least 18,000 hours. In order to demonstrate the lifetime capability of the HCA, a series of hollow cathode wear tests was performed which included a life test operated at the maximum current of the HCA. This test sought to verify hollow cathode lifetime capability and contamination control protocols. This hollow cathode accumulated 27,800 hours of operation before it failed during a restart attempt. The cathode was subsequently destructively analyzed in order to determine the failure mechanism. Microscopic examination of the cathode interior determined that relatively small changes in the cathode physical geometry had occurred and barium tungstates, which are known to limit the emission process, had formed over a majority of the electron emitter surface. Because the final state of the insert was consistent with expected impregnate chemistry, the hollow cathode was believed to have reached the end of its usable life under the test conditions.

Local potential evolutions during proton exchange membrane fuel cell operation with dead-ended anode - Part I: Impact of water diffusion and nitrogen crossover

NASA Astrophysics Data System (ADS)

Abbou, S.; Dillet, J.; Maranzana, G.; Didierjean, S.; Lottin, O.

2017-02-01

Operating a PEMFC with a dead-ended anode may lead to local fuel-starvation because of water and possibly nitrogen accumulation in the anode compartment. In previous works, we used a segmented linear cell with reference electrodes to monitor simultaneously the local potentials and current densities during dead-ended anode operation. The results indicated that water transport as well as nitrogen crossover through the membrane were most probably the two key factors governing fuel starvation. In this first from a set of two papers, we evaluated with more details the contributions of nitrogen crossover and water transport to hydrogen starvation. To assess nitrogen contribution, the fuel cell cathode compartment was first supplied with pure oxygen instead of air. The results showed that in the absence of nitrogen (in the cathode side) the fuel starvation was much slower than with air, suggesting that nitrogen contribution cannot be neglected. On the other hand, the contribution of water flooding to hydrogen starvation was investigated by using different cooling temperature on the cathode and anode sides in order to drive water toward the colder plate. The results showed that with a colder anode side, fuel starvation was faster. In the opposite case of a hotter anode plate, water accumulation in the anode compartment was limited, nitrogen crossover through the membrane was the main reason for hydrogen starvation in this case. To fully assess the impact of the thermal configurations on membrane-electrode assembly (MEA) degradation, aging protocols with a dead-ended anode and a fixed closing time were also performed. The results showed that operation with a hotter anode could help to limit significantly cathode ElectroChemical Surface Area (ECSA) losses along the cell area and performance degradation induced by hydrogen starvation.

Post-Test Inspection of NASA's Evolutionary Xenon Thruster Long-Duration Test Hardware: Discharge and Neutralizer Cathodes

NASA Technical Reports Server (NTRS)

Shastry, Rohit; Soulas, George C.

2016-01-01

The NEXT Long-Duration Test is part of a comprehensive thruster service life assessment intended to demonstrate overall throughput capability, validate service life models, quantify wear rates as a function of time and operating condition, and identify any unknown life-limiting mechanisms. The test was voluntarily terminated in February 2014 after demonstrating 51,184 hours of high-voltage operation, 918 kg of propellant throughput, and 35.5 MN-s of total impulse. The post-test inspection of the thruster hardware began shortly afterwards with a combination of non-destructive and destructive analysis techniques, and is presently nearing completion. This paper presents relevant results of the post-test inspection for both discharge and neutralizer cathodes. Discharge keeper erosion was found to be significantly reduced from what was observed in the NEXT 2 kh wear test and NSTAR Extended Life Test, providing adequate protection of vital cathode components throughout the test with ample lifetime remaining. The area of the discharge cathode orifice plate that was exposed by the keeper orifice exhibited net erosion, leading to cathode plate material building up in the cathode-keeper gap and causing a thermally-induced electrical short observed during the test. Significant erosion of the neutralizer cathode orifice was also found and is believed to be the root cause of an observed loss in flow margin. Deposition within the neutralizer keeper orifice as well as on the downstream surface was thicker than expected, potentially resulting in a facility-induced impact on the measured flow margin from plume mode. Neutralizer keeper wall erosion on the beam side was found to be significantly lower compared to the NEXT 2 kh wear test, likely due to the reduction in beam extraction diameter of the ion optics that resulted in decreased ion impingement. Results from the post-test inspection have led to some minor thruster design improvements.

Evaluation of gas and carbon transport in a methanogenic bioelectrochemical system (BES).

PubMed

Dykstra, Christy M; Pavlostathis, Spyros G

2017-05-01

Bioelectrochemical systems (BESs) may be used to upgrade anaerobic digester biogas by directly converting CO 2 to CH 4 . The objective of this study was to evaluate gas (N 2 , CO 2 , CH 4 , and H 2 ) and carbon transport within a methanogenic BES. Four BES configurations were evaluated: abiotic anode with abiotic cathode (AAn-ACa), bioanode with abiotic cathode (BAn-ACa), abiotic anode with biocathode (AAn-BCa), and bioanode with biocathode (BAn-BCa). Transport of N 2 , a gas commonly used for flushing anoxic systems, out of the anode headspace ranged from 3.7 to 6.2 L/d-atm-m 2 , normalized to the proton exchange membrane (PEM) surface area and net driving pressure (NDP). CO 2 was transported from the cathode to the anode headspace at rates from 3.7 to 5.4 L/d-atm-m 2 . The flux of H 2 from cathode to anode headspace was 48% greater when the system had a biocathode (AAn-BCa) than when H 2 was produced at an abiotic cathode (BAn-ACa), even though the abiotic cathode headspace had 75% more H 2 than the AAn-BCa biocathode at the end of 1 day. A 7-day carbon balance of a batch-fed BAn-BCa BES showed transient microbial carbon storage and a net transport of carbon from anode to cathode. After a 7-day batch incubation, the CH 4 production in the biocathode was 27% greater on a molar basis than the initial CO 2 supplied to the biocathode headspace, indicating conversion of CO 2 produced in the anode. This research expands the current understanding of methanogenic BES operation, which may be used in improving the assessment of BES performance and/or in the development of alternative BES designs and mathematical models. Biotechnol. Bioeng. 2017;114: 961-969. © 2016 Wiley Periodicals, Inc. © 2016 Wiley Periodicals, Inc.

Ultrahigh-Capacity Lithium-Oxygen Batteries Enabled by Dry-Pressed Holey Graphene Air Cathodes.

PubMed

Lin, Yi; Moitoso, Brandon; Martinez-Martinez, Chalynette; Walsh, Evan D; Lacey, Steven D; Kim, Jae-Woo; Dai, Liming; Hu, Liangbing; Connell, John W

2017-05-10

Lithium-oxygen (Li-O 2 ) batteries have the highest theoretical energy density of all the Li-based energy storage systems, but many challenges prevent them from practical use. A major obstacle is the sluggish performance of the air cathode, where both oxygen reduction (discharge) and oxygen evolution (charge) reactions occur. Recently, there have been significant advances in the development of graphene-based air cathode materials with a large surface area and catalytically active for both oxygen reduction and evolution reactions, especially with additional catalysts or dopants. However, most studies reported so far have examined air cathodes with a limited areal mass loading rarely exceeding 1 mg/cm 2 . Despite the high gravimetric capacity values achieved, the actual (areal) capacities of those batteries were far from sufficient for practical applications. Here, we present the fabrication, performance, and mechanistic investigations of high-mass-loading (up to 10 mg/cm 2 ) graphene-based air electrodes for high-performance Li-O 2 batteries. Such air electrodes could be easily prepared within minutes under solvent-free and binder-free conditions by compression-molding holey graphene materials because of their unique dry compressibility associated with in-plane holes on the graphene sheet. Li-O 2 batteries with high air cathode mass loadings thus prepared exhibited excellent gravimetric capacity as well as ultrahigh areal capacity (as high as ∼40 mAh/cm 2 ). The batteries were also cycled at a high curtailing areal capacity (2 mAh/cm 2 ) and showed a better cycling stability for ultrathick cathodes than their thinner counterparts. Detailed post-mortem analyses of the electrodes clearly revealed the battery failure mechanisms under both primary and secondary modes, arising from the oxygen diffusion blockage and the catalytic site deactivation, respectively. These results strongly suggest that the dry-pressed holey graphene electrodes are a highly viable architectural platform for high-capacity, high-performance air cathodes in Li-O 2 batteries of practical significance.

Ultra-high-vacuum electrical feedthrough

NASA Technical Reports Server (NTRS)

Gavaler, J. R.; Janocko, M. A.

1976-01-01

Device for cathodic sputtering utilizes cathode dark-space region adjacent to high negative-potential surfaces. Feedthrough is made of metal and glass, is helium leaktight, and is bakeable; it can be incorporated into any vacuum apparatus.

Study of a DC gas discharge with a copper cathode in a water flow

NASA Astrophysics Data System (ADS)

Tazmeev, G. Kh.; Timerkaev, B. A.; Tazmeev, Kh. K.

2017-07-01

A dc gas discharge between copper electrodes in the current range of 5-20 A was studied experimentally. The discharge gap length was varied within 45-70 mm. The cathode was a 10-mm-diameter rod placed in the water flowing out from a dielectric tube. Three discharge configurations differing in the position of the cathode upper end with respect to the water surface were considered: (i) above water; (ii) flush with the water surface, and (iii) under water. The electric and optical characteristics of the discharge in the second configuration were studied in more detail. It is established that the discharge properties are similar to those of an electric arc. Considerable cathode erosion was observed in the third configuration. It is revealed that fine-dispersed copper grains form in the course of erosion.

High intensity, plasma-induced electron emission from large area carbon nanotube array cathodes

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

Liao Qingliang; Yang Ya; Qi Junjie

2010-02-15

The plasma-induced electron emission properties of large area carbon nanotube (CNT) array cathodes under different pulse electric fields were investigated. The formation and expansion of cathode plasmas were proved; in addition, the cathodes have higher emission current in the double-pulse mode than that in the single-pulse mode due to the expansion of plasma. Under the double-pulse electric field of 8.16 V/mum, the plasma's expansion velocity is about 12.33 cm/mus and the highest emission current density reached 107.72 A/cm{sup 2}. The Cerenkov radiation was used to diagnose the distribution of electron beams, and the electron beams' generating process was plasma-induced emission.

A flexible curvilinear electromagnetic filter for direct current cathodic arc source.

PubMed

Dai, Hua; Shen, Yao; Li, Liuhe; Li, Xiaoling; Cai, Xun; Chu, Paul K

2007-09-01

Widespread applications of direct current (dc) cathodic arc deposition are hampered by macroparticle (MP) contamination, although a cathodic arc offers many unique merits such as high ionization rate, high deposition rate, etc. In this work, a flexible curvilinear electromagnetic filter is described to eliminate MPs from a dc cathodic arc source. The filter which has a relatively large size with a minor radius of about 85 mm is suitable for large cathodes. The filter is open and so the MPs do not rebound inside the filter. The flexible design allows the ions to be transported from the cathode to the sample surface optimally. Our measurements with a saturated ion current probe show that the efficiency of this flexible filter reaches about 2.0% (aluminum cathode) when the filter current is about 250 A. The MP density measured from TiN films deposited using this filter is two to three orders of magnitude less than that from films deposited with a 90 degrees duct magnetic filter and three to four orders of magnitude smaller than those deposited without a filter. Furthermore, our experiments reveal that the potential of the filter coil and the magnetic field on the surface of the cathode are two important factors affecting the efficacy of the filter. Different biasing potentials can enhance the efficiency to up to 12-fold, and a magnetic field at about 4.0 mT can improve it by a factor of 2 compared to 5.4 mT.

Theory, Investigation and Stability of Cathode Electrocatalytic Activity

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

Ding, Dong; Liu, Mingfei; Lai, Samson

2012-09-30

The main objective of this project is to systematically characterize the surface composition, morphology, and electro-catalytic properties of catalysts coated on LSCF, aiming to establish the scientific basis for rational design of high-performance cathodes by combining a porous backbone (such as LSCF) with a thin catalyst coating. The understanding gained will help us to optimize the composition and morphology of the catalyst layer and microstructure of the LSCF backbone for better performance. More specifically, the technical objectives include: (1) to characterize the surface composition, morphology, and electro-catalytic properties of catalysts coated on LSCF; (2) to characterize the microscopic details andmore » stability of the LSCF-catalyst (e.g., LSM) interfaces; (3) to establish the scientific basis for rational design of high-performance cathodes by combining a porous backbone (such as LSCF) with a thin catalyst coating; and (4) to demonstrate that the performance and stability of porous LSCF cathodes can be enhanced by the application of a thin-film coating of LSM through a solution infiltration process in small homemade button cells and in commercially available cells of larger dimension. We have successfully developed dense, conformal LSM films with desired structure, composition, morphology, and thickness on the LSCF surfaces by two different infiltration processes: a non-aqueous and a water-based sol-gel process. It is demonstrated that the activity and stability of LSCF cathodes can be improved by the introduction of a thin-film LSM coating through an infiltration process. Surface and interface of the LSM-coated LSCF cathode were systematically characterized using advanced microscopy and spectroscopy techniques. TEM observation suggests that a layer of La and Sr oxide was formed on LSCF surfaces after annealing. With LSM infiltration, in contrast, we no longer observe such La/Sr oxide layer on the LSM-coated LSCF samples after annealing under similar conditions. This was also confirmed by x-ray analyses. For example, soft x-ray XANES data reveal that Co cations displace the Mn cations as being more favored to be reduced. Variations in the Sr-O in the annealed LSCF Fourier-transformed (FT) EXAFS suggest that some Sr segregation is occurring, but is not present in the annealed LSM-infiltrated LSCF cathode materials. Further, a surface enhanced Raman technique was also developed into to probe and map LSM and LSCF phase on underlying YSZ substrate, enabling us to capture important chemical information of cathode surfaces under practical operating conditions. Electrochemical models for the design of test cells and understanding of mechanism have been developed for the exploration of fundamental properties of electrode materials. Novel catalyst coatings through particle depositions (SDC, SSC, and LCC) or continuous thin films (PSM and PSCM) were successfully developed to improve the activity and stability of LSCF cathodes. Finally, we have demonstrated enhanced activity and stability of LSCF cathodes over longer periods of time in homemade and commercially available cells by an optimized LSM infiltration process. Microstructure examination of the tested cells did not show obvious differences between blank and infiltrated cells, suggesting that the infiltrated LSM may form a coherent film on the LSCF cathodes. There was no significant change in the morphology or microstructure of the LSCF cathode due to the structural similarity of LSCF and LSM. Raman analysis of the tested cells indicated small peaks emerging on the blank cells that correspond to trace amounts of secondary phase formation during operation (e.g., CoO{sub x}). The formation of this secondary phase might be attributed to performance degradation. In contrast, there was no such secondary phase observed in the LSM infiltrated cells, indicating that the LSM modification staved off secondary phase formation and thus improved the stability.« less

Hollow Cathode Assembly Development for the HERMeS Hall Thruster

NASA Technical Reports Server (NTRS)

Sarver-Verhey, Timothy R.; Kamhawi, Hani; Goebel, Dan M.; Polk, James E.; Peterson, Peter Y.; Robinson, Dale A.

2016-01-01

To support the operation of the HERMeS 12.5 kW Hall Thruster for NASA's Asteroid Redirect Robotic Mission, hollow cathodes using emitters based on barium oxide impregnate and lanthanum hexaboride are being evaluated through wear-testing, performance characterization, plasma modeling, and review of integration requirements. This presentation will present the development approach used to assess the cathode emitter options. A 2,000-hour wear-test of development model Barium Oxide (BaO) hollow cathode is being performed as part of the development plan. Specifically this test is to identify potential impacts cathode emitter life during operation in the HERMeS thruster. The cathode was operated with a magnetic field-equipped anode that simulates the HERMeS hall thruster operating environment. Cathode discharge performance has been stable with the device accumulating 743 hours at the time of this report. Observed voltage changes are attributed to keeper surface condition changes during testing. Cathode behavior during characterization sweeps exhibited stable behavior, including cathode temperature. The details of the cathode assembly operation of the wear-test will be presented.

Vertically aligned carbon nanotubes as anode and air-cathode in single chamber microbial fuel cells

NASA Astrophysics Data System (ADS)

Amade, R.; Moreno, H. A.; Hussain, S.; Vila-Costa, M.; Bertran, E.

2016-10-01

Electrode optimization in microbial fuel cells is a key issue to improve the power output and cell performance. Vertically aligned carbon nanotubes (VACNTs) grown on low cost stainless-steel mesh present an attractive approach to increase the cell performance while avoiding the use of expensive Pt-based materials. In comparison with non-aligned carbon nanotubes (NACNTs), VACNTs increase the oxygen reduction reaction taking place at the cathode by a factor of two. In addition, vertical alignment also increases the power density up to 2.5 times with respect to NACNTs. VACNTs grown at the anode can further improve the cell performance by increasing the electrode surface area and thus the electron transfer between bacteria and the electrode. The maximum power density obtained using VACNTs was 14 mW/m2 and 160 mV output voltage.

Potentiostatic current and galvanostatic potential oscillations during electrodeposition of cadmium.

PubMed

López-Sauri, D A; Veleva, L; Pérez-Ángel, G

2015-09-14

Cathodic current and potential oscillations were observed during electrodeposition of cadmium from a cyanide electrolyte on a vertical platinum electrode, in potentiostatic and galvanostatic experiments. Electrochemical impedance spectroscopy experiments revealed a region of negative real impedance in a range of non-zero frequencies, in the second descending branch with a positive slope of the N-shape current-potential curve. This kind of dynamical behaviour is characteristic of the HN-NDR oscillators (oscillators with the N-Shape current-potential curve and hidden negative differential resistance). The oscillations could be mainly attributed to the changes in the real active cathodic area, due to the adsorption of hydrogen molecules and their detachment from the surface. The instabilities of the electrochemical processes were characterized by time series, Fast Fourier Transforms and 2-D phase portraits showing quasi-periodic oscillations.

Metal segregation in hierarchically structured cathode materials for high-energy lithium batteries

DOE PAGES

Lin, Feng; Xin, Huolin L.; Nordlund, Dennis; ...

2016-01-11

Controlling surface and interfacial properties of battery materials is key to improving performance in rechargeable Li-ion devices. Surface reconstruction from a layered to a rock salt structure in metal oxide cathode materials is commonly observed and results in poor high-voltage cycling performance, impeding attempts to improve energy density. Hierarchically structured LiNi 0.4Mn 0.4Co 0.2O 2 (NMC-442) spherical powders, made by spray pyrolysis, exhibit local elemental distribution gradients that deviate from the global NMC-442 composition; specifically, they are Ni-rich and Mn-poor at particle surfaces. These materials demonstrate improved Coulombic efficiencies, discharge capacities, and high-voltage capacity retention in lithium half-cell configurations. Themore » subject powders show superior resistance against surface reconstruction due to the tailored surface chemistry, compared to conventional NMC-442 materials. This paves the way towards the development of a new generation of robust and stable high-energy NMC cathodes for Li-ion batteries.« less

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.

