Capacity Fade Analysis of Sulfur Cathodes in Lithium–Sulfur Batteries

Science.gov (United States)

Yan, Jianhua; Liu, Xingbo

2016-01-01

Rechargeable lithium–sulfur (Li–S) batteries are receiving ever‐increasing attention due to their high theoretical energy density and inexpensive raw sulfur materials. However, their rapid capacity fade has been one of the key barriers for their further improvement. It is well accepted that the major degradation mechanisms of S‐cathodes include low electrical conductivity of S and sulfides, precipitation of nonconductive Li2S2 and Li2S, and poly‐shuttle effects. To determine these degradation factors, a comprehensive study of sulfur cathodes with different amounts of electrolytes is presented here. A survey of the fundamentals of Li–S chemistry with respect to capacity fade is first conducted; then, the parameters obtained through electrochemical performance and characterization are used to determine the key causes of capacity fade in Li–S batteries. It is confirmed that the formation and accumulation of nonconductive Li2S2/Li2S films on sulfur cathode surfaces are the major parameters contributing to the rapid capacity fade of Li–S batteries. PMID:27981001

Reduced graphene oxide encapsulated sulfur spheres for the lithium-sulfur battery cathode

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Feiyan Liu

Full Text Available Reduced graphene oxide (rGO encapsulated sulfur spheres for the Li-S batteries were prepared via the redox reaction between sodium polysulfide. XRD spectra showed that the diffraction peak of graphite oxide (GO at 10° disappeared, while the relatively weak diffraction peak at 27° belongs to graphene emerged. FT-IR spectra showed that the vibrations of the functional groups of GO, such as 3603 cm−1, 1723 cm−1and 1619 cm−1 which contributed from OH, COC and CO respectively, disappeared when compared to the spectra of GSC. SEM observations indicated that the optimum experimental condition followed as: mass ratio of GO and S was 1:1, 10% NaOH was used to adjust the pH. EDX analysis showed that the sulfur content reached at 68.8% of the composite material. The resultant electric resistance was nearly less than GO’s resistance in three orders of magnitude under same condition. Further electrochemical performance tests showed a coulombic efficiency was 96% from the first cycle capacity was 827 mAh g−1, to 388 mAh g−1 in the 100 cycles. This study carries substantial significance to the development of Li-S battery cathode materials. Keywords: Lithium-sulfur battery, Graphene, Sulfur spheres, Cathode material

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

Science.gov (United States)

Li, Zhengzheng

2018-02-01

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

Conductive framework of inverse opal structure for sulfur cathode in lithium-sulfur batteries.

Science.gov (United States)

Jin, Lu; Huang, Xiaopeng; Zeng, Guobo; Wu, Hua; Morbidelli, Massimo

2016-09-07

As a promising cathode inheritor for lithium-ion batteries, the sulfur cathode exhibits very high theoretical volumetric capacity and energy density. In its practical applications, one has to solve the insulating properties of sulfur and the shuttle effect that deteriorates cycling stability. The state-of-the-art approaches are to confine sulfur in a conductive matrix. In this work, we utilize monodisperse polystyrene nanoparticles as sacrificial templates to build polypyrrole (PPy) framework of an inverse opal structure to accommodate (encapsulate) sulfur through a combined in situ polymerization and melting infiltration approach. In the design, the interconnected conductive PPy provides open channels for sulfur infiltration, improves electrical and ionic conductivity of the embedded sulfur, and reduces polysulfide dissolution in the electrolyte through physical and chemical adsorption. The flexibility of PPy and partial filling of the inverse opal structure endure possible expansion and deformation during long-term cycling. It is found that the long cycling stability of the cells using the prepared material as the cathode can be substantially improved. The result demonstrates the possibility of constructing a pure conductive polymer framework to accommodate insulate sulfur in ion battery applications.

Graphene-wrapped sulfur/metal organic framework-derived microporous carbon composite for lithium sulfur batteries

Energy Technology Data Exchange (ETDEWEB)

Chen, Renjie, E-mail: kx210@cam.ac.uk, E-mail: chenrj@bit.edu.cn; Zhao, Teng [Beijing Key Laboratory of Environmental Science and Engineering, School of Chemical Engineering and Environment, Beijing Institute of Technology, Beijing 100081 (China); Department of Materials Science and Metallurgy, University of Cambridge, Cambridge CB3 0FS (United Kingdom); Tian, Tian; Fairen-Jimenez, David [Department of Chemical Engineering and Biotechnology, University of Cambridge, Pembroke Street, Cambridge CB2 3RA (United Kingdom); Cao, Shuai; Coxon, Paul R.; Xi, Kai, E-mail: kx210@cam.ac.uk, E-mail: chenrj@bit.edu.cn; Vasant Kumar, R.; Cheetham, Anthony K. [Department of Materials Science and Metallurgy, University of Cambridge, Cambridge CB3 0FS (United Kingdom)

2014-12-01

A three-dimensional hierarchical sandwich-type graphene sheet-sulfur/carbon (GS-S/C{sub ZIF8-D}) composite for use in a cathode for a lithium sulfur (Li-S) battery has been prepared by an ultrasonic method. The microporous carbon host was prepared by a one-step pyrolysis of Zeolitic Imidazolate Framework-8 (ZIF-8), a typical zinc-containing metal organic framework (MOF), which offers a tunable porous structure into which electro-active sulfur can be diffused. The thin graphene sheet, wrapped around the sulfur/zeolitic imidazolate framework-8 derived carbon (S/C{sub ZIF8-D}) composite, has excellent electrical conductivity and mechanical flexibility, thus facilitating rapid electron transport and accommodating the changes in volume of the sulfur electrode. Compared with the S/C{sub ZIF8-D} sample, Li-S batteries with the GS-S/C{sub ZIF8-D} composite cathode showed enhanced capacity, improved electrochemical stability, and relatively high columbic efficiency by taking advantage of the synergistic effects of the microporous carbon from ZIF-8 and a highly interconnected graphene network. Our results demonstrate that a porous MOF-derived scaffold with a wrapped graphene conductive network structure is a potentially efficient design for a battery electrode that can meet the challenge arising from low conductivity and volume change.

Graphene-wrapped sulfur/metal organic framework-derived microporous carbon composite for lithium sulfur batteries

Directory of Open Access Journals (Sweden)

Renjie Chen

2014-12-01

Full Text Available A three-dimensional hierarchical sandwich-type graphene sheet-sulfur/carbon (GS-S/CZIF8-D composite for use in a cathode for a lithium sulfur (Li-S battery has been prepared by an ultrasonic method. The microporous carbon host was prepared by a one-step pyrolysis of Zeolitic Imidazolate Framework-8 (ZIF-8, a typical zinc-containing metal organic framework (MOF, which offers a tunable porous structure into which electro-active sulfur can be diffused. The thin graphene sheet, wrapped around the sulfur/zeolitic imidazolate framework-8 derived carbon (S/CZIF8-D composite, has excellent electrical conductivity and mechanical flexibility, thus facilitating rapid electron transport and accommodating the changes in volume of the sulfur electrode. Compared with the S/CZIF8-D sample, Li-S batteries with the GS-S/CZIF8-D composite cathode showed enhanced capacity, improved electrochemical stability, and relatively high columbic efficiency by taking advantage of the synergistic effects of the microporous carbon from ZIF-8 and a highly interconnected graphene network. Our results demonstrate that a porous MOF-derived scaffold with a wrapped graphene conductive network structure is a potentially efficient design for a battery electrode that can meet the challenge arising from low conductivity and volume change.

Stabilized sulfur as cathodes for room temperature sodium-ion batteries.

Energy Technology Data Exchange (ETDEWEB)

Xu, Yunhua [Univ. of Maryland, College Park, MD (United States). Dept. of Chemical and Biomolecular Engineering; Liu, Yang [Sandia National Laboratories (SNL-NM), Albuquerque, NM (United States). Center for Integrated Nanotechnologies; Zhu, Yujie [Univ. of Maryland, College Park, MD (United States). Dept. of Chemical and Biomolecular Engineering; Zheng, Shiyou [Univ. of Maryland, College Park, MD (United States). Dept. of Chemical and Biomolecular Engineering; Liu, Yihang [Univ. of Maryland, College Park, MD (United States). Dept. of Chemical and Biomolecular Engineering; Luo, Chao [Univ. of Maryland, College Park, MD (United States). Dept. of Chemical and Biomolecular Engineering; Gaskell, Karen [Univ. of Maryland, College Park, MD (United States). Dept. of Chemistry and Biochemistry; Eichhorn, Bryan [Univ. of Maryland, College Park, MD (United States). Dept. of Chemistry and Biochemistry; Wang, Chunsheng [Univ. of Maryland, College Park, MD (United States). Dept. of Chemical and Biomolecular Engineering

2013-05-01

Sodium-sulfur batteries, offering high capacity and low cost, are promising alternative to lithium-ion batteries for large-scale energy storage applications. The conventional sodium-sulfur batteries, operating at a high temperature of 300–350°C in a molten state, could lead to severe safety problems. However, the room temperature sodium-sulfur batteries using common organic liuid electrolytes still face a significant challenge due to the dissolution of intermediate sodium polysulfides. For this study, we developed room temperatue sodium-sulfur batteries using a unique porous carbon/sulfur (C/S) composite cathode, which was synthesized by infusing sulfur vapor into porous carbon sphere particles at a high temperatrure of 600°C. The porous C/S composites delivered a reversible capacity of ~860 mAh/g and retained 83% after 300 cycles. The Coulombic efficiency of as high as 97% was observed over 300 cycles. The superior electrochemical performance is attrbuted to the super sulfur stability as evidenced by its lower sensitivity to probe beam irradiation in TEM, XPS and Raman charaterization and high evaperation temperature in TGA. The results make it promising for large-scale grid energy storage and electric vehicles.

Preparation of mesohollow and microporous carbon nanofiber and its application in cathode material for lithium–sulfur batteries

International Nuclear Information System (INIS)

Wu, Yuanhe; Gao, Mingxia; Li, Xiang; Liu, Yongfeng; Pan, Hongge

2014-01-01

Highlights: • Mesohollow and microporous carbon fibers were prepared via electrospinning and carbonization. • Sulfur (S) incorporated into the porous fibers by thermal heating in 60 wt.%, forming composite. • S fills fully in the micropores and partially in the mesohollows of the carbon fibers. • The composite shows high capacity and capacity retention as cathode material for Li–S batteries. • Mesohollow and microporous structure is effective in improving the property of S cathode. - Abstract: Mesohollow and microporous carbon nanofibers (MhMpCFs) were prepared by a coaxial electrospinning with polyacrylonitrile (PAN) and polymethylmethacrylate (PMMA) as outer and inner spinning solutions followed by a carbonization. The carbon fibers were thermal treated with sublimed sulfur to form S/MhMpCFs composite, which was used as cathode material for lithium–sulfur batteries. Electrochemical study shows that the S/MhMpCFs cathode material provides a maximum capacity of 815 mA h/g after several cycles of activation, and the capacity retains 715 mA h/g after 70 cycles, corresponding to a retention of 88%. The electrochemical property of the S/MhMpCFs composite is much superior than the S-incorporated solid carbon fibers prepared from electrospinning of single PAN. The mechanism of the enhanced electrochemical property of the S/MhMpCFs composite is discussed

Strong lithium polysulfide chemisorption on electroactive sites of nitrogen-doped carbon composites for high-performance lithium-sulfur battery cathodes.

Science.gov (United States)

Song, Jiangxuan; Gordin, Mikhail L; Xu, Terrence; Chen, Shuru; Yu, Zhaoxin; Sohn, Hiesang; Lu, Jun; Ren, Yang; Duan, Yuhua; Wang, Donghai

2015-03-27

Despite the high theoretical capacity of lithium-sulfur batteries, their practical applications are severely hindered by a fast capacity decay, stemming from the dissolution and diffusion of lithium polysulfides in the electrolyte. A novel functional carbon composite (carbon-nanotube-interpenetrated mesoporous nitrogen-doped carbon spheres, MNCS/CNT), which can strongly adsorb lithium polysulfides, is now reported to act as a sulfur host. The nitrogen functional groups of this composite enable the effective trapping of lithium polysulfides on electroactive sites within the cathode, leading to a much improved electrochemical performance (1200 mAh g(-1) after 200 cycles). The enhancement in adsorption can be attributed to the chemical bonding of lithium ions by nitrogen functional groups in the MNCS/CNT framework. Furthermore, the micrometer-sized spherical structure of the material yields a high areal capacity (ca. 6 mAh cm(-2)) with a high sulfur loading of approximately 5 mg cm(-2), which is ideal for practical applications of the lithium-sulfur batteries. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Sulfurized carbon: a class of cathode materials for high performance lithium/sulfur batteries

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Sheng S. Zhang

2013-12-01

Full Text Available Liquid electrolyte lithium/sulfur (Li/S batteries cannot come into practical applications because of many problems such as low energy efficiency, short cycle life, and fast self-discharge. All these problems are related to the dissolution of lithium polysulfide, a series of sulfur reduction intermediates, in the liquid electrolyte, and resulting parasitic reactions with the Li anode. Covalently binding sulfur onto carbon surface is a solution to completely eliminate the dissolution of lithium polysulfide and make the Li/S battery viable for practical applications. This can be achieved by replacing elemental sulfur with sulfurized carbon as the cathode material. This article reviews the current efforts on this subject and discusses the syntheses, electrochemical properties, and prospects of the sulfurized carbon as a cathode material in the rechargeable Li/S batteries.

Preparation and enhanced electrochemical properties of nano-sulfur/poly(pyrrole-co-aniline) cathode material for lithium/sulfur batteries

International Nuclear Information System (INIS)

Qiu Linlin; Zhang Shichao; Zhang Lan; Sun, Mingming; Wang Weikun

2010-01-01

Poly(pyrrole-co-aniline) (PPyA) copolymer nanofibers were prepared by chemical oxidation method with cetyltrimethyl ammonium chloride (CTAC) as template, and the nano-sulfur/poly(pyrrole-co-aniline) (S/PPyA) composite material in lithium batteries was achieved via co-heating the mixture of PPyA and sublimed sulfur at 160 deg. C for 24 h. The component and structure of the materials were characterized by FTIR, Raman, XRD, and SEM. PPyA with nanofiber network structure was employed as a conductive matrix, adsorbing agent and firm reaction chamber for the sulfur cathode materials. The nano-dispersed composite exhibited a specific capacity up to 1285 mAh g -1 in the initial cycle and remained 866 mAh g -1 after 40 cycles.

Micro-Spherical Sulfur/Graphene Oxide Composite via Spray Drying for High Performance Lithium Sulfur Batteries

Science.gov (United States)

Tian, Yuan; Sun, Zhenghao; Zhang, Yongguang; Yin, Fuxing

2018-01-01

An efficient, industry-accepted spray drying method was used to synthesize micro-spherical sulfur/graphene oxide (S/GO) composites as cathode materials within lithium sulfur batteries. The as-designed wrapping of the sulfur-nanoparticles, with wrinkled GO composites, was characterized by scanning electron microscopy (SEM) and transmission electron microscopy (TEM). The unique morphological design of this material enabled superior discharge capacity and cycling performance, demonstrating a high initial discharge capacity of 1400 mAh g−1 at 0.1 C. The discharge capacity remained at 828 mAh g−1 after 150 cycles. The superior electrochemical performance indicates that the S/GO composite improves electrical conductivity and alleviates the shuttle effect. This study represents the first time such a facile spray drying method has been adopted for lithium sulfur batteries and used in the fabrication of S/GO composites. PMID:29346303

Sulfur nanocrystals anchored graphene composite with highly improved electrochemical performance for lithium-sulfur batteries

Science.gov (United States)

Zhang, Jun; Dong, Zimin; Wang, Xiuli; Zhao, Xuyang; Tu, Jiangping; Su, Qingmei; Du, Gaohui

2014-12-01

Two kinds of graphene-sulfur composites with 50 wt% of sulfur are prepared using hydrothermal method and thermal mixing, respectively. Transmission Electron Microscopy (TEM) and Energy Dispersive X-ray Spectra mapping show that sulfur nanocrystals with size of ∼5 nm dispersed on graphene sheets homogeneously for the sample prepared by hydrothermal method (NanoS@G). While for the thermal mixed graphene-sulfur composite (S-G mixture), sulfur shows larger and uneven size (50-200 nm). X-ray Photoelectron Spectra (XPS) reveals the strong chemical bonding between the sulfur nanocrystals and graphene. Comparing with the S-G mixture, the NanoS@G composite shows highly improved electrochemical performance as cathode for lithium-sulfur (Li-S) battery. The NanoS@G composite delivers an initial capacity of 1400 mAh g-1 with the sulfur utilization of 83.7% at a current density of 335 mA g-1. The capacity keeps above 720 mAh g-1 over 100 cycles. The strong adherence of the sulfur nanocrystals on graphene immobilizes sulfur and polysulfides species and suppressed the "shuttle effect", resulting higher coulombic efficiency and better capacity retention. Electrochemical impedance also suggests that the strong bonding enabled rapid electronic/ionic transport and improved electrochemical kinetics, therefore good rate capability is obtained. These results demonstrate that the NanoS@G composite is a very promising candidate for high-performance Li-S batteries.

Interfacial Reaction Dependent Performance of Hollow Carbon Nanosphere – Sulfur Composite as a Cathode for Li-S Battery

International Nuclear Information System (INIS)

Zheng, Jianming; Yan, Pengfei; Gu, Meng; Wagner, Michael J.; Hays, Kevin A.; Chen, Junzheng; Li, Xiaohong; Wang, Chongmin; Zhang, Ji-Guang; Liu, Jun; Xiao, Jie

2015-01-01

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

Interfacial Reaction Dependent Performance of Hollow Carbon Nanosphere – Sulfur Composite as a Cathode for Li-S Battery

Energy Technology Data Exchange (ETDEWEB)

Zheng, Jianming; Yan, Pengfei; Gu, Meng [Pacific Northwest National Laboratory, Richland, WA (United States); Wagner, Michael J.; Hays, Kevin A. [The George Washington University, Washington, DC (United States); Chen, Junzheng; Li, Xiaohong; Wang, Chongmin; Zhang, Ji-Guang; Liu, Jun; Xiao, Jie, E-mail: jie.xiao@pnnl.gov [Pacific Northwest National Laboratory, Richland, WA (United States)

2015-05-26

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

A MnO2/Graphene Oxide/Multi-Walled Carbon Nanotubes-Sulfur Composite with Dual-Efficient Polysulfide Adsorption for Improving Lithium-Sulfur Batteries.

Science.gov (United States)

Li, Yong; Ye, Daixin; Liu, Wen; Shi, Bin; Guo, Rui; Zhao, Hongbin; Pei, Haijuan; Xu, Jiaqiang; Xie, Jingying

2016-10-26

Lithium-sulfur batteries can potentially be used as a chemical power source because of their high energy density. However, the sulfur cathode has several shortcomings, including fast capacity attenuation, poor electrochemical activity, and low Coulombic efficiency. Herein, multi-walled carbon nanotubes (CNTs), graphene oxide (GO), and manganese dioxide are introduced to the sulfur cathode. A MnO 2 /GO/CNTs-S composite with a unique three-dimensional (3D) architecture was synthesized by a one-pot chemical method and heat treatment approach. In this structure, the innermost CNTs work as a conducting additive and backbone to form a conducting network. The MnO 2 /GO nanosheets anchored on the sidewalls of CNTs have a dual-efficient absorption capability for polysulfide intermediates as well as afford adequate space for sulfur loading. The outmost nanosized sulfur particles are well-distributed on the surface of the MnO 2 /GO nanosheets and provide a short transmission path for Li + and the electrons. The sulfur content in the MnO 2 /GO/CNTs-S composite is as high as 80 wt %, and the as-designed MnO 2 /GO/CNTs-S cathode displays excellent comprehensive performance. The initial specific capacities are up to 1500, 1300, 1150, 1048, and 960 mAh g -1 at discharging rates of 0.05, 0.1, 0.2, 0.5, and 1 C, respectively. Moreover, the composite cathode shows a good cycle performance: the specific capacity remains at 963.5 mAh g -1 at 0.2 C after 100 cycles when the area density of sulfur is 2.8 mg cm -2 .

A Li+-conductive microporous carbon–sulfur composite for Li-S batteries

International Nuclear Information System (INIS)

Zhang, Wenhua; Qiao, Dan; Pan, Jiaxin; Cao, Yuliang; Yang, Hanxi; Ai, Xinping

2013-01-01

Highlights: ► A carbon–sulfur composite was prepared by vaporizing sulfur into the nanopores of Li + -conductive carbon microspheres. ► The redox reaction of S 8 molecules embedded in the nanopores of carbon microspheres proceeds through a solid–solid mechanism at the S/C interfaces. ► The carbon–sulfur composite exhibits a stable cycling performance and a superior high coulombic efficiency of 100%. - Abstract: In this paper, we propose a new strategy to develop high performance sulfur electrode by impregnating sulfur into the micropores of a Li + -insertable carbon matrix with the simultaneous use of a carbonate electrolyte, which does not dissolve polysulfides, to restrain the solution of the reaction intermediates of sulfur. To proof this concept, we prepared a Li + -insertable microporous carbon–sulfur composite by vaporizing sulfur into the micropores of the nanofiber-wired carbon microspheres. The experimental results demonstrate that, in the carbonate electrolyte of 1 M LiPF 6 /PC-EC-DEC, such S/C composite electrode exhibits not only stable cycling performance with a reversible capacity of 720 mAh g −1 after 100 cycles, but also superior high coulombic efficiency of ∼100% upon extended cycling (except the first three cycles). The structural and electrochemical analysis indicates that the improved electrochemical behaviors of the S/C composite arise from a new reaction mechanism, in which Li + ions and electrons transport through the carbon matrix into the interior of the cathode and then react with the embedded sulfur in the S/C solid–solid interfaces, avoiding the solution of the intermediates into the bulk electrolyte. More significantly, the structural design and working mechanism of such a sulfur cathode could be extended to a variety of poorly conductive and easily soluble redox-active materials for battery applications.

Confine sulfur in mesoporous metal–organic framework @ reduced graphene oxide for lithium sulfur battery

International Nuclear Information System (INIS)

Bao, Weizhai; Zhang, Zhian; Qu, Yaohui; Zhou, Chengkun; Wang, Xiwen; Li, Jie

2014-01-01

Highlights: • Metal organic framework @ reduced graphene oxide was applied for sulfur cathode. • MIL-101(Cr)@rGO/S composites are synthesized by a facile two-step liquid method. • Cycling stability of MIL-101(Cr)@rGO/S sulfur cathode was improved. -- Abstract: Mesoporous metal organic framework @ reduced graphene oxide (MIL-101(Cr)@rGO) materials have been used as a host material to prepare the multi-composite sulfur cathode through a facile and effective two-step liquid phase method successfully, which is different from the simple MIL-101(Cr)/S mixed preparation method. The successful reduced graphene oxide coating in the MIL-101(Cr)@rGO improve the electronic conductivity of meso-MOFs effectively. The discharge capacity and capacity retention rate of MIL-101(Cr)@rGO/S composite sulfur cathode are as high as 650 mAh g −1 and 66.6% at the 50th cycle at the current density of 335 mA g −1 . While the discharge capacity and capacity retention rate of MIL-101(Cr)/S mixed sulfur cathode is 458 mAh g −1 and 37.3%. Test results indicate that the MIL-101(Cr)@rGO is a promising host material for the sulfur cathode in the lithium–sulfur battery applications

Hybrid polyacrylamide/carbon coating on sulfur cathode for advanced lithium sulfur battery

International Nuclear Information System (INIS)

Li, Tao; Yuan, Yan; Hong, Bo; Cao, Huawei; Zhang, Kai; Lai, Yanqing; Liu, Yexiang; Huang, Zixin

2017-01-01

Commercialized conductive slurry consisting of polyacrylamide (PAM) and two kinds of carbon black was coated on the surface of sulfur cathode. The hybrid PAM/C coating not only physically blocks but also chemically anchors polysulfides within the cathode, confining their out-diffusion and shuttle. Besides, the flexible and highly-conductive coating layer buffers volume change of the cathode during discharge-charge process and reduces charge transfer resistance. A specific capacity of as high as ∼900 mAh g −1 after 300 cycles is demonstrated for the PAM/C coated cathode, which is a significant improvement of reversible capacity and cycle capability compared to uncoated or conventional PVDF/C coated cathode.

Is overprotection of the sulfur cathode good for Li-S batteries?

Science.gov (United States)

Gao, Tian; Shao, Jie; Li, Xingxing; Zhu, Guobin; Lu, Qiujian; Han, Yuyao; Qu, Qunting; Zheng, Honghe

2015-08-11

How to restrain the dissolution of polysulfides from the sulfur cathode is the current research focus of Li-S batteries. Here, we find that moderate dissolution of polysulfides is of great importance for high-efficiency and stable discharge/charge cycling. Both overprotection and inadequate protection of the sulfur cathode are unfavorable for the cycling of Li-S batteries.

Effect of cathode component on the energy density of lithium-sulfur battery

International Nuclear Information System (INIS)

Choi, Yun Seok; Kim, Seok; Choi, Soo Seok; Han, Ji Sung; Kim, Jan Dee; Jeon, Sang Eun; Jung, Bok Hwan

2004-01-01

The effect of the carbon black types and the sulfur particle size on the discharge capacity or the utilization of sulfur was investigated for the cathode having high loading of sulfur. The DBP (dibutyl phthalate) absorption number of the used carbon black has a strong effect on the utilization while the specific surface area is not so critical to it. It was also found that the sulfur particle size is a factor having an effect on the utilization. We have improved the cathode component and achieved the utilization of about 50%. By using that cathode, the volumetric energy density of about 330 Wh/l was obtained for the full size Li-S battery (3.8 mm thickness, 35 mm width and 62 mm height)

Advanced Sulfur Cathode Enabled by Highly Crumpled Nitrogen-Doped Graphene Sheets for High-Energy-Density Lithium-Sulfur Batteries.

Science.gov (United States)

Song, Jiangxuan; Yu, Zhaoxin; Gordin, Mikhail L; Wang, Donghai

2016-02-10

Herein, we report a synthesis of highly crumpled nitrogen-doped graphene sheets with ultrahigh pore volume (5.4 cm(3)/g) via a simple thermally induced expansion strategy in absence of any templates. The wrinkled graphene sheets are interwoven rather than stacked, enabling rich nitrogen-containing active sites. Benefiting from the unique pore structure and nitrogen-doping induced strong polysulfide adsorption ability, lithium-sulfur battery cells using these wrinkled graphene sheets as both sulfur host and interlayer achieved a high capacity of ∼1000 mAh/g and exceptional cycling stability even at high sulfur content (≥80 wt %) and sulfur loading (5 mg sulfur/cm(2)). The high specific capacity together with the high sulfur loading push the areal capacity of sulfur cathodes to ∼5 mAh/cm(2), which is outstanding compared to other recently developed sulfur cathodes and ideal for practical applications.

Structural change of the porous sulfur cathode using gelatin as a binder during discharge and charge

International Nuclear Information System (INIS)

Wang You; Huang Yaqin; Wang Weikun; Huang Chongjun; Yu Zhongbao; Zhang, Hao; Sun Jing; Wang Anbang; Yuan Keguo

2009-01-01

The structural change of the porous sulfur cathode using gelatin as a binder was studied by means of scanning electron microscopy (SEM) and X-ray diffractometry (XRD). The original sulfur cathode exhibited a homogenous distribution of sulfur, carbon and pores. During the discharge process, the pores and elemental sulfur disappeared gradually. However, those changes were reversed and elemental sulfur was reformed after the charge process, which improved the electrochemical performance of lithium-sulfur batteries.

Synthesis of three-dimensionally interconnected sulfur-rich polymers for cathode materials of high-rate lithium-sulfur batteries

Science.gov (United States)

Kim, Hoon; Lee, Joungphil; Ahn, Hyungmin; Kim, Onnuri; Park, Moon Jeong

2015-06-01

Elemental sulfur is one of the most attractive cathode active materials in lithium batteries because of its high theoretical specific capacity. Despite the positive aspect, lithium-sulfur batteries have suffered from severe capacity fading and limited rate capability. Here we report facile large-scale synthesis of a class of organosulfur compounds that could open a new chapter in designing cathode materials to advance lithium-sulfur battery technologies. Porous trithiocyanuric acid crystals are synthesized for use as a soft template, where the ring-opening polymerization of elemental sulfur takes place along the thiol surfaces to create three-dimensionally interconnected sulfur-rich phases. Our lithium-sulfur cells display discharge capacity of 945 mAh g-1 after 100 cycles at 0.2 C with high-capacity retention of 92%, as well as lifetimes of 450 cycles. Particularly, the organized amine groups in the crystals increase Li+-ion transfer rate, affording a rate performance of 1210, mAh g-1 at 0.1 C and 730 mAh g-1 at 5 C.

Synthesis of three-dimensionally interconnected sulfur-rich polymers for cathode materials of high-rate lithium–sulfur batteries

Science.gov (United States)

Kim, Hoon; Lee, Joungphil; Ahn, Hyungmin; Kim, Onnuri; Park, Moon Jeong

2015-01-01

Elemental sulfur is one of the most attractive cathode active materials in lithium batteries because of its high theoretical specific capacity. Despite the positive aspect, lithium–sulfur batteries have suffered from severe capacity fading and limited rate capability. Here we report facile large-scale synthesis of a class of organosulfur compounds that could open a new chapter in designing cathode materials to advance lithium–sulfur battery technologies. Porous trithiocyanuric acid crystals are synthesized for use as a soft template, where the ring-opening polymerization of elemental sulfur takes place along the thiol surfaces to create three-dimensionally interconnected sulfur-rich phases. Our lithium–sulfur cells display discharge capacity of 945 mAh g−1 after 100 cycles at 0.2 C with high-capacity retention of 92%, as well as lifetimes of 450 cycles. Particularly, the organized amine groups in the crystals increase Li+-ion transfer rate, affording a rate performance of 1210, mAh g−1 at 0.1 C and 730 mAh g−1 at 5 C. PMID:26065407

A Universal Strategy To Prepare Sulfur-Containing Polymer Composites with Desired Morphologies for Lithium-Sulfur Batteries.

Science.gov (United States)

Zeng, Shao-Zhong; Zeng, Xierong; Tu, Wenxuan; Huang, Haitao; Yu, Liang; Yao, Yuechao; Jin, Nengzhi; Zhang, Qi; Zou, Jizhao

2018-06-19

Lithium-sulfur (Li-S) batteries are probably the most promising candidates for the next-generation batteries owing to their high energy density. However, Li-S batteries face severe technical problems where the dissolution of intermediate polysulfides is the biggest problem because it leads to the degradation of the cathode and the lithium anode, and finally the fast capacity decay. Compared with the composites of elemental sulfur and other matrices, sulfur-containing polymers (SCPs) have strong chemical bonds to sulfur and therefore show low dissolution of polysulfides. Unfortunately, most SCPs have very low electron conductivity and their morphologies can hardly be controlled, which undoubtedly depress the battery performances of SCPs. To overcome these two weaknesses of SCPs, a new strategy was developed for preparing SCP composites with enhanced conductivity and desired morphologies. With this strategy, macroporous SCP composites were successfully prepared from hierarchical porous carbon. The composites displayed discharge/charge capacities up to 1218/1139, 949/922, and 796/785 mA h g -1 at the current rates of 5, 10, and 15 C, respectively. Considering the universality of this strategy and the numerous morphologies of carbon materials, this strategy opens many opportunities for making carbon/SCP composites with novel morphologies.