Apparatus for electroplating particles of small dimension

DOEpatents

Yu, Conrad M.; Illige, John D.

1982-01-01

The thickness, uniformity, and surface smoothness requirements for surface coatings of glass microspheres for use as targets for laser fusion research are critical. Because of their minute size, the microspheres are difficult to manipulate and control in electroplating systems. The electroplating apparatus (10) of the present invention addresses these problems by providing a cathode cell (20) having a cell chamber (22), a cathode (23) and an anode (26) electrically isolated from each other and connected to an electrical power source (24). During the plating process, the cathode (23) is controllably vibrated along with solution pulse to maintain the particles in random free motion so as to attain the desired properties.

GEIGER-MULLER TYPE COUNTER TUBE

DOEpatents

Fowler, I.L.; Watt, L.A.K.

1959-12-15

A single counter tube capable of responding to a wide range of intensities is described. The counter tube comprises a tubular cathode and an anode extending centrally of the cathode. The spacing between the outer surface of the anode and the inner surface of the cathode is varied along the length of the tube to provide different counting volumes in adjacent portions of the tube. A large counting volume in one portion adjacent to a low-energy absorption window gives adequate sensitivity for measuring lowintensity radiation, while a smaller volume with close electrode spacing is provided in the counter to make possible measurement of intense garnma radiation fields.

Pre-treatment of pyridine wastewater by new cathodic-anodic-electrolysis packing.

PubMed

Jin, Yang; Yue, Qinyan; Yang, Kunlun; Wu, Suqing; Li, Shengjie; Gao, Baoyu; Gao, Yuan

2018-01-01

A novel cathodic-anodic-electrolysis packing (CAEP) used in the treatment of pyridine wastewater was researched, which mainly consisted of 4,4'-diamino-2,2'-disulfonic acid (DSD acid) industrial iron sludge. The physical properties and morphology of the packing were studied. The CAEP was used in a column reactor during the pretreatment of pyridine wastewater. The influence of pH, hydraulic retention time (HRT), the air-liquid ratio (A/L) and the initial concentration of pyridine were investigated by measuring the removal of total organic carbon (TOC) and pyridine. The characterization results showed that the bulk density, grain density, water absorption percentage and specific surface area were 921kg/m 3 , 1086kg/m 3 , 25% and 29.89m 2 /g, respectively; the removal of TOC and pyridine could reach 50% and 58% at the optimal experimental conditions (pH=3, HRT=8hr, A/L=2). Notably, the surface of the packing was renewed constantly during the running of the filter, and the handling capacity was stable after running for three months. Copyright © 2017. Published by Elsevier B.V.

A ceramic radial insulation structure for a relativistic electron beam vacuum diode.

PubMed

Xun, Tao; Yang, Hanwu; Zhang, Jiande; Liu, Zhenxiang; Wang, Yong; Zhao, Yansong

2008-06-01

For one kind of a high current diode composed of a small disk-type alumina ceramic insulator water/vacuum interface, the insulation structure was designed and experimentally investigated. According to the theories of vacuum flashover and the rules for radial insulators, a "cone-column" anode outline and the cathode shielding rings were adopted. The electrostatic field along the insulator surface was obtained by finite element analysis simulating. By adjusting the outline of the anode and reshaping the shielding rings, the electric fields were well distributed and the field around the cathode triple junction was effectively controlled. Area weighted statistical method was applied to estimate the surface breakdown field. In addition, the operating process of an accelerator based on a spiral pulse forming line (PFL) was simulated through the PSPICE software to get the waveform of charging and diode voltage. The high voltage test was carried out on a water dielectric spiral PFL accelerator with long pulse duration, and results show that the diode can work stably in 420 kV, 200 ns conditions. The experimental results agree with the theoretical and simulated results.

The use of the ion probe mass spectrometer in the measurement of hydrogen concentration gradients in Monel K 500

NASA Technical Reports Server (NTRS)

Truhan, J. J., Jr.; Hehemann, R. F.

1974-01-01

The ion probe mass spectrometer was used to measure hydrogen concentration gradients in cathodically charged Monel K 500. Initial work with the ion probe involved the calibration of the instrument and the establishment of a suitable experimental procedure for this application. Samples of Monel K 500 were cathodically charged in a weak sulfuric acid solution. By varying the current density, different levels of hydrogen were introduced into the samples. Hydrogen concentration gradients were taken by ion sputtering on the surface of these samples and monitoring the behavior of the hydrogen mass peak as a function of time. An attempt was made to determine the relative amounts of hydrogen in the bulk and grain boundaries by analyzing a fresh fracture surface with a higher proportion of grain boundary area. It was found that substantially more hydrogen was detected in the grain boundaries than in the bulk, confirming the predictions of previous workers. A sputter rate determination was made in order to establish the rate of erosion.

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

PubMed

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

2016-01-26

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

Electrochemically induced dual reactive barriers for transformation of TCE and mixture of contaminants in groundwater.

PubMed

Mao, Xuhui; Yuan, Songhu; Fallahpour, Noushin; Ciblak, Ali; Howard, Joniqua; Padilla, Ingrid; Loch-Caruso, Rita; Alshawabkeh, Akram N

2012-11-06

A novel reactive electrochemical flow system consisting of an iron anode and a porous cathode is proposed for the remediation of mixture of contaminants in groundwater. The system consists of a series of sequentially arranged electrodes, a perforated iron anode, a porous copper cathode followed by a mesh-type mixed metal oxide anode. The iron anode generates ferrous species and a chemically reducing environment, the porous cathode provides a reactive electrochemically reducing barrier, and the inert anode provides protons and oxygen to neutralize the system. The redox conditions of the electrolyte flowing through this system can be regulated by controlling the distribution of the electric current. Column experiments are conducted to evaluate the process and study the variables. The electrochemical reduction on a copper foam cathode produced an electrode-based reductive potential capable of reducing TCE and nitrate. Rational electrodes arrangement, longer residence time of electrolytes and higher surface area of the foam electrode improve the reductive transformation of TCE. More than 82.2% TCE removal efficiency is achieved for the case of low influent concentration (<7.5 mg/L) and high current (>45 mA). The ferrous species produced from the iron anode not only enhance the transformation of TCE on the cathode, but also facilitates transformation of other contaminants including dichromate, selenate and arsenite. Removal efficiencies greater than 80% are achieved for these contaminants in flowing contaminated water. The overall system, comprising the electrode-based and electrolyte-based barriers, can be engineered as a versatile and integrated remedial method for a relatively wide spectrum of contaminants and their mixtures.

Formic acid fuel cells and catalysts

DOEpatents

Masel, Richard I.; Larsen, Robert; Ha, Su Yun

2010-06-22

An exemplary fuel cell of the invention includes a formic acid fuel solution in communication with an anode (12, 134), an oxidizer in communication with a cathode (16, 135) electrically linked to the anode, and an anode catalyst that includes Pd. An exemplary formic acid fuel cell membrane electrode assembly (130) includes a proton-conducting membrane (131) having opposing first (132) and second surfaces (133), a cathode catalyst on the second membrane surface, and an anode catalyst including Pd on the first surface.

Enhanced electro-Fenton Mineralization of Acid Orange 7 Using a Carbon Nanotube Fiber Based Cathode

NASA Astrophysics Data System (ADS)

Huong Le, Thi Xuan; Alemán, Belén; Vilatela, Juan J.; Bechelany, Mikhael; Cretin, Marc

2018-02-01

A new cathodic material for electro-Fenton (EF) process was prepared based on a macroscopic fiber (CNTF) made of mm long carbon nanotubes directly spun from the gas phase by floating catalyst CVD, on a carbon fiber (CF) substrate. CNTF@CF electrode is a highly graphitic material combining a high surface area ( 260 m2/g) with high electrical conductivity and electrochemical stability . One kind of azo dye, acid orange 7 (AO7), was used as model bio-refractory pollutant to be treated at CNTF@CF cathode in acidic aqueous medium (pH 3.0). The experimental results pointed out that AO7 and its organic intermediate compounds were totally mineralized by hydroxyl radical generated from Fenton reaction. In fact, 96.7 % of the initial TOC was eliminated in 8h of electrolysis by applying a current of -25 mA and ferrous ions as catalyst at concentration of 0.2 mM. At the same electrolysis time, only 23.7 % of TOC removal found on CF support which proved the high mineralization efficiency of new material thanks to CNTs deposition. The CNTF@CF cathode maintained stable its activity during five experimental cycles of EF set-up. The results indicated that CNTF@CF material could be a potential choice for wastewater treatment containing bio-refractory by electrochemical advanced oxidation processes (EAOPs).

Carbon nanostructures modified LiFePO4 cathodes for lithium ion battery applications: optimized porosity and composition

NASA Astrophysics Data System (ADS)

Mahmoud, Lama; Singh Lalia, Boor; Hashaikeh, Raed

2016-12-01

Lithium iron phosphate (LiFePO4) battery cathode was fabricated without using any metallic current collector and polymeric binder. Carbon nanostructures (CNS) were used as microbinders for LiFePO4 particles and at the same time as a 3D current collector. A facile and cost effective method of fabricating composite cathodes of CNS and LiFePO4 was developed. Thick electrodes with high loading of active material (20-25 mg cm-2) were obtained that are almost 2-3 folds higher than commercial electrodes. SEM images confirm that the 3D CNS conductive network encapsulated the LiFePO4 particles homogenously facilitating the charge transfer at the electrode-CNS interface. The composition, scan rate and porosity of the paper-like cathode were sequentially varied and their influence was systematically monitored by means of linear sweep cyclic voltammetry and AC electrochemical impedance spectroscopy. Addition of CNS improved the electrode’s bulk electronic conductivity, mechanical integrity, surface area and double layer capacitance, yet compromised the charge transfer resistance at the electrode-electrolyte interface. Based on a range of the tested binder-free electrodes, this study proposes that electrodes with 20 wt% CNS having 49 ± 2.5% porosity had realized best improvements of two folds and four folds in the electronic conductivity and diffusion coefficient, respectively.

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

DOE PAGES

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

2017-05-08

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

Electron reversal ionizer for detection of trace species using a spherical cathode

NASA Technical Reports Server (NTRS)

Boumsellek, Said (Inventor); Chutjian, Ara (Inventor)

1994-01-01

A reversal electron, high-current ionizer capable of focusing a beam of electrons to a reversal region employs an indirectly heated cathode having a concave emitting surface of width of W less than 2r, where r is the radius of curvature and preferably a ratio of width to radius approximately equal to one for optimum high current for a given cathode width.

Electrolytic/fuel cell bundles and systems including a current collector in communication with an electrode thereof

DOEpatents

Hawkes, Grant L.; Herring, James S.; Stoots, Carl M.; O& #x27; Brien, James E.

2013-03-05

Electrolytic/fuel cell bundles and systems including such bundles include an electrically conductive current collector in communication with an anode or a cathode of each of a plurality of cells. A cross-sectional area of the current collector may vary in a direction generally parallel to a general direction of current flow through the current collector. The current collector may include a porous monolithic structure. At least one cell of the plurality of cells may include a current collector that surrounds an outer electrode of the cell and has at least six substantially planar exterior surfaces. The planar surfaces may extend along a length of the cell, and may abut against a substantially planar surface of a current collector of an adjacent cell. Methods for generating electricity and for performing electrolysis include flowing current through a conductive current collector having a varying cross-sectional area.

Determination of the mechanism and extent of surface degradation in Ni-based cathode materials after repeated electrochemical cycling

NASA Astrophysics Data System (ADS)

Hwang, Sooyeon; Kim, Se Young; Chung, Kyung Yoon; Stach, Eric A.; Kim, Seung Min; Chang, Wonyoung

2016-09-01

We take advantage of scanning transmission electron microscopy and electron energy loss spectroscopy to investigate the changes in near-surface electronic structure and quantify the degree of local degradation of Ni-based cathode materials with the layered structure (LiNi0.8Mn0.1Co0.1O2 and LiNi0.4Mn0.3Co0.3O2) after 20 cycles of delithiation and lithiation. Reduction of transition metals occurs in the near-surface region of cathode materials: Mn is the major element to be reduced in the case of relatively Mn-rich composition, while reduction of Ni ions is dominant in Ni-rich materials. The valences of Ni and Mn ions are complementary, i.e., when one is reduced, the other is oxidized in order to maintain charge neutrality. The depth of degradation zone is found to be much deeper in Ni-rich materials. This comparative analysis provides important insights needed for the devising of new cathode materials with high capacity as well as long lifetime.

Voltage effects on cells cultured on metallic biomedical implants

NASA Astrophysics Data System (ADS)

Haerihosseini, Seyed Morteza

Electrochemical voltage shifts in metallic biomedical implants occur in-vivo due to a number of processes including mechanically assisted corrosion. Surface potential of biomedical implants and excursions from resting open circuit potential (OCP), which is the voltage they attain while in contact with an electrolyte, can significantly change the interfacial properties of the metallic surfaces and alter the behavior of the surrounding cells, compromising the biocompatibility of metallic implants. Voltages can also be controlled to modulate cell function and fate. To date, the details of the physico-chemical phenomena and the role of different biomaterial parameters involved in the interaction between cells and metallic surfaces under cathodic bias have not been fully elucidated. In this work, changes in the interfacial properties of a CoCrMo biomedical alloy (ASTM F-1537) in phosphate-buffered saline (PBS) (pH 7.4) at different voltages was studied. Step polarization impedance spectroscopy technique was used to apply 50 mV voltage steps to samples, and the time-based current transients were recorded. A new equation was derived based on capacitive discharge through a Tafel element and generalized to deal with non-ideal impedance behavior. The new function compared to the KWW-Randles function, better matched the time-transient response. The results also showed a voltage dependent oxide resistance and capacitance behavior. Additionally, the in-vitro effect of static voltages on the behavior of MC3T3-E1 pre-osteoblasts cultured on CoCrMo alloy (ASTM-1537) was studied to determine the range of cell viability and mode of cell death beyond the viable range. Cell viability and morphology, changes in actin cytoskeleton, adhesion complexes and nucleus, and mode of cell death (necrosis, or intrinsic or extrinsic apoptosis) were characterized at different voltages ranging from -1000 to +500 mV (Ag/AgCl). Moreover, electrochemical currents and metal ion concentrations at each voltage were measured and related to the observed responses. Results show that cathodic and anodic voltages outside the voltage viability range (-400 < V < +500) lead to primarily intrinsic apoptotic and necrotic cell death, respectively. Cell death is associated with cathodic current densities of 0.1 uAcm-2 and anodic current densities of 10 uAcm-2. Significant increase in metallic ions (Co, Cr, Ni, Mo) was seen at +500 mV, and -1000 mV (Cr only) compared to open circuit potential. The number and total projected area of adhesion complexes was also lower on the polarized alloy (p < 0.05). These results show that reduction reactions on CoCrMo alloys leads to apoptosis of cells on the surface and may be a relevant mode of cell death for metallic implants in-vivo. . On the other hand, we studied how surface oxide thickness of Ti affects its voltage viability range and cellular response and whether anodic oxidation can serve as a means to extend this range. Cellular behavior (cell viability, cytoskeletal organization, and cellular adhesion) on bare and anodized Ti samples, potentiostatically held at voltages at the cathodic edge of the viability range, were assessed. Surfaces were characterized using contact angle (CA) measurement technique and atomic force microscopy (AFM), and the observed cellular response was related to the changes in the electrochemical properties (electrochemical currents, open circuit potential, and impedance spectra) of the samples. Results show that anodization at a low voltage (9 V) in phosphate buffer saline (PBS) generates a compact surface oxide with comparable surface roughness and energy to the starting native oxide on the bare surface. The anodized surface extends the viability range at 24 hours by about a 100 mV in the cathodic region, and preserved the cytoskeletal integrity and cell adhesion. Broadening of the viability range corresponds to an increase in impedance of the anodized surface at -400 mV(Ag/AgCl) and the resulting low average currents (below 0.1 uAcm-2) at the interface, which diminish the harmful cathodic reactions. Finally, cellular dynamics (size, polarity, movement) and temporal changes in the number and total area of focal adhesions in transiently transfected MC3T3-E1 pre-osteoblasts cultured on a CoCrMo alloy polarized at the cathodic and anodic edges of its voltage viability range (-400 and +500 mV(Ag/AgCl) respectively) were studied. Nucleus dynamics (size, circularity, movement) and the release of reactive oxygen species (ROS) was also studied on the polarized metal at -1000, -400, and +500 mV(Ag/AgCl). The results show that at -400 mV(Ag/AgCl) a gradual loss of adhesion occurs over 24 hours while cells shrink in size during this time. At +500 mV, cells become non-viable after 5 hours without showing any significant changes in adhesion behavior right before cell death. Nucleus size of cells at -1000 mV decreased sharply within 15 minutes after electrochemical polarization, which rendered the cells completely non-viable. No significant amount of ROS was released by cells on the polarized CoCrMo at any of these voltages.

Electrochemical and thermal studies of lithium ion batteries

NASA Astrophysics Data System (ADS)

Lu, Wenquan

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

Life Model of Hollow Cathodes Using a Barium Calcium Aluminate Impregnated Tungsten Emitter

NASA Technical Reports Server (NTRS)

Kovaleski, S. D.; Burke, Tom (Technical Monitor)

2001-01-01

Hollow cathodes with barium calcium aluminate impregnated tungsten emitters for thermionic emission are widely used in electric propulsion. These high current, low power cathodes are employed in ion thrusters, Hall thrusters, and on the International Space Station in plasma contactors. The requirements on hollow cathode life are growing more stringent with the increasing use of electric propulsion technology. The life limiting mechanism that determines the entitlement lifetime of a barium impregnated thermionic emission cathode is the evolution and transport of barium away from the emitter surface. A model is being developed to study the process of barium transport and loss from the emitter insert in hollow cathodes. The model accounts for the production of barium through analysis of the relevant impregnate chemistry. Transport of barium through the approximately static gas is also being treated. Finally, the effect of temperature gradients within the cathode are considered.

A phenomenological model for orificed hollow cathodes. Ph.D. Thesis, 1 Dec. 1981 - 1 Dec. 1982; [electrostatic thruster

NASA Technical Reports Server (NTRS)

Siegfried, D. E.

1982-01-01

A quartz hollow tube cathode was used to determine the operating conditions within a mercury orificed hollow cathode. Insert temperature profiles, cathode current distributions, plasma properties profile, and internal pressure-mass flow rate results are summarized and used in a phenomenological model which qualitatively describes electron emission and plasma production processes taking place within the cathode. By defining an idealized ion production region within which most of the plasma processes are concentrated, this model is expressed analytically as a simple set of equations which relate cathode dimensions and specifiable operating conditions, such as mass flow rate and discharge current, to such important parameters as emission surface temperature and internal plasma properties. Key aspects of the model are examined.

Physical model and experimental results of cathode erosion related to power supply ripple

NASA Technical Reports Server (NTRS)

Harris, W. J.; O'Hair, E. A.; Hatfield, L. L.; Kristiansen, M.

1992-01-01

This paper discusses the physical effects of power supply ripple on cathode erosion and cathode arc attachment in a water-cooled, 30 kW nitrogen arcjet. Experimental results are presented for 2 percent thoriated tungsten, which show that the long-term cathode erosion rate is a decreasing function of current ripple over the range 1-13 percent. Above this range, the cathode discharge becomes unstable, and the erosion rate rapidly increases. A qualitative model of this effect is given in terms of a magnetically induced radial motion of the arc column, and an overall increase in the cathode spot radius due to the higher peak current associated with higher ripple. The most important effect of power supply ripple is therefore shown to be its ability to collectively drive the cathode attachment away from the cathode center. This leads to an increase in the cathode attachment area, and a subsequent decrease in the cathode erosion rate.

Atmospheric pressure arc discharge with ablating graphite anode

NASA Astrophysics Data System (ADS)

Nemchinsky, V. A.; Raitses, Y.

2015-06-01

The anodic carbon arc discharge is used to produce carbon nanoparticles. Recent experiments with the carbon arc at atmospheric pressure helium demonstrated the enhanced ablation rate for narrow graphite anodes resulting in high deposition rates of carbonaceous products on the copper cathode (Fetterman et al 2008 Carbon 46 1322-6). The proposed model explains these results with interconnected steady-state models of the cathode and the anode processes. When considering cathode functioning, the model predicts circulation of the particles in the near-cathode region: evaporation of the cathode material, ionization of evaporated atoms and molecules in the near-cathode plasma, return of the resulting ions to the cathode, surface recombination of ions and electrons followed again by cathode evaporation etc. In the case of the low anode ablation rate, the ion acceleration in the cathode sheath provides the major cathode heating mechanism. In the case of an intensive anode ablation, an additional cathode heating is due to latent fusion heat of the atomic species evaporated from the anode and depositing at the cathode. Using the experimental arc voltage as the only input discharge parameter, the model allows us to calculate the anode ablation rate. A comparison of the results of calculations with the available experimental data shows reasonable agreement.

Formation of liquid-metal jets in a vacuum arc cathode spot: Analogy with drop impact on a solid surface

NASA Astrophysics Data System (ADS)

Gashkov, M. A.; Zubarev, N. M.

2018-01-01

Conditions of the liquid-metal jets formation in a cathode spot of a vacuum arc discharge are studied. Our consideration is based on the analogy between the processes, occurring in the liquid phase of the cathode spot, and the processes, accompanying a liquid drop impact on a flat solid surface. In the latter case there exists a wide variety of experimental data on the conditions under which the spreading regime of fluid motion (i.e., without formation of jets and secondary droplets) changes into the splashing one. In the present work, using the hydrodynamic similarity principle (processes in geometrically similar systems will proceed similarly when their Weber and Reynolds numbers coincide), criteria for molten metal splashing are formulated for different materials of the cathode. They are compared with the experimental data on the threshold conditions for vacuum arc burning.

U.sup.+4 generation in HTER

DOEpatents

Miller, William E [Naperville, IL; Gay, Eddie C [Park Forest, IL; Tomczuk, Zygmunt [Homer Glen, IL

2006-03-14

A improved device and process for recycling spent nuclear fuels, in particular uranium metal, that facilitates the refinement and recovery of uranium metal from spent metallic nuclear fuels. The electrorefiner device comprises two anodes in predetermined spatial relation to a cathode. The anodese have separate current and voltage controls. A much higher voltage than normal for the electrorefining process is applied to the second anode, thereby facilitating oxidization of uranium (III), U.sup.+, to uranium (IV), U.sup.+4. The current path from the second anode to the cathode is physically shorter than the similar current path from the second anode to the spent nuclear fuel contained in a first anode shaped as a basket. The resulting U.sup.+4 oxidizes and solubilizes rough uranium deposited on the surface of the cathode. A softer uranium metal surface is left on the cathode and is more readily removed by a scraper.

Experimental study on TiN coated racetrack-type ceramic pipe

NASA Astrophysics Data System (ADS)

Wang, Jie; Xu, Yan-Hui; Zhang, Bo; Wei, Wei; Fan, Le; Pei, Xiang-Tao; Hong, Yuan-Zhi; Wang, Yong

2015-11-01

TiN film was coated on the internal surface of a racetrack-type ceramic pipe by three different methods: radio-frequency sputtering, DC sputtering and DC magnetron sputtering. The deposition rates of TiN film under different coating methods were compared. The highest deposition rate was 156 nm/h, which was obtained by magnetron sputtering coating. Based on AFM, SEM and XPS test results, the properties of TiN film, such as film roughness and surface morphology, were analyzed. Furthermore, the deposition rates were studied with two different cathode types, Ti wires and Ti plate. According to the SEM test results, the deposition rate of TiN/Ti film was about 800 nm/h with Ti plate cathode by DC magnetron sputtering. Using Ti plate cathode rather than Ti wire cathode can greatly improve the film deposition rate. Supported by National Nature Science Foundation of China (11075157)

Tracking the Effect of Cathodal Transcranial Direct Current Stimulation on Cortical Excitability and Connectivity by Means of TMS-EEG

PubMed Central

Varoli, Erica; Pisoni, Alberto; Mattavelli, Giulia C.; Vergallito, Alessandra; Gallucci, Alessia; Mauro, Lilia D.; Rosanova, Mario; Bolognini, Nadia; Vallar, Giuseppe; Romero Lauro, Leonor J.

2018-01-01

Transcranial direct current stimulation (tDCS) is increasingly used in both research and therapeutic settings, but its precise mechanisms remain largely unknown. At a neuronal level, tDCS modulates cortical excitability by shifting the resting membrane potential in a polarity-dependent way: anodal stimulation increases the spontaneous firing rate, while cathodal decreases it. However, the neurophysiological underpinnings of anodal/cathodal tDCS seem to be different, as well as their behavioral effect, in particular when high order areas are involved, compared to when motor or sensory brain areas are targeted. Previously, we investigated the effect of anodal tDCS on cortical excitability, by means of a combination of Transcranial Magnetic Stimulation (TMS) and Electroencephalography (EEG). Results showed a diffuse rise of cortical excitability in a bilateral fronto-parietal network. In the present study, we tested, with the same paradigm, the effect of cathodal tDCS. Single pulse TMS was delivered over the left posterior parietal cortex (PPC), before, during, and after 10 min of cathodal or sham tDCS over the right PPC, while recording HD-EEG. Indexes of global and local cortical excitability were obtained both at sensors and cortical sources level. At sensors, global and local mean field power (GMFP and LMFP) were computed for three temporal windows (0–50, 50–100, and 100–150 ms), on all channels (GMFP), and in four different clusters of electrodes (LMFP, left and right, in frontal and parietal regions). After source reconstruction, Significant Current Density was computed at the global level, and for four Broadmann's areas (left/right BA 6 and 7). Both sensors and cortical sources results converge in showing no differences during and after cathodal tDCS compared to pre-stimulation sessions, both at global and local level. The same holds for sham tDCS. These data highlight an asymmetric impact of anodal and cathodal stimulation on cortical excitability, with a diffuse effect of anodal and no effect of cathodal tDCS over the parietal cortex. These results are consistent with the current literature: while anodal-excitatory and cathodal-inhibitory effects are well-established in the sensory and motor domains, both at physiological and behavioral levels, results for cathodal stimulation are more controversial for modulation of exitability of higher order areas. PMID:29867330

Surface study of stainless steel electrode deposition from soil electrokinetic (EK) treatment using X-ray photoelectron spectroscopy (XPS)

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

Embong, Zaidi, E-mail: zaidi@uthm.edu.my; Research Centre for Soft Soils; Johar, Saffuwan

2015-04-29

Electrokinetic (EK) remediation relies upon application of a low-intensity direct current through the soil between stainless steel electrodes that are divided into a cathode array and an anode array. This mobilizes charged species, causing ions and water to move toward the electrodes. Metal ions and positively charged organic compounds move toward the cathode. Anions such as chloride, fluoride, nitrate, and negatively charged organic compounds move toward the anode. Here, this remediation techniques lead to a formation of a deposition at the both cathode and anode surface that mainly contributed byanion and cation from the remediated soil. In this research, Renggam-Jerangaumore » soil species (HaplicAcrisol + RhodicFerralsol) with a surveymeter reading of 38.0 ± 3.9 μR/hr has been investigation in order to study the mobility of the anion and cation under the influence electric field. Prior to the EK treatment, the elemental composition of the soil and the stainless steel electrode are measured using XRF analyses. Next, the soil sample is remediated at a constant electric potential of 30 V within an hour of treatment period. A surface study for the deposition layer of the cathode and anode using X-ray Photoelectron spectroscopy (XPS) revealed that a narrow photoelectron signal from oxygen O 1s, carbon, C 1s silica, Si 2p, aluminium, Al 2p and chromium, Cr 2p exhibited on the electrode surface and indicate that a different in photoelectron intensity for each element on both electrode surface. In this paper, the mechanism of Si{sup 2+} and Al{sup 2+} cation mobility under the influence of voltage potential between the cathode and anode will be discussed in detail.« less

Electro-thermal modelling of anode and cathode in micro-EDM

NASA Astrophysics Data System (ADS)

Yeo, S. H.; Kurnia, W.; Tan, P. C.

2007-04-01

Micro-electrical discharge machining is an evolution of conventional EDM used for fabricating three-dimensional complex micro-components and microstructure with high precision capabilities. However, due to the stochastic nature of the process, it has not been fully understood. This paper proposes an analytical model based on electro-thermal theory to estimate the geometrical dimensions of micro-crater. The model incorporates voltage, current and pulse-on-time during material removal to predict the temperature distribution on the workpiece as a result of single discharges in micro-EDM. It is assumed that the entire superheated area is ejected from the workpiece surface while only a small fraction of the molten area is expelled. For verification purposes, single discharge experiments using RC pulse generator are performed with pure tungsten as the electrode and AISI 4140 alloy steel as the workpiece. For the pulse-on-time range up to 1000 ns, the experimental and theoretical results are found to be in close agreement with average volume approximation errors of 2.7% and 6.6% for the anode and cathode, respectively.

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

Beilis, I. I.

Experiments in the last decade showed that for cathode spots in a magnetic field that obliquely intercepts the cathode surface, the current per spot increased with the transverse component of the magnetic field and decreased with the normal component. The present work analyzes the nature of cathode spot splitting in an oblique magnetic field. A physical model for cathode spot current splitting was developed, which considered the relation between the plasma kinetic pressure, self-magnetic pressure, and applied magnetic pressure in a current carrying cathode plasma jet. The current per spot was calculated, and it was found to increase with themore » tangential component of the magnetic field and to decrease with the normal component, which agrees well with the experimental dependence.« less

Unraveling the Role of Transport, Electrocatalysis, and Surface Science in the Solid Oxide Fuel Cell Cathode Oxygen Reduction Reaction

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

Gopalan, Srikanth

2017-04-06

This final report for project FE0009656 covers the period from 10/01/2012 to 09/30/2015 and covers research accomplishments on the effects of carbon dioxide on the surface composition and structure of cathode materials for solid oxide fuel cells (SOFCs), specifically La1-xSrxFeyCo1- yO3-δ (LSCF). Epitaxially deposited thin films of LSCF on various single-crystal substrates have revealed the selective segregation of strontium to the surface thereby resulting in a surface enrichment of strontium. The near surface compositional profile in the films have been measured using total x-ray fluorescence (TXRF), and show that the kinetics of strontium segregation are higher at higher partial pressuresmore » of carbon dioxide. Once the strontium segregates to the surface, it leads to the formation of precipitates of SrO which convert to SrCO3 in the presence of even modest concentrations of carbon dioxide in the atmosphere. This has important implications for the performance of SOFCs which is discussed in this report. These experimental observations have also been verified by Density Functional Theory calculations (DFT) which predict the conditions under which SrO and SrCO3 can occur in LSCF. Furthermore, a few cathode compositions which have received attention in the literature as alternatives to LSCF cathodes have been studied in this work and shown to be thermodynamically unstable under the operating conditions of the SOFCs.« less

Selecting the Best Graphite for Long-Life, High-Energy Li-Ion Batteries

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

Mao, Chengyu; Wood, Marissa; David, Lamuel Abraham

Here, most lithium-ion batteries still rely on intercalation-type graphite materials for anodes, so it is important to consider their role in full cells for applications in electric vehicles. Here, we systematically evaluate the chemical and physical properties of six commercially-available natural and synthetic graphites to establish which factors have the greatest impact on the cycling stability of full cells with nickel-rich LiNi0.8Mn0.1Co0.1O2 (NMC811) cathodes. Electrochemical data and post-mortem characterization explain the origin of capacity fade. The NMC811 cathode shows large irreversible capacity loss and impedance growth, accounting for much of full cell degradation. However, six graphite anodes demonstrate significant differencesmore » with respect to structural change, surface area, impedance growth, and SEI chemistry, which impact overall capacity retention. We found long cycle life correlated most strongly with stable graphite crystallite size. In addition, graphites with lower surface area generally had higher coulombic efficiencies during formation cycles, which led to more stable long-term cycling. The best graphite screened here enables a capacity retention around 90% in full pouch cells over extensive long-term cycling compared to only 82% for cells with the lowest performing graphite. The results show that optimal graphite selection improves cycling stability of high energy lithium-ion cells.« less

Durability of Pt-Co Alloy Polymer Electrolyte Fuel Cell Cathode Catalysts under Accelerated Stress Tests

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

Papadias, D. D.; Ahluwalia, R. K.; Kariuki, N.

The durability of Pt-Co alloy cathode catalysts supported on high surface area carbon is investigated by subjecting them to accelerated stress tests (ASTs). The catalysts had different initial Co contents and nanoparticle morphologies: a “spongy” porous morphology for the high-Co (H) content catalyst, and a fully alloyed crystalline morphology for the medium-Co (M) and low-Co (L) content catalysts. The specific activity of the catalysts depends on their initial Co content, morphology and nanoparticle size, and remained higher than 1000 μA/cm 2-Pt after 27–50% Co loss. The H-catalyst electrode showed the smallest kinetic overpotentials (η c s) due to higher initialmore » Pt loading than the other two electrodes, but it had the fastest increase in ηcs with AST cycling due to lower Co retention; the L-catalyst electrode showed higher η c s due to a lower initial Pt loading, but had a smaller increase in η c s with aging due to higher Co retention; the M-catalyst electrode showed a similar increase in η c s with aging, but this increase was due to the combined effects of Co dissolution and electrochemically active surface area (ECSA) loss. In conclusion, the modeled increase in mass transfer overpotentials with aging correlates with the initial Pt loading, ECSA loss and the initial catalyst morphology« less

Durability of Pt-Co Alloy Polymer Electrolyte Fuel Cell Cathode Catalysts under Accelerated Stress Tests

DOE PAGES

Papadias, D. D.; Ahluwalia, R. K.; Kariuki, N.; ...

2018-03-17

The durability of Pt-Co alloy cathode catalysts supported on high surface area carbon is investigated by subjecting them to accelerated stress tests (ASTs). The catalysts had different initial Co contents and nanoparticle morphologies: a “spongy” porous morphology for the high-Co (H) content catalyst, and a fully alloyed crystalline morphology for the medium-Co (M) and low-Co (L) content catalysts. The specific activity of the catalysts depends on their initial Co content, morphology and nanoparticle size, and remained higher than 1000 μA/cm 2-Pt after 27–50% Co loss. The H-catalyst electrode showed the smallest kinetic overpotentials (η c s) due to higher initialmore » Pt loading than the other two electrodes, but it had the fastest increase in ηcs with AST cycling due to lower Co retention; the L-catalyst electrode showed higher η c s due to a lower initial Pt loading, but had a smaller increase in η c s with aging due to higher Co retention; the M-catalyst electrode showed a similar increase in η c s with aging, but this increase was due to the combined effects of Co dissolution and electrochemically active surface area (ECSA) loss. In conclusion, the modeled increase in mass transfer overpotentials with aging correlates with the initial Pt loading, ECSA loss and the initial catalyst morphology« less

Selecting the Best Graphite for Long-Life, High-Energy Li-Ion Batteries

DOE PAGES

Mao, Chengyu; Wood, Marissa; David, Lamuel Abraham; ...

2018-06-16

Here, most lithium-ion batteries still rely on intercalation-type graphite materials for anodes, so it is important to consider their role in full cells for applications in electric vehicles. Here, we systematically evaluate the chemical and physical properties of six commercially-available natural and synthetic graphites to establish which factors have the greatest impact on the cycling stability of full cells with nickel-rich LiNi0.8Mn0.1Co0.1O2 (NMC811) cathodes. Electrochemical data and post-mortem characterization explain the origin of capacity fade. The NMC811 cathode shows large irreversible capacity loss and impedance growth, accounting for much of full cell degradation. However, six graphite anodes demonstrate significant differencesmore » with respect to structural change, surface area, impedance growth, and SEI chemistry, which impact overall capacity retention. We found long cycle life correlated most strongly with stable graphite crystallite size. In addition, graphites with lower surface area generally had higher coulombic efficiencies during formation cycles, which led to more stable long-term cycling. The best graphite screened here enables a capacity retention around 90% in full pouch cells over extensive long-term cycling compared to only 82% for cells with the lowest performing graphite. The results show that optimal graphite selection improves cycling stability of high energy lithium-ion cells.« less

Analyses of microstructural and elastic properties of porous SOFC cathodes based on focused ion beam tomography

NASA Astrophysics Data System (ADS)

Chen, Zhangwei; Wang, Xin; Giuliani, Finn; Atkinson, Alan

2015-01-01

Mechanical properties of porous SOFC electrodes are largely determined by their microstructures. Measurements of the elastic properties and microstructural parameters can be achieved by modelling of the digitally reconstructed 3D volumes based on the real electrode microstructures. However, the reliability of such measurements is greatly dependent on the processing of raw images acquired for reconstruction. In this work, the actual microstructures of La0.6Sr0.4Co0.2Fe0.8O3-δ (LSCF) cathodes sintered at an elevated temperature were reconstructed based on dual-beam FIB/SEM tomography. Key microstructural and elastic parameters were estimated and correlated. Analyses of their sensitivity to the grayscale threshold value applied in the image segmentation were performed. The important microstructural parameters included porosity, tortuosity, specific surface area, particle and pore size distributions, and inter-particle neck size distribution, which may have varying extent of effect on the elastic properties simulated from the microstructures using FEM. Results showed that different threshold value range would result in different degree of sensitivity for a specific parameter. The estimated porosity and tortuosity were more sensitive than surface area to volume ratio. Pore and neck size were found to be less sensitive than particle size. Results also showed that the modulus was essentially sensitive to the porosity which was largely controlled by the threshold value.