Graphene-wrapped sulfur nanospheres with ultra-high sulfur loading for high energy density lithium–sulfur batteries

Energy Technology Data Exchange (ETDEWEB)

Liu, Ya; Guo, Jinxin; Zhang, Jun, E-mail: zhangjun@zjnu.cn; Su, Qingmei; Du, Gaohui, E-mail: gaohuidu@zjnu.edu.cn

2015-01-01

Graphical abstract: - Highlights: • A graphene-wrapped sulfur nanospheres composite with 91 wt% S is prepared. • It shows highly improved electrochemical performance as cathode for Li–S cell. • The PVP coating and conductive graphene minimize polysulfides dissolution. • The flexible coatings with void space accommodate the volume expansion of sulfur. - Abstract: Lithium–sulfur (Li–S) battery with high theoretical energy density is one of the most promising energy storage systems for electric vehicles and intermittent renewable energy. However, due to the poor conductivity of the active material, considerable weight of the electrode is occupied by the conductive additives. Here we report a graphene-wrapped sulfur nanospheres composite (S-nanosphere@G) with sulfur content up to 91 wt% as the high energy density cathode material for Li–S battery. The sulfur nanospheres with diameter of 400–500 nm are synthesized through a solution-based approach with the existence of polyvinylpyrrolidone (PVP). Then the sulfur nanospheres are uniformly wrapped by conductive graphene sheets through the electrostatic interaction between graphene oxide and PVP, followed by reducing of graphene oxide with hydrazine. The design of graphene wrapped sulfur nanoarchitecture provides flexible conductive graphene coating with void space to accommodate the volume expansion of sulfur and to minimize polysulfide dissolution. As a result, the S-nanosphere@G nanocomposite with 91 wt% sulfur shows a reversible initial capacity of 970 mA h g{sup −1} and an average columbic efficiency > 96% over 100 cycles at a rate of 0.2 C. Taking the total mass of electrode into account, the S-nanosphere@G composite is a promising cathode material for high energy density Li–S batteries.

Surface-initiated growth of thin oxide coatings for Li-sulfur battery cathodes

Energy Technology Data Exchange (ETDEWEB)

Lee, Kyu Tae; Black, Robert; Yim, Taeeun; Ji, Xiulei; Nazar, Linda F. [University of Waterloo, Department of Chemistry, Waterloo, ON (Canada)

2012-12-15

The concept of surface-initiated growth of oxides on functionalized carbons is introduced as a method to inhibit the dissolution of polysulfide ions in Li-S battery cathode materials. MO{sub x} (M: Si, V) thin layers are homogeneously coated on nanostructured carbon-sulfur composites. The coating significantly inhibits the dissolution of polysulfides on cycling, resulting in enhanced cycle performance and coulombic efficiency of the Li-S battery. (Copyright copyright 2012 WILEY-VCH Verlag GmbH and Co. KGaA, Weinheim)

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

Science.gov (United States)

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

2018-01-01

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

Sulfur impregnated in tunable porous N-doped carbon as sulfur cathode: effect of pore size distribution

International Nuclear Information System (INIS)

Wang, Sha; Zhao, Zhenxia; Xu, Hui; Deng, Yuanfu; Li, Zhong; Chen, Guohua

2015-01-01

Highlights: •Effects of pore size were investigated on electrochemistry for S cathode. •Activation energy of sulfur desorption from the PDA-C was estimated. •Strong interaction was formed between sulfur and porous N-doped carbon. •PDA-C@S showed good cycling performance of 608 mA h g −1 at 2 C over 300 cycles. •PDA-C@S showed good rate stability and high rate capacity. -- Abstract: A novel porous N-doped carbon microsphere (polymer-dopamine derived carbon, PDA-C) with high specific surface area was synthesized as sulfur host for high performance of lithium-sulfur batteries. We used KOH to adjust the pore size and surface area of the PDA-C materials, and then impregnated sulfur into the PDA-C samples by vapor-melting diffusion method. Effects of pore size of the PDA-C samples on the electrochemical performance of the PDA-C@sulfur cathodes were systematically investigated. Raman spectra indicated an enhanced trend of the degree of graphitization of the PDA-C samples with increasing calcination temperature. The surface area of the PDA-C samples increases with amount of the KOH in the pore-creating process. The graphitized porous N-doped carbon provides the high electronic conductive network. Meanwhile, the PDA-C with high surface area and uniform micropores ensures a high interaction toward sulfur as well as the high dispersion of nanoscale sulfur layer on it. The microporous PDA-C@S cathode material exhibits the excellent high rate discharge capability (636 mA h g −1 at 2.0 C) and good low/high-rate cycling stability (893 mA h g −1 (0.5 C) and 608 mA h g −1 (2.0 C) over 100 and 300 cycles). Cyclic voltammogram curves and electrochemical impedance plots show that both the impedance and polarization of the cells increase with decreasing pore size

Organic anodes and sulfur/selenium cathodes for advanced Li and Na batteries

Science.gov (United States)

Luo, Chao

To address energy crisis and environmental pollution induced by fossil fuels, there is an urgent demand to develop sustainable, renewable, environmental benign, low cost and high capacity energy storage devices to power electric vehicles and enhance clean energy approaches such as solar energy, wind energy and hydroenergy. However, the commercial Li-ion batteries cannot satisfy the critical requirements for next generation rechargeable batteries. The commercial electrode materials (graphite anode and LiCoO 2 cathode) are unsustainable, unrenewable and environmental harmful. Organic materials derived from biomasses are promising candidates for next generation rechargeable battery anodes due to their sustainability, renewability, environmental benignity and low cost. Driven by the high potential of organic materials for next generation batteries, I initiated a new research direction on exploring advanced organic compounds for Li-ion and Na-ion battery anodes. In my work, I employed croconic acid disodium salt and 2,5-Dihydroxy-1,4-benzoquinone disodium salt as models to investigate the effects of size and carbon coating on electrochemical performance for Li-ion and Na-ion batteries. The results demonstrate that the minimization of organic particle size into nano-scale and wrapping organic materials with graphene oxide can remarkably enhance the rate capability and cycling stability of organic anodes in both Li-ion and Na-ion batteries. To match with organic anodes, high capacity sulfur and selenium cathodes were also investigated. However, sulfur and selenium cathodes suffer from low electrical conductivity and shuttle reaction, which result in capacity fading and poor lifetime. To circumvent the drawbacks of sulfur and selenium, carbon matrixes such as mesoporous carbon, carbonized polyacrylonitrile and carbonized perylene-3, 4, 9, 10-tetracarboxylic dianhydride are employed to encapsulate sulfur, selenium and selenium sulfide. The resulting composites exhibit

Polyamidoamine dendrimer-based binders for high-loading lithium–sulfur battery cathodes

Energy Technology Data Exchange (ETDEWEB)

Bhattacharya, Priyanka; Nandasiri, Manjula I.; Lv, Dongping; Schwarz, Ashleigh M.; Darsell, Jens T.; Henderson, Wesley A.; Tomalia, Donald A.; Liu, Jun; Zhang, Ji-Guang; Xiao, Jie

2016-01-01

Lithium-sulfur (Li-S) batteries are regarded as one of the most promising candidates for next generation energy storage systems because of their ultra high theoretical specific energy. To realize the practical application of Li-S batteries, however, a high S active material loading is essential (>70 wt% in the carbon-sulfur (C-S) composite cathode and >2 mg cm-2 in the electrode). A critical challenge to achieving this high capacity in practical electrodes is the dissolution of the longer lithium polysulfide reaction intermediates in the electrolyte (resulting in loss of active material from the cathode and contamination of the anode due to the polysulfide shuttle mechanism). The binder material used for the cathode is therefore crucial as this is a key determinant of the bonding interactions between the active material (S) and electronic conducting support (C), as well as the maintenance of intimate contact between the electrode materials and current collector. The battery performance can thus be directly correlated with the choice of binder, but this has received only minimal attention in the relevant Li-S battery published literature. Here, we investigated the application of polyamidoamine (PAMAM) dendrimers as functional binders in Li-S batteries—a class of materials which has been unexplored for electrode design. By using dendrimers, it is demonstrated that high S loadings (>4 mg cm-2) can be easily achieved using "standard" (not specifically tailored) materials and simple processing methods. An exceptional electrochemical cycling performance was obtained (as compared to cathodes with conventional linear polymeric binders such as carboxymethyl cellulose (CMC) and styrene-butadiene rubber (SBR)) with >100 cycles and 85-98% capacity retention, thus demonstrating the significant utility of this new binder architecture which exhibits critical physicochemical properties and flexible nanoscale design parameters (CNDP's).

Synthesis of a Flexible Freestanding Sulfur/Polyacrylonitrile/Graphene Oxide as the Cathode for Lithium/Sulfur Batteries

Directory of Open Access Journals (Sweden)

Huifen Peng

2018-04-01

Full Text Available Rechargeable lithium/sulfur (Li/S batteries have received quite significant attention over the years because of their high theoretical specific capacity (1672 mAh·g−1 and energy density (2600 mAh·g−1 which has led to more efforts for improvement in their electrochemical performance. Herein, the synthesis of a flexible freestanding sulfur/polyacrylonitrile/graphene oxide (S/PAN/GO as the cathode for Li/S batteries by simple method via vacuum filtration is reported. The S/PAN/GO hybrid binder-free electrode is considered as one of the most promising cathodes for Li/S batteries. Graphene oxide (GO slice structure provides effective ion conductivity channels and increases structural stability of the ternary system, resulting in excellent electrochemical properties of the freestanding S/PAN/GO cathode. Additionally, graphene oxide (GO membrane was able to minimize the polysulfides’ dissolution and their shuttle, which was attributed to the electrostatic interactions between the negatively-charged species and the oxygen functional groups on GO. Furthermore, these oxygen-containing functional groups including carboxyl, epoxide and hydroxyl groups provide active sites for coordination with inorganic materials (such as sulfur. It exhibits the initial reversible specific capacity of 1379 mAh·g−1 at a constant current rate of 0.2 C and maintains 1205 mAh·g−1 over 100 cycles (~87% retention. In addition, the freestanding S/PAN/GO cathode displays excellent coulombic efficiency (~100% and rate capability, delivering up to 685 mAh·g−1 capacity at 2 C.

Performance Enhancement of a Sulfur/Carbon Cathode by Polydopamine as an Efficient Shell for High-Performance Lithium-Sulfur Batteries.

Science.gov (United States)

Zhang, Xuqing; Xie, Dong; Zhong, Yu; Wang, Donghuang; Wu, Jianbo; Wang, Xiuli; Xia, Xinhui; Gu, Changdong; Tu, Jiangping

2017-08-04

Lithium-sulfur batteries (LSBs) are considered to be among the most promising next-generation high-energy batteries. It is a consensus that improving the conductivity of sulfur cathodes and impeding the dissolution of lithium polysulfides are two key accesses to high-performance LSBs. Herein we report a sulfur/carbon black (S/C) cathode modified by self-polymerized polydopamine (pDA) with the assistance of polymerization treatment. The pDA acts as a novel and effective shell on the S/C cathode to stop the shuttle effect of polysulfides. By the synergistic effect of enhanced conductivity and multiple blocking effect for polysulfides, the S/C@pDA electrode exhibits improved electrochemical performances including large specific capacity (1135 mAh g -1 at 0.2 C), high rate capability (533 mAh g -1 at 5 C) and long cyclic life (965 mAh g -1 after 200 cycles). Our smart design strategy may promote the development of high-performance LSBs. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

A dual coaxial nanocable sulfur composite for high-rate lithium-sulfur batteries.

Science.gov (United States)

Li, Zhen; Yuan, Lixia; Yi, Ziqi; Liu, Yang; Xin, Ying; Zhang, Zhaoliang; Huang, Yunhui

2014-01-01

Lithium-sulfur batteries have great potential for some high energy applications such as in electric vehicles and smart grids due to their high capacity, natural abundance, low cost and environmental friendliness. But they suffer from rapid capacity decay and poor rate capability. The problems are mainly related to the dissolution of the intermediate polysulfides in the electrolyte, and to the poor conductivity of sulfur and the discharge products. In this work, we propose a novel dual coaxial nanocable sulfur composite fabricated with multi-walled nanotubes (MWCNT), nitrogen-doped porous carbon (NPC) and polyethylene glycol (PEG), i.e. MWCNTs@S/NPC@PEG nanocable, as a cathode material for Li-S batteries. In such a coaxial structure, the middle N-doped carbon with hierarchical porous structure provides a nanosized capsule to contain and hold the sulfur particles; the inner MWCNTs and the outer PEG layer can further ensure the fast electronic transport and prevent the dissolution of the polysulfides into the electrolyte, respectively. The as-designed MWCNT@S/NPC@PEG composite shows good cycling stability and excellent rate capability. The capacity is retained at 527 mA h g(-1) at 1 C after 100 cycles, and 791 mA h g(-1) at 0.5 C and 551 mA h g(-1) at 2 C after 50 cycles. Especially, the high-rate capability is outstanding with 400 mA h g(-1) at 5 C.

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

Directory of Open Access Journals (Sweden)

Ji-Yoon Song

2018-02-01

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

Hollow Carbon Nanofiber-Encapsulated Sulfur Cathodes for High Specific Capacity Rechargeable Lithium Batteries

KAUST Repository

Zheng, Guangyuan

2011-10-12

Sulfur has a high specific capacity of 1673 mAh/g as lithium battery cathodes, but its rapid capacity fading due to polysulfides dissolution presents a significant challenge for practical applications. Here we report a hollow carbon nanofiber-encapsulated sulfur cathode for effective trapping of polysulfides and demonstrate experimentally high specific capacity and excellent electrochemical cycling of the cells. The hollow carbon nanofiber arrays were fabricated using anodic aluminum oxide (AAO) templates, through thermal carbonization of polystyrene. The AAO template also facilitates sulfur infusion into the hollow fibers and prevents sulfur from coating onto the exterior carbon wall. The high aspect ratio of the carbon nanofibers provides an ideal structure for trapping polysulfides, and the thin carbon wall allows rapid transport of lithium ions. The small dimension of these nanofibers provides a large surface area per unit mass for Li2S deposition during cycling and reduces pulverization of electrode materials due to volumetric expansion. A high specific capacity of about 730 mAh/g was observed at C/5 rate after 150 cycles of charge/discharge. The introduction of LiNO3 additive to the electrolyte was shown to improve the Coulombic efficiency to over 99% at C/5. The results show that the hollow carbon nanofiber-encapsulated sulfur structure could be a promising cathode design for rechargeable Li/S batteries with high specific energy. © 2011 American Chemical Society.

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

Science.gov (United States)

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.

Acetylene Black/Sulfur Composites Synthesized by a Solution Evaporation Concentration Crystallization Method and Their Electrochemical Properties for Li/S Batteries

Directory of Open Access Journals (Sweden)

Zhigao Yang

2013-07-01

Full Text Available A novel technique to prepare carbon/sulfur composites as cathode materials for Li/S batteries is proposed, which we call the ‘solution evaporation concentration crystallization’ method. Three composites with different S loadings were prepared, subject to two different solvent evaporation rates from acetylene black (AB/sulfur in carbon disulfide solutions. X-ray diffraction, environmental scanning electron microscopy, transmission electron microscopy, and Brunauer-Emmett-Teller measurements all show that the porous AB structure is well-filled with S. Composites prepared at a lower solvent evaporation rate with 50 wt % S content, had good electrochemical properties, with 1609.67 mAh g−1 after 100 cycles. Composites with better dispersibility at a low solvent evaporation rate can effectively prevent polysulfide from dissolving in the electrolyte, and serve to stabilize the structure of the S cathode during the charge-discharge process.

A sulfur host based on titanium monoxide@carbon hollow spheres for advanced lithium-sulfur batteries.

Science.gov (United States)

Li, Zhen; Zhang, Jintao; Guan, Buyuan; Wang, Da; Liu, Li-Min; Lou, Xiong Wen David

2016-10-20

Lithium-sulfur batteries show advantages for next-generation electrical energy storage due to their high energy density and cost effectiveness. Enhancing the conductivity of the sulfur cathode and moderating the dissolution of lithium polysulfides are two key factors for the success of lithium-sulfur batteries. Here we report a sulfur host that overcomes both obstacles at once. With inherent metallic conductivity and strong adsorption capability for lithium-polysulfides, titanium monoxide@carbon hollow nanospheres can not only generate sufficient electrical contact to the insulating sulfur for high capacity, but also effectively confine lithium-polysulfides for prolonged cycle life. Additionally, the designed composite cathode further maximizes the lithium-polysulfide restriction capability by using the polar shells to prevent their outward diffusion, which avoids the need for chemically bonding all lithium-polysulfides on the surfaces of polar particles.

Promotional role of Li4Ti5O12 as polysulfide adsorbent and fast Li+ conductor on electrochemical performances of sulfur cathode

Science.gov (United States)

Zeng, Tianbiao; Hu, Xuebu; Ji, Penghui; Shang, Biao; Peng, Qimeng; Zhang, Yaoyao; Song, Ruiqiang

2017-08-01

Lithium-sulfur (Li-S) batteries attract much attention due to its high specific capacity and energy density compared to lithium-ion batteries (LiBs). Herein, a novel composite named as (void/nano-Li4Ti5O12 pieces)@C [(v/n-L)@C] was designed and prepared as a sulfur host. Spinel Li4Ti5O12 here as a multifunctional additive played as polysulfide adsorbent agent and fast Li+ conductor, and carbon shell was designed as electronic conductor, as well as volume barrier to limit the volume expansion caused by sulfur. As-prepared (S/nano-Li4Ti5O12 pieces)@C [(S/n-L)@C] are core-shell spheres, which are about 200 nm in size. Nano-Li4Ti5O12 and sulfur were coated by the outer carbon shell with a thickness of about 20 nm. The experimental results show that electrochemical performances of (S/n-L)@C cathode were enhanced effectively compared to S@C cathode. At 0.5C and 1C, the discharge capacity of (S/n-L)@C was 33.5% and 40.1% higher than that of S@C at 500th cycle. Even at 2C, its capacity reached 600.9 mAh g-1 at 1000th cycle. Li+ conductivity of (S/n-L)@C was one order of magnitude higher than that of S@C, which was reach to 2.55 × 10-8 S cm-1. The experiment results indicate Li4Ti5O12 plays a promotional role on electrochemical performances of sulfur cathode, especially for stable cycling performance and high rate performance.

Hollow Carbon Nanofiber-Encapsulated Sulfur Cathodes for High Specific Capacity Rechargeable Lithium Batteries

KAUST Repository

Zheng, Guangyuan; Yang, Yuan; Cha, Judy J.; Hong, Seung Sae; Cui, Yi

2011-01-01

Sulfur has a high specific capacity of 1673 mAh/g as lithium battery cathodes, but its rapid capacity fading due to polysulfides dissolution presents a significant challenge for practical applications. Here we report a hollow carbon nanofiber

Sulfur X-ray absorption fine structure in porous Li–S cathode films measured under argon atmospheric conditions

International Nuclear Information System (INIS)

Müller, Matthias; Choudhury, Soumyadip; Gruber, Katharina; Cruz, Valene B.; Fuchsbichler, Bernd; Jacob, Timo; Koller, Stefan; Stamm, Manfred; Ionov, Leonid; Beckhoff, Burkhard

2014-01-01

In this paper we present the first results for the characterization of highly porous cathode materials with pore sizes below 1 μm for Lithium Sulfur (Li–S) batteries by Near Edge X-ray Absorption Fine Structure (NEXAFS) spectroscopy. A novel cathode material of porous carbon films fabricated with colloidal array templates has been investigated. In addition, an electrochemical characterization has been performed aiming on an improved correlation of physical and chemical parameters with the electrochemical performance. The performed NEXAFS measurements of cathode materials allowed for a chemical speciation of the sulfur content inside the cathode material. The aim of the presented investigation was to evaluate the potential of the NEXAFS technique to characterize sulfur in novel battery material. The long term goal for the characterization of the battery materials is the sensitive identification of undesired side reactions, such as the polysulfide shuttle, which takes place during charging and discharging of the battery. The main drawback associated with the investigation of these materials is the fact that NEXAFS measurements can usually only be performed ex situ due to the limited in situ instrumentation being available. For Li–S batteries this problem is more pronounced because of the low photon energies needed to study the sulfur K absorption edge at 2472 eV. We employed 1 μm thick Si 3 N 4 windows to construct sealed argon cells for NEXAFS measurements under ultra high vacuum (UHV) conditions as a first step towards in situ measurements. The cells keep the sample under argon atmosphere at any time and the X-ray beam passes mainly through vacuum which enables the detection of the low energy X-ray emission of sulfur. Using these argon cells we found indications for the presence of lithium polysulfides in the cathode films whereas the correlations to the offline electrochemical results remain somewhat ambiguous. As a consequence of these findings one may

Graphene derived carbon confined sulfur cathodes for lithium-sulfur batteries: Electrochemical impedance studies

International Nuclear Information System (INIS)

Ganesan, Aswathi; Varzi, Alberto; Passerini, Stefano; Shaijumon, Manikoth M.

2016-01-01

Highlights: • Graphene-derived carbon (GDC) with distinctive porosity characteristics are prepared. • Effect of micro-/mesoporosity of GDC for improved Li-S battery performance is studied. • Impedance studies reveal insights into Li-S redox reactions and capacity fading phenomena. - Abstract: Sulfur nanocomposites are prepared by using graphene derived carbon (GDC), with controlled porosity characteristics, as confining matrix and are studied as efficient cathodes for lithium-sulfur (Li-S) batteries. To understand the effect of micro-/mesoporosity in porous carbon for the effective encapsulation of sulfur and polysulfides towards improved Li-S battery performance, two different GDC samples with controlled porosity characteristics, one with predominantly micropores (GDC-1) and a surface area of 1970 m 2 g −1 and the other with a surface area of 3239 m 2 g −1 , having more or less equal contribution of micro- and mesopores (GDC-2), are used to synthesize nanocomposite sulfur electrodes following melt diffusion process. Electrochemical studies are carried out by using cyclic voltammetry, galvanostatic charge/discharge cycling and electrochemical impedance spectroscopy (EIS). EIS spectra collected at different depth of discharge (DOD) in the first cycle as well as upon cycling give valuable insights into the Li-S redox reactions and capacity fading phenomena in these electrodes. The impedance response of GDC-S electrodes suggests a detrimental effect of the mesopores, where insoluble reaction products can easily accumulate, resulting in the loss of active material leading to capacity fading of Li-S cells.

Nanostructured lanthanum manganate composite cathode

DEFF Research Database (Denmark)

Wang, Wei Guo; Liu, Yi-Lin; Barfod, Rasmus

2005-01-01

that the (La1-xSrx)(y)MnO3 +/-delta (LSM) composite cathodes consist of a network of homogenously distributed LSM, yttria-stabilized zirconia (YSZ), and pores. The individual grain size of LSM or YSZ is approximately 100 nm. The degree of contact between cathode and electrolyte is 39% on average. (c) 2005...

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

Science.gov (United States)

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.

Lithium Sulfur Primary Battery with Super High Energy Density: Based on the Cauliflower-like Structured C/S Cathode

Science.gov (United States)

Ma, Yiwen; Zhang, Hongzhang; Wu, Baoshan; Wang, Meiri; Li, Xianfeng; Zhang, Huamin

2015-10-01

The lithium-sulfur primary batteries, as seldom reported in the previous literatures, were developed in this work. In order to maximize its practical energy density, a novel cauliflower-like hierarchical porous C/S cathode was designed, for facilitating the lithium-ions transport and sulfur accommodation. This kind of cathode could release about 1300 mAh g-1 (S) capacity at sulfur loading of 6 ~ 14 mg cm-2, and showed excellent shelf stability during a month test at room temperature. As a result, the assembled Li-S soft package battery achieved an energy density of 504 Wh kg-1 (654 Wh L-1), which was the highest value ever reported to the best of our knowledge. This work might arouse the interests on developing primary Li-S batteries, with great potential for practical application.

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

Science.gov (United States)

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.

Sandwich-like graphene-mesoporous carbon as sulfur host for enhanced lithium-sulfur batteries

Science.gov (United States)

Tian, Ting; Li, Bin; Zhu, Mengqi; Liu, Jianhua; Li, Songmei

2017-10-01

Graphene-mesoporous carbon/sulfur composites (G-MPC/S) were constructed by melt-infiltration of sulfur into graphene-mesoporous carbon which was synthesized by soft template method. The SEM and BET results of the graphene-mesoporous carbon show that the as-prepared sandwich-like G-MPC composites with a unique microporous-mesoporous structure had a high specific surface area of 554.164 m2 · g-1 and an average pore size of about 13 nm. The XRD analysis presents the existence of orthorhombic sulfur in the G-MPC/S composite, which indicates the complete infiltration of sulfur into the pores of the G-MPC. When the graphene-mesoporous carbon/surfur composites (G-MPC/S) with 53.9 wt.% sulfur loading were used as the cathode for lithium-sulfur (Li-S) batteries, it exhibited an outstanding electrochemical performance including excellent initial discharge specific capacity of 1393 mAh · g-1 at 0.1 °C, high cycle stability (731 mAh · g-1 at 200 cycles) and good rate performance (1038 mAh · g-1, 770 mAh · g-1, 518 mAh · g-1 and 377 mAh · g-1 at 0.1 °C, 0.2 °C, 0.5 °C and 1 °C, respectively), which suggested the important role of the G-MPC composite in providing more electrons and ions channels, in addition, the shuttle effect caused by the dissolved polysulfide was also suppressed.

Graphene-sulfur nanocomposites for rechargeable lithium-sulfur battery electrodes

Science.gov (United States)

Liu, Jun; Lemmon, John P; Yang, Zhenguo; Cao, Yuiliang; Li, Xiaolin

2014-06-17

Rechargeable lithium-sulfur batteries having a cathode that includes a graphene-sulfur nanocomposite can exhibit improved characteristics. The graphene-sulfur nanocomposite can be characterized by graphene sheets with particles of sulfur adsorbed to the graphene sheets. The sulfur particles have an average diameter less than 50 nm..

A Facile Bottom-Up Approach to Construct Hybrid Flexible Cathode Scaffold for High-Performance Lithium-Sulfur Batteries.

Science.gov (United States)

Ghosh, Arnab; Manjunatha, Revanasiddappa; Kumar, Rajat; Mitra, Sagar

2016-12-14

Lithium-sulfur batteries mostly suffer from the low utilization of sulfur, poor cycle life, and low rate performances. The prime factors that affect the performance are enormous volume change of the electrode, soluble intermediate product formation, poor electronic and ionic conductivity of S, and end discharge products (i.e., Li 2 S 2 and Li 2 S). The attractive way to mitigate these challenges underlying in the fabrication of a sulfur nanocomposite electrode consisting of different nanoparticles with distinct properties of lithium storage capability, mechanical reinforcement, and ionic as well as electronic conductivity leading to a mechanically robust and mixed conductive (ionic and electronic conductive) sulfur electrode. Herein, we report a novel bottom-up approach to synthesize a unique freestanding, flexible cathode scaffold made of porous reduced graphene oxide, nanosized sulfur, and Mn 3 O 4 nanoparticles, and all are three-dimensionally interconnected to each other by hybrid polyaniline/sodium alginate (PANI-SA) matrix to serve individual purposes. A capacity of 1098 mAh g -1 is achieved against lithium after 200 cycles at a current rate of 2 A g -1 with 97.6% of initial capacity at a same current rate, suggesting the extreme stability and cycling performance of such electrode. Interestingly, with the higher current density of 5 A g -1 , the composite electrode exhibited an initial capacity of 1015 mA h g -1 and retained 71% of the original capacity after 500 cycles. The in situ Raman study confirms the polysulfide absorption capability of Mn 3 O 4 . This work provides a new strategy to design a mechanically robust, mixed conductive nanocomposite electrode for high-performance lithium-sulfur batteries and a strategy that can be used to develop flexible large power storage devices.

Mathematical micro-model of a solid oxide fuel cell composite cathode

International Nuclear Information System (INIS)

Kenney, B.; Karan, K.

2004-01-01

In a solid oxide fuel cell (SOFC), the cathode processes account for a majority of the overall electrochemical losses. A composite cathode comprising a mixture of ion-conducting electrolyte and electron-conducting electro-catalyst can help minimize cathode losses provided microstructural parameters such as particle-size, composition, and porosity are optimized. The cost of composite cathode research can be greatly reduced by incorporating mathematical models into the development cycle. Incorporated with reliable experimental data, it is possible to conduct a parametric study using a model and the predicted results can be used as guides for component design. Many electrode models treat the cathode process simplistically by considering only the charge-transfer reaction for low overpotentials or the gas-diffusion at high overpotentials. Further, in these models an average property of the cathode internal microstructure is assumed. This paper will outline the development of a 1-dimensional SOFC composite cathode micro-model and the experimental procedures for obtaining accurate parameter estimates. The micro-model considers the details of the cathode microstructure such as porosity, composition and particle-size of the ionic and electronic phases, and their interrelationship to the charge-transfer reaction and mass transport processes. The micro-model will be validated against experimental data to determine its usefulness for performance prediction. (author)

The analysis of thermoplastic characteristics of special polymer sulfur composite

Science.gov (United States)

Książek, Mariusz

2017-01-01

Specific chemical environments step out in the industry objects. Portland cement composites (concrete and mortar) were impregnated by using the special polymerized sulfur and technical soot as a filler (polymer sulfur composite). Sulfur and technical soot was applied as the industrial waste. Portland cement composites were made of the same aggregate, cement and water. The process of special polymer sulfur composite applied as the industrial waste is a thermal treatment process in the temperature of about 150-155°C. The result of such treatment is special polymer sulfur composite in a liquid state. This paper presents the plastic constants and coefficients of thermal expansion of special polymer sulfur composites, with isotropic porous matrix, reinforced by disoriented ellipsoidal inclusions with orthotropic symmetry of the thermoplastic properties. The investigations are based on the stochastic differential equations of solid mechanics. A model and algorithm for calculating the effective characteristics of special polymer sulfur composites are suggested. The effective thermoplastic characteristics of special polymer sulfur composites, with disoriented ellipsoidal inclusions, are calculated in two stages: First, the properties of materials with oriented inclusions are determined, and then effective constants of a composite with disoriented inclusions are determined on the basis of the Voigt or Rice scheme. A brief summary of new products related to special polymer sulfur composites is given as follows: Impregnation, repair, overlays and precast polymer concrete will be presented. Special polymer sulfur as polymer coating impregnation, which has received little attention in recent years, currently has some very interesting applications.

A study of the behavior of a cathode film formed in chromium plating with radioactive tracers

International Nuclear Information System (INIS)

Yoshida, Katsuyoshi; Suzuki, Akihira; Doi, Kazuyuki; Arai, Katsutoshi

1979-01-01

The behavior and composition of a cathode film formed on a steel cathode during chromium plating were studied with radioactive tracers. A special cell with a rapid washing compartment was used for preventing the cathode film from dissolving in electrolyte after plating. The cathode film was composed of two layers. The outer layer facing to the electrolyte had a loose structure and contained more sulfuric anions than the inner layer, for sulfuric acid probably concentrated in the outer layer. This outer layer is called L-film in this paper. The L-film was easily dissolved in the electrolyte solution. The inner layer (called C-film, compact film) was stable against electrolytes and contained less anions than that of L-film. The C-film had a thickness equivalent to 5 mg/m 2 and the concentration of anions unaffected by the composition of electrolytes. The C-film was not reduced to metallic chromium, but it remained in the cathode film during and after plating. This suggests that chromic acid in the cathode film is not reduced to metallic chromium, that metallic chromium is deposited from chromium complexes reaching the cathode surface through the cathode film, and that the complexes do not play a role on the construction of the cathode film. (author)

In-situ sulfuration synthesis of sandwiched spherical tin sulfide/sulfur-doped graphene composite with ultra-low sulfur content

Science.gov (United States)

Zhao, Bing; Yang, Yaqing; Wang, Zhixuan; Huang, Shoushuang; Wang, Yanyan; Wang, Shanshan; Chen, Zhiwen; Jiang, Yong

2018-02-01

SnS is widely studied as anode materials since of its superior structural stability and physicochemical property comparing with other Sn-based composites. Nevertheless, the inconvenience of phase morphology control and excessive consumption of sulfur sources during synthesis hinder the scalable application of SnS nanocomposites. Herein, we report a facile in-situ sulfuration strategy to synthesize sandwiched spherical SnS/sulfur-doped graphene (SnS/S-SG) composite. An ultra-low sulfur content with approximately stoichiometric ratio of Sn:S can effectively promote the sulfuration reaction of SnO2 to SnS and simultaneous sulfur-doping of graphene. The as-prepared SnS/S-SG composite shows a three-dimensional interconnected spherical structure as a whole, in which SnS nanoparticles are sandwiched between the multilayers of graphene sheets forming a hollow sphere. The sandwiched sphere structure and high S doping amount can improve the binding force between SnS and graphene, as well as the structural stability and electrical conductivity of the composite. Thus, a high reversibility of conversion reaction, promising specific capacity (772 mAh g-1 after 100 cycles at 0.1 C) and excellent rate performance (705 and 411 mAh g-1 at 1 C and 10 C, respectively) are exhibited in the SnS/S-SG electrode, which are much higher than that of the SnS/spherical graphene synthesized by traditional post-sulfuration method.

Flexible carbon nanofiber/polyvinylidene fluoride composite membranes as interlayers in high-performance Lithiumsbnd Sulfur batteries

Science.gov (United States)

Wang, Zhenhua; Zhang, Jing; Yang, Yuxiang; Yue, Xinyang; Hao, Xiaoming; Sun, Wang; Rooney, David; Sun, Kening

2016-10-01

Traditionally polyvinylidene fluoride membranes have been used in applications such as membrane distillation, wastewater treatment, desalination and separator fabrication. Within this work we demonstrate that a novel carbon nanofiber/polyvinylidene fluoride (CNF/PVDF) composite membrane can be used as an interlayer for Lithiumsbnd Sulfur (Lisbnd S) batteries yielding both high capacity and long cycling life. This PVDF membrane is shown to effectively separate dissolved lithium polysulfide with the high electronic conductivity CNF not only reducing the internal resistance in the sulfur cathode but also helping immobilize the polysulfide through its abundant nanospaces. The resulting Lisbnd S battery assembled with the CNF/PVDF composite membrane effectively solves the polysulfide permeation problem and exhibits excellent electrochemical performance. It is further shown that the CNF/PVDF electrode has an excellent cycling stability and retains a capacity of 768.6 mAh g-1 with a coulombic efficiency above 99% over 200 cycles at 0.5C, which is more than twice that of a cell without CNF/PVDF (374 mAh g-1). In addition, the low-cost raw materials and the simple preparation process of CNF/PVDF composite membrane is also amenable for industrial production.

Layered sulfur/PEDOT:PSS nano composite electrodes for lithium sulfur cell applications

Science.gov (United States)

Anilkumar, K. M.; Jinisha, B.; Manoj, M.; Pradeep, V. S.; Jayalekshmi, S.

2018-06-01

Lithium-Sulfur (Li-S) cells are emerging as the next generation energy storage devices owing to their impressive electrochemical properties with high theoretical specific capacity of 1675 mAh/g. Lack of electronic conductivity of sulfur, its volume expansion during high lithium intake and the shuttling effect due to the formation of soluble polysulfides are the main limitations, delaying the commercialization of this technology. To address these challenges, in the present work, the conducting polymer PEDOT:PSS is used as the covering matrix over the sulfur particles to improve their Li storage properties. The sulfur/PEDOT:PSS nanocomposite is synthesised using the hydrothermal process and its formation with the polymer coating over sulfur nanoparticles is established from the XRD, Raman spectroscopy, FE-SEM and TEM studies. The electrochemical studies show that the cells assembled using the sulfur/PEDOT:PSS nanocomposite as the cathode, with the components taken in the weight ratio of 9:1, offer a reversible capacity of 1191 mAh g-1 at 0.1C rate. These cells display stable electrochemical capacities over 200 cycles at gradually increasing current rates. The polymer layer facilitates electronic conduction and suppresses the polysulfide formation and the volume expansion of sulfur. A reversible capacity of 664 mAh g-1 is observed after 200 cycles at 1C rate with the capacity retention of 75 % of the initial stable capacity. The highlight of the present work is the possibility to achieve high discharge capacities at high C rates and the retention of a good percentage of the initial capacity over 200 cycles, for these Li-S cells.

Effect of sulfur content in a sulfur-activated carbon composite on the electrochemical properties of a lithium/sulfur battery

Energy Technology Data Exchange (ETDEWEB)

Park, Jin-Woo; Kim, Changhyeon; Ryu, Ho-Suk; Cho, Gyu-Bong; Cho, Kwon-Koo; Kim, Ki-Won [School of Materials Science and Engineering, Gyeongsang National University, Jinju (Korea, Republic of); Ahn, Jou-Hyeon [Department of Chemical & Biological Engineering, Gyeongsang National University, Jinju (Korea, Republic of); Wang, Guoxiu [School of Chemistry and Forensic Science, University of Technology Sydney, Sydney, NSW 2007 (Australia); Ahn, Jae-Pyeung [Advanced Analysis Center, Research Planning & Coordination Division, KIST, Seoul (Korea, Republic of); Ahn, Hyo-Jun, E-mail: ahj@gnu.ac.kr [School of Materials Science and Engineering, Gyeongsang National University, Jinju (Korea, Republic of)

2015-09-15

Highlights: • The content of sulfur in activated carbon was controlled by solution process. • The sulfur electrode with low sulfur content shows the best performance. • The Li/S battery has capacity of 1360 mAh/g at 1 C and 702 mAh/g at 10 C. - Abstract: The content of sulfur in sulfur/activated carbon composite is controlled from 32.37 wt.% to 55.33 wt.% by a one-step solution-based process. When the sulfur content is limited to 41.21 wt.%, it can be loaded into the pores of an activated carbon matrix in a highly dispersed state. On the contrary, when the sulfur content is 55.33 wt.%, crystalline sulfur can be detected on the surface of the activated carbon matrix. The best electrochemical performance can be obtained for a sulfur electrode with the lowest sulfur content. The sulfur/activated carbon composite with 32.37 wt.% sulfur afforded the highest first discharge capacity of 1360 mAh g{sup −1} at 1 C rate and a large reversible capacity of 702 mAh g{sup −1} at 10 C (16.75 A/g)

Low temperature sulfur and sodium metal battery for grid-scale energy storage application

Science.gov (United States)

Liu, Gao; Wang, Dongdong

2018-03-27

A re-chargeable battery comprising a non-dendrite forming sodium (Na)/potassium (K) liquid metal alloy anode, a sulfur and polyacrylonitrile (PAN) conductive polymer composite cathode, a polyethyleneoxide (PEO) solid electrolyte, a solid electrolyte interface (SEI) formed on the PEO solid electrolyte; and a cell housing, wherein the anode, cathode, and electrolyte are assembled into the cell housing with the PEO solid electrolyte disposed between the cathode and anode.

A composite of hollow carbon nanospheres and sulfur-rich polymers for lithium-sulfur batteries

Science.gov (United States)

Zeng, Shao-Zhong; Yao, Yuechao; Zeng, Xierong; He, Qianjun; Zheng, Xianfeng; Chen, Shuangshuang; Tu, Wenxuan; Zou, Jizhao

2017-07-01

Lithium-sulfur batteries are the most promising candidates for future high-energy applications because of the unparalleled capacity of sulfur (1675 mAh g-1). However, lithium-sulfur batteries have limited cycle life and rate capability due to the dissolution of polysulfides and the extremely low electronic conductivity of sulfur. To solve these issues, various porous carbons including hollow carbon nanospheres (HCNs) have been used for improving the conductivity. However, these methods still suffer from polysulfides dissolution/loss owing to their weak physical adsorption to polysulfides. Herein, we introduced a covalent grafting route to composite the HCNs and the vulcanized trithiocyanuric acid (TTCA). The composite exhibits a high loading of the vulcanized TTCA by the HCNs with high surface area and large pore volume, and covalent bonds to sulfur, effectively depressing the dissolution of polysulfides. The first discharge capacity of the composite reaches 1430 mAh g-1 at 0.1 C and 1227 mAh g-1 at 0.2 C.

Cathode Composition in a Saltwater Metal-Air Battery

Directory of Open Access Journals (Sweden)

William Shen

2017-01-01

Full Text Available Metal-air batteries consist of a solid metal anode and an oxygen cathode of ambient air, typically separated by an aqueous electrolyte. Here, simple saltwater-based models of aluminum-air and zinc-air cells are used to determine the differences between theoretical cell electric potentials and experimental electric potentials. A substantial difference is observed. It is also found that the metal cathode material is crucial to cell electric potential, despite the cathode not participating in the net reaction. Finally, the material composition of the cathode appears to have a more significant impact on cell potential than the submerged surface area of the cathode.

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

Science.gov (United States)

Qin, Ya

Solid oxide fuel cell (SOFC) systems are of particular interest as electrochemical power systems that can operate on various hydrocarbon fuels with high fuel-to-electrical energy conversion efficiency. Within the SOFC stack, La0.8Sr 0.2Ga0.8Mg0.115Co0.085O3-delta (LSGMC) has been reported as an optimized composition of lanthanum gallate based electrolytes to achieve higher oxygen ionic conductivity at intermediate temperatures, i.e., 500-700°C. The electrocatalytic properties of interfaces between LSGMC electrolytes and various candidate intermediate-temperature SOFC cathodes have been investigated. Sm0.5Sr0.5CoO 3-delta (SSC), and La0.6Sr0.4Co0.2Fe 0.8O3-delta (LSCF), in both pure and composite forms with LSGMC, were investigated with regards to both oxygen reduction and evolution, A range of composite cathode compositions, having ratios of SSC (in wt.%) with LSGMC (wt.%) spanning the compositions 9:1, 8:2, 7:3, 6:4 and 5:5, were investigated to determine the optimal cathode-electrolyte interface performance at intermediate temperatures. All LSGMC electrolyte and cathode powders were synthesized using the glycine-nitrate process (GNP). Symmetrical electrochemical cells were investigated with three-electrode linear dc polarization and ac impedance spectroscopy to characterize the kinetics of the interfacial reactions in detail. Composite cathodes were found to perform better than the single phase cathodes due to significantly reduced polarization resistances. Among those composite SSC-LSGMC cathodes, the 7:3 composition has demonstrated the highest current density at the equivalent overpotential values, indicating that 7:3 is an optimal mixing ratio of the composite cathode materials to achieve the best performance. For the composite SC-LSGMC cathode/LSGMC interface, the cathodic overpotential under 1 A/cm2 current density was as low as 0.085 V at 700°C, 0.062V at 750°C and 0.051V at 800°C in air. Composite LSCF-LSGMC cathode/LSGMC interfaces were found to have

Graphene-Based Composites as Cathode Materials for Lithium Ion Batteries

Directory of Open Access Journals (Sweden)

Libao Chen

2013-01-01

Full Text Available Owing to the superior mechanical, thermal, and electrical properties, graphene was a perfect candidate to improve the performance of lithium ion batteries. Herein, we review the recent advances in graphene-based composites and their application as cathode materials for lithium ion batteries. We focus on the synthesis methods of graphene-based composites and the superior electrochemical performance of graphene-based composites as cathode materials for lithium ion batteries.

Development of a high-performance composite cathode for LT-SOFC

Science.gov (United States)

Lee, Byung Wook

carried out to develop a high-performance composite cathode, in particular, for LT-SOFC operating 650°C and below since stability and compatibility of the materials in interest are secured at low temperatures. First, a nano-sized pyrochlore bismuth ruthenate (Bi2Ru 2O7 or BRO7 shortly), one of the promising cathode materials, was successfully synthesized using glycine-nitrate combustion (GNC) route. Stoichiometric Bi2Ru2O7 without any impurity phase was achieved with considerably improved processing condition, leading to the crystallite size of ~24nm in diameter. Even though the resulting powder tends to agglomerate, resulting in overall 200~400nm size range, it still showed better quality than the one prepared by solid state (SS) reaction route followed by extra milling steps such as vibro-milling and sonication for further particle size reduction. Glycine-to-nitrate (G/N) ratio was found to play a critical role in determining the reaction temperature and reaction duration, thus phase purity and particle morphology (particle size, shape, and agglomeration etc). Composite cathodes of such prepared BRO7 (GNC BRO7) combined with SS erbia-stabilized bismuth oxide, Bi1.6Er0.4O3 or ESB, showed better electrochemical performance than vibro-milled BRO7 (VM BRO7)-SS ESB. ASR values of 0.123Ocm2 at 700°C and 4.59cOm 2 at 500°C, respectively, were achieved, which follows well the trend of particle size effect on performance of composite cathodes. Additionally, the number of processing steps (thus time) was reduced by GNC route. Several issues in regard to synthesis process and characteristics of BRO7 material itself will be addressed in this dissertation. Secondly, a unique in-situ composite cathode synthesis was successfully developed and applied for BRO7-ESB composite cathodes to improve percolation and to reduce agglomeration of each phase inside the cathode so that the effective triple phase boundary (TPB) length was extended. To disperse and stabilize ESB powder in de

Air plasma spray processing and electrochemical characterization of SOFC composite cathodes

Science.gov (United States)

White, B. D.; Kesler, O.; Rose, Lars

Air plasma spraying has been used to produce porous composite cathodes containing (La 0.8Sr 0.2) 0.98MnO 3- y (LSM) and yttria-stabilized zirconia (YSZ) for use in solid oxide fuel cells (SOFCs). Preliminary investigations focused on determining the range of plasma conditions under which each of the individual materials could be successfully deposited. A range of conditions was thereby determined that was suitable for the deposition of a composite cathode from pre-mixed LSM and YSZ powders. A number of composite cathodes were produced using different combinations of parameter values within the identified range according to a Uniform Design experimental grid. Coatings were then characterized for composition and microstructure using EDX and SEM. As a result of these tests, combinations of input parameter values were identified that are best suited to the production of coatings with microstructures appropriate for use in SOFC composite cathodes. A selection of coatings representative of the types of observed microstructures were then subjected to electrochemical testing to evaluate the performance of these cathodes. From these tests, it was found that, in general, the coatings that appeared to have the most suitable microstructures also had the highest electrochemical performances, provided that the deposition efficiency of both phases was sufficiently high.

Air plasma spray processing and electrochemical characterization of SOFC composite cathodes

Energy Technology Data Exchange (ETDEWEB)

White, B.D. [Department of Mechanical Engineering, The University of British Columbia, 2054-6250 Applied Sciences Lane, Vancouver, British Columbia (Canada); Kesler, O. [Department of Mechanical and Industrial Engineering, University of Toronto, 5 King' s College Road, Toronto, Ontario (Canada); Rose, Lars [Department of Materials Engineering, The University of British Columbia, 309-6350 Stores Road, Vancouver, British Columbia (Canada); National Research Council (Canada)

2008-03-15

Air plasma spraying has been used to produce porous composite cathodes containing (La{sub 0.8}Sr{sub 0.2}){sub 0.98}MnO{sub 3-y} (LSM) and yttria-stabilized zirconia (YSZ) for use in solid oxide fuel cells (SOFCs). Preliminary investigations focused on determining the range of plasma conditions under which each of the individual materials could be successfully deposited. A range of conditions was thereby determined that was suitable for the deposition of a composite cathode from pre-mixed LSM and YSZ powders. A number of composite cathodes were produced using different combinations of parameter values within the identified range according to a Uniform Design experimental grid. Coatings were then characterized for composition and microstructure using EDX and SEM. As a result of these tests, combinations of input parameter values were identified that are best suited to the production of coatings with microstructures appropriate for use in SOFC composite cathodes. A selection of coatings representative of the types of observed microstructures were then subjected to electrochemical testing to evaluate the performance of these cathodes. From these tests, it was found that, in general, the coatings that appeared to have the most suitable microstructures also had the highest electrochemical performances, provided that the deposition efficiency of both phases was sufficiently high. (author)

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

International Nuclear Information System (INIS)

Han, Binghong; Paulauskas, Tadas; Key, Baris; Peebles, Cameron; Park, Joong Sun

2017-01-01

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, homogeneity 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.

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

Science.gov (United States)

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.

Impedance of porous IT-SOFC LSCF:CGO composite cathodes

DEFF Research Database (Denmark)

Nielsen, Jimmi; Jacobsen, Torben; Wandel, Marie

2011-01-01

The impedance of technological relevant LSCF:CGO composite IT-SOFC cathodes was studied over a very wide performance range. This was experimentally achieved by impedance measurements on symmetrical cells with three different microstructures in the temperature range 550–850 °C. In order to account...... for the impedance spectra of the poor performing cathodes the Finite-Length-Gerischer (FLG) impedance was derived and applied to the impedance data. The FLG impedance describes for a given microstructure the situation where the cathode is made too thin from a cathode development point of view. The moderate...... performing cathodes showed a slightly suppressed Gerischer impedance, while the impedance spectra of the well performing cathodes showed the presence of an arc due to oxygen gas diffusion. The overall impedance of the well performing cathodes could be described with a slightly suppressed Gerischer impedance...

Biomass-Derived Oxygen and Nitrogen Co-Doped Porous Carbon with Hierarchical Architecture as Sulfur Hosts for High-Performance Lithium/Sulfur Batteries

Directory of Open Access Journals (Sweden)

Yan Zhao

2017-11-01

Full Text Available In this work, a facile strategy to synthesize oxygen and nitrogen co-doped porous carbon (ONPC is reported by one-step pyrolysis of waste coffee grounds. As-prepared ONPC possesses highly rich micro/mesopores as well as abundant oxygen and nitrogen co-doping, which is applied to sulfur hosts as lithium/sulfur batteries’ appropriate cathodes. In battery testing, the sulfur/oxygen and nitrogen co-doped porous carbon (S/ONPC composite materials reveal a high initial capacity of 1150 mAh·g−1 as well as a reversible capacity of 613 mAh·g−1 after the 100th cycle at 0.2 C. Furthermore, when current density increases to 1 C, a discharge capacity of 331 mAh·g−1 is still attainable. Due to the hierarchical porous framework and oxygen/nitrogen co-doping, the S/ONPC composite exhibits a high utilization of sulfur and good electrochemical performance via the immobilization of the polysulfides through strong chemical binding.

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

Science.gov (United States)

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

2016-12-01

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

A Lithium-Ion Battery using a 3 D-Array Nanostructured Graphene-Sulfur Cathode and a Silicon Oxide-Based Anode.

Science.gov (United States)

Benítez, Almudena; Di Lecce, Daniele; Elia, Giuseppe Antonio; Caballero, Álvaro; Morales, Julián; Hassoun, Jusef

2018-05-09

An efficient lithium-ion battery was assembled by using an enhanced sulfur-based cathode and a silicon oxide-based anode and proposed as an innovative energy-storage system. The sulfur-carbon composite, which exploits graphene carbon with a 3 D array (3DG-S), was synthesized by a reduction step through a microwave-assisted solvothermal technique and was fully characterized in terms of structure and morphology, thereby revealing suitable features for lithium-cell application. Electrochemical tests of the 3DG-S electrode in a lithium half-cell indicated a capacity ranging from 1200 to 1000 mAh g -1 at currents of C/10 and 1 C, respectively. Remarkably, the Li-alloyed anode, namely, Li y SiO x -C prepared by the sol-gel method and lithiated by surface treatment, showed suitable performance in a lithium half-cell by using an electrolyte designed for lithium-sulfur batteries. The Li y SiO x -C/3DG-S battery was found to exhibit very promising properties with a capacity of approximately 460 mAh g S -1 delivered at an average voltage of approximately 1.5 V over 200 cycles, suggesting that the characterized materials would be suitable candidates for low-cost and high-energy-storage applications. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Effect of Nickel Coated Multi-Walled Carbon Nanotubes on Electrochemical Performance of Lithium-Sulfur Rechargeable Batteries.

Science.gov (United States)

Wu, Xiao; Yao, Shanshan; Hou, Jinli; Jing, Maoxiang; Qian, Xinye; Shen, Xiangqian; Xiang, Jun; Xi, Xiaoming

2017-04-01

Conventional lithium-sulfur batteries suffer from severe capacity fade, which is induced by low electron conductivity and high dissolution of intermediated polysulfides. Recent studies have shown the metal (Pt, Au, Ni) as electrocatalyst of lithium polysulfides and improved the performance for lithium sulfur batteries. In this work, we present the nickel coated multi-walled carbon nanotubes (Ni-MWNTs) as additive materials for elemental sulfur positive electrodes for lithium-sulfur rechargeable batteries. Compared with MWNTs, the obtained Ni-MWNTs/sulfur composite cathode demonstrate a reversible specific capacity approaching 545 mAh after 200 cycles at a rate of 0.5C as well as improved cycling stability and excellent rate capacity. The improved electrochemical performance can be attributed to the fact the MWNTs shows a vital role on polysulfides adsorption and nickel has a catalytic effect on the redox reactions during charge–discharge process. Meanwhile, the Ni-MWNTs is a good electric conductor for sulfur cathode.

Dual-shell hollow polyaniline/sulfur-core/polyaniline composites improving the capacity and cycle performance of lithium–sulfur batteries

Energy Technology Data Exchange (ETDEWEB)

An, Yanling; Wei, Pan; Fan, Meiqiang, E-mail: fanmeiqiang@126.com; Chen, Da; Chen, Haichao; Ju, QiangJian; Tian, Guanglei; Shu, Kangying

2016-07-01

Highlights: • A dual core-shell hPANI/S/PANI composite was prepared in situ synthesis. • Cycle performance of the hPANI/S/PANI composite was enhanced. • The improvement was due to fine sulfur particles wrapped by two PANI films. • Some positive effects were elaborated. - Abstract: In this study, a dual-shell hollow polyaniline/sulfur-core/polyaniline (hPANI/S/PANI) composite was prepared by successively depositing PANI, S, and PANI on the surface of a template silicon sphere. The electrochemical properties of this composite were evaluated using a lithium plate as an anode in lithium/sulfur cells. The hPANI/S/PANI composite showed a discharge capacity of 572.2 mAh g{sup −1} after 214 cycles at 0.1 C, and the Coulombic efficiency was above 87% in the whole charge/discharge cycle. The improved cycle property of the hPANI/S/PANI composite can be ascribed to the fine sulfur particles homogeneously deposited on the PANI surface and sprawled inside the two PANI layers during the charge/discharge cycle. This behavior stabilized the nanostructure of sulfur and enhanced its conductivity.

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

Energy Technology Data Exchange (ETDEWEB)

Franz, Robert, E-mail: robert.franz@unileoben.ac.at; Mendez Martin, Francisca; Hawranek, Gerhard [Montanuniversität Leoben, Franz-Josef-Strasse 18, 8700 Leoben (Austria); Polcik, Peter [Plansee Composite Materials GmbH, Siebenbürgerstrasse 23, 86983 Lechbruck am See (Germany)

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 result 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.

Non-isothermal electrochemical model for lithium-ion cells with composite cathodes

Science.gov (United States)

Basu, Suman; Patil, Rajkumar S.; Ramachandran, Sanoop; Hariharan, Krishnan S.; Kolake, Subramanya Mayya; Song, Taewon; Oh, Dukjin; Yeo, Taejung; Doo, Seokgwang

2015-06-01

Transition metal oxide cathodes for Li-ion batteries offer high energy density and high voltage. Composites of these materials have shown excellent life expectancy and improved thermal performance. In the present work, a comprehensive non-isothermal electrochemical model for a Lithium ion cell with a composite cathode is developed. The present work builds on lithium concentration-dependent diffusivity and thermal gradient of cathode potential, obtained from experiments. The model validation is performed for a wide range of temperature and discharge rates. Excellent agreement is found for high and room temperature with moderate success at low temperatures, which can be attributed to the low fidelity of material properties at low temperature. Although the cell operation is limited by electronic conductivity of NCA at room temperature, at low temperatures a shift in controlling process is seen, and operation is limited by electrolyte transport. At room temperature, the lithium transport in Cathode appears to be the main source of heat generation with entropic heat as the primary contributor at low discharge rates and ohmic heat at high discharge rates respectively. Improvement in electronic conductivity of the cathode is expected to improve the performance of these composite cathodes and pave way for its wider commercialization.

Catalytic Surface Promotion of Composite Cathodes in Protonic Ceramic Fuel Cells

DEFF Research Database (Denmark)

Solis, Cecilia; Navarrete, Laura; Bozza, Francesco

2015-01-01

Composite cathodes based on an electronic conductor and a protonic conductor show advantages for protonic ceramic fuel cells. In this work, the performance of a La5.5WO11.25-δ/ La0.8Sr0.2MnO3+δ (LWO/LSM) composite cathode in a fuel cell based on an LWO protonic conducting electrolyte is shown...

Studies of local degradation phenomena in composite cathodes for lithium-ion batteries

International Nuclear Information System (INIS)

Kerlau, Marie; Marcinek, Marek; Srinivasan, Venkat; Kostecki, Robert M.

2007-01-01

LiNi 0.8 Co 0.15 Al 0.05 O 2 and LiNi 1/3 Co 1/3 Mn 1/3 O 2 composite cathodes were cycled in model cells to study interfacial phenomena that could lead to electrode degradation. Ex situ spectroscopic analysis of the tested cathodes, which suffered substantial power and capacity loss, showed that the state of charge (SOC) of oxide particles on the cathode surface was highly non-uniform despite the deep discharge of the Li-ion cell at the end of the test. The inconsistent kinetic behavior of individual oxide particles was attributed to the degradation of electronic pathways within the composite cathodes. A simple theoretical model based on a distributed network showed that an increase of the contact resistance between composite electrode particles may be responsible for non-uniform local kinetic behavior of individual oxide particles and the overall degradation of electrochemical performance of composite electrodes

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

Science.gov (United States)

Hagh, Nader; Skandan, Ganesh

2012-01-01

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

Vanadium Pentoxide-Based Composite Synthesized Using Microwave Water Plasma for Cathode Material in Rechargeable Magnesium Batteries

Directory of Open Access Journals (Sweden)

Tatsuhiko Yajima

2013-10-01

Full Text Available Multivalent cation rechargeable batteries are expected to perform well as high-capacity storage devices. Rechargeable magnesium batteries have an advantage in terms of resource utilization and safety. Here, we report on sulfur-doped vanadium pentoxide (S-V2O5 as a potential material for the cathodes of such a battery; S-V2O5 showed a specific capacity of 300 mAh·g−1. S-V2O5 was prepared by a method using a low-temperature plasma generated by carbon felt and a 2.45 GHz microwave generator. This study investigates the ability of S-V2O5 to achieve high capacity when added to metal oxide. The highest recorded capacity (420 mAh·g−1 was reached with MnO2 added to composite SMn-V2O5, which has a higher proportion of included sulfur than found in S-V2O5. Results from transmission electron microscopy, energy-dispersive X-ray spectroscopy, Micro-Raman spectroscopy, and X-ray photoelectron spectroscopy show that the bulk of the SMn-V2O5 was the orthorhombic V2O5 structure; the surface was a xerogel-like V2O5 and a solid solution of MnO2 and sulfur.

High-Capacity, High-Voltage Composite Oxide Cathode Materials

Science.gov (United States)

Hagh, Nader M.

2015-01-01

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

Cathode spot movements along the carbon fibres in carbon/carbon composites

International Nuclear Information System (INIS)

Zhang Chengyu; Qiao Shengru; Yang Zhimao; Ding Bingjun

2007-01-01

The cathode spot movements on a polyacrilonitrile (PAN)-based carbon felt reinforced C/C composite and a three dimensional PAN-based carbon fibre reinforced C/C composite (3D-C/C) were investigated by a scanning electron microscope and a digital high-speed video camera. It was found that the carbon fibres have a higher ability to withstand the vacuum arc erosion than the carbon matrix. The cathode spot walks on the matrix, rather than on the carbon fibres. The cathode spot motion is controlled by the architecture of carbon fibres in C/C. The cathode spots move along the carbon fibres by a step-by-step manner rather than a random walk. The cathode spot tracks spread over a wide zone on the 3D-C/C surface parallel to the carbon fibre. The average arc spreading velocity is estimated to be about 0.9 m s -1 and the transient arc spreading velocity is in the range of 0.54-4.5 m s -1

Comparative Study of Ether-Based Electrolytes for Application in Lithium-Sulfur Battery.

Science.gov (United States)

Carbone, Lorenzo; Gobet, Mallory; Peng, Jing; Devany, Matthew; Scrosati, Bruno; Greenbaum, Steve; Hassoun, Jusef

2015-07-01

Herein, we report the characteristics of electrolytes using various ether-solvents with molecular composition CH3O[CH2CH2O]nCH3, differing by chain length, and LiCF3SO3 as the lithium salt. The electrolytes, considered as suitable media for lithium-sulfur batteries, are characterized in terms of thermal properties (TGA, DSC), lithium ion conductivity, lithium interface stability, cyclic voltammetry, self-diffusion properties of the various components, and lithium transference number measured by NMR. Furthermore, the electrolytes are characterized in lithium cells using a sulfur-carbon composite cathode by galvanostatic charge-discharge tests. The results clearly evidence the influence of the solvent chain length on the species mobility within the electrolytes that directly affects the behavior in lithium sulfur cell. The results may effectively contribute to the progress of an efficient, high-energy lithium-sulfur battery.

Nanostructured nitrogen-doped mesoporous carbon derived from polyacrylonitrile for advanced lithium sulfur batteries

Energy Technology Data Exchange (ETDEWEB)

Liu, Ying; Zhao, Xiaohui; Chauhan, Ghanshyam S. [Department of Chemical Engineering and Research Institute for Green Energy Convergence Technology, Gyeongsang National University, 501 Jinju-daero, Jinju 660-701 (Korea, Republic of); Ahn, Jou-Hyeon, E-mail: jhahn@gnu.ac.kr [Department of Chemical Engineering and Research Institute for Green Energy Convergence Technology, Gyeongsang National University, 501 Jinju-daero, Jinju 660-701 (Korea, Republic of); Department of Materials Engineering and Convergence Technology and RIGET, Gyeongsang National University, 501 Jinju-daero, Jinju 660-701 (Korea, Republic of)

2016-09-01

Graphical abstract: Well-ordered nitrogen-doped mesoporous carbon materials were prepared by in-situ polymerization of polyacrylonitrile in SBA-15 template. The composite of sulfur and nitrogen-doped carbon was successfully used as a cathode material for lithium sulfur battery. - Highlights: • N-doped mesoporous carbons were prepared with PAN as carbon source. • Highly ordered pore system facilitates sulfur loading. • Ladder-type carbon matrix provides good structural stability for confining sulfur. • N-doping ensures an improved absorbability of soluble polysulfides. - Abstract: Nitrogen doping in carbon matrix can effectively improve the wettability of electrolyte and increase electric conductivity of carbon by ensuring fast transfer of ions. We synthesized a series of nitrogen-doped mesoporous carbons (CPANs) via in situ polymerization of polyacrylonitrile (PAN) in SBA-15 template followed by carbonization at different temperatures. Carbonization results in the formation of ladder structure which enhances the stability of the matrix. In this study, CPAN-800, carbon matrix synthesized by the carbonization at 800 °C, was found to possess many desirable properties such as high specific surface area and pore volume, moderate nitrogen content, and highly ordered mesoporous structure. Therefore, it was used to prepare S/CPAN-800 composite as cathode material in lithium sulfur (Li-S) batteries. The S/CPAN-800 composite was proved to be an excellent material for Li-S cells which delivered a high initial discharge capacity of 1585 mAh g{sup −1} and enhanced capacity retention of 862 mAh g{sup −1} at 0.1 C after 100 cycles.