Tailoring the surface properties of LiNi 0.4Mn 0.4Co 0.2O₂ by titanium substitution for improved high voltage cycling performance

DOE PAGES

Wolff-Goodrich, Silas; Xin, Huolin L.; Lin, Feng; ...

2015-07-30

The present research aims to provide insights into the behavior of LiNi0.4Mn0.4Co0.2O2 (NMC442) and LiNi 0.4Mn 0.4Co 0.2O₂ (NMC442-Ti02) cathode materials under galvanostatic cycling to high potentials, in the context of previous work which predicted that Ti-substituted variants should deliver higher capacities and exhibit better cycling stability than the unsubstituted compounds. It is found that NMC cathodes containing Ti show equivalent capacity fading but greater specific capacity than those without Ti in the same potential range. When repeatedly charged to the same degree of delithiation, NMC cathodes containing Ti showed better capacity retention. Soft x-ray absorption spectroscopy (XAS) spectra formore » Mn and Co indicated increased reduction in these elements for NMC cathodes without Ti, indicating that the substitution of Ti for Co acts to suppress the formation of a high impedance rock salt phase at the surface of NMC cathode particles. The results of this study validate the adoption of a facile change to existing NMC chemistries to improve cathode capacity retention under high voltage cycling conditions.« less

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.

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

PubMed Central

2013-01-01

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

Effect of cathode shape on vertical buffered electropolishing for niobium SRF cavities

NASA Astrophysics Data System (ADS)

Jin, S.; Wu, A. T.; Lu, X. Y.; Rimmer, R. A.; Lin, L.; Zhao, K.; Mammosser, J.; Gao, J.

2013-09-01

This paper reports the research results of the effect of cathode shape during vertical buffered electropolishing (BEP) by employing a demountable single cell niobium (Nb) superconducting radio frequency (SRF) cavity. Several different cathode shapes such as, for instance, bar, ball, ellipsoid, and wheels of different diameters have been tested. Detailed electropolishing parameters including I-V characteristic, removal rate, surface roughness, and polishing uniformity at different locations inside the demountable cavity are measured. Similar studies are also done on conventional electropolishing (EP) for comparison. It is revealed that cathode shape has dominant effects for BEP especially on the obtaining of a suitable polishing condition and a uniform polishing rate in an Nb SRF single cell cavity. EP appears to have the same tendency. This paper demonstrates that a more homogeneous polishing result can be obtained by optimizing the electric field distribution inside the cavity through the modification of the cathode shape given the conditions that temperature and electrolyte flow are kept constant. Electric field distribution and electrolyte flow patterns inside the cavity are simulated via Poisson-Superfish and Solidworks respectively. With the optimal cathode shape, BEP shows a much faster polishing rate of ∼2.5 μm/min and is able to produce a smoother surface finish in the treatments of single cell cavities in comparison with EP.

Synthesis, strctural and electrochemical characterizations of lithium- manganese- rich composite cathode materials for lithium ion batteries

NASA Astrophysics Data System (ADS)

Wang, Dapeng

The electrification trend for transportation systems requires alternative cathode materials to LiCoO2 with improved safety, lowered cost and extended cycle life. Lithium- manganese- rich composite cathode materials, which can be presented in a two component notation as xLi2MnO3·(1-x)LiMO 2, (M= Ni, Co or Mn) have superior cost and energy density advantages. These cathode materials have shown success in laboratory scale experiments, but are still facing challenges such as voltage fade, moderate rate capacity and tap density for commercialization. The synthesis of precursors with high packing density and suitable physical properties is critical to achieve high energy density as well as the other acceptable electrochemical performance for the next generation lithium ion batteries. The aim of this study is to correlate the electrochemical properties of materials to their structural, morphological, and physical properties by coordinating the science of synthesis with the science of function, in order to enable the use of these compounds in vehicle technologies. Three different precursors including carbonate, hydroxide and oxalate were synthesized by co-precipitation reactions using continuous stirred tank reactor (CSTR) under various conditions. Research focused on areas such as nucleation and growth mechanisms, synthesis optimizations, and intrinsic limitations of each co-precipitation method. A combination of techniques such as PSA, BET, SEM, EDX FIB, TEM, Raman, FTIR, TGA-DSC, XRD, and ICP-MS, as well as electrochemical test methods such as cycling, CV, EIS and HPPC tests were used in correlation with each other in order to deepen our understanding to these materials. Related topics such as the composite structure formation process during the solid state reaction, lithium and nickel content effects on the cathode properties were also discussed. Additionally, the side reactions between the active materials and electrolyte as a result of the high charge potential were mitigated through a simple wet chemical surface coating method, and the positive effect of the surface coating on the cells' performance was also discussed.

Field-Induced Crystalline-to-Amorphous Phase Transformation on the Si Nano-Apex and the Achieving of Highly Reliable Si Nano-Cathodes

PubMed Central

Huang, Yifeng; Deng, Zexiang; Wang, Weiliang; Liang, Chaolun; She, Juncong; Deng, Shaozhi; Xu, Ningsheng

2015-01-01

Nano-scale vacuum channel transistors possess merits of higher cutoff frequency and greater gain power as compared with the conventional solid-state transistors. The improvement in cathode reliability is one of the major challenges to obtain high performance vacuum channel transistors. We report the experimental findings and the physical insight into the field induced crystalline-to-amorphous phase transformation on the surface of the Si nano-cathode. The crystalline Si tip apex deformed to amorphous structure at a low macroscopic field (0.6~1.65 V/nm) with an ultra-low emission current (1~10 pA). First-principle calculation suggests that the strong electrostatic force exerting on the electrons in the surface lattices would take the account for the field-induced atomic migration that result in an amorphization. The arsenic-dopant in the Si surface lattice would increase the inner stress as well as the electron density, leading to a lower amorphization field. Highly reliable Si nano-cathodes were obtained by employing diamond like carbon coating to enhance the electron emission and thus decrease the surface charge accumulation. The findings are crucial for developing highly reliable Si-based nano-scale vacuum channel transistors and have the significance for future Si nano-electronic devices with narrow separation. PMID:25994377

Pulsed metallic-plasma generators.

NASA Technical Reports Server (NTRS)

Gilmour, A. S., Jr.; Lockwood, D. L.

1972-01-01

A pulsed metallic-plasma generator is described which utilizes a vacuum arc as the plasma source. The arc is initiated on the surface of a consumable cathode which can be any electrically conductive material. Ignition is accomplished by using a current pulse to vaporize a portion of a conductive film on the surface of an insulator separating the cathode from the ignition electrode. The film is regenerated during the ensuing arc. Over 100 million ignition cycles have been accomplished by using four 0.125-in. diameter zinc cathodes operating in parallel and high-density aluminum-oxide insulators. Among the applications being investigated for the generator are metal deposition, vacuum pumping, electric propulsion, and high-power dc arc interruption.

Nanoscale morphological and chemical changes of high voltage lithium-manganese rich NMC composite cathodes with cycling.

PubMed

Yang, Feifei; Liu, Yijin; Martha, Surendra K; Wu, Ziyu; Andrews, Joy C; Ice, Gene E; Pianetta, Piero; Nanda, Jagjit

2014-08-13

Understanding the evolution of chemical composition and morphology of battery materials during electrochemical cycling is fundamental to extending battery cycle life and ensuring safety. This is particularly true for the much debated high energy density (high voltage) lithium-manganese rich cathode material of composition Li(1 + x)M(1 - x)O2 (M = Mn, Co, Ni). In this study we combine full-field transmission X-ray microscopy (TXM) with X-ray absorption near edge structure (XANES) to spatially resolve changes in chemical phase, oxidation state, and morphology within a high voltage cathode having nominal composition Li1.2Mn0.525Ni0.175Co0.1O2. Nanoscale microscopy with chemical/elemental sensitivity provides direct quantitative visualization of the cathode, and insights into failure. Single-pixel (∼ 30 nm) TXM XANES revealed changes in Mn chemistry with cycling, possibly to a spinel conformation and likely including some Mn(II), starting at the particle surface and proceeding inward. Morphological analysis of the particles revealed, with high resolution and statistical sampling, that the majority of particles adopted nonspherical shapes after 200 cycles. Multiple-energy tomography showed a more homogeneous association of transition metals in the pristine particle, which segregate significantly with cycling. Depletion of transition metals at the cathode surface occurs after just one cycle, likely driven by electrochemical reactions at the surface.

Nanoscale Morphological and Chemical Changes of High Voltage Lithium–Manganese Rich NMC Composite Cathodes with Cycling

PubMed Central

2015-01-01

Understanding the evolution of chemical composition and morphology of battery materials during electrochemical cycling is fundamental to extending battery cycle life and ensuring safety. This is particularly true for the much debated high energy density (high voltage) lithium–manganese rich cathode material of composition Li1 + xM1 – xO2 (M = Mn, Co, Ni). In this study we combine full-field transmission X-ray microscopy (TXM) with X-ray absorption near edge structure (XANES) to spatially resolve changes in chemical phase, oxidation state, and morphology within a high voltage cathode having nominal composition Li1.2Mn0.525Ni0.175Co0.1O2. Nanoscale microscopy with chemical/elemental sensitivity provides direct quantitative visualization of the cathode, and insights into failure. Single-pixel (∼30 nm) TXM XANES revealed changes in Mn chemistry with cycling, possibly to a spinel conformation and likely including some Mn(II), starting at the particle surface and proceeding inward. Morphological analysis of the particles revealed, with high resolution and statistical sampling, that the majority of particles adopted nonspherical shapes after 200 cycles. Multiple-energy tomography showed a more homogeneous association of transition metals in the pristine particle, which segregate significantly with cycling. Depletion of transition metals at the cathode surface occurs after just one cycle, likely driven by electrochemical reactions at the surface. PMID:25054780

Semiconductor nanostructures for plasma energetic systems

NASA Astrophysics Data System (ADS)

Mustafaev, Alexander; Smerdov, Rostislav; Klimenkov, Boris

2017-10-01

In this talk we discuss the research results of the three types of ultrasmall electrodes namely the nanoelectrode arrays based on composite nanostructured porous silicon (PS) layers, porous GaP and nanocrystals of ZnO. These semiconductor materials are of great interest to nano- and optoelectronic applications by virtue of their high specific surface area and extensive capability for surface functionalization. The use of semiconductor (GaN) cathodes in photon-enhanced thermionic emission systems has also proved to be effective although only a few (less than 1%) of the incident photons exceed the 3.3 eV GaN band gap. This significant drawback provided us with a solid foundation for our research in the field of nanostructured PS, and composite materials based on it exhibiting nearly optimal parameters in terms of the band gap (1.1 eV). The band gap modification for PS nanostructured layers is possible in the range of less than 1 eV and 3 eV due to the existence of quantum confinement effect and the remarkable possibilities of PS surface alteration thus providing us with a suitable material for both cathode and anode fabrication. The obtained results are applicable for solar concentration and thermionic energy conversion systems. Dr. Sci., Ph.D, Principal Scientist, Professor.

Fluorination effect of activated carbons on performance of asymmetric capacitive deionization

NASA Astrophysics Data System (ADS)

Jo, Hanjoo; Kim, Kyung Hoon; Jung, Min-Jung; Park, Jae Hyun; Lee, Young-Seak

2017-07-01

Activated carbons (ACs) were fluorinated and fabricated into electrodes to investigate the effect of fluorination on asymmetric capacitive deionization (CDI). Fluorine functional groups were introduced on the AC surfaces via fluorination. The specific capacitance of the fluorinated AC (Fsbnd AC) electrode increased drastically from 261 to 337 F/g compared with the untreated AC (Rsbnd AC) electrode at a scan rate of 5 mV/s, despite a decrease in the specific surface area and total pore volume after fluorination. The desalination behavior of asymmetric CDI cells assembled with an Rsbnd AC electrode as the counter electrode and an Fsbnd AC electrode as the cathode (R || F-) or anode (R || F +) was studied. For R || F-, the salt adsorption capacity and charge efficiency increased from 10.6 mg/g and 0.58-12.4 mg/g and 0.75, respectively, compared with the CDI cell assembled with identical Rsbnd AC electrodes at 1 V. This CDI cell exhibited consistently better salt adsorption capacity and charge efficiency at different applied voltages because Fsbnd AC electrodes have a cation attractive effect originating from the partially negatively charged fluorine functional groups on the AC surface. Therefore, co-ion expulsion in the Fsbnd AC electrode as the cathode is effectively diminished, leading to enhanced CDI performance.

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.

Paper-Based Analytical Devices Relying on Visible-Light-Enhanced Glucose/Air Biofuel Cells.

PubMed

Wu, Kaiqing; Zhang, Yan; Wang, Yanhu; Ge, Shenguang; Yan, Mei; Yu, Jinghua; Song, Xianrang

2015-11-04

A strategy that combines visible-light-enhanced biofuel cells (BFCs) and electrochemical immunosensor into paper-based analytical devices was proposed for sensitive detection of the carbohydrate antigen 15-3 (CA15-3). The gold nanoparticle modified paper electrode with large surface area and good conductibility was applied as an effective matrix for primary antibodies. The glucose dehydrogenase (GDH) modified gold-silver bimetallic nanoparticles were used as bioanodic biocatalyst and signal magnification label. Poly(terthiophene) (pTTh), a photoresponsive conducting polymer, served as catalyst in cathode for the reduction of oxygen upon illumination by visible light. In the bioanode, electrons were generated through the oxidation of glucose catalyzed by GDH. The amount of electrons is determined by the amount of GDH, which finally depended on the amount of CA15-3. In the cathode, electrons from the bioanode could combine with the generated holes in the HOMO energy level of cathode catalysts pTTh. Meanwhile, the high energy level photoexcited electrons were generated in the LUMO energy level and involved in the oxygen reduction reaction, finally resulting in an increasing current and a decreasing overpotential. According to the current signal, simple and efficient detection of CA15-3 was achieved.

Spatial structure of radio frequency ring-shaped magnetized discharge sputtering plasma using two facing ZnO/Al2O3 cylindrical targets for Al-doped ZnO thin film preparation

NASA Astrophysics Data System (ADS)

Sumiyama, Takashi; Fukumoto, Takaya; Ohtsu, Yasunori; Tabaru, Tatsuo

2017-05-01

Spatial structure of high-density radio frequency ring-shaped magnetized discharge plasma sputtering with two facing ZnO/Al2O3 cylindrical targets mounted in ring-shaped hollow cathode has been measured and Al-doped ZnO (AZO) thin film is deposited without substrate heating. The plasma density has a peak at ring-shaped hollow trench near the cathode. The radial profile becomes uniform with increasing the distance from the target cathode. A low ion current flowing to the substrate of 0.19 mA/cm2 is attained. Large area AZO films with a resistivity of 4.1 - 6.7×10-4 Ω cm can be prepared at a substrate room temperature. The transmittance is 84.5 % in a visible region. The surface roughnesses of AZO films are 0.86, 0.68, 0.64, 1.7 nm at radial positions of r = 0, 15, 30, 40 mm, respectively, while diffraction peak of AZO films is 34.26°. The grains exhibit a preferential orientation along (002) axis.

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

NASA Astrophysics Data System (ADS)

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

2015-10-01

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

Fibrous polyaniline@manganese oxide nanocomposites as supercapacitor electrode materials and cathode catalysts for improved power production in microbial fuel cells.

PubMed

Ansari, Sajid Ali; Parveen, Nazish; Han, Thi Hiep; Ansari, Mohammad Omaish; Cho, Moo Hwan

2016-04-07

Fibrous Pani-MnO2 nanocomposite were prepared using a one-step and scalable in situ chemical oxidative polymerization method. The formation, structural and morphological properties were investigated using a range of characterization techniques. The electrochemical capacitive behavior of the fibrous Pani-MnO2 nanocomposite was examined by cyclic voltammetry and galvanostatic charge-discharge measurements using a three-electrode experimental setup in an aqueous electrolyte. The fibrous Pani-MnO2 nanocomposite achieved high capacitance (525 F g(-1) at a current density of 2 A g(-1)) and excellent cycling stability of 76.9% after 1000 cycles at 10 A g(-1). Furthermore, the microbial fuel cell constructed with the fibrous Pani-MnO2 cathode catalyst showed an improved power density of 0.0588 W m(-2), which was higher than that of pure Pani and carbon paper, respectively. The improved electrochemical supercapacitive performance and cathode catalyst performance in microbial fuel cells were attributed mainly to the synergistic effect of Pani and MnO2 in fibrous Pani-MnO2, which provides high surface area for the electrode/electrolyte contact as well as electronic conductive channels and exhibits pseudocapacitance behavior.

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

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.

PLUTONIUM ELECTROREFINING CELLS

DOEpatents

Mullins, L.J. Jr.; Leary, J.A.; Bjorklund, C.W.; Maraman, W.J.

1963-07-16

Electrorefining cells for obtaining 99.98% plutonium are described. The cells consist of an impure liquid plutonium anode, a molten PuCl/sub 3/-- alkali or alkaline earth metal chloanode, a molten PuCl/sub 3/-alkali or alkaline earth metal chloride electrolyte, and a nonreactive cathode, all being contained in nonreactive ceramic containers which separate anode from cathode by a short distance and define a gap for the collection of the purified liquid plutonium deposited on the cathode. Important features of these cells are the addition of stirrer blades on the anode lead and a large cathode surface to insure a low current density. (AEC)

Fast turn-on osmium coated cathode

NASA Astrophysics Data System (ADS)

Marrian, C. R. K.; Haas, G. A.; Shih, A.

1984-03-01

This abstract discloses a fast turn-on refractory coated cathode comprising a porous tungsten metal matrix impregnated with barium calcium aluminate and coated with osmium. The osmium coating has a planned series of interruptions with each interruption being on the order of several microns in width to thereby expose the tungsten. These interruptions permit the barium and oxygen from the impregnant to rise to the cathode surface during activation or reactivation to form a desired near monolayer of barium and oxygen to enhance electron emission. Thus, this cathode design provides a fast turn-on characteristic even after shelf storage.