Preparation of sulfur/multiple pore size porous carbon composite via gas-phase loading method for lithium-sulfur batteries

International Nuclear Information System (INIS)

Li, Long-Yan; Chen, Yan-Xiao; Guo, Xiao-Dong; Zhong, Ben-He; Zhong, Yan-Jun

2014-01-01

A porous carbon with multiple pore size distribution was synthesized, and regarded as a carrier to obtain the sulfur/carbon (S/C) composite via a gas-phase loading method. We proposed this novel gas-phase loading method by using a specially designed fluid-bed reactor to encapsulate and sequester gas-phase sulfur molecules into the porous carbon in current study. The nitrogen Brunauer-Emmett-Teller (BET), scanning electron microscopy (SEM) and X-ray powder diffraction (XRD) characterizations were investigated on both the porous carbon and the sulfur/carbon composite. The results show that the gas-phase loading method contributes to the combination of sulfur molecules and matrix porous carbon. Furthermore, the sulfur/multiple pore size distribution carbon composite based on the gas-phase loading method demonstrate an excellent electrochemical property. The initial specific discharge capacity is 795.0 mAh g −1 at 800 mA g −1 , with a capacity retention of 86.3% after 100 cycles

Sulfur based electrode materials for secondary batteries

Science.gov (United States)

Hao, Yong

Developing next generation secondary batteries has attracted much attention in recent years due to the increasing demand of high energy and high power density energy storage for portable electronics, electric vehicles and renewable sources of energy. This dissertation investigates sulfur based advanced electrode materials in Lithium/Sodium batteries. The electrochemical performances of the electrode materials have been enhanced due to their unique nano structures as well as the formation of novel composites. First, a nitrogen-doped graphene nanosheets/sulfur (NGNSs/S) composite was synthesized via a facile chemical reaction deposition. In this composite, NGNSs were employed as a conductive host to entrap S/polysulfides in the cathode part. The NGNSs/S composite delivered an initial discharge capacity of 856.7 mAh g-1 and a reversible capacity of 319.3 mAh g-1 at 0.1C with good recoverable rate capability. Second, NGNS/S nanocomposites, synthesized using chemical reaction-deposition method and low temperature heat treatment, were further studied as active cathode materials for room temperature Na-S batteries. Both high loading composite with 86% gamma-S8 and low loading composite with 25% gamma-S8 have been electrochemically evaluated and compared with both NGNS and S control electrodes. It was found that low loading NGNS/S composite exhibited better electrochemical performance with specific capacity of 110 and 48 mAh g-1 at 0.1C at the 1st and 300th cycle, respectively. The Coulombic efficiency of 100% was obtained at the 300th cycle. Third, high purity rock-salt (RS), zinc-blende (ZB) and wurtzite (WZ) MnS nanocrystals with different morphologies were successfully synthesized via a facile solvothermal method. RS-, ZB- and WZ-MnS electrodes showed the capacities of 232.5 mAh g-1, 287.9 mAh g-1 and 79.8 mAh g-1 at the 600th cycle, respectively. ZB-MnS displayed the best performance in terms of specific capacity and cyclability. Interestingly, MnS electrodes

Strong Capillarity, Chemisorption, and Electrocatalytic Capability of Crisscrossed Nanostraws Enabled Flexible, High-Rate, and Long-Cycling Lithium-Sulfur Batteries.

Science.gov (United States)

Ma, Lianbo; Zhang, Wenjun; Wang, Lei; Hu, Yi; Zhu, Guoyin; Wang, Yanrong; Chen, Renpeng; Chen, Tao; Tie, Zuoxiu; Liu, Jie; Jin, Zhong

2018-05-22

The development of flexible lithium-sulfur (Li-S) batteries with high energy density and long cycling life are very appealing for the emerging flexible, portable, and wearable electronics. However, the progress on flexible Li-S batteries was limited by the poor flexibility and serious performance decay of existing sulfur composite cathodes. Herein, we report a freestanding and highly flexible sulfur host that can simultaneously meet the flexibility, stability, and capacity requirements of flexible Li-S batteries. The host consists of a crisscrossed network of carbon nanotubes reinforced CoS nanostraws (CNTs/CoS-NSs). The CNTs/CoS-NSs with large inner space and high conductivity enable high loading and efficient utilization of sulfur. The strong capillarity effect and chemisorption of CNTs/CoS-NSs to sulfur species were verified, which can efficiently suppress the shuttle effect and promote the redox kinetics of polysulfides. The sulfur-encapsulated CNTs/CoS-NSs (S@CNTs/CoS-NSs) cathode in Li-S batteries exhibits superior performance, including high discharge capacity, rate capability (1045 mAh g -1 at 0.5 C and 573 mAh g -1 at 5.0 C), and cycling stability. Intriguingly, the soft-packed Li-S batteries based on S@CNTs/CoS-NSs cathode show good flexibility and stability upon bending.

Construction of tubular polypyrrole-wrapped biomass-derived carbon nanospheres as cathode materials for lithium–sulfur batteries

International Nuclear Information System (INIS)

Yu, Qiuhong; Lu, Yang; Peng, Tao; Hou, Xiaoyi; Luo, Rongjie; Wang, Yange; Yan, Hailong; Luo, Yongsong; Liu, Xianming; Kim, Jang-Kyo

2017-01-01

A promising hybrid material composed of tubular polypyrrole (T-PPy)-wrapped monodisperse biomass-derived carbon nanospheres (BCSs) was first synthesized successfully via a simple hydrothermal approach by using watermelon juice as the carbon source, and further used as an anchoring object for sulfur (S) of lithium–sulfur (Li–S) batteries. The use of BCSs with hydrophilic nature as a framework could provide large interface areas between the active materials and electrolyte, and improve the dispersion of T-PPy, which could help in the active material utilization. As a result, BCS@T-PPy/S as a cathode material exhibited a high capacity of 1143.6 mA h g −1 and delivered a stable capacity up to 685.8 mA h g −1 after 500 cycles at 0.5 C, demonstrating its promising application for rechargeable Li–S batteries. (paper)

Composite cathode based on yttria stabilized bismuth oxide for low-temperature solid oxide fuel cells

International Nuclear Information System (INIS)

Xia Changrong; Zhang Yuelan; Liu Meilin

2003-01-01

Composites consisting of silver and yttria stabilized bismuth oxide (YSB) have been investigated as cathodes for low-temperature honeycomb solid oxide fuel cells with stabilized zirconia as electrolytes. At 600 deg. C, the interfacial polarization resistances of a porous YSB-Ag cathode is about 0.3 Ω cm 2 , more than one order of magnitude smaller than those of other reported cathodes on stabilized zirconia. For example, the interfacial resistances of a traditional YSZ-lanthanum maganites composite cathode is about 11.4 Ω cm 2 at 600 deg. C. Impedance analysis indicated that the performance of an YSB-Ag composite cathode fired at 850 deg. C for 2 h is severely limited by gas transport due to insufficient porosity. The high performance of the YSB-Ag cathodes is very encouraging for developing honeycomb fuel cells to be operated at temperatures below 600 deg. C

Polyaniline-Coated Activated Carbon Aerogel/Sulfur Composite for High-performance Lithium-Sulfur Battery

Science.gov (United States)

Tang, Zhiwei; Jiang, Jinglin; Liu, Shaohong; Chen, Luyi; Liu, Ruliang; Zheng, Bingna; Fu, Ruowen; Wu, Dingcai

2017-12-01

An activated carbon aerogel (ACA-500) with high surface area (1765 m2 g-1), pore volume (2.04 cm3 g-1), and hierarchical porous nanonetwork structure is prepared through direct activation of organic aerogel (RC-500) with a low potassium hydroxide ratio (1:1). Based on this substrate, a polyaniline (PANi)-coated activated carbon aerogel/sulfur (ACA-500-S@PANi) composite is prepared via a simple two-step procedure, including melt-infiltration of sublimed sulfur into ACA-500, followed by an in situ polymerization of aniline on the surface of ACA-500-S composite. The obtained ACA-500-S@PANi composite delivers a high reversible capacity up to 1208 mAh g-1 at 0.2C and maintains 542 mAh g-1 even at a high rate (3C). Furthermore, this composite exhibits a discharge capacity of 926 mAh g-1 at the initial cycle and 615 mAh g-1 after 700 cycles at 1C rate, revealing an extremely low capacity decay rate (0.48‰ per cycle). The excellent electrochemical performance of ACA-500-S@PANi can be attributed to the synergistic effect of hierarchical porous nanonetwork structure and PANi coating. Activated carbon aerogels with high surface area and unique three-dimensional (3D) interconnected hierarchical porous structure offer an efficient conductive network for sulfur, and a highly conductive PANi-coating layer further enhances conductivity of the electrode and prevents the dissolution of polysulfide species.

Sulfur biogeochemistry of oil sands composite tailings

Energy Technology Data Exchange (ETDEWEB)

Warren, Lesley; Stephenson, Kate [Earth Sciences, McMaster University (Canada)], email: warrenl@mcmaster.ca; Penner, Tara [Syncrude Environmental Research (Canada)

2011-07-01

This paper discusses the sulfur biogeochemistry of oil sands composite tailings (CT). The Government of Alberta is accelerating reclamation activities on composite tailings. As a CT pilot reclamation operation, Syncrude is currently constructing the first freshwater fen. Minor unpredicted incidents with H2S gas released from the dewatering process associated with these reclamations have been reported. The objective of this study is to ascertain the connection between microbial activity and H2S generation within CT and to assess the sulfur biogeochemistry of untreated and treated (fen) CT over seasonal and annual timescales. The microbial geochemical interactions taking place are shown using a flow chart. CT is composed of gypsum, sand, clay and organics like naphthenic acids and bitumen. Sulfur and Fe cycling in mining systems and their microbial activities are presented. The chemistry and the processes involved within CT are also given along with the results. It can be said that the diverse Fe and S metabolizing microorganisms confirm the ecology involved in H2S dynamics.

Lithiated Nafion as polymer electrolyte for solid-state lithium sulfur batteries using carbon-sulfur composite cathode

Science.gov (United States)

Gao, Jing; Sun, Chunshui; Xu, Lei; Chen, Jian; Wang, Chong; Guo, Decai; Chen, Hao

2018-04-01

Due to flexible property and light weight, the lithiated Nafion membrane swollen with PC (PC-Li-Nafion) has been employed as both solid-state electrolyte and separator to fabricate solid-state Li-S cells. The electrochemical measurements of PC-Li-Nafion membrane show that its Li-ion transference number is 0.928, ionic conductivity of 2.1 × 10-4 S cm-1 can be achieved at 70 °C and its electrochemical window is 0 ∼ +4.1 V vs. Li+/Li. It is observed that the Li dendrites are suppressed by using PC-Li-Nafion membrane due to its single-ion conducting property. The amounts of Li-Nafion resin binder and conductive carbon in the cathode are optimized as 40% and 10% respectively to make a balance of ionic and electronic conductivities. A thin-layer Li-Nafion resin with a thickness of around 2 μm is fabricated between the cathode and PC-Li-Nafion membrane to improve the interfacial contact and further enhance the specific capacity of the cell. When measured at 70 °C, the Li-S cell delivers a reversible specific capacity of 1072.8 mAh g-1 (S) at 0.05 C and 895 mAh g-1 (S) at 1 C. The capacity retention at 1 C is 89% after 100 cycles. These results suggest that high-performance solid-state Li-S cells can be fabricated with the Li-Nafion polymer electrolyte.

A Cable-Shaped Lithium Sulfur Battery.

Science.gov (United States)

Fang, Xin; Weng, Wei; Ren, Jing; Peng, Huisheng

2016-01-20

A carbon nanostructured hybrid fiber is developed by integrating mesoporous carbon and graphene oxide into aligned carbon nanotubes. This hybrid fiber is used as a 1D cathode to fabricate a new cable-shaped lithium-sulfur battery. The fiber cathode exhibits a decent specific capacity and lifespan, which makes the cable-shaped lithium-sulfur battery rank far ahead of other fiber-shaped batteries. © 2015 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Sulfur contents and sulfur-isotope compositions of thiotrophic symbioses in bivalve molluscs and vestimentiferan worms

Science.gov (United States)

Vetter, R.D.; Fry, B.

1998-01-01

Total sulfur (S(TOT)), elemental sulfur (S??) and sulfur-isotope compositions (??34S) of marine animals were analyzed to determine whether these chemical characteristics could help distinguish animals with a sulfur-based, thiotrophic nutrition from animals whose nutrition is based on methanotrophy or on more normal consumption of phytoplankton-derived organic matter. The presence of S??was almost entirely confined to the symbiont-containing tissues of thiotrophs, but was sometimes undetectable in thiotrophic species where sulfide availability was probably low. When S??contents were subtracted, the remaining tissue-sulfur concentrations were similar for all nutritional groups. ??34S values were typically lower for thiotrophs than for other groups, although there was overlap in methanotroph and thiotroph values at some sites. Field evidence supported the existence of small to moderate (1 to 10???)34S fractionations in the uptake of sulfides and metabolism of thiosulfate. In general, a total sulfur content of >3% dry weight, the presence of elemental sulfur, and ??34S values less than + 5??? can be used to infer a thiotrophic mode of nutrition.

Facile synthesis of graphene oxide @ mesoporous carbon hybrid nanocomposites for lithium sulfur battery

International Nuclear Information System (INIS)

Bao, Weizhai; Zhang, Zhian; Chen, Wei; Zhou, Chengkun; Lai, Yanqing; Li, Jie

2014-01-01

Graphical abstract: - Highlights: • A novel design and synthesis of GO@Meso-C using GO@MOF-5 as precursor. • GO@Meso-C hybrid material as a host material was applied for sulfur cathode. • Electrochemical performances were improved in sulfur cathode using Go@Meso-C. - Abstract: We present a design and synthesis of a hierarchical architecture of graphene oxide @ mesoporous carbon (GO@Meso-C) using graphene oxide @ metal-organic framework hybrid materials (GO@MOF-5) as both the template and precursor. Active sulfur is encapsulated into the GO@Meso-C matrix prepared via carbonize GO@MOF-5 polyhedrons for high performance lithium sulfur battery. The initial and 100th cycle discharge capacity of GO@Meso-C/S sulfur cathode are as high as 1122 mAh g −1 and 820 mAh g −1 at a current rate of 0.2 C. The remarkably high special capacity and capacity retention rate indicate that the GO@Meso-C is a promising host material for the sulfur cathode in the lithium sulfur battery applications

Deposition of Composite LSCF-SDC and SSC-SDC Cathodes by Axial-Injection Plasma Spraying

Science.gov (United States)

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.

Mathematical modeling of current density distribution in composite cathode of solid oxide fuel cells. Paper no. IGEC-1-099

International Nuclear Information System (INIS)

Kenney, B.; Karan, K.

2005-01-01

Cathodes processes in a solid oxide fuel cell (SOFC) are thought to dominate the overall electrochemical losses. One strategy for minimizing the cathode electrochemical losses in a state-of-the-art SOFC that utilize lanthanum-strontium-manganate (LSM) electrocatalyst and yttria-stabilized-zirconia (YSZ) electrolyte is to utilize composite cathodes comprising a mixture of LSM and YSZ. Composite cathodes improve performance by extending the active reaction zone from electrolyte-electrode interface to throughout the electrode. In this study, a two-dimensional composite cathode model was developed to assess cathode performance in terms of current density distributions. The model results indicate that geometric and microstructural parameters strongly influence current density distribution. In addition electrode composition affects magnitude and distribution of current. An optimum composition for equal-sized LSM/YSZ is 40 vol% LSM and 60 vol% YSZ at 900 o C. (author)

Self-assembled peptides for coating of active sulfur nanoparticles in lithium–sulfur battery

International Nuclear Information System (INIS)

Jewel, Yead; Yoo, Kisoo; Liu, Jin; Dutta, Prashanta

2016-01-01

Development of lithium–sulfur (Li–S) battery is hindered by poor cyclability due to the loss of sulfur, although Li–S battery can provide high energy density. Coating of sulfur nanoparticles can help maintain active sulfur in the cathode of Li–S battery, and hence increase the cyclability. Among myriad of coating materials, synthetic peptides are very attractive because of their spontaneous self-assembly as well as electrical conductive characteristics. In this study, we explored the use of various synthetic peptides as a coating material for sulfur nanoparticles. Atomistic simulations were carried out to identify optimal peptide structure and density for coating sulfur nanoparticles. Three different peptide models, poly-proline, poly(leucine–lysine) and poly-histidine, are selected for this study based on their peptide–peptide and peptide-sulfur interactions. Simulation results show that both poly-proline and poly(leucine–lysine) can form self-assembled coating on sulfur nanoparticles (2–20 nm) in pyrrolidinone, a commonly used solvent for cathode slurry. We also studied the structural integrity of these synthetic peptides in organic [dioxolane (DOL) and dimethoxyethane (DME)] electrolyte used in Li–S battery. Both peptides show stable structures in organic electrolyte (DOL/DME) used in Li–S battery. Furthermore, the dissolution of sulfur molecules in organic electrolyte is investigated in the absence and presence of these peptide coatings. It was found that only poly(leucine–lysine)-based peptide can most effectively suppress the sulfur loss in electrolyte, suggesting its potential applications in Li–S battery as a coating material.Graphical abstract

Novel nitrogen-doped hierarchically porous coralloid carbon materials as host matrixes for lithium–sulfur batteries

International Nuclear Information System (INIS)

Yang, Jing; Wang, Shuyuan; Ma, Zhipeng; Du, Zhiling; Li, Chunying; Song, Jianjun; Wang, Guiling; Shao, Guangjie

2015-01-01

Highlights: • Nitrogen-doped hierarchically porous coralloid carbon/sulfur composites were prepared • Nitrogen atoms were introduced to improve electrochemical properties • The intriguing structural features benefited discharge capacity and cycling stability - Abstract: Nitrogen-doped hierarchically porous coralloid carbon/sulfur composites (N-HPCC/S) served as attractive cathode materials for lithium–sulfur (Li–S) batteries were fabricated for the first time. The nitrogen-doped hierarchically porous coralloid carbon (N-HPCC) with an appropriate nitrogen content (1.29 wt%) was synthesized via a facile hydrothermal approach, combined with subsequent carbonization–activation. The N-HPCC/S composites prepared by a simple melt–diffusion method displayed an excellent electrochemical performance. With a high sulfur content (58 wt%) in the total electrode weight, the N-HPCC/S cathode delivered a high initial discharge capacity of 1626.8 mA h g −1 and remained high up to 1086.3 mA h g −1 after 50 cycles at 100 mA g −1 , which is about 1.86 times as that of activated carbon. Particularly, the reversible discharge capacity still maintained 607.2 mA h g −1 after 200 cycles even at a higher rate of 800 mA g −1 . The enhanced electrochemical performance was attributed to the synergetic effect between the intriguing hierarchically porous coralloid structure and appropriate nitrogen doping, which could effectively trap polysulfides, alleviate the volume expansion, enhance the electronic conductivity and improve the surface interaction between the carbon matrix and polysulfides

Graphene oxide as a sulfur immobilizer in high performance lithium/sulfur cells

Science.gov (United States)

Zhang, Yuegang; Cairns, Elton J.; Ji, Liwen; Rao, Mumin

2017-06-06

The loss of sulfur cathode material as a result of polysulfide dissolution causes significant capacity fading in rechargeable lithium/sulfur cells. Embodiments of the invention use a chemical approach to immobilize sulfur and lithium polysulfides via the reactive functional groups on graphene oxide. This approach obtains a uniform and thin (.about.tens of nanometers) sulfur coating on graphene oxide sheets by a chemical reaction-deposition strategy and a subsequent low temperature thermal treatment process. Strong interaction between graphene oxide and sulfur or polysulfides demonstrate lithium/sulfur cells with a high reversible capacity of 950-1400 mAh g.sup.-1, and stable cycling for more than 50 deep cycles at 0.1 C.

Graphene oxide as a sulfur immobilizer in high performance lithium/sulfur cells

Energy Technology Data Exchange (ETDEWEB)

Zhang, Yuegang; Cairns, Elton J.; Ji, Liwen; Rao, Mumin

2017-12-26

The loss of sulfur cathode material as a result of polysulfide dissolution causes significant capacity fading in rechargeable lithium/sulfur cells. Embodiments of the invention use a chemical approach to immobilize sulfur and lithium polysulfides via the reactive functional groups on graphene oxide. This approach obtains a uniform and thin (.about.tens of nanometers) sulfur coating on graphene oxide sheets by a chemical reaction-deposition strategy and a subsequent low temperature thermal treatment process. Strong interaction between graphene oxide and sulfur or polysulfides demonstrate lithium/sulfur cells with a high reversible capacity of 950-1400 mAh g.sup.-1, and stable cycling for more than 50 deep cycles at 0.1 C.

Effects of compatibility of polymer binders with solvate ionic liquid electrolytes on discharge and charge reactions of lithium-sulfur batteries

Science.gov (United States)

Nakazawa, Toshitada; Ikoma, Ai; Kido, Ryosuke; Ueno, Kazuhide; Dokko, Kaoru; Watanabe, Masayoshi

2016-03-01

Electrochemical reactions in Li-S cells with a solvate ionic liquid (SIL) electrolyte composed of tetraglyme (G4) and Li[TFSA] (TFSA: bis(trifluoromethanesulfonyl)amide) are studied. The sulfur cathode (S cathode) comprises sulfur, carbon powder, and a polymer binder. Poly(ethylene oxide) (PEO) and poly(vinyl alcohol) (PVA-x) with different degrees of saponification (x%) are used as binders to prepare the composite cathodes. For the Li-S cell containing PEO binder, lithium polysulfides (Li2Sm, 2 ≤ m ≤ 8), reaction intermediates of the S cathode, dissolve into the electrolyte, and Li2Sm acts as a redox shuttle in the Li-S cell. In contrast, in the Li-S cell with PVA-x binder, the dissolution of Li2Sm is suppressed, leading to high columbic efficiencies during charge-discharge cycles. The compatibility of the PVA-x binder with the SIL electrolyte changes depending on the degree of saponification. Decreasing the degree of saponification leads to increased electrolyte uptake by the PVA-x binder, increasing the charge and discharge capacities of Li-S cell. The rate capability of Li-S cell is also enhanced by the partial swelling of the PVA-x binder. The enhanced performance of Li-S cell containing PVA-x is attributed to the lowering of resistance of Li+ ion transport in the composite cathode.

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

Science.gov (United States)

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.

Mechanical and physical properties of wood fiber-reinforced, sulfur-based wood composites

Science.gov (United States)

Chung-Yun Hse; Ben S. Bryant

1993-01-01

Sulfur-based composite was made from sulfur impregnated, oven dried, wet-formed fiber mats. The fiber mats consisted of a 50/50 mixture of recycled newsprint pulp and mechanical hardwood pulp from several species made from chips in a laboratory refiner. The thickness of the composites was 0.125 inch and the specific gravity of the unimpregnated fiber mat was 0.2. The...

Microstructural characterization of composite cobaltite and lanthanum-based ceria for use as fuel cell cathodes

International Nuclear Information System (INIS)

Rodrigues, E.R.T.; Nascimento, R.M.; Miranda, A.C. de; Lima, A.M. de; Macedo, D.A.

2016-01-01

Fuel cells are devices that convert chemical energy into electricity via redox reactions. In this work, the lanthanum cobaltite doped with strontium and iron (La_0_,_6Sr_0_,_4Co_0_,_2Fe_0_,_8O_3 - LSCF) a traditional cathodes material of the fuel cell was mixed with an electrolyte material (composite) to the base ceria doped with gadolinia and a eutectic mixture of lithium carbonates and sodium (CGO-NLC). The powders of LSCF and CGO-NLC were obtained by the citrate method and mixed to obtain a composite cathode. Samples obtained by uniaxial pressure between 5 and 10 MPa were sintered at 1100°C and investigated by X-ray diffraction, scanning electron microscopy and micro hardness test. A symmetric cell cathode / electrolyte / cathode, obtained by co-pressing and co-sintering was investigated by electron microscopy. The results indicated that the composite is chemically stable up to the sintering temperature used. The hardness ranged between 51 and 227 HV. (author)

Fabrication of Lanthanum Strontium Cobalt Ferrite-Gadolinium-Doped Ceria Composite Cathodes Using a Low-Price Inkjet Printer.

Science.gov (United States)

Han, Gwon Deok; Choi, Hyung Jong; Bae, Kiho; Choi, Hyeon Rak; Jang, Dong Young; Shim, Joon Hyung

2017-11-15

In this work, we have successfully fabricated lanthanum strontium cobalt ferrite (LSCF)-gadolinium-doped ceria (GDC) composite cathodes by inkjet printing and demonstrated their functioning in solid oxide fuel cells (SOFCs). The cathodes are printed using a low-cost HP inkjet printer, and the LSCF and GDC source inks are synthesized with fluidic properties optimum for inkjet printing. The composition and microstructure of the LSCF and GDC layers are successfully controlled by controlling the color level in the printed images and the number of printing cycles, respectively. Anode-support type SOFCs with optimized LSCF-GDC composite cathodes synthesized by our inkjet printing method have achieved a power output of over 570 mW cm -2 at 650 °C, which is comparable to the performance of a commercial SOFC stack. Electrochemical impedance analysis is carried out to establish a relationship between the cell performance and the compositional and structural characteristics of the printed LSCF-GDC composite cathodes.

Sulphured Polyacrylonitrile Composite Analysed by in operando UV-Visible Spectroscopy and 4-electrode Swagelok Cell.

Science.gov (United States)

Dominko, Robert; Patel, Manu U M; Bele, Marjan; Pejovnik, Stane

2016-01-01

The electrochemical characteristics of sulfurized polyacrylonitrile composite (PAN/S) cathodes were compared with the commonly used carbon/S-based composite material. The difference in the working mechanism of these composites was examined. Analytical investigations were performed on both kinds of cathode electrode composites by using two reliable analytical techniques, in-situ UV-Visible spectroscopy and a four-electrode Swagelok cell. This study differentiates the working mechanisms of PAN/S composites from conventional elemental sulphur/carbon composite and also sheds light on factors that could be responsible for capacity fading in the case of PAN/S composites.

Research on the Composition and Distribution of Organic Sulfur in Coal.

Science.gov (United States)

Zhang, Lanjun; Li, Zenghua; Yang, Yongliang; Zhou, Yinbo; Li, Jinhu; Si, Leilei; Kong, Biao

2016-05-13

The structure and distribution of organic sulfur in coals of different rank and different sulfur content were studied by combining mild organic solvent extraction with XPS technology. The XPS results have shown that the distribution of organic sulfur in coal is related to the degree of metamorphism of coal. Namely, thiophenic sulfur content is reduced with decreasing metamorphic degree; sulfonic acid content rises with decreasing metamorphic degree; the contents of sulfate sulfur, sulfoxide and sulfone are rarely related with metamorphic degree. The solvent extraction and GC/MS test results have also shown that the composition and structure of free and soluble organic sulfur small molecules in coal is closely related to the metamorphic degree of coal. The free organic sulfur small molecules in coal of low metamorphic degree are mainly composed of aliphatic sulfides, while those in coal of medium and high metamorphic degree are mainly composed of thiophenes. Besides, the degree of aromatization of organic sulfur small molecules rises with increasing degree of coalification.

A combined theoretical and experimental study on the oxygenated graphitic carbon nitride as a promising sulfur host for lithium-sulfur batteries

Science.gov (United States)

He, Feng; Li, Kai; Yin, Cong; Ding, Yingchun; Tang, Hao; Wang, Ying; Wu, Zhijian

2018-01-01

To effectively restrain the dissolution of soluble polysulfides and fully utilize the active sulfur materials in lithium-sulfur (Li-S) batteries, host materials with unique compositions and porous structures have been pursued. Herein, we have investigated the mechanism of the excellent activity of oxygenated g-C3N4 for Li-S batteries from theoretical perspective, and the further experiment confirms that our O-g-C3N4-S cathode exhibits much better electrochemical performance compared with those in previous reports. Our DFT calculations reveal that the oxygenated material has better electrical conductivity and stronger adsorption ability with the Li2Sx species compared with the pristine g-C3N4 and other two-dimensional (2D) materials. Furthermore, we have confirmed experimentally that the O-g-C3N4-S composite cathode exhibits excellent electrochemical performance in Li-S batteries with high reversible discharge capacity of 1030 mAh g-1 after 100 cycles at 0.2 C, great rate capability with the discharge capacity of 364 mAh g-1 even at 5.0 C, and outstanding long-term cyclic stability with the discharge capacity of 465 mAh g-1 after 1000 cycles at 1.0 C (capacity decay was only 0.046% per cycle). Our results also suggest that theoretical study will play a significant role in predicting and screening novel materials with better performance.

Exploring hierarchical FeS2/C composite nanotubes arrays as advanced cathode for lithium ion batteries

Science.gov (United States)

Pan, G. X.; Cao, F.; Xia, X. H.; Zhang, Y. J.

2016-11-01

Rational construction of advanced FeS2 cathode is one of research hotspots, and of great importance for developing high-performance lithium ion batteries (LIBs). Herein we report a facile hydrolysis-sulfurization method for fabrication of FeS2/C nanotubes arrays with the help of sacrificial Co2(OH)2CO3 nanowires template and glucose carbonization. Self-supported FeS2/C nanotubes consist of interconnected nanoburrs of 5-20 nm, and show hierarchical porous structure. The FeS2/C nanotubes arrays are demonstrated with enhanced cycling life and noticeable high-rate capability with capacities ranging from 735 mAh g-1 at 0.25 C to 482 mAh g-1 at 1.5 C, superior to those FeS2 counterparts in the literature. The composite nanotubes arrays architecture plays positive roles in the electrochemical enhancement due to combined advantages of large electrode-electrolyte contact area, good strain accommodation, improved electrical conductivity, and enhanced structural stability.

A Combined Thermodynamics & Computational Method to Assess Lithium Composition in Anode and Cathode of Lithium Ion Batteries

International Nuclear Information System (INIS)

Zhang, Wenyu; Jiang, Lianlian; Van Durmen, Pauline; Saadat, Somaye; Yazami, Rachid

2016-01-01

With aim to address the open question of accurate determination of lithium composition in anode and cathode at a defined state of charge (SOC) of lithium ion batteries (LIB), we developed a method combining electrochemical thermodynamic measurements (ETM) and computational data fitting protocol. It is a common knowledge that in a lithium ion battery the SOC of anode and cathode differ from the SOC of the full-cell. Differences are in large part due to irreversible lithium losses within cell and to electrode mass unbalance. This implies that the lithium composition range in anode and in cathode during full charge and discharge cycle in full-cell is different from the composition range achieved in lithium half-cells of anode and cathode over their respective full SOC ranges. To the authors knowledge there is no unequivocal and practical method to determine the actual lithium composition of electrodes in a LIB, hence their SOC. Yet, accurate lithium composition assessment is fundamental not only for understanding the physics of electrodes but also for optimizing cell performances, particularly energy density and cycle life.