An update of the JPL program to develop Li-SOCl2 cells

NASA Technical Reports Server (NTRS)

Halpert, S.; Ang, V.; Banes, R.; Dawson, S.; Frank, H.; Subbarao, S.; Whitcanack, L.

1985-01-01

The goal of producing spiral wound D cell was met. The cell design and electrodes, particularly the carbon cathodes were produced in-house. Also all parts were assembled, the welding performed, the electrolyte aided and the cells sealed in-house. The lithium capacity (theoretical) was 19.3 Ah and that of the SOCl2 in the 1.8 m LiAlCl4 electrolyte, 16.4 Ah (a greater excess of SOCl2 is necessary for safe high rate operation). The electrode surface area was 452 sq cm. The carbon electrode comprised Shawinigen Black/Teflon -30 (90/10 by weight) mixture 0.020 inches thick on an expanded metal screen prepared in the JPL laboratory. There were two tab connections to the cathode. The 0.0078 inch thick lithium foil was rolled into an expanded nickel screen. The separator was Mead 934-5 fiberglass material.

Silicon etch with chromium ions generated by a filtered or non-filtered cathodic arc discharge

PubMed Central

Scopece, Daniele; Döbeli, Max; Passerone, Daniele; Maeder, Xavier; Neels, Antonia; Widrig, Beno; Dommann, Alex; Müller, Ulrich; Ramm, Jürgen

2016-01-01

Abstract The pre-treatment of substrate surfaces prior to deposition is important for the adhesion of physical vapour deposition coatings. This work investigates Si surfaces after the bombardment by energetic Cr ions which are created in cathodic arc discharges. The effect of the pre-treatment is analysed by X-ray diffraction, Rutherford backscattering spectroscopy, scanning electron microscopy and in-depth X-ray photoemission spectroscopy and compared for Cr vapour produced from a filtered and non-filtered cathodic arc discharge. Cr coverage as a function of ion energy was also predicted by TRIDYN Monte Carlo calculations. Discrepancies between measured and simulated values in the transition regime between layer growth and surface removal can be explained by the chemical reactions between Cr ions and the Si substrate or between the substrate surface and the residual gases. Simulations help to find optimum and more stable parameters for specific film and substrate combinations faster than trial-and-error procedure. PMID:27877854

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

PubMed

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

2016-09-08

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

Negative ion source with hollow cathode discharge plasma

DOEpatents

Hershcovitch, Ady; Prelec, Krsto

1983-01-01

A negative ion source of the type where negative ions are formed by bombarding a low-work-function surface with positive ions and neutral particles from a plasma, wherein a highly ionized plasma is injected into an anode space containing the low-work-function surface. The plasma is formed by hollow cathode discharge and injected into the anode space along the magnetic field lines. Preferably, the negative ion source is of the magnetron type.

PROCESS OF SEPARATING PLUTONIUM VALUES BY ELECTRODEPOSITION

DOEpatents

Whal, A.C.

1958-04-15

A process is described of separating plutonium values from an aqueous solution by electrodeposition. The process consists of subjecting an aqueous 0.1 to 1.0 N nitric acid solution containing plutonium ions to electrolysis between inert metallic electrodes. A current density of one milliampere io one ampere per square centimeter of cathode surface and a temperature between 10 and 60 d C are maintained. Plutonium is electrodeposited on the cathode surface and recovered.

Electrocatalysis paradigm for protection of cathode materials in high-voltage lithium-ion batteries

DOE PAGES

Shkrob, Ilya A.; Abraham, Daniel P.

2016-07-06

A new mechanistic framework is suggested to account for the protective action of certain electrolyte additives on high-voltage positive electrode (cathode) materials. The mechanism involves inactivation of catalytically active centers on the electrode active materials through fragmentation reactions involving molecules at its surface. The cathode protection additives oxidize before the solvent and serve as sacrificial inhibitors of the catalytic centers. Without the additive, the surface oxidation of the solvent (like solvent oxidation in the bulk) yields H loss radicals and releases the proton that can combine with anions forming corrosive acids. This proton-release reaction is demonstrated experimentally for boronate additives.more » Specific radical reactions for the latter additives on the electrode surface are suggested. Furthermore, the same approach can be used to rationalize the protective action of other additives and account for various observations regarding their performance.« less

Electrocatalysis paradigm for protection of cathode materials in high-voltage lithium-ion batteries

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

Shkrob, Ilya A.; Abraham, Daniel P.

A new mechanistic framework is suggested to account for the protective action of certain electrolyte additives on high-voltage positive electrode (cathode) materials. The mechanism involves inactivation of catalytically active centers on the electrode active materials through fragmentation reactions involving molecules at its surface. The cathode protection additives oxidize before the solvent and serve as sacrificial inhibitors of the catalytic centers. Without the additive, the surface oxidation of the solvent (like solvent oxidation in the bulk) yields H loss radicals and releases the proton that can combine with anions forming corrosive acids. This proton-release reaction is demonstrated experimentally for boronate additives.more » Specific radical reactions for the latter additives on the electrode surface are suggested. Furthermore, the same approach can be used to rationalize the protective action of other additives and account for various observations regarding their performance.« less

Enhancing Electrochemical Water-Splitting Kinetics by Polarization-Driven Formation of Near-Surface Iron(0): An In Situ XPS Study on Perovskite-Type Electrodes**

PubMed Central

Opitz, Alexander K; Nenning, Andreas; Rameshan, Christoph; Rameshan, Raffael; Blume, Raoul; Hävecker, Michael; Knop-Gericke, Axel; Rupprechter, Günther; Fleig, Jürgen; Klötzer, Bernhard

2015-01-01

In the search for optimized cathode materials for high-temperature electrolysis, mixed conducting oxides are highly promising candidates. This study deals with fundamentally novel insights into the relation between surface chemistry and electrocatalytic activity of lanthanum ferrite based electrolysis cathodes. For this means, near-ambient-pressure X-ray photoelectron spectroscopy (NAP-XPS) and impedance spectroscopy experiments were performed simultaneously on electrochemically polarized La0.6Sr0.4FeO3−δ (LSF) thin film electrodes. Under cathodic polarization the formation of Fe0 on the LSF surface could be observed, which was accompanied by a strong improvement of the electrochemical water splitting activity of the electrodes. This correlation suggests a fundamentally different water splitting mechanism in presence of the metallic iron species and may open novel paths in the search for electrodes with increased water splitting activity. PMID:25557533

Evolution of the lithium morphology from cycling of thin film solid state batteries

DOE PAGES

Dudney, Nancy J.

2017-03-11

Thin film batteries with a Lipon electrolyte and Li metal anode can be cycled thousands of times. During this time there is a gradual redistribution of the lithium at the top surface; the morphology that develops depends on a number of factors but is largely driven by dewetting. In this work, this redistribution is characterized as functions of the cycle number, duty cycle, cathode composition, and protective coating over the lithium. Observations of wrinkled and pitted surfaces are discussed considering the effects of defects and diffusion in the lithium and influences of film stresses and surface energy. In conclusion, similarmore » processes may impact solid state lithium batteries with higher energy per active area.« less

Evolution of the lithium morphology from cycling of thin film solid state batteries

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

Dudney, Nancy J.

Thin film batteries with a Lipon electrolyte and Li metal anode can be cycled thousands of times. During this time there is a gradual redistribution of the lithium at the top surface; the morphology that develops depends on a number of factors but is largely driven by dewetting. In this work, this redistribution is characterized as functions of the cycle number, duty cycle, cathode composition, and protective coating over the lithium. Observations of wrinkled and pitted surfaces are discussed considering the effects of defects and diffusion in the lithium and influences of film stresses and surface energy. In conclusion, similarmore » processes may impact solid state lithium batteries with higher energy per active area.« less

Recent Advances in Catalyst Accelerated Stress Tests for Polymer Electrolyte Membrane Fuel Cells

DOE PAGES

Stariha, Sarah; Macauley, Natalia; Sneed, Brian T.; ...

2018-03-15

The U.S. Department of Energy (DOE) set the 2020 durability target for polymer electrolyte membrane fuel cell transportation applications at 5000 hours. Since it is impractical to test every fuel cell for this length of time, there is ever increasing interest in developing accelerated stress tests (ASTs) that can accurately simulate the material component degradation in the membrane electrode assembly (MEA) observed under automotive operating conditions, but over a much shorter time frame. In this study, a square-wave catalyst AST was examined that shows a 5X time acceleration factor over the triangle-wave catalyst AST and a 25X time acceleration factormore » over the modified wet drive-cycle catalyst durability protocol, significantly decreasing the testing time. These acceleration factors were correlated to the platinum (Pt) particle size increase and associated decrease in electrochemical surface area (ECSA). This square-wave AST has been adopted by the DOE as a standard protocol to evaluate catalyst durability. We also compare three catalyst-durability protocols using state-of-the-art platinum-cobalt catalysts supported on high surface area carbon (SOA Pt-Co/HSAC) in the cathode catalyst layer. The results for each of the three tests showed both catalyst particle size increase and transition metal leaching. Moreover the acceleration factors for the alloy catalysts were smaller due to Co leaching being the predominant mechanism of voltage decay in ~5 nm PtCo/C catalysts. Finally, an extremely harsh carbon corrosion AST was run using the same SOA Pt-Co/HSAC catalyst. This showed minimal change in particle size and a low percentage Co loss from the cathode catalyst particles, despite a significant loss in catalyst layer thickness and cell performance. The carbon corrosion rates during these various ASTs were directly measured by monitoring the CO 2 emission from the cathode, further confirming the ability of the square-wave AST to evaluate the electro-catalyst independently of the support.« less

Recent Advances in Catalyst Accelerated Stress Tests for Polymer Electrolyte Membrane Fuel Cells

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

Stariha, Sarah; Macauley, Natalia; Sneed, Brian T.

The U.S. Department of Energy (DOE) set the 2020 durability target for polymer electrolyte membrane fuel cell transportation applications at 5000 hours. Since it is impractical to test every fuel cell for this length of time, there is ever increasing interest in developing accelerated stress tests (ASTs) that can accurately simulate the material component degradation in the membrane electrode assembly (MEA) observed under automotive operating conditions, but over a much shorter time frame. In this study, a square-wave catalyst AST was examined that shows a 5X time acceleration factor over the triangle-wave catalyst AST and a 25X time acceleration factormore » over the modified wet drive-cycle catalyst durability protocol, significantly decreasing the testing time. These acceleration factors were correlated to the platinum (Pt) particle size increase and associated decrease in electrochemical surface area (ECSA). This square-wave AST has been adopted by the DOE as a standard protocol to evaluate catalyst durability. We also compare three catalyst-durability protocols using state-of-the-art platinum-cobalt catalysts supported on high surface area carbon (SOA Pt-Co/HSAC) in the cathode catalyst layer. The results for each of the three tests showed both catalyst particle size increase and transition metal leaching. Moreover the acceleration factors for the alloy catalysts were smaller due to Co leaching being the predominant mechanism of voltage decay in ~5 nm PtCo/C catalysts. Finally, an extremely harsh carbon corrosion AST was run using the same SOA Pt-Co/HSAC catalyst. This showed minimal change in particle size and a low percentage Co loss from the cathode catalyst particles, despite a significant loss in catalyst layer thickness and cell performance. The carbon corrosion rates during these various ASTs were directly measured by monitoring the CO 2 emission from the cathode, further confirming the ability of the square-wave AST to evaluate the electro-catalyst independently of the support.« less

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

Stariha, Sarah; Macauley, Natalia; Sneed, Brian T.

The U.S. Department of Energy (DOE) set the 2020 durability target for polymer electrolyte membrane fuel cell transportation applications at 5000 hours. Since it is impractical to test every fuel cell for this length of time, there is ever increasing interest in developing accelerated stress tests (ASTs) that can accurately simulate the material component degradation in the membrane electrode assembly (MEA) observed under automotive operating conditions, but over a much shorter time frame. In this study, a square-wave catalyst AST was examined that shows a 5X time acceleration factor over the triangle-wave catalyst AST and a 25X time acceleration factormore » over the modified wet drive-cycle catalyst durability protocol, significantly decreasing the testing time. These acceleration factors were correlated to the platinum (Pt) particle size increase and associated decrease in electrochemical surface area (ECSA). This square-wave AST has been adopted by the DOE as a standard protocol to evaluate catalyst durability. We also compare three catalyst-durability protocols using state-of-the-art platinum-cobalt catalysts supported on high surface area carbon (SOA Pt-Co/HSAC) in the cathode catalyst layer. The results for each of the three tests showed both catalyst particle size increase and transition metal leaching. Moreover the acceleration factors for the alloy catalysts were smaller due to Co leaching being the predominant mechanism of voltage decay in ~5 nm PtCo/C catalysts. Finally, an extremely harsh carbon corrosion AST was run using the same SOA Pt-Co/HSAC catalyst. This showed minimal change in particle size and a low percentage Co loss from the cathode catalyst particles, despite a significant loss in catalyst layer thickness and cell performance. The carbon corrosion rates during these various ASTs were directly measured by monitoring the CO 2 emission from the cathode, further confirming the ability of the square-wave AST to evaluate the electro-catalyst independently of the support.« less

Replacing thermal sprayed zinc anodes on cathodically protected steel reinforced concrete bridges.

DOT National Transportation Integrated Search

2011-09-01

This research aimed to address questions underlying the replacement of arc-sprayed zinc anodes on cathodically protected steel reinforced concrete bridges and to develop a protocol to prepare the concrete surface for the new anode, through a combinat...

Replacing thermal sprayed zinc anodes on cathodically protected steel reinforced concrete bridges.

DOT National Transportation Integrated Search

2011-08-01

"This research aimed to address questions underlying the replacement of arc-sprayed zinc anodes on cathodically protected steel reinforced concrete bridges and to develop a protocol to prepare the concrete surface for the new anode, through a combina...

Modification of polymer velvet cathode via metallic Mo coating for enhancement of high-current electron emission performances

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

Xiong, Ying; Wang, Bing; Yi, Yong

2013-09-15

The effect of surface Mo coating on the high-current electron emission performances for polymer velvet cathode has been investigated in a diode with A-K gap of 11.5 cm by the combination of time-resolved electrical diagnostic and temporal pressure variation. Compared with uncoated polymer velvet cathode under the single-pulsed emission mode, the Mo-coated one shows lower outgassing levels (∼0.40 Pa L), slower cathode plasma expansion velocity (∼2.30 cm/μs), and higher emission stability as evidences by the change in cathode current, temporal pressure variation, and diode perveance. Moreover, after Mo coating, the emission consistency of the polymer velvet cathode between two adjacentmore » pulses is significantly improved in double-pulsed emission mode with ∼500 ns interval between two pulses, which further confirms the effectiveness of Mo coating for enhancement of electron emission performance of polymer velvet cathodes. These results should be of interest to the high-repetitive high-power microwave systems with cold cathodes.« less

Inkjet-Printed Porous Silver Thin Film as a Cathode for a Low-Temperature Solid Oxide Fuel Cell.

PubMed

Yu, Chen-Chiang; Baek, Jong Dae; Su, Chun-Hao; Fan, Liangdong; Wei, Jun; Liao, Ying-Chih; Su, Pei-Chen

2016-04-27

In this work we report a porous silver thin film cathode that was fabricated by a simple inkjet printing process for low-temperature solid oxide fuel cell applications. The electrochemical performance of the inkjet-printed silver cathode was studied at 300-450 °C and was compared with that of silver cathodes that were fabricated by the typical sputtering method. Inkjet-printed silver cathodes showed lower electrochemical impedance due to their porous structure, which facilitated oxygen gaseous diffusion and oxygen surface adsorption-dissociation reactions. A typical sputtered nanoporous silver cathode became essentially dense after the operation and showed high impedance due to a lack of oxygen supply. The results of long-term fuel cell operation show that the cell with an inkjet-printed cathode had a more stable current output for more than 45 h at 400 °C. A porous silver cathode is required for high fuel cell performance, and the simple inkjet printing technique offers an alternative method of fabrication for such a desirable porous structure with the required thermal-morphological stability.

Surface Modification Technique of Cathode Materials for LI-ION Battery

NASA Astrophysics Data System (ADS)

Jia, Yongzhong; Han, Jinduo; Jing, Yan; Jin, Shan; Qi, Taiyuan

Cathode materials for Li-ion battery LiMn2O4 and LiCo0.1Mn1.9O4 were prepared by soft chemical method. Carbon, which was made by decomposing organic compounds, was used as modifying agent. Cathode material matrix was mixed with water solution that had contained organic compound such as cane sugar, soluble amylum, levulose et al. These mixture were reacted at 150 200 °C for 0.5 4 h in a Teflon-lined autoclave to get a series of homogeneously C-coated cathode materials. The new products were analyzed by X-ray diffraction (XRD) and infrared (IR). Morphology of cathode materials was characterized by scanning electron microscope (SEM) and transition electron microscope (TEM). The new homogeneously C-coated products that were used as cathode materials of lithium-ion battery had good electrochemical stability and cycle performance. This technique has free-pollution, low cost, simpleness and easiness to realize the industrialization of the cathode materials for Li-ion battery.

Deposition of Composite LSCF-SDC and SSC-SDC Cathodes by Axial-Injection Plasma Spraying

NASA Astrophysics Data System (ADS)

Harris, Jeffrey; Qureshi, Musab; Kesler, Olivera

2012-06-01

The performance of solid oxide fuel cell cathodes can be improved by increasing the number of electrochemical reaction sites, by controlling microstructures, or by using composite materials that consist of an ionic conductor and a mixed ionic and electronic conductor. LSCF (La0.6Sr0.4Co0.2Fe0.8O3-δ) and SSC (Sm0.5Sr0.5CoO3) cathodes were manufactured by axial-injection atmospheric plasma spraying, and composite cathodes were fabricated by mixing SDC (Ce0.8Sm0.2O1.9) into the feedstock powders. The plasma power was varied by changing the proportion of nitrogen in the plasma gas. The microstructures of cathodes produced with different plasma powers were characterized by scanning electron microscopy and gas permeation measurements. The deposition efficiencies of these cathodes were calculated based on the mass of the sprayed cathode. Particle surface temperatures were measured in-flight to enhance understanding of the relationship between spray parameters, microstructure, and deposition efficiency.

Robust, easily shaped, and epoxy-free carbon-fiber-aluminum cathodes for generating high-current electron beams.