Modeling the Effects of the Cathode Composition of a Lithium Iron Phosphate Battery on the Discharge Behavior

Directory of Open Access Journals (Sweden)

Won Il Cho

2013-10-01

Full Text Available This paper reports a modeling methodology to predict the effects on the discharge behavior of the cathode composition of a lithium iron phosphate (LFP battery cell comprising a LFP cathode, a lithium metal anode, and an organic electrolyte. A one-dimensional model based on a finite element method is presented to calculate the cell voltage change of a LFP battery cell during galvanostatic discharge. To test the validity of the modeling approach, the modeling results for the variations of the cell voltage of the LFP battery as a function of time are compared with the experimental measurements during galvanostatic discharge at various discharge rates of 0.1C, 0.5C, 1.0C, and 2.0C for three different compositions of the LFP cathode. The discharge curves obtained from the model are in good agreement with the experimental measurements. On the basis of the validated modeling approach, the effects of the cathode composition on the discharge behavior of a LFP battery cell are estimated. The modeling results exhibit highly nonlinear dependencies of the discharge behavior of a LFP battery cell on the discharge C-rate and cathode composition.

Improved Cyclability of Liquid Electrolyte Lithium/Sulfur Batteries by Optimizing Electrolyte/Sulfur Ratio

Directory of Open Access Journals (Sweden)

Sheng S. Zhang

2012-12-01

Full Text Available A liquid electrolyte lithium/sulfur (Li/S cell is a liquid electrochemical system. In discharge, sulfur is first reduced to highly soluble Li2S8, which dissolves into the organic electrolyte and serves as the liquid cathode. In solution, lithium polysulfide (PS undergoes a series of complicated disproportionations, whose chemical equilibriums vary with the PS concentration and affect the cell’s performance. Since the PS concentration relates to a certain electrolyte/sulfur (E/S ratio, there is an optimized E/S ratio for the cyclability of each Li/S cell system. In this work, we study the optimized E/S ratio by measuring the cycling performance of Li/S cells, and propose an empirical method for determination of the optimized E/S ratio. By employing an electrolyte of 0.25 m LiSO3CF3-0.25 m LiNO3 dissolved in a 1:1 (wt:wt mixture of dimethyl ether (DME and 1,3-dioxolane (DOL in an optimized E/S ratio, we show that the Li/S cell with a cathode containing 72% sulfur and 2 mg cm−2 sulfur loading is able to retain a specific capacity of 780 mAh g−1 after 100 cycles at 0.5 mA cm−2 between 1.7 V and 2.8 V.

Fuel composition effect on cathode airflow control in fuel cell gas turbine hybrid systems

Science.gov (United States)

Zhou, Nana; Zaccaria, Valentina; Tucker, David

2018-04-01

Cathode airflow regulation is considered an effective means for thermal management in solid oxide fuel cell gas turbine (SOFC-GT) hybrid system. However, performance and controllability are observed to vary significantly with different fuel compositions. Because a complete system characterization with any possible fuel composition is not feasible, the need arises for robust controllers. The sufficiency of robust control is dictated by the effective change of operating state given the new composition used. It is possible that controller response could become unstable without a change in the gains from one state to the other. In this paper, cathode airflow transients are analyzed in a SOFC-GT system using syngas as fuel composition, comparing with previous work which used humidified hydrogen. Transfer functions are developed to map the relationship between the airflow bypass and several key variables. The impact of fuel composition on system control is quantified by evaluating the difference between gains and poles in transfer functions. Significant variations in the gains and the poles, more than 20% in most cases, are found in turbine rotational speed and cathode airflow. The results of this work provide a guideline for the development of future control strategies to face fuel composition changes.

Sulfur Isotope Composition of Some Polymetallic Deposits in the Republic of Macedonia

International Nuclear Information System (INIS)

Serafimovski, Todor; Tasev, Goran

2005-01-01

The attempt to obtain an exact information about the origin of sulfur and other metals present in polymetallic deposits at the territory of the Republic of Macedonia have resulted in a detailed sulfur isotope composition study, which have enclosed the following deposits: Toranica, Sasa, Zletovo, Buchim and Alshar deposit. Results obtained for the formerly mentioned deposits have shown that sulfur isotope composition β 34 S is in the range -7.52 to +2.18 per mils in Toranica, -1.22 -- +6.94 per mils in Sasa, -3.12 -- +3.40 per mils in Zletovo (without ore associated barites), +0.00 to +2.53 per mils in Buchim (the narrowest range of all studied deposits) and -6.84 to +0.351 per mils β 34 S in Alshar. Therefore, the most probably origin of primary sulfur in studied deposits from Earth's crust or eventually Upper Mantle. Such sources of sulfur and other mineralizing metals confirmed the theories about the endo gene origin of mineralization fluids, which have formed studied deposits. (Author)

A highly efficient polysulfide mediator for lithium-sulfur batteries

Science.gov (United States)

Liang, Xiao; Hart, Connor; Pang, Quan; Garsuch, Arnd; Weiss, Thomas; Nazar, Linda F.

2015-01-01

The lithium-sulfur battery is receiving intense interest because its theoretical energy density exceeds that of lithium-ion batteries at much lower cost, but practical applications are still hindered by capacity decay caused by the polysulfide shuttle. Here we report a strategy to entrap polysulfides in the cathode that relies on a chemical process, whereby a host—manganese dioxide nanosheets serve as the prototype—reacts with initially formed lithium polysulfides to form surface-bound intermediates. These function as a redox shuttle to catenate and bind ‘higher’ polysulfides, and convert them on reduction to insoluble lithium sulfide via disproportionation. The sulfur/manganese dioxide nanosheet composite with 75 wt% sulfur exhibits a reversible capacity of 1,300 mA h g-1 at moderate rates and a fade rate over 2,000 cycles of 0.036%/cycle, among the best reported to date. We furthermore show that this mechanism extends to graphene oxide and suggest it can be employed more widely.

Chemical behavior of lanthanides-tungsten composite materials used in thermo-emissive cathodes

International Nuclear Information System (INIS)

Cadoret, K.; Cachard, J. de; Martinez, L.; Millot, F.; Hennet, L.; Douy, A.; Licheron, M.

2001-01-01

This work presents the crystallography and chemistry of new lanthanides-tungsten composite materials developed to manufacture thermionic cathodes for power grid tubes, based on the same principle than thorium-free cathodes. By mean of x-Ray diffraction at high temperature and under vacuum with synchrotron radiation facilities, we followed in real time the different phases and phase transitions that can occur during the heating process and the carburization at 1550 o C of such tungstates deposits on thin tungsten ribbons. Melting points for composition between 9 La 2 O 3 - 1 WO 3 and 2 La 2 O 3 - 9 WO 3 were specified under the pressure of 1x10 -6 mbar. After interpretation of x-ray diffraction results, phase diagram of n La 2 O 3 - m WO 3 system under vacuum in equilibrium with metallic tungsten have been deduced. Moreover we underline by these works the fact that using a lanthanum-rich tungstate involves better stability and chemical homogeneity of the cathodes surfaces with temperature. (author)

COMPONENT DEVELOPMENT NEEDS FOR THE HYBRID SULFUR ELECTROLYZER

Energy Technology Data Exchange (ETDEWEB)

Hobbs, D; Hector Colon-Mercado, H; Mark Elvington, M

2008-05-30

Fiscal year 2008 studies in electrolyzer component development have focused on the characterization of membrane electrode assemblies (MEA) after performance tests in the single cell electrolyzer, evaluation of electrocatalysts and membranes using a small scale electrolyzer and evaluating the contribution of individual cell components to the overall electrochemical performance. Scanning electron microscopic (SEM) studies of samples taken from MEAs testing in the SRNL single cell electrolyzer test station indicates a sulfur-rich layer forms between the cathode catalyst layer and the membrane. Based on a review of operating conditions for each of the MEAs evaluated, we conclude that the formation of the layer results from the reduction of sulfur dioxide as it passes through the MEA and reaches the catalyst layer at the cathode-membrane interface. Formation of the sulfur rich layer results in partial delamination of the cathode catalyst layer leading to diminished performance. Furthermore we believe that operating the electrolyzer at elevated pressure significantly increases the rate of formation due to increased adsorption of hydrogen on the internal catalyst surface. Thus, identification of a membrane that exhibits much lower transport of sulfur dioxide is needed to reduce the quantity of sulfur dioxide that reaches the cathode catalyst and is reduced to produce the sulfur-rich layer. Three candidate membranes are currently being evaluated that have shown promise from preliminary studies, (1) modified Nafion{reg_sign}, (2) polybenzimidazole (PBI), and (3) sulfonated Diels Alder polyphenylene (SDAPP). Testing examined the activity for the sulfur dioxide oxidation of platinum (Pt) and platinum-alloy catalysts in 30 wt% sulfuric acid solution. Linear sweep voltammetry showed an increase in activity when catalysts in which Pt is alloyed with non-noble transition metals such as cobalt and chromium. However when Pt is alloyed with noble metals, such as iridium or ruthenium

Cathode material for lithium batteries

Science.gov (United States)

Park, Sang-Ho; Amine, Khalil

2013-07-23

A method of manufacture an article of a cathode (positive electrode) material for lithium batteries. The cathode material is a lithium molybdenum composite transition metal oxide material and is prepared by mixing in a solid state an intermediate molybdenum composite transition metal oxide and a lithium source. The mixture is thermally treated to obtain the lithium molybdenum composite transition metal oxide cathode material.

Enhancing the performance of single-chambered microbial fuel cell using manganese/palladium and zirconium/palladium composite cathode catalysts.

Science.gov (United States)

Jadhav, Dipak A; Deshpande, Parag A; Ghangrekar, Makarand M

2017-08-01

Application of ZrO 2 , MnO 2 , palladium, palladium-substituted-zirconium oxide (Zr 0.98 Pd 0.02 O 2 ) and palladium-substituted-manganese oxide (Mn 0.98 Pd 0.02 O 2 ) cathode catalysts in a single-chambered microbial fuel cell (MFC) was explored. The highest power generation (1.28W/m 3 ) was achieved in MFC with Mn 0.98 Pd 0.02 O 2 catalyst, which was higher than that with MnO 2 (0.58W/m 3 ) alone; whereas, MFC having Zr 0.98 Pd 0.02 O 2 catalyzed cathode and non-catalyzed cathode produced powers of 1.02 and 0.23W/m 3 , respectively. Also, low-cost zirconium-palladium-composite showed better catalytic activity and capacitance over ZrO 2 with 20A/m 3 current production and demonstrated its suitability for MFC applications. Cyclic voltammetry analyses showed higher well-defined redox peaks in composite catalysts (Mn/Zr-Pd-C) over other catalyzed MFCs containing MnO 2 or ZrO 2 . Electrochemical behaviour of composite catalysts on cathode showed higher availability of adsorption sites for oxygen reduction and, hence, enhanced the rate of cathodic reactions. Thus, Mn/Zr-Pd-C-based composite catalysts exhibited superior cathodic performance and could be proposed as alternatives to costly Pd-catalyst for field applications. Copyright © 2017 Elsevier Ltd. All rights reserved.

Method of making sulfur-resistant composite metal membranes

Science.gov (United States)

Way, J Douglas [Boulder, CO; Lusk, Mark [Golden, CO; Thoen, Paul [Littleton, CO

2012-01-24

The invention provides thin, hydrogen-permeable, sulfur-resistant membranes formed from palladium or palladium-alloy coatings on porous, ceramic or metal supports. Also disclosed are methods of making these membranes via sequential electroless plating techniques, wherein the method of making the membrane includes decomposing any organic ligands present on the substrate, reducing the palladium crystallites on the substrate to reduced palladium crystallites, depositing a film of palladium metal on the substrate and then depositing a second, gold film on the palladium film. These two metal films are then annealed at a temperature between about 200.degree. C. and about 1200.degree. C. to form a sulfur-resistant, composite PdAu alloy membrane.

Electrochemical performance of polypyrrole/silver vanadium oxide composite cathodes in lithium primary batteries

Science.gov (United States)

Anguchamy, Yogesh K.; Lee, Jong-Won; Popov, Branko N.

Polypyrrole (PPy)/silver vanadium oxide (SVO) composite cathode materials were synthesized by polymerizing pyrrole onto the surface of pure SVO particles. Electrochemical characterization was carried out by performing galvanostatic discharge, pulse discharge and ac-impedance experiments. The composite electrode exhibited better performance than pristine SVO in all the experiments. The composite electrodes yielded a higher discharge capacity and a better pulse discharge capability when compared to the pristine SVO electrode. The pulse discharge and ac-impedance studies indicated that PPy forms an effective conductive network on the SVO surface and thereby reduces the particle-to-particle contact resistance and facilitates the interfacial charge transfer kinetics. To determine the thermal stability of the composite cathode, galvanostatic discharge and ac-impedance experiments were performed at different temperatures. The capacity increased with temperature due to enhanced charge transfer kinetics and low mass transfer limitations. The peak capacity was obtained at 60 °C, after which the performance degraded with any further increase in temperature.

Electrochemical performance of polypyrrole/silver vanadium oxide composite cathodes in lithium primary batteries

Energy Technology Data Exchange (ETDEWEB)

Anguchamy, Yogesh K.; Lee, Jong-Won; Popov, Branko N. [Center for Electrochemical Engineering, Department of Chemical Engineering, University of South Carolina, Columbia, SC 29208 (United States)

2008-09-15

Polypyrrole (PPy)/silver vanadium oxide (SVO) composite cathode materials were synthesized by polymerizing pyrrole onto the surface of pure SVO particles. Electrochemical characterization was carried out by performing galvanostatic discharge, pulse discharge and ac-impedance experiments. The composite electrode exhibited better performance than pristine SVO in all the experiments. The composite electrodes yielded a higher discharge capacity and a better pulse discharge capability when compared to the pristine SVO electrode. The pulse discharge and ac-impedance studies indicated that PPy forms an effective conductive network on the SVO surface and thereby reduces the particle-to-particle contact resistance and facilitates the interfacial charge transfer kinetics. To determine the thermal stability of the composite cathode, galvanostatic discharge and ac-impedance experiments were performed at different temperatures. The capacity increased with temperature due to enhanced charge transfer kinetics and low mass transfer limitations. The peak capacity was obtained at 60 C, after which the performance degraded with any further increase in temperature. (author)

One-step hydrothermal synthesis of three-dimensional porous graphene aerogels/sulfur nanocrystals for lithium–sulfur batteries

International Nuclear Information System (INIS)

Jiang, Yong; Lu, Mengna; Ling, Xuetao; Jiao, Zheng; Chen, Lingli; Chen, Lu; Hu, Pengfei; Zhao, Bing

2015-01-01

Highlights: • 3D porous GA/S nanocrystals are prepared by a one-step hydrothermal method. • The structure is affected by hydrothermal temperature and liquid sulfur’s viscosity. • The hybrid delivers a capacity of 716.2 mA h g −1 after 50 cycles at 100 mA g −1 . • The nanosized S, strong adsorbability and intimate contact of GNS are main factors. - Abstract: Lithium–sulfur (Li–S) batteries are receiving significant attention as a new energy source because of its high theoretical capacity and specific energy. However, the low sulfur loading and large particles (usually in submicron dimension) in the cathode greatly offset its advantage in high energy density and lead to the instability of the cathode and rapid capacity decay. Herein, we introduce a one-step hydrothermal synthesis of three-dimensional porous graphene aerogels/sulfur nanocrystals to suppress the rapid fading of sulfur electrode. It is found that the hydrothermal temperature and viscosity of liquid sulfur have significant effects on particle size and loading mass of sulfur nanocrystals, graphitization degree of graphene and chemical bonding between sulfur and oxygen-containing groups of graphene. The hybrid could deliver a specific capacity of 716.2 mA h g −1 after 50 cycles at a current density of 100 mA g −1 and reversible capacity of 517.9 mA h g −1 at 1 A g −1 . The performance we demonstrate herein suggests that Li–S battery may provide an opportunity for development of rechargeable battery systems

Chemical Immobilization Effect on Lithium Polysulfides for Lithium-Sulfur Batteries.

Science.gov (United States)

Li, Caixia; Xi, Zhucong; Guo, Dexiang; Chen, Xiangju; Yin, Longwei

2018-01-01

Despite great progress in lithium-sulfur batteries (LSBs), great obstacles still exist to achieve high loading content of sulfur and avoid the loss of active materials due to the dissolution of the intermediate polysulfide products in the electrolyte. Relationships between the intrinsic properties of nanostructured hosts and electrochemical performance of LSBs, especially, the chemical interaction effects on immobilizing polysulfides for LSB cathodes, are discussed in this Review. Moreover, the principle of rational microstructure design for LSB cathode materials with strong chemical interaction adsorbent effects on polysulfides, such as metallic compounds, metal particles, organic polymers, and heteroatom-doped carbon, is mainly described. According to the chemical immobilizing mechanism of polysulfide on LSB cathodes, three kinds of chemical immobilizing effects, including the strong chemical affinity between polar host and polar polysulfides, the chemical bonding effect between sulfur and the special function groups/atoms, and the catalytic effect on electrochemical reaction kinetics, are thoroughly reviewed. To improve the electrochemical performance and long cycling life-cycle stability of LSBs, possible solutions and strategies with respect to the rational design of the microstructure of LSB cathodes are comprehensively analyzed. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Temporal development of the composition of Zr and Cr cathodic arc plasma streams in a N2 environment

International Nuclear Information System (INIS)

Rosen, Johanna; Anders, Andre; Hultman, Lars; Schneider, Jochen M.

2003-01-01

We describe the temporal development of the plasma composition in a pulsed plasma stream generated by cathodic arc. Cathodes of Zr and Cr were operated at various nitrogen pressures. The time-resolved plasma composition for the cathode materials was analyzed with time-of-flight charge-to-mass spectrometry, and was found to be a strong function of the nitrogen pressure. Large plasma composition gradients were detected within the first 60 μs of the pulse, the nitrogen ion concentration increasing with increasing pressure. The results are explained by the formation and erosion of a compound layer formed at the cathode surface in the presence of a reactive gas. The average charge state was also found to be affected by the reactive gas pressure as well as by the time after ignition. The charge states were highest in the beginning of the pulse at low nitrogen pressure, decreasing to a steady-state value at higher pressure. These results are of importance for reactive plasma processing and for controlling the evolution of thin film composition and microstructure

Analytical, 1-Dimensional Impedance Model of a Composite Solid Oxide Fuel Cell Cathode

DEFF Research Database (Denmark)

Mortensen, Jakob Egeberg; Søgaard, Martin; Jacobsen, Torben

2014-01-01

An analytical, 1-dimensional impedance model for a composite solid oxide fuel cell cathode is derived. It includes geometrical parameters of the cathode, e.g., the internal surface area and the electrode thickness, and also material parameters, e.g., the surface reaction rate and the vacancy...... diffusion coefficient. The model is successfully applied to a total of 42 impedance spectra, obtained in the temperature range 555°C–852°C and in the oxygen partial pressure range 0.028 atm–1.00 atm for a cathode consisting of a 50/50 wt% mixture of (La0.6Sr0.4)0.99CoO3 − δ and Ce0.9Gd0.1O1.95 − δ...... and providing both qualitative and quantitative information on the evolution of the impedance spectra of cathodes with changing parameters....

Role of LiNO3 in rechargeable lithium/sulfur battery

International Nuclear Information System (INIS)

Zhang, Sheng S.

2012-01-01

Highlights: ► Effect of LiNO 3 on the Li anode and cathode of Li/S battery is studied, respectively. ► LiNO 3 participates in the formation of a stable passivation film on the Li anode surface. ► LiNO 3 may be reduced irreversibly on the cathode, affecting Li/S battery performance. ► Discharge mechanism of Li/S battery is explained from the viewpoint of phase transition. - Abstract: In this work we study the effect of LiNO 3 on the Li anode and sulfur cathode, respectively, of Li/S battery by using a Li/Li symmetric cell and a liquid Li/Li 2 S 9 cell. On the Li anode, LiNO 3 participates in the formation of a stable passivation film, and the resulting passivation film grows infinitely with the consumption of LiNO 3 . The passivation film formed with LiNO 3 is known to effectively suppress the redox shuttle of the dissolved lithium polysulfides on Li anode. On the cathode, LiNO 3 undergoes a large and irreversible reduction starting at 1.6 V in the first discharge, and the irreversible reduction disappears in the subsequent cycles. Moreover, the insoluble reduction products of LiNO 3 on the cathode adversely affect the redox reversibility of sulfur cathode. These results indicate that both the Li anode and sulfur cathode consume LiNO 3 , and that the best benefit of LiNO 3 to Li/S battery occurs at the potentials higher than 1.6 V. By limiting the irreversible reduction of LiNO 3 on the cathode, we have shown that the Li/S cell with a 0.2 m LiNO 3 as the co-salt can provide a stable capacity of ∼500 mAh g −1 .

Effect of N{sub 2} and Ar gas on DC arc plasma generation and film composition from Ti-Al compound cathodes

Energy Technology Data Exchange (ETDEWEB)

Zhirkov, Igor, E-mail: igozh@ifm.liu.se; Rosen, Johanna [Thin Film Physics Division, Department of Physics, Chemistry and Biology (IFM), Linköping University, SE-581 83 Linköping (Sweden); Oks, Efim [Institute of High Current Electronics SB RAS, 2/3 Akademichesky Avenue, 634055 Tomsk (Russian Federation)

2015-06-07

DC arc plasma from Ti, Al, and Ti{sub 1−x}Al{sub x} (x = 0.16, 0.25, 0.50, and 0.70) compound cathodes has been characterized with respect to plasma chemistry (charged particles) and charge-state-resolved ion energy for Ar and N{sub 2} pressures in the range 10{sup −6} to 3 × 10{sup −2} Torr. Scanning electron microscopy was used for exploring the correlation between the cathode and film composition, which in turn was correlated with the plasma properties. In an Ar atmosphere, the plasma ion composition showed a reduction of Al of approximately 5 at. % compared to the cathode composition, while deposited films were in accordance with the cathode stoichiometry. Introducing N{sub 2} above ∼5 × 10{sup −3} Torr, lead to a reduced Al content in the plasma as well as in the film, and hence a 1:1 correlation between the cathode and film composition cannot be expected in a reactive environment. This may be explained by an influence of the reactive gas on the arc mode and type of erosion of Ti and Al rich contaminations, as well as on the plasma transport. Throughout the investigated pressure range, a higher deposition rate was obtained from cathodes with higher Al content. The origin of generated gas ions was investigated through the velocity rule, stating that the most likely ion velocities of all cathode elements from a compound cathode are equal. The results suggest that the major part of the gas ions in Ar is generated from electron impact ionization, while gas ions in a N{sub 2} atmosphere primarily originate from a nitrogen contaminated layer on the cathode surface. The presented results provide a contribution to the understanding processes of plasma generation from compound cathodes. It also allows for a more reasonable approach to the selection of composite cathode and experimental conditions for thin film depositions.

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

Science.gov (United States)

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.

One-step hydrothermal synthesis of three-dimensional porous graphene aerogels/sulfur nanocrystals for lithium–sulfur batteries

Energy Technology Data Exchange (ETDEWEB)

Jiang, Yong; Lu, Mengna; Ling, Xuetao; Jiao, Zheng; Chen, Lingli; Chen, Lu [School of Environmental and Chemical Engineering, Shanghai University, Shanghai 200444 (China); Hu, Pengfei [Instrumental Analysis and Research Center, Shanghai University, Shanghai 200444 (China); Zhao, Bing, E-mail: bzhao@shu.edu.cn [School of Environmental and Chemical Engineering, Shanghai University, Shanghai 200444 (China)

2015-10-05

Highlights: • 3D porous GA/S nanocrystals are prepared by a one-step hydrothermal method. • The structure is affected by hydrothermal temperature and liquid sulfur’s viscosity. • The hybrid delivers a capacity of 716.2 mA h g{sup −1} after 50 cycles at 100 mA g{sup −1}. • The nanosized S, strong adsorbability and intimate contact of GNS are main factors. - Abstract: Lithium–sulfur (Li–S) batteries are receiving significant attention as a new energy source because of its high theoretical capacity and specific energy. However, the low sulfur loading and large particles (usually in submicron dimension) in the cathode greatly offset its advantage in high energy density and lead to the instability of the cathode and rapid capacity decay. Herein, we introduce a one-step hydrothermal synthesis of three-dimensional porous graphene aerogels/sulfur nanocrystals to suppress the rapid fading of sulfur electrode. It is found that the hydrothermal temperature and viscosity of liquid sulfur have significant effects on particle size and loading mass of sulfur nanocrystals, graphitization degree of graphene and chemical bonding between sulfur and oxygen-containing groups of graphene. The hybrid could deliver a specific capacity of 716.2 mA h g{sup −1} after 50 cycles at a current density of 100 mA g{sup −1} and reversible capacity of 517.9 mA h g{sup −1} at 1 A g{sup −1}. The performance we demonstrate herein suggests that Li–S battery may provide an opportunity for development of rechargeable battery systems.

Composite cathode La0.15Bi0.85O1.5-Ag for intermediate-temperature solid oxide fuel cells

International Nuclear Information System (INIS)

Gao Zhan; Mao Zongqiang; Huang Jianbing; Gao Ruifeng; Wang Cheng; Liu Zhixiang

2008-01-01

Composites consisting of silver and lanthanum stabilized bismuth oxide (La 0.15 Bi 0.85 O 1.5 ) were investigated as cathodes for intermediate-temperature solid oxide fuel cells with doped ceria as electrolyte. No stable phases were formed via reaction between La 0.15 Bi 0.85 O 1.5 and Ag. The microstructure of the interfaces between composite cathodes and Ce 0.8 Sm 0.2 O 1.5 electrolytes was studied by scanning electron microscopy after sintering at various temperatures. Impedance spectroscopy measurements revealed that the performance of cathode fired at 700 deg. C was the best. When the optimum fraction of Ag was 50 vol.%, polarization resistance values for the LSB-Ag50 cathode were as low as 0.14 Ω cm 2 at 700 deg. C and 0.18 Ω cm 2 at 650 deg. C. The steady-state polarization investigations on LSB and LSB-Ag50 cathodes were performed using typical three-electrode test cells in air. The results showed that the LSB-Ag50 composite cathode exhibited a lower overpotential and higher exchange current density than LSB, which indicated the electrochemical performance of LSB-Ag50 for the oxygen reduction reaction was superior to the LSB

Stable hydrogen, oxygen and sulfur isotopes composition in different tissues of cattle

International Nuclear Information System (INIS)

Sun Fengmei; Shi Guangyu; Wang Huiwen; Yang Shuming

2012-01-01

In order to research on stable hydrogen, oxygen, sulfur isotopes composition in different tissues of cattle, as well as the breed, δ 2 H and δ 34 S values of different defatted muscle, cattle tail hair, blood, liver, also δ 2h and δ 18 O values of water from muscle were determined by isotope ratio mass spectrometry. The stable sulfur isotope composition was not affected by cattle variety, meanwhile the hydrogen was uncertain; the δ 2 H and δ 34 S values between different defatted muscle, blood, liver, cattle hair were significantly different, at the same time the δ 34 S and δ 2 H values between each tissue were not significantly correlated; the δ 2 H values were strongly correlated with the δ 18 O values of muscle water. The above results indicated that stable sulfur and hydrogen isotopes fractionation in the various tissues were discrepant, thus the proper tissue should be selected according to the purpose and object in the beef traceability. (authors)

Yolk-Shelled C@Fe3 O4 Nanoboxes as Efficient Sulfur Hosts for High-Performance Lithium-Sulfur Batteries.

Science.gov (United States)

He, Jiarui; Luo, Liu; Chen, Yuanfu; Manthiram, Arumugam

2017-09-01

Owing to the high theoretical specific capacity (1675 mA h g -1 ) and low cost, lithium-sulfur (Li-S) batteries offer advantages for next-generation energy storage. However, the polysulfide dissolution and low electronic conductivity of sulfur cathodes limit the practical application of Li-S batteries. To address such issues, well-designed yolk-shelled carbon@Fe 3 O 4 (YSC@Fe 3 O 4 ) nanoboxes as highly efficient sulfur hosts for Li-S batteries are reported here. With both physical entrapment by carbon shells and strong chemical interaction with Fe 3 O 4 cores, this unique architecture immobilizes the active material and inhibits diffusion of the polysulfide intermediates. Moreover, due to their high conductivity, the carbon shells and the polar Fe 3 O 4 cores facilitate fast electron/ion transport and promote continuous reactivation of the active material during the charge/discharge process, resulting in improved electrochemical utilization and reversibility. With these merits, the S/YSC@Fe 3 O 4 cathodes support high sulfur content (80 wt%) and loading (5.5 mg cm -2 ) and deliver high specific capacity, excellent rate capacity, and long cycling stability. This work provides a new perspective to design a carbon/metal-oxide-based yolk-shelled framework as a high sulfur-loading host for advanced Li-S batteries with superior electrochemical properties. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

A novel and efficient water-based composite binder for LiCoO{sub 2} cathodes in lithium-ion batteries

Energy Technology Data Exchange (ETDEWEB)

Chu, Yung-Ju [Department of Materials and Mineral Resources Engineering, National Taipei University of Technology, Taipei (China); Peng, Xing-Wei [Institute of Materials Science and Engineering, National Taipei University of Technology, Taipei (China); Wang, Fu-Ming; Yang, Chang-Rung [Material and Chemical Research Laboratories, Industrial Technology Research Institute, Chutung, Hsinchu (China); Li, Chia-Chen [Department of Materials and Mineral Resources Engineering, National Taipei University of Technology, Taipei (China); Institute of Materials Science and Engineering, National Taipei University of Technology, Taipei (China); Lee, Jyh-Tsung

2007-11-15

The dispersion, adhesion strength, electrical, and electrochemical properties of LiCoO{sub 2} cathodes in lithium-ion batteries with the addition of a new composite binder composed of two acrylic emulsions, poly(butyl acrylate)-based (PBA) and polyacrylonitrile-based (PA) latex in a ratio of 3:7, were evaluated. PBA binder has a low-glass transition temperature of 10 C, which can improve the flexibility of the electrode. This new composite binder has a very good binding ability as same as the typical organic solvent-based binder, poly(vinylidene fluoride). The dispersions of the water-based cathode slurries with the composite binder were measured by analyzing the viscosity and sedimentation behaviors. The results show that the new composite binder can well disperse the LiCoO{sub 2}. Moreover, using the new composite binder could greatly improve the rate capabilities and the cycle stability of water-based LiCoO{sub 2} cathodes. (author)

Hybrid lithium-ion capacitor with LiFePO4/AC composite cathode - Long term cycle life study, rate effect and charge sharing analysis

Science.gov (United States)

Shellikeri, A.; Yturriaga, S.; Zheng, J. S.; Cao, W.; Hagen, M.; Read, J. A.; Jow, T. R.; Zheng, J. P.