PubMed

Liu, Lie; Li, Limin; Wen, Jianchun; Wan, Hong

2009-02-01

This paper presents the construction of carbon-fiber-aluminum (CFA) cathode by squeezing casting and its applications for generating high-current electron beams to drive high-power microwave sources. The fabrication process avoided using epoxy, a volatile deteriorating the vacuum system. These cathodes had a higher hardness than conventional aluminum, facilitating machining. After surface treatment, carbon fibers became the dominator determining emission property. A multineedle CFA cathode was utilized in a triode virtual cathode oscillator (vircator), powered by a approximately 450 kV, approximately 400 ns pulse. It was found that 300-400 MW, approximately 250 ns microwave was radiated at a dominant frequency of 2.6 GHz. Further, this cathode can endure high-current-density emission without detectable degradation in performance as the pulse shot proceeded, showing the robust nature of carbon fibers as explosive emitters. Overall, this new class of cold cathodes offers a potential prospect of developing high-current electron beam sources.

Space-charge-limited currents for cathodes with electric field enhanced geometry

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

Lai, Dingguo, E-mail: laidingguo@nint.ac.cn; Qiu, Mengtong; Xu, Qifu

This paper presents the approximate analytic solutions of current density for annulus and circle cathodes. The current densities of annulus and circle cathodes are derived approximately from first principles, which are in agreement with simulation results. The large scaling laws can predict current densities of high current vacuum diodes including annulus and circle cathodes in practical applications. In order to discuss the relationship between current density and electric field on cathode surface, the existing analytical solutions of currents for concentric cylinder and sphere diodes are fitted from existing solutions relating with electric field enhancement factors. It is found that themore » space-charge-limited current density for the cathode with electric-field enhanced geometry can be written in a general form of J = g(β{sub E}){sup 2}J{sub 0}, where J{sub 0} is the classical (1D) Child-Langmuir current density, β{sub E} is the electric field enhancement factor, and g is the geometrical correction factor depending on the cathode geometry.« less

Preliminary Design Options for Meteor Burst Communications Systems Buoy Relays

DTIC Science & Technology

1986-12-01

FIELDS BRAYTON OTTO ELECTROSTATIC FIELDS SUPERCRITICAL Figure 5.1. Structure of current power source technology for ocean applications. 32 L / P 9 t ~A...As in the sulphur dioxide cell, a low weight, high surface area, carbon positive elec- trode acts as a catalyst for the reduction of the cathode...Operating Transmit Power No. (Relay/Service) Type Covert Covert Mode Duty Cycle (watts) 2.1 Trans Ocean Relay Shore/Ship No Yes Remote 20 Msg/hr 0.9

Origin of microplasma instabilities during DC operation of silicon based microhollow cathode devices

NASA Astrophysics Data System (ADS)

Felix, Valentin; Lefaucheux, Philippe; Aubry, Olivier; Golda, Judith; Schulz-von der Gathen, Volker; Overzet, Lawrence J.; Dussart, Rémi

2016-04-01

The failure mechanisms of micro hollow cathode discharges (MHCD) in silicon have been investigated using their I-V characteristics, high speed photography and scanning electron microscopy. Experiments were carried out in helium. We observed I-V instabilities in the form of rapid voltage decreases associated with current spikes. The current spikes can reach values more than 100 times greater than the average MHCD current. (The peaks can be more than 1 Ampere for a few 10’s of nanoseconds.) These current spikes are correlated in time with 3-10 μm diameter optical flashes that occur inside the cavities. The SEM characterizations indicated that blister-like structures form on the Si surface during plasma operation. Thin Si layers detach from the surface in localized regions. We theorize that shallow helium implantation occurs and forms the ‘blisters’ whenever the Si is biased as the cathode. These blisters ‘explode’ when the helium pressure inside them becomes too large leading to the transient micro-arcs seen in both the optical emission and the I-V characteristics. We noted that blisters were never found on the metal counter electrode, even when it was biased as the cathode (and the Si as the anode). This observation led to a few suggestions for delaying the failure of Si MHCDs. One may coat the Si cathode (cavities) with blister resistant material; design the MHCD array to operate with the Si as the anode rather than as the cathode; or use a gas additive to prevent surface damage. Regarding the latter, tests using SF6 as the gas additive successfully prevented blister formation through rapid etching. The result was an enhanced MHCD lifetime.

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

NASA Astrophysics Data System (ADS)

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

2018-02-01

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

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.

A new coating method for alleviating surface degradation of LiNi0.6Co0.2Mn0.2O2 cathode material: nanoscale surface treatment of primary particles.

PubMed

Kim, Hyejung; Kim, Min Gyu; Jeong, Hu Young; Nam, Haisol; Cho, Jaephil

2015-03-11

Structural degradation of Ni-rich cathode materials (LiNi(x)M(1-x)O2; M = Mn, Co, and Al; x > 0.5) during cycling at both high voltage (>4.3 V) and high temperature (>50 °C) led to the continuous generation of microcracks in a secondary particle that consisted of aggregated micrometer-sized primary particles. These microcracks caused deterioration of the electrochemical properties by disconnecting the electrical pathway between the primary particles and creating thermal instability owing to oxygen evolution during phase transformation. Here, we report a new concept to overcome those problems of the Ni-rich cathode material via nanoscale surface treatment of the primary particles. The resultant primary particles' surfaces had a higher cobalt content and a cation-mixing phase (Fm3̅m) with nanoscale thickness in the LiNi0.6Co0.2Mn0.2O2 cathode, leading to mitigation of the microcracks by suppressing the structural change from a layered to rock-salt phase. Furthermore, the higher oxidation state of Mn(4+) at the surface minimized the oxygen evolution at high temperatures. This approach resulted in improved structural and thermal stability in the severe cycling-test environment at 60 °C between 3.0 and 4.45 V and at elevated temperatures, showing a rate capability that was comparable to that of the pristine sample.

Increasing the Energy Efficiency of Aluminum-Reduction Cells Using Modified Cathodes

NASA Astrophysics Data System (ADS)

Jianping, Peng; Yang, Song; Yuezhong, Di; Yaowu, Wang; Naixiang, Feng

2017-10-01

A cathode with an inclined surface (5°) and increased bar collector height (230 mm high) was incorporated into two 300-kA industrial aluminum-reduction cells. The voltage of the cells with the modified cathode was reduced by approximately 200 mV when compared with that of a conventional cell with a flat cathode. Through the use of simulations, the reduction in the cell voltage was attributed to the cathode modification (40 mV) and a reduced electrolyte level of 0.5 cm (160 mV). As a result of reduced anode cathode distance (ACD), the ledge toe was extended to the anode shadow by 12 cm. This caused a large inverted horizontal current and a velocity increase. The ledge profile returned to the desired position when the cells were insulated more effectively, and the metal velocity and metal crest in the modified cells were reduced accordingly.

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.

High Performance Pillared Vanadium Oxide Cathode for Lithium Ion Batteries

DTIC Science & Technology

2015-04-24

As a result, two major approaches have been taken to increase electrode- electrolyte interfacial area while minimizing lithium diffusion lengths...Performance Pillared Vanadium Oxide Cathode for Lithium Ion Batteries Siu on Tung, Krista L. Hawthorne, Yi Ding, James Mainero, and Levi T. Thompson...Automotive Research Development and Engineering Center, Warren, MI 48387, USA Keywords: nanostructured materials, lithium ion batteries, cathode

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

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

NASA Astrophysics Data System (ADS)

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

2013-08-01

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

Scalable synthesis of Na3V2(PO4)(3)/C porous hollow spheres as a cathode for Na-ion batteries

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

Mao, JF; Luo, C; Gao, T

2015-01-01

Na3V2(PO4)(3) (NVP) has been considered as a very promising cathode material for sodium-ion batteries (SIBs) due to its typical NASICON structure, which provides an open and three dimensional (3D) framework for Na+ migration. However, the low electronic conductivity of NVP limits its rate capability and cycling ability. In this study, carbon coated hollow structured NVP/C composites are synthesized via a template-free and scalable ultrasonic spray pyrolysis process, where the carbon coated NVP particles are uniformly decorated on the inner and outer surfaces of the porous hollow carbon spheres. When evaluated as a cathode material for SIBs, the unique NVP/C porousmore » hollow sphere cathode delivers an initial discharge capacity of 99.2 mA h g(-1) and retains 89.3 mA h g(-1) after 300 charge/discharge cycles with a very low degradation rate of 0.035% per cycle. For comparison, the NVP/C composite, prepared by the traditional sol-gel method, delivers a lower initial discharge capacity of 97.4 mA h g(-1) and decreases significantly to 71.5 mA h g(-1) after 300 cycles. The superior electrochemical performance of NVP/C porous hollow spheres is attributed to their unique porous, hollow and spherical structures, as well as the carbon-coating layer, which provides a high contact area between electrode/electrolyte, high electronic conductivity, and high mechanical strength.« less

Efficient degradation of rhodamine B using modified graphite felt gas diffusion electrode by electro-Fenton process.

PubMed

Tian, Jiangnan; Olajuyin, Ayobami Matthew; Mu, Tingzhen; Yang, Maohua; Xing, Jianmin

2016-06-01

The electro-Fenton (EF) process treatment of 0.1-M (rhodamine B) RhB solution was studied with different graphite cathode materials, and graphite felt (GF) was selected as a promising material in further investigation. Then, the degradation performances of gas diffusion electrode (GDE) and graphite felt (GF) were compared, and GDE was confirmed to be more efficient in RhB removal. The operational parameters such as Fe(2+) dosage and current density were optimized, and comparison among different modified methods-polytetrafluoroethylene-carbon black (PTFE-CB), polytetrafluoroethylene-carbon nanotube (PTFE-CNT), electrodeposition-CB, and electrodeposition-CNT-showed 98.49 % RhB removal by PTFE-CB-modified cathode in 0.05 M Na2SO4 at a current density of 50 A/m(2) and an air flow rate of 1 L/min after 20 min. Meanwhile, after cathode modified by PTFE-CB, the mineralization efficiency and mineralization current efficiency performed absolutely better than the pristine one. Cyclic voltammograms, SEM images, contact angles, and BET surface area were carried out to demonstrate stronger current responses and higher hydrophilicity of GF after modified. The value of biochemical oxygen demand/chemical oxygen demand (BOD5/COD) increased from 0.049 to 0.331 after 90-min treatment, suggesting the solution was biodegradable, and the modified cathode was confirmed to be stable after ten circle runs. Finally, a proposed degradation pathway of RhB was put forward.

[Copper recovery from artificial bioleaching lixivium of waste printed circuit boards].

PubMed

Cheng, Dan; Zhu, Neng-Wu; Wu, Ping-Xiao; Zou, Ding-Hui; Xing, Yi-Jia

2014-04-01

The key step to realize metal recovery from bioleaching solutions is the recovery of copper from bioleaching lixivium of waste printed circuit boards in high-grade form. The influences of cathode material, current density, initial pH and initial copper ion concentration on the efficiency and energy consumption of copper recovery from artificial bioleaching lixivium under condition of constant current were investigated using an electro-deposition approach. The results showed that the larger specific surface area of the cathode material (carbon felt) led to the higher copper recovery efficiency (the recovery efficiencies of the anode and the cathode chambers were 96.56% and 99.25%, respectively) and the smaller the total and unit mass product energy consumption (the total and unit mass product energy consumptions were 0.022 kW x h and 15.71 kW x h x kg(-1), respectively). The copper recovery efficiency and energy consumption increased with the increase of current density. When the current density was 155.56 mA x cm(-2), the highest copper recovery efficiencies in the anode and cathode chambers reached 98.51% and 99.37%, respectively. Accordingly, the highest total and unit mass product energy consumptions were 0.037 kW x h and 24.34 kW x h x kg(-1), respectively. The copper recovery efficiency was also significantly affected by the initial copper ion concentration. The increase of the initial copper ion concentration would lead to faster decrease of copper ion concentration, higher total energy consumption, and lower unit mass product consumption. However, the initial pH had no significant effect on the copper recovery efficiency. Under the optimal conditions (carbon felt for cathode materials, current density of 111.11 mA x cm(-2), initial pH of 2.0, and initial copper ion concentration of 10 g x L(-1)), the copper recovery efficiencies of the anode and cathode chambers were 96.75% and 99.35%, and the total and unit mass product energy consumptions were 0.021 kW x h and 14.61 kW x h x kg(-1), respectively. The deposited copper on the cathode material was fascicularly distributed and no oxygen was detected.

Cold cathode vacuum discharge tube

DOEpatents

Boettcher, Gordon E.

1998-01-01

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

Two-photon photoemission from a copper cathode in an Χ-band photoinjector

DOE PAGES

Li, H.; Limborg-Deprey, C.; Adolphsen, C.; ...

2016-02-24

This study presents two-photon photoemission from a copper cathode in an X-band photoinjector. We experimentally verified that the electron bunch charge from photoemission out of a copper cathode scales with laser intensity (I) square for 400 nm wavelength photons. We compare this two-photon photoemission process with the single photon process at 266 nm. Despite the high reflectivity (R) of the copper surface for 400 nm photons (R=0.48) and higher thermal energy of photoelectrons (two-photon at 200 nm) compared to 266 nm photoelectrons, the quantum efficiency of the two-photon photoemission process (400 nm) exceeds the single-photon process (266 nm) when themore » incident laser intensity is above 300 GW/cm 2. At the same laser pulse energy (E) and other experimental conditions, emitted charge scales inversely with the laser pulse duration. A thermal emittance of 2.7 mm-mrad per mm root mean square (rms) was measured on our cathode which exceeds by sixty percent larger compared to the theoretical predictions, but this discrepancy is similar to previous experimental thermal emittance on copper cathodes with 266 nm photons. The damage of the cathode surface of our first-generation X-band gun from both rf breakdowns and laser impacts mostly explains this result. Using a 400 nm laser can substantially simplify the photoinjector system, and make it an alternative solution for compact pulsed electron sources.« less

Synthesis of lithium nickel cobalt manganese oxide cathode materials by infrared induction heating

NASA Astrophysics Data System (ADS)

Hsieh, Chien-Te; Chen, Yu-Fu; Pai, Chun-Ting; Mo, Chung-Yu

2014-12-01

This study adopts an in-situ infrared (IR) sintering incorporated with carbonization technique to synthesize carbon-coated LiNi1/3Co1/3Mn1/3O2 (LNCM) cathode materials for Li-ion batteries. Compared with electric resistance heating, the in-situ IR sintering is capable of rapidly producing highly-crystalline LNCM powders at 900 °C within a short period, i.e., 3 h in this case. Glucose additive is employed to serve a carbon precursor, which is carbonized and coated over the surface of LNCM crystals during the IR sintering process. The electrochemical performance of LNCM cathodes is well examined by charge-discharge cycling at 0.1-5C. An appropriate carbon coating is capable of raising discharge capacity (i.e., 181.5 mAh g-1 at 0.1C), rate capability (i.e., 75.0 mAh g-1 at 5C), and cycling stability (i.e., capacity retention: 94.2% at 1C after 50 cycles) of LNCM cathodes. This enhanced performance can be ascribed to the carbon coating onto the external surface of LNCM powders, creating an outer circuit of charge-transfer pathway and preventing cathode corrosion from direct contact to the electrolyte. Accordingly, the in-situ IR sintering technique offers a potential feasibility for synthesizing cathode materials commercially in large scale.

Research to develop guidelines for cathodic protection of concentric neutral cables, volume 2

NASA Astrophysics Data System (ADS)

Hanck, J. A.; Nekoksa, G.

1981-08-01

Data from field tests and sieve analyses presented in support of an effort to develop guidelines for the installation of underground transmission primary cables. Anodic and cathodic polarization curves and the surface and cable potential gradients from 38 bellholes.

Fusion Welding Research.

DTIC Science & Technology

1983-04-30

contaminants from the surface. Further studies of this effect of oxygen on cathodic cleaning of aluminum are being held pending further results of GMAW of...oxygen on cathodic cleaning of aluminum has resulted from these tests, but much more information on the fundamentals of metal transfer in pulsed GMAW

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

PubMed

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

2018-06-06

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

Negative ion source with hollow cathode discharge plasma

DOEpatents

Hershcovitch, A.; Prelec, K.

1980-12-12

A negative ion source of the type where negative ions are formed by bombarding a low-work-function surface with positive ions and neutral particles from a plasma, wherein a highly ionized plasma is injected into an anode space containing the low-work-function surface is described. The plasma is formed by hollow cathode discharge and injected into the anode space along the magnetic field lines. Preferably, the negative ion source is of the magnetron type.

The Surface Coating of Commercial LiFePO4 by Utilizing ZIF-8 for High Electrochemical Performance Lithium Ion Battery

NASA Astrophysics Data System (ADS)

Xu, XiaoLong; Qi, CongYu; Hao, ZhenDong; Wang, Hao; Jiu, JinTing; Liu, JingBing; Yan, Hui; Suganuma, Katsuaki

2018-03-01

The requirement of energy-storage equipment needs to develop the lithium ion battery (LIB) with high electrochemical performance. The surface modification of commercial LiFePO4 (LFP) by utilizing zeolitic imidazolate frameworks-8 (ZIF-8) offers new possibilities for commercial LFP with high electrochemical performances. In this work, the carbonized ZIF-8 (CZIF-8) was coated on the surface of LFP particles by the in situ growth and carbonization of ZIF-8. Transmission electron microscopy indicates that there is an approximate 10 nm coating layer with metal zinc and graphite-like carbon on the surface of LFP/CZIF-8 sample. The N2 adsorption and desorption isotherm suggests that the coating layer has uniform and simple connecting mesopores. As cathode material, LFP/CZIF-8 cathode-active material delivers a discharge specific capacity of 159.3 mAh g-1 at 0.1C and a discharge specific energy of 141.7 mWh g-1 after 200 cycles at 5.0C (the retention rate is approximate 99%). These results are attributed to the synergy improvement of the conductivity, the lithium ion diffusion coefficient, and the degree of freedom for volume change of LFP/CZIF-8 cathode. This work will contribute to the improvement of the cathode materials of commercial LIB.[Figure not available: see fulltext.

Perovskite-type La0.8Sr0.2Co0.8Fe0.2O3 with uniform dispersion on N-doped reduced graphene oxide as an efficient bi-functional Li-O2 battery cathode.

PubMed

Cheng, Junfang; Jiang, Yuexing; Zhang, Ming; Zou, Lu; Huang, Yizhen; Wang, Ziling; Chi, Bo; Pu, Jian; Li, Jian

2017-04-19

A composite cathode including N-rGO with homogeneously dispersed perovskite La 0.8 Sr 0.2 Co 0.8 Fe 0.2 O 3 on the surface is studied. Li-O 2 batteries with LSCF@N-rGO cathode show better performance than those with LSCF-SP or N-rGO cathode. EIS and morphology analysis indicate that LSCF is beneficial to remold the shape of Li 2 O 2 and catalyze the decomposition of Li 2 O 2 .

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.

Device for providing high-intensity ion or electron beam

DOEpatents

McClanahan, Edwin D.; Moss, Ronald W.

1977-01-01

A thin film of a low-thermionic-work-function material is maintained on the cathode of a device for producing a high-current, low-pressure gas discharge by means of sputter deposition from an auxiliary electrode. The auxiliary electrode includes a surface with a low-work-function material, such as thorium, uranium, plutonium or one of the rare earth elements, facing the cathode but at a disposition and electrical potential so as to extract ions from the gas discharge and sputter the low-work-function material onto the cathode. By continuously replenishing the cathode film, high thermionic emissions and ion plasmas can be realized and maintained over extended operating periods.

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.

Morphology Engineering of Co3O4 Nanoarrays as Free-Standing Catalysts for Lithium-Oxygen Batteries.

PubMed

He, Mu; Zhang, Peng; Xu, Shan; Yan, Xingbin

2016-09-14

The effective shape-controlled synthesis of Co3O4 nanoarrays on nickel foam substrates has been achieved through a simple hydrothermal strategy. When they served as the binder- and conductive-agent-free porous cathodes for nonaqueous Li-O2 batteries, they sufficiently reflect the favorable catalytic characteristic of Co3O4 and alleviate the problems of serious pore blocking and surface passivation caused by insoluble and insulating discharge products. In particular, Co3O4 rectangular nanosheets exhibit superior electrocatalytic performance comparing with Co3O4 nanowires and hexagonal nanosheets, leading to higher specific capacity and better cycling stability over 54 cycles at 100 mA g(-1), which relate to their good pore structure, large specific surface area, and highly active {112} exposed plane, effectively promoting the mass transport and reversible formation and decomposition of discharge products in the cathode. These comparisons further indicate the morphology effect of nanostructured Co3O4 on their performances as free-standing catalysts for Li-O2 batteries, which also have been proved through the further analysis of discharge products on different shapes of Co3O4 nanoarrays electrodes.

The cathode material for a plasma-arc heater

NASA Astrophysics Data System (ADS)

Yelyutin, A. V.; Berlin, I. K.; Averyanov, V. V.; Kadyshevskii, V. S.; Savchenko, A. A.; Putintseva, R. G.

1983-11-01

The cathode of a plasma arc heater experiences a large thermal load. The temperature of its working surface, which is in contact with the plasma, reaches high values, as a result of which the electrode material is subject to erosion. Refractory metals are usually employed for the cathode material, but because of the severe erosion do not usually have a long working life. The most important electrophysical characteristic of the electrode is the electron work function. The use of materials with a low electron work function allows a decrease in the heat flow to the cathode, and this leads to an increase in its erosion resistance and working life. The electroerosion of certain materials employed for the cathode in an electric arc plasma generator in the process of reduction smelting of refractory metals was studied.

Miniature Reservoir Cathode: An Update

NASA Technical Reports Server (NTRS)

Vancil, Bernard K.; Wintucky, Edwin G.

2002-01-01

We report on recent work to produce a small low power, low cost reservoir cathode capable of long life (more than 100,000 hours) at high loading (> 5 A/sq cm). Our objective is a highly manufacturable, commercial device costing less than $30. Small highly loaded cathodes are needed, especially for millimeter wave tubes, where focusing becomes difficult when area convergence ratios are too high. We currently have 3 models ranging from .060-inch diameter to. 125-inch diameter. Reservoir type barium dispenser cathodes have a demonstrated capability for simultaneous high emission density and long life. Seven reservoir cathodes continue to operate on the cathode life test facility at NSWC, Crane, Indiana at 2 and 4 amps/sq cm. They have accumulated nearly 100,000 hours with practically no change in emission levels or knee temperature.

Testing a GaAs cathode in SRF gun

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

Wang, E.; Kewisch, J.; Ben-Zvi, I.

RF electron guns with a strained superlattice GaAs cathode are expected to generate polarized electron beams of higher brightness and lower emittance than do DC guns, due to their higher field gradient at the cathode's surface and lower cathode temperature. We plan to install a bulk GaAs:Cs in a SRF gun to evaluate the performance of both the gun and the cathode in this environment. The status of this project is: In our 1.3 GHz 1/2 cell SRF gun, the vacuum can be maintained at nearly 10{sup -12} Torr because of cryo-pumping at 2K. With conventional activation of bulk GaAs,more » we obtained a QE of 10% at 532 nm, with lifetime of more than 3 days in the preparation chamber and have shown that it can survive in transport from the preparation chamber to the gun. The beam line has been assembled and we are exploring the best conditions for baking the cathode under vacuum. We report here the progress of our test of the GaAs cathode in the SRF gun. Future particle accelerators, such as eRHIC and the ILC require high-brightness, high-current polarized electrons. Strained superlattice GaAs:Cs has been shown to be an efficient cathode for producing polarized electrons. Activation of GaAs with Cs,O(F) lowers the electron affinity and makes it energetically possible for all the electrons, excited into the conduction band that drift or diffuse to the emission surface, to escape into the vacuum. Presently, all operating polarized electron sources, such as the CEBAF, are DC guns. In these devices, the excellent ultra-high vacuum extends the lifetime of the cathode. However, the low field gradient on the photocathode's emission surface of the DC guns limits the beam quality. The higher accelerating gradients, possible in the RF guns, generate a far better beam. Until recently, most RF guns operated at room temperature, limiting the vacuum to {approx}10{sup -9} Torr. This destroys the GaAs's NEA surface. The SRF guns combine the excellent vacuum conditions of DC guns and the high accelerating gradient of the RF guns, potentially offering a long lived cathode with very low emittance. Testing this concept requires preparation of the cathode, transportation to the SRF gun and evaluation of the performance of the cathode and the gun at cryogenic temperatures. In our work at BNL, we successfully activated the bulk GaAs in the preparation chamber. The highest quantum efficient was 10% at 532 nm that fell to 0.5% after 100 hours. We explored three different ways to activate the GaAs. We verified that the GaAs photocathode remains stable for 30 hours in a 10{sup -11} Torr vacuum. Passing the photocathode through the low 10{sup -9} Torr transfer section in several seconds caused the QE to drop to 0.8%. The photocathode with 0.8% QE can be tested for the SRF gun. The gun and beam pipe were prepared and assembled. After baking at 200 C baking, the vacuum of the gun and beam pipe can sustain a low 10{sup -11} Torr at room temperature. The final test to extract electrons from the gun is ongoing. In this paper, we discuss our progress with this SRF gun and the results of the photocathode in preparation chamber and in magnet transfer line.« less

Using quality control to limit bismuth in copper cathodes

NASA Astrophysics Data System (ADS)

Serrano, John R.; Berger, Dennis; Bridges, Bill

1994-10-01

This article describes quality-control work at Phelps Dodge, undertaken as part of ISO 9003 certification, to better identify and prevent the contamination of copper cathodes by bismuth. It also overviews the implementation of a production control system as well as associated training designed to minimize the possibility of bismuth-contaminated copper progressing beyond the cathode stage to other areas of manufacturing or distribution.

Matrix Cathode Development

DTIC Science & Technology

1976-01-01

18 2.3.1 Cross-Sections 18 2.3.2 Surface Finishing 27 2.3.3 Hardness and Ductility 27 2.3.4 Defects and Imperfections 30 2.3.4.1 Cauliflower ...ATHODE CRIMPED DOWN EARS NICKEL HEATER Figure 4. The Cylindrical Cathode as Proposed by G. Haas. It is a l/S1 Nickel Cylinder wit^ a Blind Hole...Machined in One End and A Heater Inserted. The Cathode is Fixed to the Blind End by Crimping Down Ears . L± !V ,-.■...■ I-’"«:-, . mUtmr

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.

Cold cathode vacuum discharge tube

DOEpatents

Boettcher, G.E.

1998-03-10

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

Cold cathode vacuum discharge tube

DOEpatents

Boettcher, G.E.

1998-04-14

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

Methods and systems for in-situ electroplating of electrodes

DOEpatents

Zappi, Guillermo Daniel; Zarnoch, Kenneth Paul; Huntley, Christian Andrew; Swalla, Dana Ray

2015-06-02

The present techniques provide electrochemical devices having enhanced electrodes with surfaces that facilitate operation, such as by formation of a porous nickel layer on an operative surface, particularly of the cathode. The porous metal layer increases the surface area of the electrode, which may result in increasing the efficiency of the electrochemical devices. The formation of the porous metal layer is performed in situ, that is, after the assembly of the electrodes into an electrochemical device. The in situ process offers a number of advantages, including the ability to protect the porous metal layer on the electrode surface from damage during assembly of the electrochemical device. The enhanced electrode and the method for its processing may be used in any number of electrochemical devices, and is particularly well suited for electrodes in an electrolyzer useful for splitting water into hydrogen and oxygen.

Theoretical study of cathode surfaces and high-temperature superconductors

NASA Technical Reports Server (NTRS)

Mueller, Wolfgang

1994-01-01

The surface-dipole properties of model cathode surfaces have been investigated with relativistic scattered-wave cluster calculations. Work-function/coverage curves have been derived from these data by employing the depolarization model of interacting surface dipoles. Accurate values have been obtained for the minimum work functions of several low-work-function surfaces. In the series BaO on bcc W, hcp Os, and fcc Pt, BaO/Os shows a lower and BaO/Pt a higher work function than BaO/W, which is attributed to the different substrate crystal structures involved. Results are also presented on the electronic structure of the high-temperature superconductor YBa2Cu3O7, which has been investigated with fully relativistic calculations for the first time.

Two 3D structured Co-Ni bimetallic oxides as cathode catalysts for high-performance alkaline direct methanol fuel cells

NASA Astrophysics Data System (ADS)

Liu, Yan; Shu, Chengyong; Fang, Yuan; Chen, Yuanzhen; Liu, Yongning

2017-09-01

Two NiCo2O4 bimetallic oxides were synthesized via a facile hydrothermal method. SEM and TEM observations show that these materials have three-dimensional (3D) dandelion-like (DL) and flower-like (FL) morphologies. Their large specific surface areas (90.68 and 19.8 m2·g-1) and porous structures provide many active sites and effective transport pathways for the oxygen reduction reaction (ORR). Electrochemical measurements with a rotating ring-disc electrode (RRDE) indicate that the electron transfer numbers of the NiCo2O4-DL and NiCo2O4-FL catalysts for ORR in an alkaline solution are 3.97 and 3.91, respectively. Fuel cells were assembled with the bimetallic oxides, PtRu/C and a polymer fiber membrane (PFM) as cathode catalysts, anode catalyst and electrolyte film, respectively. For NiCo2O4-DL, the peak power density reaches up to 73.5 mW·cm-2 at 26 °C, which is the highest room-temperature value reported to date. The high catalytic activity of NiCo2O4 is mainly attributed to the presence of many Co3+ cations that directly donate electrons to O2 to reduce it via a more efficient and effective route. Furthermore, the catalytic performance of NiCo2O4-DL is superior to that of NiCo2O4-FL because it has a higher specific surface area and is less crystalline.

Microstructural Analysis and Transport Resistances of Low-Platinum-Loaded PEFC Electrodes

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

Cetinbas, Firat C.; Wang, Xiaohua; Ahluwalia, Rajesh K.

In this study, we present microstructural characterization for polymer electrolyte fuel cell (PEFC) cathodes with low platinum loadings (low-PGM). The characterization results are used to quantify the contribution of mass transport resistances to cell voltage losses observed in polarization curve data. Three-dimensional pore morphology and ionomer distribution are resolved using nano-scale X-ray computed tomography (nano-CT). Electrode structural properties are reported along with analysis of the impact of microstructure on the effective charge and reactant transport properties. These characterizations are incorporated with a two-dimensional multi-physics model that accounts for energy, charge, and mass transport along with the effect of liquid watermore » flooding. Defining a total mass transport resistance for the whole polarization curve, contributions of transport mechanisms are identified. Analysis of the experimental polarization curves at different operating pressures and temperatures indicates that the mass transport resistance in the cathode is dominated by the transport processes in the electrode. It is shown that flooding in the electrode is a major contributor to transport losses especially at elevated operating pressures while the pressure-independent resistance at the catalyst surface due to transport through the ionomer film plays a significant role, especially at low temperatures and low catalyst loading. In addition, by performing a parametric study for varying catalyst loadings, the importance of electrode roughness (i.e, electrochemically-active surface area/geometric electrode area) in determining the mass transport losses is highlighted.« less

Microstructural Analysis and Transport Resistances of Low-Platinum-Loaded PEFC Electrodes

DOE PAGES

Cetinbas, Firat C.; Wang, Xiaohua; Ahluwalia, Rajesh K.; ...

2017-12-09

In this study, we present microstructural characterization for polymer electrolyte fuel cell (PEFC) cathodes with low platinum loadings (low-PGM). The characterization results are used to quantify the contribution of mass transport resistances to cell voltage losses observed in polarization curve data. Three-dimensional pore morphology and ionomer distribution are resolved using nano-scale X-ray computed tomography (nano-CT). Electrode structural properties are reported along with analysis of the impact of microstructure on the effective charge and reactant transport properties. These characterizations are incorporated with a two-dimensional multi-physics model that accounts for energy, charge, and mass transport along with the effect of liquid watermore » flooding. Defining a total mass transport resistance for the whole polarization curve, contributions of transport mechanisms are identified. Analysis of the experimental polarization curves at different operating pressures and temperatures indicates that the mass transport resistance in the cathode is dominated by the transport processes in the electrode. It is shown that flooding in the electrode is a major contributor to transport losses especially at elevated operating pressures while the pressure-independent resistance at the catalyst surface due to transport through the ionomer film plays a significant role, especially at low temperatures and low catalyst loading. In addition, by performing a parametric study for varying catalyst loadings, the importance of electrode roughness (i.e, electrochemically-active surface area/geometric electrode area) in determining the mass transport losses is highlighted.« less

Solvothermal synthesis of Mg-doped Li2FeSiO4/C nanocomposite cathode materials for lithium-ion batteries

NASA Astrophysics Data System (ADS)

Kumar, Ajay; Jayakumar, O. D.; Naik, V. M.; Nazri, G. A.; Naik, R.

Lithium transition metal orthosilicates, such as Li2FeSiO4 and Li2MnSiO4, as cathode material have attracted much attention lately due to their high theoretical capacity ( 330 mAh/g), low cost, and environmental friendliness. However, they suffer from poor electronic conductivity and slow lithium ion diffusion in the solid phase. Several cation-doped orthosilicates have been studied to improve their electrochemical performance. We have synthesized partially Mg-substituted Li2Mgx Fe1-x SiO4-C, (x = 0.0, 0.01, 0.02, and 0.04) nano-composites by solvothermal method followed by annealing at 600oC in argon flow. The structure and morphology of the composites were characterized by XRD, SEM and TEM. The surface area and pore size distribution were measured by using N2 adsorption/desorption curves. The electrochemical performance of the Li2MgxFe1-x SiO4-C composites was evaluated by Galvanostatic cycling against metallic lithium anode, electrochemical impedance spectroscopy, and cyclic voltammetry. Li2Mg0.01Fe0.99SiO4-C sample shows a capacity of 278 mAh/g (at C/30 rate in the 1.5-4.6 V voltage window) with an excellent rate capability and stability, compared to the other samples. We attribute this observation to its higher surface area, enhanced electronic conductivity and higher lithium ion diffusion coefficient.

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.

Amplification of intrinsic emittance due to rough metal cathodes: Formulation of a parameterization model

NASA Astrophysics Data System (ADS)

Charles, T. K.; Paganin, D. M.; Dowd, R. T.

2016-08-01

Intrinsic emittance is often the limiting factor for brightness in fourth generation light sources and as such, a good understanding of the factors affecting intrinsic emittance is essential in order to be able to decrease it. Here we present a parameterization model describing the proportional increase in emittance induced by cathode surface roughness. One major benefit behind the parameterization approach presented here is that it takes the complexity of a Monte Carlo model and reduces the results to a straight-forward empirical model. The resulting models describe the proportional increase in transverse momentum introduced by surface roughness, and are applicable to various metal types, photon wavelengths, applied electric fields, and cathode surface terrains. The analysis includes the increase in emittance due to changes in the electric field induced by roughness as well as the increase in transverse momentum resultant from the spatially varying surface normal. We also compare the results of the Parameterization Model to an Analytical Model which employs various approximations to produce a more compact expression with the cost of a reduction in accuracy.

Work function and surface stability of tungsten-based thermionic electron emission cathodes

NASA Astrophysics Data System (ADS)

Jacobs, Ryan; Morgan, Dane; Booske, John

2017-11-01

Materials that exhibit a low work function and therefore easily emit electrons into vacuum form the basis of electronic devices used in applications ranging from satellite communications to thermionic energy conversion. W-Ba-O is the canonical materials system that functions as the thermionic electron emitter commercially used in a range of high-power electron devices. However, the work functions, surface stability, and kinetic characteristics of a polycrystalline W emitter surface are still not well understood or characterized. In this study, we examined the work function and surface stability of the eight lowest index surfaces of the W-Ba-O system using density functional theory methods. We found that under the typical thermionic cathode operating conditions of high temperature and low oxygen partial pressure, the most stable surface adsorbates are Ba-O species with compositions in the range of Ba0.125O-Ba0.25O per surface W atom, with O passivating all dangling W bonds and Ba creating work function-lowering surface dipoles. Wulff construction analysis reveals that the presence of O and Ba significantly alters the surface energetics and changes the proportions of surface facets present under equilibrium conditions. Analysis of previously published data on W sintering kinetics suggests that fine W particles in the size range of 100-500 nm may be at or near equilibrium during cathode synthesis and thus may exhibit surface orientation fractions well described by the calculated Wulff construction.

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.

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.

The effect of cathode felt geometries on electrochemical characteristics of sodium sulfur (NaS) cells: Planar vs. tubular

NASA Astrophysics Data System (ADS)

Kim, Goun; Park, Yoon-Cheol; Lee, Younki; Cho, Namung; Kim, Chang-Soo; Jung, Keeyoung

2016-09-01

Two sodium sulfur (NaS) cells, one with a planar design and the other with a tubular design, were subject to discharge-charge cycles in order to investigate the effect of cathode felt geometries on electrochemical characteristics of NaS cells. Their discharge-charge behaviors over 200 cycles were evaluated at the operation temperature of 350 °C with the current densities of 100 mA cm-2 for discharge and 80 mA cm-2 for charge. The results showed that the deviation from theoretical open circuit voltage changes of a planar cell was smaller than those of a tubular cell resulting in potential specific power loss reduction during operation. In order to understand the effect, a three dimensional statistically representative matrix for a cathode felt has been generated using experimentally measured data. It turns out that the area specific fiber number density in the outer side area of a tubular cathode felt is smaller than that of a planar felt resulting in occurrence of larger voltage drops via retarded convection of cathode melts during cell operation.