2018-07-01

Energy storage devices, which can combine the advantages of lithium-ion battery with that of electric double layer capacitor, are of prime interest. Recently, composite cathodes, which combine a battery material with capacitor material, have shown promise in enhancing life cycle and energy/power performances. Lithium-ion capacitor (LIC), with unique charge storage mechanism of combining a pre-lithiated battery anode with a capacitor cathode, is one such device which has the potential to synergistically incorporate the composite cathode to enhance capacity and cycle life. We report here a hybrid LIC consisting of a lithium iron phosphate (LiFePO4-LFP)/Activated Carbon composite cathode in combination with a hard carbon anode, by integrating the cycle life and capacity enhancing strategies of a dry method of electrode fabrication, anode pre-lithiation and a 3:1 anode to cathode capacity ratio, demonstrating a long cycle life, while elaborating on the charge sharing between the faradaic and non-faradaic mechanism in the battery and capacitor materials, respectively in the composite cathode. An excellent cell capacity retention of 94% (1000 cycles at 1C) and 92% (100,000 cycles at 60C) were demonstrated, while retaining 78% (over 6000 cycles at 2.7C) and 67% (over 70,000 cycles at 43C) of the LFP capacity in the composite cathode.

The influence of different parameters on the discharge capacity and cycling performance of an S/C-composite cathode

OpenAIRE

Eberle, Anna-Marietta

2017-01-01

Lithium Sulfur batteries are thought to be the next generation energy storage device, because of their high theoretical capacity and energy density. At the moment, their practical application is hindered by several issues, for example fast degradation, low Sulfur (S) utilization or the often too low S loadings to give high areal capacities. Here, a Sulfur/Carbon-composite (S/C-composite) is introduced, which can be synthesised by an easy bottom-up approach with a high S-content in the resulti...

Tetrathionate and Elemental Sulfur Shape the Isotope Composition of Sulfate in Acid Mine Drainage

Directory of Open Access Journals (Sweden)

Nurgul Balci

2017-08-01

Full Text Available Sulfur compounds in intermediate valence states, for example elemental sulfur, thiosulfate, and tetrathionate, are important players in the biogeochemical sulfur cycle. However, key understanding about the pathways of oxidation involving mixed-valance state sulfur species is still missing. Here we report the sulfur and oxygen isotope fractionation effects during the oxidation of tetrathionate (S4O62− and elemental sulfur (S° to sulfate in bacterial cultures in acidic conditions. Oxidation of tetrathionate by Acidithiobacillus thiooxidans produced thiosulfate, elemental sulfur and sulfate. Up to 34% of the tetrathionate consumed by the bacteria could not be accounted for in sulfate or other intermediate-valence state sulfur species over the experiments. The oxidation of tetrathionate yielded sulfate that was initially enriched in 34S (ε34SSO4−S4O6 by +7.9‰, followed by a decrease to +1.4‰ over the experiment duration, with an average ε34SSO4−S4O6 of +3.5 ± 0.2‰ after a month of incubation. We attribute this significant sulfur isotope fractionation to enzymatic disproportionation reactions occurring during tetrathionate decomposition, and to the incomplete transformation of tetrathionate into sulfate. The oxygen isotope composition of sulfate (δ18OSO4 from the tetrathionate oxidation experiments indicate that 62% of the oxygen in the formed sulfate was derived from water. The remaining 38% of the oxygen was either inherited from the supplied tetrathionate, or supplied from dissolved atmospheric oxygen (O2. During the oxidation of elemental sulfur, the product sulfate became depleted in 34S between −1.8 and 0‰ relative to the elemental sulfur with an average for ε34SSO4−S0 of −0.9 ± 0.2‰ and all the oxygen atoms in the sulfate derived from water with an average normal oxygen isotope fractionation (ε18OSO4−H2O of −4.4‰. The differences observed in δ18OSO4 and the sulfur isotope composition of sulfate (δ34SSO4

Interaction between titanium and sulfuric acid in the electrodeposition of chalcogenide semiconductors

International Nuclear Information System (INIS)

Ortega, J.

1992-01-01

Some chalcogenide electrodeposition problems in the cathodic potential range from -0.30 V to-0.65 V vs SCE may be related to the Titanium corrosion-passivation process in aqueous solutions of sulfuric acid. This feature was discovered accidentally when it was attempted to electrodeposit Cd-Hg-Te compounds from a ternary plating bath; an anodic current of about 10 m/cm 2 was produced in the Titanium cathode at -0.50 V vs SCE, while at -0.40 and -0.60 V vs SCE the current was cathodic. In order to explain this feature, a first study has been carried out to determine the influence of the temperature and sulfuric acid concentration on the passivation current density, passivation potential and Flade potential for passivation. From Arrhenius plots of the passivation currents an apparent activation energy of 63.8 kJ/mole for Titanium passivation in sulfuric acid at -0.50 V vs SCE was obtained. The electrochemical stability of passivated Titanium was explained by assuming that the oxide film formed exhibits n-type semiconducting character, since passivation data was in good agreement with interfacial energetics for n-TiO 2 in aqueous solutions of sulfuric acid.(Author)

Effects of cathode pulse at low frequency on the structure and composition of plasma electrolytic oxidation ceramic coatings

International Nuclear Information System (INIS)

Yao Zhongping; Xu Yongjun; Jiang Zhaohua; Wang Fuping

2009-01-01

The aim of this work is to investigate the effects of the cathode pulse under the low working frequency on the structure and the composition of the ceramic coatings on Ti-6Al-4V alloys by plasma electrolytic oxidation (PEO). Ceramic coatings were prepared on Ti alloy by pulsed bi-polar plasma electrolytic oxidation in NaAlO 2 solution. The phase composition, morphology, and element distribution in the coating were investigated by X-ray diffractometry, scanning electron microscopy, and energy distribution spectroscopy. The coating was mainly composed of a large amount of Al 2 TiO 5 and a little α-Al 2 O 3 and rutile TiO 2 . Increasing the cathode pulse, the amount of rutile TiO 2 was increased while the amount of Al 2 O 3 was decreased; and decreasing the cathode pulse, the amount of Al 2 O 3 was increased while the amount of rutile TiO 2 was decreased. The thickness of the coatings was increased and then decreased with the increase of the cathode pulse. The grain sizes of Al 2 TiO 5 were increased with the cathode current densities, but changed little with the cathode pulse width. The grain size of α-Al 2 O 3 was decreased with the decrease of the cathode pulse, while the grain size of TiO 2 was increased with the increase of the cathode pulse. The proper cathode pulse was helpful to reduce the roughness and to increase the density of the coatings.

Studies of selected synthesis procedures of the conducting LiFePO{sub 4}-based composite cathode materials for Li-ion batteries

Energy Technology Data Exchange (ETDEWEB)

Ojczyk, W.; Marzec, J.; Swierczek, K.; Zajac, W.; Molenda, J. [Faculty of Materials Science and Ceramics, AGH University of Science and Technology, Al. Mickiewicza 30, 30-059 Krakow (Poland); Molenda, M.; Dziembaj, R. [Faculty of Chemistry, Jagiellonian University, ul. R. Ingardena 3, 30-060 Krakow (Poland)

2007-11-15

In this paper technological aspects of a synthesis of phospho-olivine LiFePO{sub 4} based composite cathode materials for lithium batteries are presented. An effective synthesis route yielding a highly conductive composite cathode material was developed. The structural, electrical and electrochemical properties of these materials were investigated. It was shown that the enhanced conductivity of the cathode material is due to the presence of a thin layer of the reduced material which has metallic properties, which is formed on the grain surfaces of the phospho-olivine. We propose a synthesis route yielding LiFePO{sub 4}/Fe{sub 2}P composite material. (author)

Effective sulfur and energy recovery from hydrogen sulfide through incorporating an air-cathode fuel cell into chelated-iron process.

Science.gov (United States)

Sun, Min; Song, Wei; Zhai, Lin-Feng; Cui, Yu-Zhi

2013-12-15

The chelated-iron process is among the most promising techniques for the hydrogen sulfide (H2S) removal due to its double advantage of waste minimization and resource recovery. However, this technology has encountered the problem of chelate degradation which made it difficult to ensure reliable and economical operation. This work aims to develop a novel fuel-cell-assisted chelated-iron process which employs an air-cathode fuel cell for the catalyst regeneration. By using such a process, sulfur and electricity were effectively recovered from H2S and the problem of chelate degradation was well controlled. Experiment on a synthetic sulfide solution showed the fuel-cell-assisted chelated-iron process could maintain high sulfur recovery efficiencies generally above 90.0%. The EDTA was preferable to NTA as the chelating agent for electricity generation, given the Coulombic efficiencies (CEs) of 17.8 ± 0.5% to 75.1 ± 0.5% for the EDTA-chelated process versus 9.6 ± 0.8% to 51.1 ± 2.7% for the NTA-chelated process in the pH range of 4.0-10.0. The Fe (III)/S(2-) ratio exhibited notable influence on the electricity generation, with the CEs improved by more than 25% as the Fe (III)/S(2-) molar ratio increased from 2.5:1 to 3.5:1. Application of this novel process in treating a H2S-containing biogas stream achieved 99% of H2S removal efficiency, 78% of sulfur recovery efficiency, and 78.6% of energy recovery efficiency, suggesting the fuel-cell-assisted chelated-iron process was effective to remove the H2S from gas streams with favorable sulfur and energy recovery efficiencies. Copyright © 2013 Elsevier B.V. All rights reserved.

A sulfur–microporous carbon composite positive electrode for lithium/sulfur and silicon/sulfur rechargeble batteries

Directory of Open Access Journals (Sweden)

Takuya Takahashi

2015-12-01

Full Text Available Sulfur is an advantageous material as a promising next-generation positive electrode material for high-energy lithium batteries due to a high theoretical capacity of 1672 mA h g−1 although its discharge potential is somewhat modest: ca. 2 V vs Li/Li+. However, a sulfur positive electrode has some crucial problems for practical use, which are mainly attributed to the dissolution of its intermediate products in charge–discharge processes. In order to resolve the dissolution problem of lithium polysulfide, we attempted to synthesize a sulfur–microporous activated carbon (AC composite positive electrode. Moreover, we have systematically researched the battery performance of sulfur–microporous AC positive electrode with variations of electrolytes as well as negative electrodes, and found its promising positive electrode performance for a next-generation rechargeable battery.

A multi-electron redox mediator for redox-targeting lithium-sulfur flow batteries

Science.gov (United States)

Li, Guochun; Yang, Liuqing; Jiang, Xi; Zhang, Tianran; Lin, Haibin; Yao, Qiaofeng; Lee, Jim Yang

2018-02-01

The lithium-sulfur flow battery (LSFB) is a new addition to the rechargeable lithium flow batteries (LFBs) where sulfur or a sulfur compound is used as the cathode material against the lithium anode. We report here our evaluation of an organic sulfide - dimethyl trisulfide (DMTS), as 1) a catholyte of a LFB and 2) a multi-electron redox mediator for discharging and charging a solid sulfur cathode without any conductive additives. The latter configuration is also known as the redox-targeting lithium-sulfur flow battery (RTLSFB). The LFB provides an initial discharge capacity of 131.5 mAh g-1DMTS (1.66 A h L-1), which decreases to 59 mAh g-1DMTS (0.75 A h L-1) after 40 cycles. The RTLSFB delivers a significantly higher application performance - initial discharge capacity of 1225.3 mAh g-1sulfur (3.83 A h L-1), for which 1030.9 mAh g-1sulfur (3.23 A h L-1) is still available after 40 cycles. The significant increase in the discharge and charge duration of the LFB after sulfur addition indicates that DMTS is better used as a redox mediator in a RTLSFB than as a catholyte in a LFB.

Sandwich-Type Nitrogen and Sulfur Codoped Graphene-Backboned Porous Carbon Coated Separator for High Performance Lithium-Sulfur Batteries.

Science.gov (United States)

Chen, Feng; Ma, Lulu; Ren, Jiangang; Luo, Xinyu; Liu, Bibo; Zhou, Xiangyang

2018-03-26

Lithium-sulfur (Li-S) batteries have been identified as the greatest potential next- generation energy-storage systems because of the large theoretical energy density of 2600 Wh kg -1 . However, its practical application on a massive scale is impeded by severe capacity loss resulted from the notorious polysulfides shuttle. Here, we first present a novel technique to synthesize sandwich-type nitrogen and sulfur codoped graphene-backboned porous carbon (NSGPC) to modify the commercial polypropylene separator in Li-S batteries. The as-synthesized NSGPC exhibits a unique micro/mesoporous carbon framework, large specific surface area (2439.0 m² g -1 ), high pore volume (1.78 cm³ g -1 ), good conductivity, and in situ nitrogen (1.86 at %) and sulfur (5.26 at %) co-doping. Benefiting from the particular physical properties and chemical components of NSGPC, the resultant NSGPC-coated separator not only can facilitate rapid Li⁺ ions and electrons transfer, but also can restrict the dissolution of polysulfides to alleviate the shuttle effect by combining the physical absorption and strong chemical adsorption. As a result, Li-S batteries with NSGPC-coated separator exhibit high initial reversible capacity (1208.6 mAh g -1 at 0.2 C), excellent rate capability (596.6 mAh g -1 at 5 C), and superior cycling stability (over 500 cycles at 2 C with 0.074% capacity decay each cycle). Propelling our easy-designed pure sulfur cathode to a extremely increased mass loading of 3.4 mg cm -2 (70 wt. % sulfur), the Li-S batteries with this functional composite separator exhibit a superior high initial capacity of 1171.7 mAh g -1 , which is quite beneficial to commercialized applications.

Dual functional MoS2/graphene interlayer as an efficient polysulfide barrier for advanced lithium-sulfur batteries

International Nuclear Information System (INIS)

Guo, Pengqian; Liu, Dequan; Liu, Zhengjiao; Shang, Xiaonan; Liu, Qiming; He, Deyan

2017-01-01

Highlights: •Dual functional MoS 2 /graphene interlayer was first used as an efficient polysulfide-trapping shield for lithium-sulfur batteries. •MoS 2 /graphene interlayer shows strong chemical interactions with LiPSs. •MoS 2 /graphene interlayer forms a 3D network to facilitate electron and ion transfer during the discharge-charge processes. •The resultant lithium-sulfur batteries exhibit a superior rate capacity and improved cycling capacity. -- Abstract: A dual functional interlayer consisted of composited two-dimensional MoS 2 and graphene has been developed as an efficient polysulfide barrier for lithium-sulfur batteries (LSBs). With such a configuration, LSBs show a superior rate capacity and improved cycling capacity. The excellent electrochemical performance can be attributed to the strong bonding interactions between the MoS 2 /graphene interlayer and the formed lithium polysulfides (LiPSs) as well as the good electrical conductivity of the MoS 2 /graphene composite. The MoS 2 /graphene interlayer can physically block LiPSs by the graphene nanosheets and chemically suppress the dissolution of LiPSs by the polar MoS 2 nanoflowers. Such a dual functional interlayer further provides a good contact with the surface of the sulfur cathode, acts as an upper current collector and greatly improves the sulfur utilization and the rate capability of LSBs.

Sulfur containing nanoporous materials, nanoparticles, methods and applications

Science.gov (United States)

Archer, Lynden A.; Navaneedhakrishnan, Jayaprakash

2018-01-30

Sulfur containing nanoparticles that may be used within cathode electrodes within lithium ion batteries include in a first instance porous carbon shape materials (i.e., either nanoparticle shapes or "bulk" shapes that are subsequently ground to nanoparticle shapes) that are infused with a sulfur material. A synthetic route to these carbon and sulfur containing nanoparticles may use a template nanoparticle to form a hollow carbon shape shell, and subsequent dissolution of the template nanoparticle prior to infusion of the hollow carbon shape shell with a sulfur material. Sulfur infusion into other porous carbon shapes that are not hollow is also contemplated. A second type of sulfur containing nanoparticle includes a metal oxide material core upon which is located a shell layer that includes a vulcanized polymultiene polymer material and ion conducting polymer material. The foregoing sulfur containing nanoparticle materials provide the electrodes and lithium ion batteries with enhanced performance.

Nitrogen and Sulfur Co-doped Graphene Supported Cobalt Sulfide Nanoparticles as an Efficient Air Cathode for Zinc-air Battery

International Nuclear Information System (INIS)

Ganesan, Pandian; Ramakrishnan, Prakash; Prabu, Moni; Shanmugam, Sangaraju

2015-01-01

Highlights: • CoS 2 nanoparticles supported on a nitrogen and sulfur co-doped graphene oxide is described. • Improved round trip efficiency was observed for CoS 2 (400)/N,S-GO. • CoS 2 (400)/N,S-GO possess improved durability with low over-potential. • CoS 2 (400)/N,S-GO is a promising air cathode for zinc-air battery. - ABSTRACT: Zinc-air battery is considered as one of the promising energy storage devices due to their low cost, eco-friendly and safe. Here, we present a simple approach to the preparation of cobalt sulfide nanoparticles supported on a nitrogen and sulfur co-doped graphene oxide surface. Cobalt sulfide nanoparticles dispersed on graphene oxide hybrid was successfully prepared by solid state thermolysis approach at 400 °C, using cobalt thiourea and graphene oxide. X-ray diffraction study revealed that hybrid electrode prepared at 400 °C results in pure CoS 2 phase. The hybrid CoS 2 (400)/N,S-GO electrode exhibits low over-potential gap about 0.78 V vs. Zn after 70 cycles with remarkable and robust charge and discharge profile. And also the CoS 2 (400)/N,S-GO showing deep discharge behavior with stability up to 7.5 h.

Ultra High Energy Density Cathodes with Carbon Nanotubes

Science.gov (United States)

2013-12-10

a) Carbon nanotube paper coated with NCA cathode composite for testing as positive electrode in Li-ion battery (b) Comparison of NCA specific...received and purified CNT electrodes coated with NCA cathode composite. (b) Discharge capacities as a function of rate and cycle for NCA on Al and...thickness increases. The first approach was to cast SOA NCA cathode composites onto CNT current collectors using an adjustable blade coater. The

Sandwich-Type Nitrogen and Sulfur Codoped Graphene-Backboned Porous Carbon Coated Separator for High Performance Lithium-Sulfur Batteries

Science.gov (United States)

Chen, Feng; Ma, Lulu; Ren, Jiangang; Luo, Xinyu; Liu, Bibo; Zhou, Xiangyang

2018-01-01

Lithium-sulfur (Li-S) batteries have been identified as the greatest potential next- generation energy-storage systems because of the large theoretical energy density of 2600 Wh kg−1. However, its practical application on a massive scale is impeded by severe capacity loss resulted from the notorious polysulfides shuttle. Here, we first present a novel technique to synthesize sandwich-type nitrogen and sulfur codoped graphene-backboned porous carbon (NSGPC) to modify the commercial polypropylene separator in Li-S batteries. The as-synthesized NSGPC exhibits a unique micro/mesoporous carbon framework, large specific surface area (2439.0 m2 g−1), high pore volume (1.78 cm3 g−1), good conductivity, and in situ nitrogen (1.86 at %) and sulfur (5.26 at %) co-doping. Benefiting from the particular physical properties and chemical components of NSGPC, the resultant NSGPC-coated separator not only can facilitate rapid Li+ ions and electrons transfer, but also can restrict the dissolution of polysulfides to alleviate the shuttle effect by combining the physical absorption and strong chemical adsorption. As a result, Li-S batteries with NSGPC-coated separator exhibit high initial reversible capacity (1208.6 mAh g−1 at 0.2 C), excellent rate capability (596.6 mAh g−1 at 5 C), and superior cycling stability (over 500 cycles at 2 C with 0.074% capacity decay each cycle). Propelling our easy-designed pure sulfur cathode to a extremely increased mass loading of 3.4 mg cm−2 (70 wt. % sulfur), the Li-S batteries with this functional composite separator exhibit a superior high initial capacity of 1171.7 mAh g−1, which is quite beneficial to commercialized applications. PMID:29587467

Sandwich-Type Nitrogen and Sulfur Codoped Graphene-Backboned Porous Carbon Coated Separator for High Performance Lithium-Sulfur Batteries

Directory of Open Access Journals (Sweden)

Feng Chen

2018-03-01

Full Text Available Lithium-sulfur (Li-S batteries have been identified as the greatest potential next- generation energy-storage systems because of the large theoretical energy density of 2600 Wh kg−1. However, its practical application on a massive scale is impeded by severe capacity loss resulted from the notorious polysulfides shuttle. Here, we first present a novel technique to synthesize sandwich-type nitrogen and sulfur codoped graphene-backboned porous carbon (NSGPC to modify the commercial polypropylene separator in Li-S batteries. The as-synthesized NSGPC exhibits a unique micro/mesoporous carbon framework, large specific surface area (2439.0 m2 g−1, high pore volume (1.78 cm3 g−1, good conductivity, and in situ nitrogen (1.86 at % and sulfur (5.26 at % co-doping. Benefiting from the particular physical properties and chemical components of NSGPC, the resultant NSGPC-coated separator not only can facilitate rapid Li+ ions and electrons transfer, but also can restrict the dissolution of polysulfides to alleviate the shuttle effect by combining the physical absorption and strong chemical adsorption. As a result, Li-S batteries with NSGPC-coated separator exhibit high initial reversible capacity (1208.6 mAh g−1 at 0.2 C, excellent rate capability (596.6 mAh g−1 at 5 C, and superior cycling stability (over 500 cycles at 2 C with 0.074% capacity decay each cycle. Propelling our easy-designed pure sulfur cathode to a extremely increased mass loading of 3.4 mg cm−2 (70 wt. % sulfur, the Li-S batteries with this functional composite separator exhibit a superior high initial capacity of 1171.7 mAh g−1, which is quite beneficial to commercialized applications.

Scintillation screen applications in a vacuum arc ion source with composite hydride cathode

Science.gov (United States)

Wang, X. H.; Tuo, X. G.; Yang, Z.; Peng, Y. F.; Li, J.; Lv, H. Y.; Li, J. H.; Long, J. D.

2018-05-01

Vacuum arc ion source with composite hydride cathode was developed to produce intense ion beams which can be applied in particle accelerator injections. Beam profile and beam composition are two fundamental parameters of the beam for the vacuum arc ion source in such specific applications. An aluminum-coated scintillation screen with an ICCD camera readout was used to show the space-time distribution of the beam directly. A simple magnetic analysis assembly with the scintillation screen shows the beam composition information of this kind ion source. Some physical and technical issues are discussed and analyzed in the text.

Inkjet-Printed Lithium-Sulfur Microcathodes for All-Printed, Integrated Nanomanufacturing.

Science.gov (United States)

Milroy, Craig A; Jang, Seonpil; Fujimori, Toshihiko; Dodabalapur, Ananth; Manthiram, Arumugam

2017-03-01

Improved thin-film microbatteries are needed to provide appropriate energy-storage options to power the multitude of devices that will bring the proposed "Internet of Things" network to fruition (e.g., active radio-frequency identification tags and microcontrollers for wearable and implantable devices). Although impressive efforts have been made to improve the energy density of 3D microbatteries, they have all used low energy-density lithium-ion chemistries, which present a fundamental barrier to miniaturization. In addition, they require complicated microfabrication processes that hinder cost-competitiveness. Here, inkjet-printed lithium-sulfur (Li-S) cathodes for integrated nanomanufacturing are reported. Single-wall carbon nanotubes infused with electronically conductive straight-chain sulfur (S@SWNT) are adopted as an integrated current-collector/active-material composite, and inkjet printing as a top-down approach to achieve thin-film shape control over printed electrode dimensions is used. The novel Li-S cathodes may be directly printed on traditional microelectronic semicoductor substrates (e.g., SiO 2 ) or on flexible aluminum foil. Profilometry indicates that these microelectrodes are less than 10 µm thick, while cyclic voltammetry analyses show that the S@SWNT possesses pseudocapacitive characteristics and corroborates a previous study suggesting the S@SWNT discharge via a purely solid-state mechanism. The printed electrodes produce ≈800 mAh g -1 S initially and ≈700 mAh g -1 after 100 charge/discharge cycles at C/2 rate. © 2017 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Electrochemical reduction of sulfur dioxide in sulfolane

Energy Technology Data Exchange (ETDEWEB)

Vorob' ev, A.S.; Gavrilova, A.A.; Kolosnitsyn, V.S.; Nikitin, Yu.E.

1985-09-01

Solutions of sulfur dioxide in aproptic media are promising electrolyte oxidizing agents for chemical current sources with anodes of active metals. This work describes the electrochemical reduction of sulfur dioxide in sulfolane in a lithium halide supporting electrolyte which was investigated by the methods of voltamperometry and chronopotentiometry. The dependence of the current of the cathodic peak on the concentration of the supporting electrolyte salts, sulfur dioxide and water, was studied. On the basis of the data obtained, a hypothesis was advanced on the nature of the limiting step. The investigation showed that at low polarizing current densities, a substantial influence on the reduction of sulfur dioxide in sulfolane in a lithium halide supporting electrolyte is exerted by blockage of the electrode surface by sparingly soluble reaction products.

Sulfur isotope in nature. Determination of sulfur isotope ratios in coal and petroleum by mass spectrometry

International Nuclear Information System (INIS)

Derda, M.

1999-01-01

Elementary sulfur or in chemical compounds is one of the elements widespread in the earth's crust and biosphere. Its participation in earth's crust amounts to 0.26 % by weight. Measurement of isotope composition of natural samples can deliver many information about origin, creation and transformation ranges of rocks and minerals. Sulfur isotope ratio contained in minerals is variable and for this reason investigation of isotope sulfur composition can deliver useful information about the geochemistry of each component. Therefore in the investigated sample it is necessary to determine not only the content of sulfur but also the isotope composition of each component. Differentiation of contents of sulfur-34 in natural sulfur compounds can reach up to 110 per mile. So large divergences can be explained by a kinetic effect or by bacterial reduction of sulphates. In this report a wide review of the results of investigations of isotope sulfur compositions in coal and petroleum are presented as well as the methods for the preparation of samples for mass spectrometry analysis are proposed. (author)

A Spinel-integrated P2-type Layered Composite: High-rate Cathode for Sodium-ion Batteries

Energy Technology Data Exchange (ETDEWEB)

Zheng, Jianming; Yan, Pengfei; Kan, Wang Hay; Wang, Chong M.; Manthiram, Arumugam

2016-01-14

Sodium-ion batteries (SIB) are being intensively investigated, owing to the natural abundance and low cost of Na resources. However, the SIBs still suffer from poor rate capability due to the large ionic radius of Na+ ion and the significant kinetic barrier to Na+-ion transport. Here, we present an Fd-3m spinel-integrated P2-type layered composite (P2 + Fd-3m) material as a high-rate cathode for SIBs. The P2 + Fd-3m composite material Na0.50Ni1/6Co1/6Mn2/3O2 shows significantly enhanced discharge capacity, energy density, and rate capability as compared to the pure P2-type counterpart. The composite delivers a high capacity of 85 mA h g-1 when discharging at a very high current density of 1500 mA g-1 (10C rate) between 2.0 and 4.5 V, validating it as a promising cathode candidate for high-power SIBs. The superior performance is ascribed to the improved kinetics in the presence of the integrated-spinel phase, which facilitates fast electron transport to coordinate with the timely Na+-ion insertion/extraction. The findings of this work also shed light on the importance of developing lattice doping, surface coating, and electrolyte additives to further improve the structural and interfacial stability of P2-type cathode materials and fully realize their practical applications in sodium-ion batteries.

Block Copolymer Electrolytes: Thermodynamics, Ion Transport, and Use in Solid- State Lithium/Sulfur Cells

Science.gov (United States)

Teran, Alexander Andrew

anode, the compatibility of the sulfur cathode was explored. The sulfur cathode presents many unique challenges, including the generation of soluble lithium polysulfides (Li2Sx, 2 ≤ x ≤ 8) during discharge. The solubility of such species in block copolymers and their effect on morphology was examined. The lithium polysulfides were found to exhibit similar solubility in the block copolymers as in typical organic electrolytes, however induced unusual and unexpected phase behavior in the block copolymers. Inspired by successful efforts to physically confine the soluble lithium polysulfides via nanostructured carbon-sulfur composites in the cathode, our nanostructured block copolymer electrolytes were employed in full electrochemical cells with a lithium metal anode and sulfur cathode. Different cathode compositions, electrolyte additives, and cell architectures were tested. Surprisingly, the polysulfides diffused readily from the cathode through the block copolymer electrolyte, and the normally robust SEO|Li metal interface was detrimentally affected their presence during cycling. The polysulfides appeared to change the mechanical properties of the electrolyte such that intimate contact with the lithium metal was lost. Several promising strategies to overcome this problem were investigated and offer exciting avenues for improvement for future researchers. (Abstract shortened by UMI.).

Investigation into the role of silica in lithium polysulfide adsorption for lithium sulfur battery

International Nuclear Information System (INIS)

Kim, Miso; Kang, Sung-Hwan; Manuel, James; Zhao, Xiaohui; Cho, Kwon Koo; Ahn, Jou Hyeon

2015-01-01

Highlights: • Amine functionalized silica nanoparticles (AFSN) were prepared. • Polysulfide adsorption studies were carried out with silica nanoparticles and AFSN. • Sulfur cathodes were prepared with SN and AFSN for Li–S batteries. • AFSN showed excellent polysulfide adsorption. - Abstract: A new type of sulfur electrodes with the ability for polysulfide adsorption was prepared by incorporating silica nanoparticles (SN) or amine functionalized silica nanoparticles (AFSN). AFSN was synthesized by a simple and cost-effective method. The functionalization and surface morphology of silica were confirmed with Fourier transform infrared (FTIR) spectroscopy and scanning electron microscopy (SEM), respectively. Polysulfide adsorption studies were carried out using UV–vis spectrometer, which confirmed the excellent adsorption of polysulfides by AFSN. Interaction of polysulfides with SN or AFSN was studied using FTIR and FT-Raman spectroscopy. The effective polysulfide adsorption by SN and AFSN leads to good and stable cycle performance of lithium sulfur cells. The results show that the incorporation of SN or AFSN with sulfur is a promising method to prepare cathode material for lithium sulfur batteries

Composition and oxidation state of sulfur in atmospheric particulate matter

Directory of Open Access Journals (Sweden)

A. F. Longo

2016-10-01

Full Text Available The chemical and physical speciation of atmospheric sulfur was investigated in ambient aerosol samples using a combination of sulfur near-edge x-ray fluorescence spectroscopy (S-NEXFS and X-ray fluorescence (XRF microscopy. These techniques were used to determine the composition and oxidation state of sulfur in common primary emission sources and ambient particulate matter collected from the greater Atlanta area. Ambient particulate matter samples contained two oxidation states: S0 and S+VI. Ninety-five percent of the individual aerosol particles (> 1 µm analyzed contain S0. Linear combination fitting revealed that S+VI in ambient aerosol was dominated by ammonium sulfate as well as metal sulfates. The finding of metal sulfates provides further evidence for acidic reactions that solubilize metals, such as iron, during atmospheric transport. Emission sources, including biomass burning, coal fly ash, gasoline, diesel, volcanic ash, and aerosolized Atlanta soil, and the commercially available bacterium Bacillus subtilis, contained only S+VI. A commercially available Azotobacter vinelandii sample contained approximately equal proportions of S0 and S+VI. S0 in individual aerosol particles most likely originates from primary emission sources, such as aerosolized bacteria or incomplete combustion.

Study on the Relation between the Mn/Al Mixed Oxides Composition and Performance of FCC Sulfur Transfer Agent

Directory of Open Access Journals (Sweden)

Ruiyu Jiang

2016-01-01

Full Text Available A sulfur transfer agent in catalysts can effectively reduce the emission of SO2 with minimum adverse effects on the catalytic cracking ability of the primary catalyst. In this paper, the composition and performance of sulfur transfer agents with different oxidative active components (such as Cu, Fe, Ni, Co, Ba, Zn and Cr were prepared by acid peptization technique and characterized by X-ray diffraction (XRD, Fourier transform infrared spectroscopy (FTIR and N2 adsorption-desorption technique. The relationship between the composition and performance of the new sulfur transfer agents was investigated and the regeneration and recycling of the agents were performed. The results indicates that copper is a very good desulfurization active component. Moreover, the presence of CO has no significant effect on the absorption ability of SO2 by the sulfur transfer agent.

Investigation of the Li–S Battery Mechanism by Real-Time Monitoring of the Changes of Sulfur and Polysulfide Species during the Discharge and Charge

International Nuclear Information System (INIS)

Zheng, Dong; Liu, Dan; Harris, Joshua B.; Ding, Tianyao; Si, Jingyu

2016-01-01

The mechanism of the sulfur cathode in Li-S batteries has been proposed. It was revealed by the real-time quantitative determination of polysulfide species and elemental sulfur by means of the high performance liquid chromatography in the course of the discharge and recharge of a Li-S battery. A three-step reduction mechanism including two chemical equilibrium reactions was proposed for the sulfur cathode discharge. The typical two-plateau discharge curve for sulfur cathode can be explained. A two-step oxidation mechanism for the Li_2S and Li_2S_2 with a single chemical equilibrium among soluble polysulfide ions was proposed. In conclusion, the chemical equilibrium among S_5"2"-, S_6"2"-, S_7"2"- and S_8"2"- throughout the entire oxidation process resulted for the single flat recharge curve in Li-S batteries.

Metal-Embedded Porous Graphitic Carbon Fibers Fabricated from Bamboo Sticks as a Novel Cathode for Lithium-Sulfur Batteries.

Science.gov (United States)

Zhang, Xuqing; Zhong, Yu; Xia, Xinhui; Xia, Yang; Wang, Donghuang; Zhou, Cheng'ao; Tang, Wangjia; Wang, Xiuli; Wu, J B; Tu, Jiangping

2018-04-25

Lithium-sulfur batteries (LSBs) are deemed to be among the most prospective next-generation advanced high-energy batteries. Advanced cathode materials fabricated from biological carbon are becoming more popular due to their unique properties. Inspired by the fibrous structure of bamboo, herein we put forward a smart strategy to convert bamboo sticks for barbecue into uniform bamboo carbon fibers (BCF) via a simple hydrothermal treatment proceeded in alkaline solution. Then NiCl 2 is used to etch the fibers through a heat treatment to achieve Ni-embedded porous graphitic carbon fibers (PGCF/Ni) for LSBs. The designed PGCF/Ni/S electrode exhibits improved electrochemical performances including high initial capacity (1198 mAh g -1 at 0.2 C), prolonged cycling life (1030 mAh g -1 at 0.2 C after 200 cycles), and improved rate capability. The excellent properties are attributed to the synergistic effect of 3D porous graphitic carbon fibers with highly conductive Ni nanoparticles embedded.

Mechanistic Enhancement of SOFC Cathode Durability

Energy Technology Data Exchange (ETDEWEB)

Wachsman, Eric [Univ. of Maryland, College Park, MD (United States)

2016-02-01

Durability of solid oxide fuel cells (SOFC) under “real world” conditions is an issue for commercial deployment. In particular cathode exposure to moisture, CO2, Cr vapor (from interconnects and BOP), and particulates results in long-term performance degradation issues. Here, we have conducted a multi-faceted fundamental investigation of the effect of these contaminants on cathode performance degradation mechanisms in order to establish cathode composition/structures and operational conditions to enhance cathode durability.

Long-Life Lithium-Sulfur Battery Derived from Nori-Based Nitrogen and Oxygen Dual-Doped 3D Hierarchical Biochar.

Science.gov (United States)

Wu, Xian; Fan, Lishuang; Wang, Maoxu; Cheng, Junhan; Wu, Hexian; Guan, Bin; Zhang, Naiqing; Sun, Kening

2017-06-07

Due to restrictions on the low conductivity of sulfur and soluble polysulfides during discharge, lithium sulfur batteries are unsuitable for further large scale applications. The current carbon based cathodes suffer from poor cycle stability and high cost. Recently, heteroatom doped carbons have been considered as a settlement to enhance the performance of lithium sulfur batteries. With this strategy, we report the low cost activated nori based N,O-doped 3D hierarchical carbon material (ANC) as a sulfur host. The N,O dual-doped ANC reveals an elevated electrochemical performance, which exhibits not only a good rate performance over 5 C, but also a high sulfur content of 81.2%. Further importantly, the ANC represents an excellent cycling stability, the cathode reserves a capacity of 618 mAh/g at 2 C after 1000 cycles, which shows a 0.022% capacity decay per cycle.

A simple route to improve rate performance of LiFePO4/reduced graphene oxide composite cathode by adding Mg2+ via mechanical mixing

Science.gov (United States)

Huang, Yuan; Liu, Hao; Gong, Li; Hou, Yanglong; Li, Quan

2017-04-01

Introducing Mg2+ to LiFePO4 and reduced graphene oxide composite via mechanical mixing and annealing leads to largely improved rate performance of the cathode (e.g. ∼78 mA h g-1 at 20 C for LiFePO4 and reduced graphene oxide composite with Mg2+ introduction vs. ∼37 mA h g-1 at 20 C for LiFePO4 and reduced graphene oxide composite). X-ray photoelectron spectroscopy unravels that the enhanced reduction of Fe2+ to Fe0 occurs in the simultaneous presence of Mg2+ and reduced graphene oxide, which is beneficial for the rate capability of cathode. The simple fabrication process provides a simple and effective means to improve the rate performance of the LiFePO4 and reduced graphene oxide composite cathode.

Methanol-Tolerant Cathode Catalyst Composite For Direct Methanol Fuel Cells

Science.gov (United States)

Zhu, Yimin; Zelenay, Piotr

2006-03-21

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

High Performance Cathodes for Li-Air Batteries

Energy Technology Data Exchange (ETDEWEB)

Xing, Yangchuan

2013-08-22

The overall objective of this project was to develop and fabricate a multifunctional cathode with high activities in acidic electrolytes for the oxygen reduction and evolution reactions for Li-air batteries. It should enable the development of Li-air batteries that operate on hybrid electrolytes, with acidic catholytes in particular. The use of hybrid electrolytes eliminates the problems of lithium reaction with water and of lithium oxide deposition in the cathode with sole organic electrolytes. The use of acid electrolytes can eliminate carbonate formation inside the cathode, making air breathing Li-air batteries viable. The tasks of the project were focused on developing hierarchical cathode structures and bifunctional catalysts. Development and testing of a prototype hybrid Li-air battery were also conducted. We succeeded in developing a hierarchical cathode structure and an effective bifunctional catalyst. We accomplished integrating the cathode with existing anode technologies and made a pouch prototype Li-air battery using sulfuric acid as catholyte. The battery cathodes contain a nanoscale multilayer structure made with carbon nanotubes and nanofibers. The structure was demonstrated to improve battery performance substantially. The bifunctional catalyst developed contains a conductive oxide support with ultra-low loading of platinum and iridium oxides. The work performed in this project has been documented in seven peer reviewed journal publications, five conference presentations, and filing of two U.S. patents. Technical details have been documented in the quarterly reports to DOE during the course of the project.

Solvent extraction of elemental sulfur from coal and a determination of its source using stable sulfur isotopes

Science.gov (United States)

Hackley, Keith C.; Buchanan, D.H.; Coombs, K.; Chaven, C.; Kruse, C.W.

1990-01-01

Hot tetrachloroethene (perchloroethylene, PCE) extracts significant amounts of elemental sulfur (So) from weathered coals but not from pristine coals. The objective of this study was to determine whether So extracted by PCE is an oxidation product of pyrite or whether it originates in some way from unstable, organically-bound sulfur. The isotopic composition of the PCE-extracted So was compared to the isotopic compositions of the pyritic and the organic sulfur in a coal. The So was shown to have an isotopic signature similar to the pyritic sulfur. Additionally, the isotopic differences observed between the pyritic, So and sulfatic sulfur were consistent with bacterial mediated oxidation of sulfide sulfur (pyrite) as the source of both the sulfatic and elemental sulfur. ?? 1990.

Studies on conducting polymer and conducting polymerinorganic composite electrodes prepared via a new cathodic polymerization method

Science.gov (United States)

Singh, Nikhilendra

A novel approach for the electrodeposition of conducting polymers and conducting polymer-inorganic composite materials is presented. The approach shows that conducting polymers, such as polypyrrole (PPy) and poly(3,4-ethylenedioxythiophene) (PEDOT) can be electrodeposited by the application of a cathodic bias that generates an oxidizing agent, NO+, via the in-situ reduction of nitrate anions. This new cathodic polymerization method allows for the deposition of PPy and PEDOT as three dimensional, porous films composed of spherical polymer particles. The method is also suitable for the co-deposition of inorganic species producing conducting polymer-inorganic composite electrodes. Such composites are used as high surface area electrodes in Li-ion batteries, electrochemical hydrogen evolution and in the development of various other conducting polymer-inorganic composite electrodes. New Sn-PPy and Sb-PPy composite electrodes where Sn and Sb nanoparticles are well dispersed among the PPy framework are reported. These structures allow for decreased stress during expansion and contraction of the active material (Sn, Sb) during the alloying and de-alloying processes of a Li-ion battery anode, significantly alleviating the loss of active material due to pulverization processes. The new electrochemical synthesis mechanism allows for the fabrication of Sn-PPy and Sb-PPy composite electrodes directly from a conducting substrate and eliminates the use of binding materials and conducting carbon used in modern battery anodes, which significantly simplifies their fabrication procedures. Platinum (Pt) has long been identified as the most efficient catalyst for electrochemical water splitting, while nickel (Ni) is a cheaper, though less efficient alternative to Pt. A new morphology of PPy attained via the aforementioned cathodic deposition method allows for the use of minimal quantities of Pt and Ni dispersed over a very high surface area PPy substrate. These composite electrodes

SOFC LSM:YSZ cathode degradation induced by moisture: An impedance spectroscopy study

DEFF Research Database (Denmark)

Nielsen, Jimmi; Mogensen, Mogens Bjerg

2011-01-01

The cause of the degradation effect of moisture during operation of LSM cathode based SOFCs has been investigated by means of a detailed impedance characterization on LSM:YSZ composite cathode based SOFCs. Further the role of YSZ as cathode composite material was studied by measurements on SOFCs...... with a LSM:CGO composite cathode on a CGO interdiffusion barrier layer. It was found that both types of cathodes showed similar electrochemical characteristics towards the presence of moisture during operation. Upon addition and removal of moisture in the fed air the impedance study showed a change...... in the high frequency cathode arc, which is associated with the charge transport/transfer at the LSM/YSZ interface. On prolonged operation with the presence of moisture an ongoing increase in the high frequency cathode arc resulted in a permanent loss of cathode/electrolyte contact and thus increase...

An Experimental Study of Low-Temperature Sulfurization of Carbohydrates Using Various Sulfides Reveals Insights into Structural Characteristics and Sulfur Isotope Compositions of Macromolecular Organic Matter in the Environment

Science.gov (United States)

OBeirne, M. D.; Werne, J. P.; Van Dongen, B.; Gilhooly, W., III

2017-12-01

Sulfurization of carbohydrates has been suggested as an important mechanism for the preservation of organic matter in anoxic/euxinic depositional environments. In this study, glucose was sulfurized under laboratory conditions at room temperature (24°C) using three commercially available sulfides - ammonium sulfide ([NH4]2S), sodium sulfide (Na2S), and sodium hydrosulfide (NaHS), each mixed with elemental sulfur to produce polysulfide solutions. The reaction products were analyzed using Fourier transform infrared spectroscopy (FTIR), which revealed structural differences among the products formed via the three sulfide reactants. Additionally, analysis of the bulk sulfur isotope compositions of reactants and products was used to determine the fractionation(s) associated with abiotic sulfur incorporation into organic matter. Samples from both modern (Mahoney Lake, British Colombia, Canada) and ancient (Jurassic aged Blackstone Band from the Kimmeridge Clay Formation, Dorset, United Kingdom) euxinic systems were also analyzed for comparison to laboratory samples. Results from this study provide experimental evidence for the structural and sulfur isotopic relationships of sulfurized organic matter in the geosphere.

Chromium poisoning of LSM/YSZ and LSCF/CGO composite cathodes

DEFF Research Database (Denmark)

Bentzen, Janet Jonna; Høgh, Jens Valdemar Thorvald; Barfod, Rasmus

2009-01-01

from 300 to 2,970 h. Both LSM/YSZ and LSCF/CGO cathodes were sensitive to chromium poisoning; LSCF/CGO cathodes to a lesser extent than LSM/YSZ. Humid air aggravated the degradation of the cathode performance. Post-mortem electron microscopic investigations revealed several Cr-containing compounds...

Solvent extraction of elemental sulfur from coal and a determination of its source using stable sulfur isotopes

Energy Technology Data Exchange (ETDEWEB)

Hackley, K.C.; Buchanan, D.H.; Coombs, K.; Chaven, C.; Kruse, C.W. (Eastern Illinois University, Charleston, IL (USA). Chemistry Dept.)

1990-01-01

Hot tetrachloroethene (perchloroethylen PCE) extracts significant amounts of elemental sulfur (S{sup o}) from weathered coals but not from pristine coals. The objective of this study was to determine whether S{sup o} extracted by PCE is an oxidation product of pyrite or whether it originates in some way from unstable, organically-bound sulfur. The isotopic composition of the PCE-extracted S{sup o} was compared to the isotopic compositions of the pyritic and the organic sulfur in a coal. The S{sup o} was shown to have an isotopic signature similar to the pyritic sulfur. Additionally, the isotopic differences observed between the pyritic, S{sup o} and sulfatic sulfur were consistent with bacterial mediated oxidation of sulfide sulfur (pyrite) as the source of both the sulfatic and elemental sulfur. 21 refs., 2 tabs.

Electrosorption in lithium-sulfur batteries: modeling of solvation and adsorption at nanostructured cathodes

OpenAIRE

Lück, Jessica; Danner, Timo; Latz, Arnulf

2016-01-01

Since the energy density of lithium-ion batteries is reaching its ceiling so that improvements are just of minor nature, researchers have moved their focus to systems beyond lithium-ion. One of the most promising candidates besides the lithium-air technology for future energy storage both for automotive and stationary applications are lithium-sulfur batteries. The use of sulfur as an active material offers many benefits compared to lithium-ion systems. First of all sulfur is expec...

Copper-substituted perovskite compositions for solid oxide fuel cell cathodes and oxygen reduction electrodes in other electrochemical devices

Science.gov (United States)

Rieke, Peter C [Pasco, WA; Coffey, Gregory W [Richland, WA; Pederson, Larry R [Kennewick, WA; Marina, Olga A [Richland, WA; Hardy, John S [Richland, WA; Singh, Prabhaker [Richland, WA; Thomsen, Edwin C [Richland, WA

2010-07-20

The present invention provides novel compositions that find advantageous use in making electrodes for electrochemical cells. Also provided are electrochemical devices that include active oxygen reduction electrodes, such as solid oxide fuel cells, sensors, pumps and the like. The compositions comprises a copper-substituted ferrite perovskite material. The invention also provides novel methods for making and using the electrode compositions and solid oxide fuel cells and solid oxide fuel cell assemblies having cathodes comprising the compositions.

High-Rate and Long-Term Cycle Stability of Li-S Batteries Enabled by Li2S/TiO2-Impregnated Hollow Carbon Nanofiber Cathodes.

Science.gov (United States)

Wang, Xinran; Bi, Xuanxuan; Wang, Shaona; Zhang, Yi; Du, Hao; Lu, Jun

2018-05-16

The high theoretical energy density of lithium-sulfur (Li-S) batteries makes them an alternative battery technology to lithium ion batteries. However, Li-S batteries suffer from low sulfur loading, poor charge transport, and dissolution of lithium polysulfide. In our study, we use the lithiated S, Li 2 S, as the cathode material, coupled with electrospun TiO 2 -impregnated hollow carbon nanofibers (TiO 2 -HCFs), which serve as the conductive agent and protective barrier for Li 2 S in Li-S batteries. TiO 2 -HCFs provide much improved electron/ionic conductivity and serve as a physical barrier, which prevents the dissolution of lithium polysulfides. The Li 2 S/TiO 2 -HCF composite delivers a discharge capacity of 851 mA h g Li 2 S -1 at 0.1C and the bilayer TiO 2 -HCFs/Li 2 S/TiO 2 -HCF composite delivers a high specific capacity of 400 mA h g Li 2 S -1 at 5C.

Polyaniline/multi-walled carbon nanotubes composite with core-shell structures as a cathode material for rechargeable lithium-polymer cells

Energy Technology Data Exchange (ETDEWEB)

Liu, Pan [School of Marine Science and Technology, Harbin Institute of Technology, Weihai 264209 (China); Han, Jia-Jun, E-mail: hanjiajunhitweihai@163.com [School of Marine Science and Technology, Harbin Institute of Technology, Weihai 264209 (China); Jiang, Li-Feng [Dalian Chemical Institute of Chinese Academy of Sciences, Dalian 116011 (China); Li, Zhao-Yu; Cheng, Jin-Ning [School of Marine Science and Technology, Harbin Institute of Technology, Weihai 264209 (China)

2017-04-01

Highlights: • The polyaniline multi-walled carbon nanotubes composite with core-shell structures was synthetized via in situ chemical oxidative polymerization, and the materials were characterized by physical and chemical methods. • The PANI/WMCNTs was synthetized via in situ chemical oxidative polymerization with core-shell structures. • The WMCNTs highly enhanced the conductivity of composites. • The comopsites were more conducive to the intercalation and deintercalation of anions and cations. • The much better performance as the cathode for lithium-ion cells was acquired for the composites. • The composites are low cost and eco-friendly which have a good prospect in future. - Abstract: The aniline was polymerized onto functionalized multi-walled carbon nanotubes in order to obtain a cathode material with core-shell structures for lithium batteries. The structure and morphology of the samples were investigated by Fourier transform infrared spectroscopy analysis, scanning electron microscope, transmission electron microscope and X-ray diffraction. The electrochemical properties of the composite were characterized by the cyclic voltammetry, the charge/discharge property, coulombic efficiency, and ac impedance spectroscopy in detail. At a constant current density of 0.2 C, the first specific discharge capacity of the reduced and oxidized PANI/WMCNTs were 181.8 mAh/g and 135.1 mAh/g separately, and the capacity retention rates were corresponding to 76.75% and 86.04% for 100 cycles with 99% coulombic efficiency. It was confirmed that the CNTs obviously enhanced the conductivity and electrochemical performance of polyaniline, and compared with the pure PANI, the reduced composite possessed a quite good performance for the cathode of lithium batteries.

Balancing surface adsorption and diffusion of lithium-polysulfides on nonconductive oxides for lithium?sulfur battery design

OpenAIRE

Tao, Xinyong; Wang, Jianguo; Liu, Chong; Wang, Haotian; Yao, Hongbin; Zheng, Guangyuan; Seh, Zhi Wei; Cai, Qiuxia; Li, Weiyang; Zhou, Guangmin; Zu, Chenxi; Cui, Yi

2016-01-01

Lithium?sulfur batteries have attracted attention due to their six-fold specific energy compared with conventional lithium-ion batteries. Dissolution of lithium polysulfides, volume expansion of sulfur and uncontrollable deposition of lithium sulfide are three of the main challenges for this technology. State-of-the-art sulfur cathodes based on metal-oxide nanostructures can suppress the shuttle-effect and enable controlled lithium sulfide deposition. However, a clear mechanistic understandin...

Porous-Shell Vanadium Nitride Nanobubbles with Ultrahigh Areal Sulfur Loading for High-Capacity and Long-Life Lithium-Sulfur Batteries.

Science.gov (United States)

Ma, Lianbo; Yuan, Hao; Zhang, Wenjun; Zhu, Guoyin; Wang, Yanrong; Hu, Yi; Zhao, Peiyang; Chen, Renpeng; Chen, Tao; Liu, Jie; Hu, Zheng; Jin, Zhong

2017-12-13

Lithium-sulfur (Li-S) batteries hold great promise for the applications of high energy density storage. However, the performances of Li-S batteries are restricted by the low electrical conductivity of sulfur and shuttle effect of intermediate polysulfides. Moreover, the areal loading weights of sulfur in previous studies are usually low (around 1-3 mg cm -2 ) and thus cannot fulfill the requirement for practical deployment. Herein, we report that porous-shell vanadium nitride nanobubbles (VN-NBs) can serve as an efficient sulfur host in Li-S batteries, exhibiting remarkable electrochemical performances even with ultrahigh areal sulfur loading weights (5.4-6.8 mg cm -2 ). The large inner space of VN-NBs can afford a high sulfur content and accommodate the volume expansion, and the high electrical conductivity of VN-NBs ensures the effective utilization and fast redox kinetics of polysulfides. Moreover, VN-NBs present strong chemical affinity/adsorption with polysulfides and thus can efficiently suppress the shuttle effect via both capillary confinement and chemical binding, and promote the fast conversion of polysulfides. Benefiting from the above merits, the Li-S batteries based on sulfur-filled VN-NBs cathodes with 5.4 mg cm -2 sulfur exhibit impressively high areal/specific capacity (5.81 mAh cm -2 ), superior rate capability (632 mAh g -1 at 5.0 C), and long cycling stability.

In-situ synthesis of monodisperse micro-nanospherical LiFePO4/carbon cathode composites for lithium-ion batteries

Science.gov (United States)

Gong, Hao; Xue, Hairong; Wang, Tao; He, Jianping

2016-06-01

The LiFePO4 is recognized as the promising cathode material, due to its high specific capacity, excellent, structural stability and environmental benignity. However, it is blamed for the low tap density and poor rate performance when served as the cathode materials for a long time. Here, the microspheric LiFePO4/C composites are successfully synthesized through a one-step in-situ solvothermal method combined with carbothermic reduction. These LiFePO4/C microspheres are assembled by LiFePO4 nanoparticles (∼100 nm) and uniformly coated by the carbon, which show a narrow diameter distribution of 4 μm. As a cathode material for lithium ion batteries, the LiFePO4/C composites can deliver an initiate charge capacity of 155 mAh g-1 and retain 90% of initial capacity after 200 cycles at 0.1 C. When cycled at high current densities up to 20 C, it shows a discharge capacity of ∼60 mAh g-1, exhibiting superior rate performance. The significantly improved electrochemical performance of LiFePO4/C composites material can be attributed to its special micro-nano hierarchical structure. Microspheric LiFePO4/C composites exhibit a high tap density about 1.3 g cm-3. What's more, the well-coated carbon insures the high electrical conductivity and the nano-sized LiFePO4/C particles shorten lithium ion transport, thus exhibiting the high specific capacity, high cycling stability and good rate performance.

A natural carbonized leaf as polysulfide diffusion inhibitor for high-performance lithium-sulfur battery cells.

Science.gov (United States)

Chung, Sheng-Heng; Manthiram, Arumugam

2014-06-01

Attracted by the unique tissue and functions of leaves, a natural carbonized leaf (CL) is presented as a polysulfide diffusion inhibitor in lithium-sulfur (Li-S) batteries. The CL that is covered on the pure sulfur cathode effectively suppresses the polysulfide shuttling mechanism and enables the use of pure sulfur as the cathode. A low charge resistance and a high discharge capacity of 1320 mA h g(-1) arise from the improved cell conductivity due to the innately integral conductive carbon network of the CL. The unique microstructure of CL leads to a high discharge/charge efficiency of >98 %, low capacity fade of 0.18 % per cycle, and good long-term cyclability over 150 cycles. The structural gradient and the micro/mesoporous adsorption sites of CL effectively intercept/trap the migrating polysulfides and facilitate their reutilization. The green CL polysulfide diffusion inhibitor thus offers a viable approach for developing high-performance lithium-sulfur batteries. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

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

Science.gov (United States)

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

2016-12-27

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

Method of making a sodium sulfur battery

Science.gov (United States)

Elkins, Perry E.

1981-01-01

A method of making a portion of a sodium sulfur battery is disclosed. The battery portion made is a portion of the container which defines the volume for the cathodic reactant materials which are sulfur and sodium polysulfide materials. The container portion is defined by an outer metal casing with a graphite liner contained therein, the graphite liner having a coating on its internal diameter for sealing off the porosity thereof. The steel outer container and graphite pipe are united by a method which insures that at the operating temperature of the battery, relatively low electrical resistance exists between the two materials because they are in intimate contact with one another.

Photo-assisted electrochemical abatement of trifluralin using a cathode containing a C60-carbon nanotubes composite.

Science.gov (United States)

Hasanzadeh, Aliyeh; Khataee, Alireza; Zarei, Mahmoud; Joo, Sang Woo

2018-05-01

This work reports the potential application of modified gas-diffusion electrode (GDE) with C 60 -CNT composite, as a stable and efficient cathode material for degradation of trifluralin (TRL) pesticide by photo-assisted electrochemical (PE) process. C 60 -CNT composite was prepared and characterized. Subsequently, a novel C 60 -CNT composite modified GDE cathode was developed and the electrochemical and physical characteristics of the modified GDEs were studied. C 60 -CNT composite/GDE showed great efficiencies for electro-generating H 2 O 2 , owing to huge surface area and high conductivity. Afterwards, a comparative study of TRL oxidation via photolysis, anodic oxidation (AO) and PE processes using C 60 -CNT composite/GDE revealed the degradation percentages of 42.2, 48.5 and 93.4%, respectively, after 180 min of treatment. The TRL degradation followed a pseudo-first-order kinetics, being faster in the order: photolysis composite/GDE exhibited great performance for the degradation of TRL (20 mg L -1 ) under its original pH, Na 2 SO 4 electrolyte concentration of 0.05 mol L -1 , applied current intensity of 300 mA, and flow rate of 12.5 L h -1 . TOC results displayed that 92.8% of TRL was mineralized after 8 h of PE process. In addition, a plausible pathway for mineralization of TRL was proposed according to the identified by-products detected by means of gas chromatography-mass spectroscopy (GC-MS), High-performance liquid chromatography (HPLC) and ion chromatography analyses. Copyright © 2018 Elsevier Ltd. All rights reserved.

A binder-free sulfur/reduced graphene oxide aerogel as high performance electrode materials for lithium sulfur batteries

Science.gov (United States)

Nitze, Florian; Agostini, Marco; Lundin, Filippa; Palmqvist, Anders E. C.; Matic, Aleksandar

2016-12-01

Societies’ increasing need for energy storage makes it necessary to explore new concepts beyond the traditional lithium ion battery. A promising candidate is the lithium-sulfur technology with the potential to increase the energy density of the battery by a factor of 3-5. However, so far the many problems with the lithium-sulfur system have not been solved satisfactory. Here we report on a new approach utilizing a self-standing reduced graphene oxide based aerogel directly as electrodes, i.e. without further processing and without the addition of binder or conducting agents. We can thereby disrupt the common paradigm of “no battery without binder” and can pave the way to a lithium-sulfur battery with a high practical energy density. The aerogels are synthesized via a one-pot method and consist of more than 2/3 sulfur, contained inside a porous few-layered reduced graphene oxide matrix. By combining the graphene-based aerogel cathode with an electrolyte and a lithium metal anode, we demonstrate a lithium-sulfur cell with high areal capacity (more than 3 mAh/cm2 after 75 cycles), excellent capacity retention over 200 cycles and good sulfur utilization. Based on this performance we estimate that the energy density of this concept-cell can significantly exceed the Department of Energy (DEO) 2020-target set for transport applications.

Carbonized cellulose paper as an effective interlayer in lithium-sulfur batteries

International Nuclear Information System (INIS)

Li, Shiqi; Ren, Guofeng; Hoque, Md Nadim Ferdous; Dong, Zhihua; Warzywoda, Juliusz; Fan, Zhaoyang

2017-01-01

Highlights: • A facile and economical method to fabricate interlayer for high-performance lithium-sulfur battery was demonstrated. • The performance of lithium-sulfur batteries without and with interlayer was compared. • The mechanism for the function of interlayer was explained. - Abstract: One of the several challenging problems hampering lithium-sulfur (Li-S) battery development is the so-called shuttling effect of the highly soluble intermediates (Li_2S_8–Li_2S_6). Using an interlayer inserted between the sulfur cathode and the separator to capture and trap these soluble intermediates has been found effective in diminishing this effect. Previously, most reported interlayer membranes were synthesized in a complex and expensive process, and might not be suitable for practical cheap batteries. Herein, a facile method is reported to pyrolyze the commonly used cellulose filter paper into highly flexible and conductive carbon fiber paper. When used as an interlayer, such a carbon paper can improve the cell capacity by several folds through trapping the soluble polysulfides. The enhanced electronic conductivity of the cathode, due to the interlayer, also significantly improves the cell rate performance. In addition, it was demonstrated that such an interlayer can also effectively mitigate the self-discharge problem of the Li-S batteries. This study indicates that the cost-effective pyrolyzed cellulose paper has potential as interlayer for practical Li-S batteries.

Carbonized cellulose paper as an effective interlayer in lithium-sulfur batteries

Energy Technology Data Exchange (ETDEWEB)

Li, Shiqi; Ren, Guofeng; Hoque, Md Nadim Ferdous [Department of Electrical and Computer Engineering and Nano Tech Center, Texas Tech University, Lubbock, TX 79409 (United States); Dong, Zhihua [Hangzhou Dianzi University, No. 1158, 2nd Street, Xiasha Higher Education District, Hangzhou City, Zhejiang Province (China); Warzywoda, Juliusz [Materials Characterization Center, Whitacre College of Engineering, Texas Tech University, Lubbock, TX 79409 (United States); Fan, Zhaoyang, E-mail: zhaoyang.fan@ttu.edu [Department of Electrical and Computer Engineering and Nano Tech Center, Texas Tech University, Lubbock, TX 79409 (United States)

2017-02-28

Highlights: • A facile and economical method to fabricate interlayer for high-performance lithium-sulfur battery was demonstrated. • The performance of lithium-sulfur batteries without and with interlayer was compared. • The mechanism for the function of interlayer was explained. - Abstract: One of the several challenging problems hampering lithium-sulfur (Li-S) battery development is the so-called shuttling effect of the highly soluble intermediates (Li{sub 2}S{sub 8}–Li{sub 2}S{sub 6}). Using an interlayer inserted between the sulfur cathode and the separator to capture and trap these soluble intermediates has been found effective in diminishing this effect. Previously, most reported interlayer membranes were synthesized in a complex and expensive process, and might not be suitable for practical cheap batteries. Herein, a facile method is reported to pyrolyze the commonly used cellulose filter paper into highly flexible and conductive carbon fiber paper. When used as an interlayer, such a carbon paper can improve the cell capacity by several folds through trapping the soluble polysulfides. The enhanced electronic conductivity of the cathode, due to the interlayer, also significantly improves the cell rate performance. In addition, it was demonstrated that such an interlayer can also effectively mitigate the self-discharge problem of the Li-S batteries. This study indicates that the cost-effective pyrolyzed cellulose paper has potential as interlayer for practical Li-S batteries.