Mesoporous nanostructured Nb-doped titanium dioxide microsphere catalyst supports for PEM fuel cell electrodes.

PubMed

Chevallier, Laure; Bauer, Alexander; Cavaliere, Sara; Hui, Rob; Rozière, Jacques; Jones, Deborah J

2012-03-01

Crystalline microspheres of Nb-doped TiO(2) with a high specific surface area were synthesized using a templating method exploiting ionic interactions between nascent inorganic components and an ionomer template. The microspheres exhibit a porosity gradient, with a meso-macroporous kernel, and a mesoporous shell. The material has been investigated as cathode electrocatalyst support for polymer electrolyte membrane (PEM) fuel cells. A uniform dispersion of Pt particles on the Nb-doped TiO(2) support was obtained using a microwave method, and the electrochemical properties assessed by cyclic voltammetry. Nb-TiO(2) supported Pt demonstrated very high stability, as after 1000 voltammetric cycles, 85% of the electroactive Pt area remained compared to 47% in the case of commercial Pt on carbon. For the oxygen reduction reaction (ORR), which takes place at the cathode, the highest stability was again obtained with the Nb-doped titania-based material even though the mass activity calculated at 0.9 V vs RHE was slightly lower. The microspherical structured and mesoporous Nb-doped TiO(2) is an alternative support to carbon for PEM fuel cells. © 2012 American Chemical Society

Performance and microbial diversity of microbial fuel cells coupled with different cathode types during simultaneous azo dye decolorization and electricity generation.

PubMed

Hou, Bin; Hu, Yongyou; Sun, Jian

2012-05-01

To study the effect of cathode type on performance and microbial diversity of the MFC, aerobic biocathode and air-cathode were incorporated into microbial fuel cells (MFCs) which were explored for simultaneous azo dye decolorization and electricity generation. The electrochemical impedance spectroscopy (EIS) results demonstrated that the catalytic activity of the microorganisms on the biocathode surface was comparable with that of the platinum coated on the air-cathode. The power density achieved by using biocathode was lower than air-cathode, but the biocathode could greatly improve the Congo red decolorization rate. By using the biocathode, 96.4% decolorization of Congo red was obtained within 29 h, whereas, about 107 h was required to achieve the same decolorization efficiency with the air-cathode. 16S rRNA sequencing analysis demonstrated a phylogenetic diversity in the communities of the anode biofilm and showed clear differences between the anode-attached populations in the MFCs with a different cathode type. Copyright © 2012 Elsevier Ltd. All rights reserved.

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

NASA Astrophysics Data System (ADS)

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

2018-04-01

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

Functional Testing of the Space Station Plasma Contactor

NASA Technical Reports Server (NTRS)

Patterson, Michael J.; Hamley, John A.; Sarver-Verhey, Timothy R.; Soulas, George C.

1995-01-01

A plasma contactor system has been baselined for the International Space Station Alpha (ISSA) to control the electrical potentials of surfaces to eliminate/mitigate damaging interactions with the space environment. The system represents a dual-use technology which is a direct outgrowth of the NASA electric propulsion program and, in particular, the technology development effort on ion thruster systems. The plasma contactor subsystems include a hollow cathode assembly, a power electronics unit, and an expellant management unit. Under a pre-flight development program these subsystems are being developed to the level of maturity appropriate for transfer to U.S. industry for final development. Development efforts for the hollow cathode assembly include design selection and refinement, validating its required lifetime, and quantifying the cathode performance and interface specifications. To date, cathode components have demonstrated over 10,000 hours lifetime, and a hollow cathode assembly has demonstrated over 3,000 ignitions. Additionally, preliminary integration testing of a hollow cathode assembly with a breadboard power electronics unit has been completed. This paper discusses test results and the development status of the plasma contactor subsystems for ISSA, and in particular, the hollow cathode assembly.

Structural and emission characteristics of ion-irradiated Reticulated Vitreous Carbon

NASA Astrophysics Data System (ADS)

Chacon, Judith Rebecca

Cathodes formed from Reticulated Vitreous Carbon (RVC) were treated under varying conditions of Argon-ion beam current, beam voltage and irradiation duration. Surface structures, such as balls, cones, nanowires, and nanowhiskers were formed in the RVC network through a series of ion-impact sputtering and self-diffusion reactions. Raman shifts to the D and E2g' peak suggest C=C bonding within the original RVC structure was converted to the lesser-bound C-C bonding structure. Cathodes demonstrating the most stable electronic configuration exhibited significant vertical growth to graphitic domains as determined by calculations based on XRD measurements. Carbon nanotubes at the surface were observed at the surface through micro-Raman techniques. The surface structures formed by argon-bombardment, are responsible for cathodes exhibiting lower field-emission extraction fields. The electric field required for the onset of electron emission was measured to change from 6.03 V/micron in non-irradiated RVC to 1.62V/micron for RVC irradiated for 15 minutes at a beam voltage of 1200V and beam current of 200mA (ion-beam current density 2.24mA/cm2). Treated surfaces were also responsible for increased stability in emission over time. For untreated RVC, the field required for emission dropped 25% over a 48 hour training period, whilst modestly treated RVC (15min, 1200V, 100mA, or 1.52mA/cm2) rose as little as 3%. Field-emissive RVC, is an inexpensively produced, mechanically robust cathode with potential applications in lighting, displays and microwave sources.

Electrochemical performance of LiCoO 2 cathodes by surface modification using lanthanum aluminum garnet

NASA Astrophysics Data System (ADS)

Lu, Cheng-Zhang; Chen, Jin-Ming; Cho, Yung-Da; Hsu, Wen-Hsiang; Muralidharan, P.; Fey, George Ting-Kuo

LiCoO 2 particles were coated with various wt.% of lanthanum aluminum garnets (3LaAlO 3:Al 2O 3) by an in situ sol-gel process, followed by calcination at 1123 K for 12 h in air. X-ray diffraction (XRD) patterns confirmed the formation of a 3LaAlO 3:Al 2O 3 compound and the in situ sol-gel process synthesized 3LaAlO 3:Al 2O 3-coated LiCoO 2 was a single-phase hexagonal α-NaFeO 2-type structure of the core material without any modification. Scanning electron microscope (SEM) images revealed a modification of the surface of the cathode particles. Transmission electron microscope (TEM) images exposed that the surface of the core material was coated with a uniform compact layer of 3LaAlO 3:Al 2O 3, which had an average thickness of 40 nm. Galvanostatic cycling studies demonstrated that the 1.0 wt.% 3LaAlO 3:Al 2O 3-coated LiCoO 2 cathode showed excellent cycle stability of 182 cycles, which was much higher than the 38 cycles sustained by the pristine LiCoO 2 cathode material when it was charged at 4.4 V.

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.

Apparatus for producing diamond-like carbon flakes

NASA Technical Reports Server (NTRS)

Banks, Bruce A. (Inventor)

1986-01-01

A vacuum arc from a spot at the face of a graphite cathode to a graphite anode produces a beam of carbon ions and atoms. A carbon coating from this beam is deposited on an ion beam sputtered target to produce diamond-like carbon flakes. A graphite tube encloses the cathode, and electrical isolation is provided by an insulating sleeve. The tube forces the vacuum arc spot to be confined to the surface on the outermost end of the cathode. Without the tube the arc spot will wander to the side of the cathode. This spot movement results in low rates of carbon deposition, and the properties of the deposited flakes are more graphite-like than diamond-like.

Performance and durability of carbon black-supported Pd catalyst covered with silica layers in membrane-electrode assemblies of proton exchange membrane fuel cells

NASA Astrophysics Data System (ADS)

Fujii, Keitaro; Ito, Mizuki; Sato, Yasushi; Takenaka, Sakae; Kishida, Masahiro

2015-04-01

Pd metal particles supported on a high surface area carbon black (Pd/CB) were covered with silica layers to improve the durability under severe cathode condition of proton exchange membrane fuel cells (PEMFCs). The performance and the durability of the silica-coated Pd/CB (SiO2/Pd/CB) were investigated by rotating disk electrode (RDE) in aqueous HClO4 and single cell test of the membrane-electrode assemblies (MEAs). SiO2/Pd/CB showed excellent durability exceeding Pt/CB during potential cycle in single cell test as well as in RDE measurement while Pd/CB significantly degraded. Furthermore, the MEA using SiO2/Pd/CB as the cathode catalyst showed higher performance than that using Pd/CB even in the initial state. The catalytic activity of SiO2/Pd/CB was higher than that of Pd/CB, and the drop of the cell performances due to the inhibition of electron conduction, proton conduction, and oxygen diffusion by the silica layer was not significant. It has been shown that the silica-coating is a very practical technique that can stabilize metal species originally unstable in the cathode condition of PEMFCs without a decrease in the cell performance.

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.

Characteristics of cold atmospheric plasma source based on low-current pulsed discharge with coaxial electrodes

NASA Astrophysics Data System (ADS)

Bureyev, O. A.; Surkov, Yu S.; Spirina, A. V.

2017-05-01

This work investigates the characteristics of the gas discharge system used to create an atmospheric pressure plasma flow. The plasma jet design with a cylindrical graphite cathode and an anode rod located on the axis of the system allows to realize regularly reproducible spark breakdowns mode with a frequency ∼ 5 kHz and a duration ∼ 40 μs. The device generates a cold atmospheric plasma flame with 1 cm in diameter in the flow of various plasma forming gases including nitrogen and air at about 100 mA average discharge current. In the described construction the cathode spots of individual spark channels randomly move along the inner surface of the graphite electrode creating the secondary plasma stream time-average distributed throughout the whole exit aperture area after the decay of numerous filamentary discharge channels. The results of the spectral diagnostics of plasma in the discharge gap and in the stream coming out of the source are presented. Despite the low temperature of atoms and molecules in plasma stream the cathode spots operation with temperature of ∼ 4000 °C at a graphite electrode inside a discharge system enables to saturate the plasma by CN-radicals and atomic carbon in the case of using nitrogen as the working gas.

Surface Chemistry in Cobalt Phosphide-Stabilized Lithium-Sulfur Batteries.

PubMed

Zhong, Yiren; Yin, Lichang; He, Peng; Liu, Wen; Wu, Zishan; Wang, Hailiang

2018-01-31

Chemistry at the cathode/electrolyte interface plays an important role for lithium-sulfur batteries in which stable cycling of the sulfur cathode requires confinement of the lithium polysulfide intermediates and their fast electrochemical conversion on the electrode surface. While many materials have been found to be effective for confining polysulfides, the underlying chemical interactions remain poorly understood. We report a new and general lithium polysulfide-binding mechanism enabled by surface oxidation layers of transition-metal phosphide and chalcogenide materials. We for the first time find that CoP nanoparticles strongly adsorb polysulfides because their natural oxidation (forming Co-O-P-like species) activates the surface Co sites for binding polysulfides via strong Co-S bonding. With a surface oxidation layer capable of confining polysulfides and an inner core suitable for conducting electrons, the CoP nanoparticles are thus a desirable candidate for stabilizing and improving the performance of sulfur cathodes in lithium-sulfur batteries. We demonstrate that sulfur electrodes that hold a high mass loading of 7 mg cm -2 and a high areal capacity of 5.6 mAh cm -2 can be stably cycled for 200 cycles. We further reveal that this new surface oxidation-induced polysulfide-binding scheme applies to a series of transition-metal phosphide and chalcogenide materials and can explain their stabilizing effects for lithium-sulfur batteries.

Highly active carbon supported Pd cathode catalysts for direct formic acid fuel cells

NASA Astrophysics Data System (ADS)

Mikolajczuk-Zychora, A.; Borodzinski, A.; Kedzierzawski, P.; Mierzwa, B.; Mazurkiewicz-Pawlicka, M.; Stobinski, L.; Ciecierska, E.; Zimoch, A.; Opałło, M.

2016-12-01

One of the drawbacks of low-temperature fuel cells is high price of platinum-based catalysts used for the electroreduction of oxygen at the cathode of the fuel cell. The aim of this work is to develop the palladium catalyst that will replace commonly used platinum cathode catalysts. A series of palladium catalysts for oxygen reduction reaction (ORR) were prepared and tested on the cathode of Direct Formic Acid Fuel Cell (DFAFC). Palladium nanoparticles were deposited on the carbon black (Vulcan) and on multiwall carbon nanotubes (MWCNTs) surface by reduction of palladium(II) acetate dissolved in ethanol. Hydrazine was used as a reducing agent. The effect of functionalization of the carbon supports on the catalysts physicochemical properties and the ORR catalytic activity on the cathode of DFAFC was studied. The supports were functionalized by treatment in nitric acid for 4 h at 80 °C. The structure of the prepared catalysts has been characterized by thermogravimetric analysis (TGA), X-ray diffraction (XRD), transmission electron microscope (TEM) and cyclic voltammetry (CV). Hydrophilicity of the catalytic layers was determined by measuring contact angles of water droplets. The performance of the prepared catalysts has been compared with that of the commercial 20 wt.% Pt/C (Premetek) catalyst. The maximum power density obtained for the best palladium catalyst, deposited on the surface of functionalized carbon black, is the same as that for the commercial Pt/C (Premetek). Palladium is cheaper than platinum, therefore the developed cathode catalyst is promising for future applications.

[4,4‧-bi(1,3,2-dioxathiolane)] 2,2‧-dioxide: A novel cathode additive for high-voltage performance in lithium ion batteries

NASA Astrophysics Data System (ADS)

Lee, Sang Hyun; Yoon, Sukeun; Hwang, Eui-Hyung; Kwon, Young-Gil; Lee, Young-Gi; Cho, Kuk Young

2018-02-01

High-voltage operation of lithium-ion batteries (LIBs) is a facile approach to obtaining high specific energy density, especially for LiNi0·5Mn0·3Co0·2O2 (NMC532) cathodes currently used in mid- and large-sized energy storage devices. However, high-voltage charging (>4.3 V) is accompanied by a rapid capacity fade over long cycles due to severe continuous electrolyte decomposition and instability at the cathode surface. In this study, the sulfite-based compound, [4,4‧-bi(1,3,2-dioxathiolane)] 2,2‧-dioxide (BDTD) is introduced as a novel electrolyte additive to enhance electrochemical performances of alumina-coated NMC532 cathodes cycled in the voltage range of 3.0-4.6 V. X-ray photoelectron spectroscopy (XPS) and AC impedance of cells reveal that BDTD preferentially oxidizes prior to the electrolyte solvents and forms stable film layers on to the cathode surface, preventing increased impedance caused by repeated electrolyte solvent decomposition in high-voltage operation. The cycling performance of the Li/NMC532 half-cell using an electrolyte of 1.0 M LiPF6 in ethylene carbonate/ethyl methyl carbonate (3/7, in volume) can be improved by adding a small amount of BDTD into the electrolyte. BDTD enables the usage of sulfite-type additives for cathodes in high-voltage operation.

An impressive approach to solving the ongoing stability problems of LiCoPO4 cathode: Nickel oxide surface modification with excellent core-shell principle

NASA Astrophysics Data System (ADS)

Örnek, Ahmet

2017-07-01

Nanoscale and NiO-coated LiCoPO4 cathode materials were prepared for the first time by a newly designed three-step synthesis route, which is a combined technique including advantages of the Stöber, hydrothermal and microwave synthesis methods. Using this extraordinary technique, LiCoPO4 particles are coated with a thin NiO layer with a perfect core-shell morphology and the technique's positive contribution to electrochemistry is elucidated in detail. The samples are interpreted using opto-analytical techniques and galvanostatic charge-discharge tests. The high-resolution transmission electron microscopy analysis proves that this well-elaborated technique makes it possible to achieve a continuous NiO surface coverage of 8-10 nm, a result that contributes towards solving the chronic electrochemical problems of 4.8 V cathode material. Our data reveal that NiO-coated LiCoPO4 cathode demonstrates superior cycle stability and specific capacity at relatively low rates. The 2.5% wt. NiO-coated cathode exhibits the best electrochemical property, which reaches a discharge capacity of 159 mAh g-1 at 0.l C current rate and shows almost 85% capacity retention after 80 charge-discharge cycles. It therefore achieves partial success in improving the electrochemical properties of the LiCoPO4 cathode material, which is especially crucial for energy storage to be applied in electric vehicles and plug-in hybrid electric applications.

Theoretical study of cathode surfaces and high-temperature superconductors

NASA Technical Reports Server (NTRS)

Mueller, Wolfgang

1995-01-01

Calculations are presented for the work functions of BaO on W, Os, Pt, and alloys of Re-W, Os-W, and Ir-W that are in excellent agreement with experiment. The observed emission enhancement for alloy relative to tungsten dispenser cathodes is attributed to properties of the substrate crystal structure and explained by the smaller depolarization of the surface dipole on hexagonal as compared to cubic substrates. For Ba and BaO on W(100), the geometry of the adsorbates has been determined by a comparison of inverse photoemission spectra with calculated densities of unoccupied states based on the fully relativistic embedded cluster approach. Results are also discussed for models of scandate cathodes and the electronic structure of oxygen on W(100) at room and elevated temperatures. A detailed comparison is made for the surface electronic structure of the high-temperature superconductor YBa2Cu3O7 as obtained with non-, quasi-, and fully relativistic cluster calculations.

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.

The fractal nature of vacuum arc cathode spots

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

Anders, Andre

2005-05-27

Cathode spot phenomena show many features of fractals, for example self-similar patterns in the emitted light and arc erosion traces. Although there have been hints on the fractal nature of cathode spots in the literature, the fractal approach to spot interpretation is underutilized. In this work, a brief review of spot properties is given, touching the differences between spot type 1 (on cathodes surfaces with dielectric layers) and spot type 2 (on metallic, clean surfaces) as well as the known spot fragment or cell structure. The basic properties of self-similarity, power laws, random colored noise, and fractals are introduced. Severalmore » points of evidence for the fractal nature of spots are provided. Specifically power laws are identified as signature of fractal properties, such as spectral power of noisy arc parameters (ion current, arc voltage, etc) obtained by fast Fourier transform. It is shown that fractal properties can be observed down to the cutoff by measurement resolution or occurrence of elementary steps in physical processes. Random walk models of cathode spot motion are well established: they go asymptotically to Brownian motion for infinitesimal step width. The power spectrum of the arc voltage noise falls as 1/f {sup 2}, where f is frequency, supporting a fractal spot model associated with Brownian motion.« less

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.