The preparation and electrochemical performances of LiFePO4-multiwalled nanotubes composite cathode materials for lithium ion batteries

International Nuclear Information System (INIS)

Feng Yan

2010-01-01

LiFePO 4 -MWCNTs (multi-walled carbon nanotubes) composite cathode materials were prepared by mixing LiFePO 4 and MWCNTs in ethanol followed by heat-treatment at 500 deg. C for 5 h. The structural, morphology and electrochemical performances of LiFePO 4 -MWCNTs composite materials were investigated by X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), galvanostatic charge-discharge cycle tests, cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS). The results indicated that MWCNTs adding improved the electronic conductivity, the discharge capacity, cycle stability and lithium ion diffusion kinetics of LiFePO 4 , but MWCNTs adding did not charge the orthorhombic olivine-type structure of LiFePO 4 . In all these prepared LiFePO 4 with x wt.% MWCNTs (x = 4, 7, 10) composites, 7 wt.% MWCNTs adding composite cathode shows the best electrochemical performance, which gets an initial discharge capacity of 152.7 mAh g -1 at 0.18 C discharge rates with capacity retention ratio of 97.77% after 100 cycles.

Conductive additive content balance in Li-ion battery cathodes: Commercial carbon blacks vs. in situ carbon from LiFePO{sub 4}/C composites

Energy Technology Data Exchange (ETDEWEB)

Palomares, Veronica; Goni, Aintzane; Muro, Izaskun Gil de; Rojo, Teofilo [Departamento de Quimica Inorganica, Universidad del Pais Vasco UPV/EHU, P.O. Box. 644, 48080, Bilbao (Spain); de Meatza, Iratxe; Bengoechea, Miguel [Energy Department, CIDETEC-IK4, P Miramon 196, Parque Tecnologico de San Sebastian, 20009, San Sebastian (Spain); Cantero, Igor [Departamento I+D+i Nuevas Tecnologias, CEGASA, Artapadura, 11, 01013 Vitoria-Gasteiz (Spain)

2010-11-15

Two samples of commercial conducting carbon black and the carbon generated in situ during LiFePO{sub 4}/C composite synthesis from citric acid are studied, with the aim of finding out whether carbon from the composite can fulfil the same function as carbon black in the electrode blend for a Li-ion battery. For this purpose, the carbon samples are analyzed by several techniques, such as X-ray diffraction, Raman spectroscopy, transmission electron microscopy, granulometry, BET specific area and conductivity measurements. Different cathode compositions and component proportions are tested for pellet and cast electrodes. Electrochemical results show that a moderate reduction of commercial carbon black content in both kinds of cathodes, by adding more LiFePO{sub 4}/C composite, enhanced the electrochemical behaviour by around 10%. In situ generated carbon can partially replace commercial conducting carbon black because its high specific surface probably enhances electrolyte penetration into the cathode, but it is always necessary to maintain a minimum amount of carbon black that provides better conductivity in order to obtain a good electrochemical response. (author)

Cathodic corrosion: Part 2. Properties of nanoparticles synthesized by cathodic corrosion

International Nuclear Information System (INIS)

Yanson, A.I.; Yanson, Yu.I.

2013-01-01

We demonstrate how cathodic corrosion in concentrated aqueous solutions enables one to prepare nanoparticles of various metals and metal alloys. Using various characterization methods we show that the composition of nanoparticles remains that of the starting material, and the resulting size distribution remains rather narrow. For the case of platinum we show how the size and possibly even the shape of the nanoparticles can be easily controlled by the parameters of corrosion. Finally, we discuss the advantages of using the nanoparticles prepared by cathodic corrosion for applications in (electro-)catalysis.

The base metal of the oxide-coated cathode

International Nuclear Information System (INIS)

Poret, F.; Roquais, J.M.

2005-01-01

The oxide-coated cathode has been the most widely used electron emitter in vacuum electronic devices. From one manufacturing company to another the emissive oxide is either a double-Ba, Sr-or a triple-Ba, Sr, Ca-oxide, having always the same respective compositions. Conversely, the base metal composition is very often proprietary because of its importance in the cathode emission performances. The present paper aims at explaining the operation of the base metal through a review. After a brief introduction, the notion of activator is detailed along with their diffusivities and their associated interfacial compounds. Then, the different cathode life models are described prior to few comments on the composition choice of a base metal. Finally, the specificities of the RCA/Thomson 'bimetal' base metal are presented with a discussion on the optimized composition choice illustrated by a long-term life-test of five different melts

Electrochemical performance of NCM/LFP/Al composite cathode materials for lithium-ion batteries

Science.gov (United States)

Allahyari, Ehsan; Ghorbanzadeh, Milad; Riahifar, Reza; Hadavi, S. M. M.

2018-05-01

The LiNi0.5Mn0.3Co0.2O2 (NCM) was synthesized via conventional solution combustion synthesis method. Different amounts of LiFePO4 (10, 20 and 30 wt%) were added to NCM via the ball milling technique to improve electrochemical performance including discharge capacity, cycle stability, and rate capability. The LiNi0.5Mn0.3Co0.2O2/LiFePO4 containing 20 wt% LiFePO4 was considered as the optimum composition according to the electrochemical results and SEM images. The Al powder was added to optimum LiNi0.5Mn0.3Co0.2/LiFePO4-0.2 composite through planetary ball mill to enhance the conductivity of LiNi0.5Mn0.3Co0.2O2/LiFePO4-0.2. The LiNi0.5Mn0.3Co0.2O2/LiFePO4-0.2/Al composite cathodes provide better electrochemical performance compared to pure LiNi0.5Mn0.3Co0.2O2 cathodes. The results indicate that by addition of 20 wt% of LiFePO4, the internal resistance of the electrode as well as the charge transfer resistance are reduced. Due to the strong P–O bond of the PO4 in LiFePO4, side reactions between the active electrode and electrolyte is prevented. In addition, according to weakness of the Ionic conductivity in solid electrolyte, in this paper aluminum powders added to the electrode for resolving this problem.

Electrochemical characterization of Pr2CuO4–Ce0.9Gd0.1O1.95 composite cathodes for solid oxide fuel cells

International Nuclear Information System (INIS)

Kolchina, L.M.; Lyskov, N.V.; Petukhov, D.I.; Mazo, G.N.

2014-01-01

Highlights: • PCO–GDC composites are studied as a cathode for SOFCs. • The rate-determined step of the overall electrode process vs. temperature was defined. • PCO–GDC33 composite gave the lowest area surface resistance of 0.41 Ω cm 2 at 700 °C. • PCO–GDC33 is preferred to use as a cathode material for IT-SOFCs. - Abstract: Pr 2 CuO 4 –Ce 0.9 Gd 0.1 O 1.95 (PCO–GDC) composites screen printed on Ce 0.9 Gd 0.1 O 1.95 (GDC) electrolyte were considered as a cathode material for intermediate temperature solid oxide fuel cells (IT-SOFCs). Phase composition, microstructure and electrochemical properties were investigated by X-ray powder diffraction (XRD), scanning electron microscopy and AC impedance spectroscopy, respectively. The oxygen reduction on porous PCO–GDC electrode applied on CGO electrolyte was studied in a symmetrical cell configuration by AC impedance spectroscopy at OCV conditions at 670–730 °C and p O 2 =10 -2 -0.21atm. The charge transfer process and the dissociation of adsorbed molecular oxygen were found to be rate-determining steps of the oxygen reduction reaction. Results reveal that both GDC addition and electrode morphology have strong influence on area specific resistance (ASR) of the electrode/electrolyte interface. The lowest ASR value of 0.41 Ω cm 2 was achieved for the composition containing 33 wt.% GDC at 700 °S in air. The data obtained allow to consider the PCO–GDC33 composite as a promising cathode material for IT-SOFCs

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

Science.gov (United States)

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.

Effects of Electrospun Carbon Nanofibers’ Interlayers on High-Performance Lithium–Sulfur Batteries

Directory of Open Access Journals (Sweden)

Tianji Gao

2017-03-01

Full Text Available Two different interlayers were introduced in lithium–sulfur batteries to improve the cycling stability with sulfur loading as high as 80% of total mass of cathode. Melamine was recommended as a nitrogen-rich (N-rich amine component to synthesize a modified polyacrylic acid (MPAA. The electrospun MPAA was carbonized into N-rich carbon nanofibers, which were used as cathode interlayers, while carbon nanofibers from PAA without melamine was used as an anode interlayer. At the rate of 0.1 C, the initial discharge capacity with two interlayers was 983 mAh g−1, and faded down to 651 mAh g−1 after 100 cycles with the coulombic efficiency of 95.4%. At the rate of 1 C, the discharge capacity was kept to 380 mAh g−1 after 600 cycles with a coulombic efficiency of 98.8%. It apparently demonstrated that the cathode interlayer is extremely effective at shutting down the migration of polysulfide ions. The anode interlayer induced the lithium ions to form uniform lithium metal deposits confined on the fiber surface and in the bulk to strengthen the cycling stability of the lithium metal anode.

A revolution in electrodes: recent progress in rechargeable lithium-sulfur batteries.

Science.gov (United States)

Fang, Xin; Peng, Huisheng

2015-04-01

As a promising candidate for future batteries, the lithium-sulfur battery is gaining increasing interest due to its high capacity and energy density. However, over the years, lithium-sulfur batteries have been plagued by fading capacities and the low Coulombic efficiency derived from its unique electrochemical behavior, which involves solid-liquid transition reactions. Moreover, lithium-sulfur batteries employ metallic lithium as the anode, which engenders safety vulnerability of the battery. The electrodes play a pivotal role in the performance of lithium-sulfur batteries. A leap forward in progress of lithium-sulfur batteries is always accompanied by a revolution in the electrode technology. In this review, recent progress in rechargeable lithium-sulfur batteries is summarized in accordance with the evolution of the electrodes, including the diversified cathode design and burgeoning metallic-lithium-free anodes. Although the way toward application has still many challenges associated, recent progress in lithium-sulfur battery technology still paints an encouraging picture of a revolution in rechargeable batteries. © 2014 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

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

Science.gov (United States)

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 LiMn2-y-zLiyMzO4 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.

Facile Assembly of 3D Porous Reduced Graphene Oxide/Ultrathin MnO2 Nanosheets-S Aerogels as Efficient Polysulfide Adsorption Sites for High-Performance Lithium-Sulfur Batteries.

Science.gov (United States)

Zhao, Xiaojun; Wang, Hui; Zhai, Gaohong; Wang, Gang

2017-05-23

Rechargeable lithium-sulfur (Li-S) batteries are receiving much attention due to their high specific capacity, low cost, and environmental friendliness. Nonetheless, fast capacity decay and low specific capacity still limit their practical implementation. Herein, we report a facile strategy to overcome these challenges by the design and fabrication of 3D porous reduced graphene oxide/ultrathin MnO 2 nanosheets-S aerogel (rGM-SA) composites for Li-S batteries. By a simple solvothermal reaction process, nanosized S atoms are homogeneously decorated into the 3D scaffold formed by reduced graphene oxide (rGO) and MnO 2 nanosheets, which can form the homogeneous rGM-SA composites. In this porous network architecture, rGO serves as an electron and ion transfer pathway, a physical adsorption site for polysulfides, and provides structural stability. The ultrathin MnO 2 nanosheets provide strong binding sites for trapping polysulfide intermediates. The 3D porous rGO/MnO 2 architecture enables rapid ion transport and buffers volume expansion of sulfur during discharge. The rGM-SA composites can be directly used as lithium-sulfur battery cathodes without using binder and conductive additive. As a result of this multifunctional arrangement, the rGM-SA composites exhibit high and stable-specific capacities over 200 cycles and excellent high-rate performances. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Volcanogenic Sulfur on Earth and Io: Composition and Spectroscopy

Science.gov (United States)

Kargel, J.S.; Delmelle, P.; Nash, D.B.

1999-01-01

The causes of Io's variegated surface, especially the roles of sulfur, and the geochemical history of sulfur compounds on Io are not well understood. Suspecting that minor impurities in sulfur might be important, we have investigated the major and trace element chemistry and spectroscopic reflectance of natural sulfur from a variety of terrestrial volcanic-hydrothermal environments. Evidence suggests that Io may be substantially coated with impure sulfur. On Earth, a few tenths of a percent to a few percent of chalcophile trace elements (e.g., As and Se) comonly occur in sulfur and appear to stabilize material of yellow, brown, orange, and red hues, which may persist even at low temperatures. Percentage levels of chalcophile impurities are reasonably expected to occur on Io in vapor sublimate deposits and flows derived from such deposits. Such impurities join a host of other mechanisms that might explain Io's reds and yellows. Two-tenths to two percent opaque crystalline impurities, particularly pyrite (FeS2), commonly produces green, gray, and black volcanic sulfur on Earth and might explain areas of Io having deposits of these colors. Pyrite produces a broad absorption near 1 ??m that gradually diminishes out to 1.6 ??m - similar but not identical to the spectrum of Io seen in Galileo NIMS data. Percentage amounts of carbonaceous impurities and tens of percent SiO2 (as silicates) also strongly affect the spectral properties of Earth's sulfur. Io's broad absorption between 0.52 and 0.64 ??m remains unexplained by these data but could be due to sodium sulfides, as suggested previously by others, or to As, Se, or other impurities. These impurities and others, such as P and Cl (which could exist on Io's surface in amounts over 1% that of sulfur), greatly alter the molecular structure of molten and solid sulfur. Minor impurities could impact Io's geology, such as the morphology of sulfur lava flows and the ability of sulfur to sustain high relief. We have not found

Recent Advances on the Understanding of Structural and Composition Evolution of LMR Cathodes for Li-ion Batteries

Energy Technology Data Exchange (ETDEWEB)

Yan, Pengfei [Environmental Molecular Sciences Laboratory, Pacific Northwest National Laboratory, Richland, WA (United States); Zheng, Jianming; Xiao, Jie [Energy and Environment Directorate, Pacific Northwest National Laboratory, Richland, WA (United States); Wang, Chong-Min, E-mail: chongmin.wang@pnnl.gov [Environmental Molecular Sciences Laboratory, Pacific Northwest National Laboratory, Richland, WA (United States); Zhang, Ji-Guang, E-mail: chongmin.wang@pnnl.gov [Energy and Environment Directorate, Pacific Northwest National Laboratory, Richland, WA (United States)

2015-06-08

Lithium-and-manganese-rich (LMR) cathode materials have been regarded as very promising for lithium (Li)-ion battery applications. However, their practical application is still limited by several barriers such as their limited electrochemical stability and rate capability. In this work, we present recent progress on the understanding of structural and compositional evolution of LMR cathode materials, with an emphasis being placed on the correlation between structural/chemical evolution and electrochemical properties. In particular, using Li[Li{sub 0.2}Ni{sub 0.2}Mn{sub 0.6}]O{sub 2} as a typical example, we clearly illustrate the structural characteristics of pristine materials and their dependence on the material-processing history, cycling-induced structural degradation/chemical partition, and their correlation with electrochemical performance degradation. The fundamental understanding that resulted from this work may also guide the design and preparation of new cathode materials based on the ternary system of transitional metal oxides.

A Transient Model for Fuel Cell Cathode-Water Propagation Behavior inside a Cathode after a Step Potential

Directory of Open Access Journals (Sweden)

Der-Sheng Chan

2010-04-01

Full Text Available Most of the voltage losses of proton exchange membrane fuel cells (PEMFC are due to the sluggish kinetics of oxygen reduction on the cathode and the low oxygen diffusion rate inside the flooded cathode. To simulate the transient flooding in the cathode of a PEMFC, a transient model was developed. This model includes the material conservation of oxygen, vapor, water inside the gas diffusion layer (GDL and micro-porous layer (MPL, and the electrode kinetics in the cathode catalyst layer (CL. The variation of hydrophobicity of each layer generated a wicking effect that moves water from one layer to the other. Since the GDL, MPL, and CL are made of composite materials with different hydrophilic and hydrophobic properties, a linear function of saturation was used to calculate the wetting contact angle of these composite materials. The balance among capillary force, gas/liquid pressure, and velocity of water in each layer was considered. Therefore, the dynamic behavior of PEMFC, with saturation transportation taken into account, was obtained in this study. A step change of the cell voltage was used to illustrate the transient phenomena of output current, water movement, and diffusion of oxygen and water vapor across the entire cathode.

Balancing surface adsorption and diffusion of lithium-polysulfides on nonconductive oxides for lithium-sulfur battery design.

Science.gov (United States)

Tao, Xinyong; Wang, Jianguo; Liu, Chong; Wang, Haotian; Yao, Hongbin; Zheng, Guangyuan; Seh, Zhi Wei; Cai, Qiuxia; Li, Weiyang; Zhou, Guangmin; Zu, Chenxi; Cui, Yi

2016-04-05

Lithium-sulfur batteries have attracted attention due to their six-fold specific energy compared with conventional lithium-ion batteries. Dissolution of lithium polysulfides, volume expansion of sulfur and uncontrollable deposition of lithium sulfide are three of the main challenges for this technology. State-of-the-art sulfur cathodes based on metal-oxide nanostructures can suppress the shuttle-effect and enable controlled lithium sulfide deposition. However, a clear mechanistic understanding and corresponding selection criteria for the oxides are still lacking. Herein, various nonconductive metal-oxide nanoparticle-decorated carbon flakes are synthesized via a facile biotemplating method. The cathodes based on magnesium oxide, cerium oxide and lanthanum oxide show enhanced cycling performance. Adsorption experiments and theoretical calculations reveal that polysulfide capture by the oxides is via monolayered chemisorption. Moreover, we show that better surface diffusion leads to higher deposition efficiency of sulfide species on electrodes. Hence, oxide selection is proposed to balance optimization between sulfide-adsorption and diffusion on the oxides.

Balancing surface adsorption and diffusion of lithium-polysulfides on nonconductive oxides for lithium–sulfur battery design

Science.gov (United States)

Tao, Xinyong; Wang, Jianguo; Liu, Chong; Wang, Haotian; Yao, Hongbin; Zheng, Guangyuan; Seh, Zhi Wei; Cai, Qiuxia; Li, Weiyang; Zhou, Guangmin; Zu, Chenxi; Cui, Yi

2016-01-01

Lithium–sulfur batteries have attracted attention due to their six-fold specific energy compared with conventional lithium-ion batteries. Dissolution of lithium polysulfides, volume expansion of sulfur and uncontrollable deposition of lithium sulfide are three of the main challenges for this technology. State-of-the-art sulfur cathodes based on metal-oxide nanostructures can suppress the shuttle-effect and enable controlled lithium sulfide deposition. However, a clear mechanistic understanding and corresponding selection criteria for the oxides are still lacking. Herein, various nonconductive metal-oxide nanoparticle-decorated carbon flakes are synthesized via a facile biotemplating method. The cathodes based on magnesium oxide, cerium oxide and lanthanum oxide show enhanced cycling performance. Adsorption experiments and theoretical calculations reveal that polysulfide capture by the oxides is via monolayered chemisorption. Moreover, we show that better surface diffusion leads to higher deposition efficiency of sulfide species on electrodes. Hence, oxide selection is proposed to balance optimization between sulfide-adsorption and diffusion on the oxides. PMID:27046216

Ti substrate coated with composite Cr–MoO2 coatings as highly selective cathode materials in hypochlorite production

International Nuclear Information System (INIS)

Lačnjevac, U.Č.; Jović, B.M.; Gajić-Krstajić, Lj.M.; Kovač, J.; Jović, V.D.; Krstajić, N.V.

2013-01-01

Highlights: ► Composite Cr–MoO 2 coatings were prepared by electrodeposition onto mild steel and Ti substrates. ► Ti/Cr–MoO 2 electrodes were investigated as cathode materials for the hypochlorite production. ► Selectivity of electrodes increased with the increase of the content of MoO 2 in the coating. ► The current efficiency for the HER exceeded 97% at the best cathode. ► The suppression of hypochlorite reduction is caused by the presence of Cr 2 O 3 at the surface. -- Abstract: The aim of this work was to investigate the possibility of preparation of the composite Cr–MoO 2 coatings onto steel and titanium substrates as cathode materials with high selective properties which imply the suppression of hypochlorite reduction as a side reaction during hypochlorite commercial production. The electrodes were prepared by simultaneous deposition of chromium and suspended MoO 2 particles on titanium substrate from acid chromium (VI) bath. The current efficiency for electrodeposition of the composite coatings did not vary significantly with the concentration of suspended MoO 2 particles. The content of molybdenum in the deposits was relatively low (0.2–1.5 at.%) and increased with increasing the concentration of suspended MoO 2 particles in the bath, in the range from 0 to 10 g dm −3 . With further increase in the concentration of MoO 2 , the content of molybdenum in the coating varied insignificantly. X-ray photoelectron spectroscopy-XPS and EDS analysis were applied to analyze elemental composition and chemical bonding of elements on the surface and in the sub-surface region of obtained coatings. When the concentration of MoO 2 particles in the bath was raised above 5 g dm −3 , the appearance of the coating changed from the typical pure chromium deposit to needle-like deposit with the appearance of black inclusions on the surface. XPS analysis and corresponding Cr 2p spectra showed the presence of chromium oxide, probably Cr 2 O 3 with Cr(3

The influence of reduced graphene oxide on electrical conductivity of LiFePO4-based composite as cathode material

International Nuclear Information System (INIS)

Arifin, Muhammad; Aimon, Akfiny Hasdi; Winata, Toto; Abdullah, Mikrajuddin; Iskandar, Ferry

2016-01-01

LiFePO 4 is fascinating cathode active materials for Li-ion batteries application because of their high electrochemical performance such as a stable voltage at 3.45 V and high specific capacity at 170 mAh.g −1 . However, their low intrinsic electronic conductivity and low ionic diffusion are still the hindrance for their further application on Li-ion batteries. Therefore, the efforts to improve their conductivity are very important to elevate their prospecting application as cathode materials. Herein, we reported preparation of additional of reduced Graphene Oxide (rGO) into LiFePO 4 -based composite via hydrothermal method and the influence of rGO on electrical conductivity of LiFePO 4 −based composite by varying mass of rGO in composition. Vibration of LiFePO 4 -based composite was detected on Fourier Transform Infrared Spectroscopy (FTIR) spectra, while single phase of LiFePO 4 nanocrystal was observed on X-Ray Diffraction (XRD) pattern, it furthermore, Scanning Electron Microscopy (SEM) images showed that rGO was distributed around LiFePO4-based composite. Finally, the 4-point probe measurement result confirmed that the optimum electrical conductivity is in additional 2 wt% rGO for range 1 to 2 wt% rGO

Sulfur polymer cement concrete

International Nuclear Information System (INIS)

Weber, H.H.; McBee, W.C.

1990-01-01

Sulfur-based composite materials formulated using sulfur polymer cement (SPC) and mineral aggregates are described and compared with conventional portland cement based materials. Materials characteristics presented include mechanical strength, chemical resistance, impact resistance, moisture permeation, and linear shrinkage during placement and curing. Examples of preparation and placement of sulfur polymer cement concrete (SC) are described using commercial scale equipment. SC applications presented are focused into hostile chemical environments where severe portland cement concrete (PCC) failure has occurred

Formation of CuxS Layers on Polypropylene Sulfurized by Molten Sulfur

Directory of Open Access Journals (Sweden)

Rasa ALABURDAITĖ

2011-11-01

Full Text Available The processes of formation of electrically conductive layers of copper sulfides CuxS by the sorption-diffusion method on polypropylene (PP using molten sulfur as sulfurizing agent was investigated. The amount of sorbed sulfur increased with the increase of the duration of treatment. Copper sulfide layers were formed on the surface of polypropylene after the treatment of sulfurized polymer with Cu(II/I salt solution. The amount of copper sulfide in layer increased with the increase of treatment duration in copper salt solution. XRD spectra of PP films treated for 3 min with molten sulfur and then with Cu(II/I salt solution for the different time showed that the copper sulfide phases, mostly digenite, Cu2-xS and a-chalcocite, Cu2S were formed in the layers. Electromotive force measurement results confirmed the composition of formed CuxS layers on PP. The phase composition of layers also changed after the annealing. The value of electrical resistance of copper sulfide layers on PP varied from 20 W/cm2 to 80 W/cm2 and after annealing at 80 °C - in the interval of 10 W/cm2 - 60 W/cm2.http://dx.doi.org/10.5755/j01.ms.17.4.776

Influence of sulfur dioxide on the mineral composition of needles from spruces

Energy Technology Data Exchange (ETDEWEB)

Materna, J

1961-01-01

Until recently all the authors knew about changes in the mineral composition of plants exposed to air pollution was that the sulfur content increases considerably. The question arises whether other mineral substances, too, accumulate in the assimilating organs of smoke injured plants, particularly cations such as calcium, potassium and magnesium. Results of analyses of spruce needles from an air polluted forest in the Erzebirge in Czechoslovakia yielded no relationship between the accumulation of sulfates and the mentioned cations.

High-Performance Lithium-Sulfur Batteries with a Self-Assembled Multiwall Carbon Nanotube Interlayer and a Robust Electrode-Electrolyte Interface.

Science.gov (United States)

Kim, Hee Min; Hwang, Jang-Yeon; Manthiram, Arumugam; Sun, Yang-Kook

2016-01-13

Elemental sulfur electrode has a huge advantage in terms of charge-storage capacity. However, the lack of electrical conductivity results in poor electrochemical utilization of sulfur and performance. This problem has been overcome to some extent previously by using a bare multiwall carbon nanotube (MWCNT) paper interlayer between the sulfur cathode and the polymeric separator, resulting in good electron transport and adsorption of dissolved polysulfides. To advance the interlayer concept further, we present here a self-assembled MWCNT interlayer fabricated by a facile, low-cost process. The Li-S cells fabricated with the self-assembled MWCNT interlayer and a high loading of 3 mg cm(-2) sulfur exhibit a first discharge specific capacity of 1112 mAh g(-1) at 0.1 C rate and retain 95.8% of the capacity at 0.5 C rate after 100 cycles as the self-assembled MWCNT interlayer facilitates good interfacial contact between the interlayer and the sulfur cathode and fast electron and lithium-ion transport while trapping and reutilizing the migrating polysulfides. The approach presented here has the potential to advance the commercialization feasibility of the Li-S batteries.

Hydrothermal synthesis and photoelectrochemical performance enhancement of TiO{sub 2}/graphene composite in photo-generated cathodic protection

Energy Technology Data Exchange (ETDEWEB)

Zhang, Weiwei, E-mail: vivizhg@yahoo.com [College of Material Science and Engineering, Shandong University of Science and Technology, Qingdao 266590 (China); State Key Laboratory of Mining Disaster Prevention and Control Co-founded by Shandong Province and the Ministry of Science and Technology, Shandong University of Science and Technology, Qingdao 266590 (China); Guo, Hanlin; Sun, Haiqing [College of Material Science and Engineering, Shandong University of Science and Technology, Qingdao 266590 (China); Zeng, Rong-Chang [College of Material Science and Engineering, Shandong University of Science and Technology, Qingdao 266590 (China); State Key Laboratory of Mining Disaster Prevention and Control Co-founded by Shandong Province and the Ministry of Science and Technology, Shandong University of Science and Technology, Qingdao 266590 (China)

2016-09-30

Highlights: • TiO{sub 2}/graphene composites were synthesized through one-step hydrothermal method. • A bicrystalline framework of anatase and brookite formed. • Electrons transfer in the biphasic TiO{sub 2} results in electron-hole separation. • Graphene lead to a negative shift of the Fermi level. • The transfer barrier in the TiO{sub 2} and 304 stainless steel interface is decreased. - Abstract: TiO{sub 2}/graphene composites were synthesized through one-step hydrothermal method. The composites show an enhancement in photo-generated cathodic protection as the time-dependent profiles of photocurrent responses has confirmed. XRD data show that a bicrystalline framework of anatase and brookite formed as graphene provided donor groups in the hydrothermal process. The transfer of photoinduced electrons in the biphasic TiO{sub 2} results in effective electron-hole separation. Moreover, graphene lead to a negative shift of the Fermi level as evidenced by Mott–Schottky analysis, which decreases the Schottky barrier formed in the TiO{sub 2} and 304 stainless steel interface and results in the enhancement of photo-generated cathodic protection.

Anode and cathode geometry and shielding gas interdependence in GTAW

International Nuclear Information System (INIS)

Key, J.F.

1979-01-01

Parametric analyses and high-speed photography of the interdependence of electrode (cathode) tip geometry, shielding gas composition, and groove (anode) geometry indicate that spot-on-plate tests show that blunt cathode shapes have penetration effects similar to addition of a high ionization potential inert gas (such as helium) to the argon shielding gas. Electrode shape and shielding gas composition effects are not synergistic. The time required to develop a given penetration is a function of anode and cathode geometry and shielding gas composition, in addition to other essential welding variables. Spot-on-plate tests are a valid analysis of radical pulsed GTAW. Bead-on-plate tests are a valid analysis of mild pulsed or constant current GTAW

INFLUENCE OF SINTERING TEMPERATURE ON THE POLARIZATION RESISTANCE OF LaO20.6SrO20.4CoO20.2FeO20.8O3-δ - SDC CARBONATE COMPOSITE CATHODE

Directory of Open Access Journals (Sweden)

Nurul Akidah Baharuddin

2016-05-01

Full Text Available The effects of sintering temperature of an LSCF-samarium-doped ceria carbonate (SDCC cathode composite film on its polarization resistance (Rp were evaluated in this study. An LSCF-SDCC composite cathode was prepared for cathode film development by electrophoretic deposition (EPD. The LSCF-SDCC composite cathode was prepared at 50:50 weight percentage ratio. An EPD suspension which is based on an organic aqueous solution was used, and a mixture of ethanol and deionized water was used as medium with poly diallyl dimethyl ammonium chloride (PDADMAC as a dispersing agent. SDCC substrate was used, and EPD was performed on both sides. A symmetrical cell with cathode composite LSCF-SDCC films on both sides of the substrate was subjected to sintering at five different temperatures (from 550°C to 750°C. A symmetrical cell was painted using silver paste before undergoing electrochemical performance test (air condition, in which the impedance, Z data, was measured. The effects of sintering temperature change on element content and film porosity were first investigated by energy-dispersive X-ray spectroscopy, field emission scanning electron microscopy, and J-image analysis. Ceramic-based cathode LSCF-SDCC that was sintered at 600°C exhibited the lowest Rp at a value of 0.68 Ω when operated at 650°C. This study proved that EPD has potential in developing IT-LT solid oxide fuel cell cathode components with high electrochemical performance in terms of Rp values.

Effects of cathode pulse at high frequency on structure and composition of Al2TiO5 ceramic coatings on Ti alloy by plasma electrolytic oxidation

International Nuclear Information System (INIS)

Yao Zhongping; Liu Yunfu; Xu Yongjun; Jiang Zhaohua; Wang Fuping

2011-01-01

Research highlights: → Al 2 TiO 5 in the coating on Ti alloy by PEO treatment changes with the increase of the cathode pulse, regardless of the amount and the grain size. → The cathode pulse brings about the decrease of γ-Al 2 O 3 and the increase of rutile TiO 2 in the coating. → The appropriate cathode pulse during PEO process is beneficial to reduce residual discharging channels and improve the density of the coating. - Abstract: The aim of this work is to investigate the effects of cathode pulse under high working frequency on structure and composition of ceramic coatings on Ti-6Al-4V alloys by plasma electrolytic oxidation (PEO). Ceramic coatings were prepared on Ti alloy by pulsed bi-polar plasma electrolytic oxidation in NaAlO 2 solution. The phase composition, morphology and element distribution in the coating were investigated by X-ray diffractometry, scanning electron microscopy and energy distribution spectroscopy, respectively. The coating was mainly composed of a large amount of Al 2 TiO 5 . As the cathode pulse was increased, the amount and grain size of Al 2 TiO 5 were first increased, and then decreased. γ-Al 2 O 3 in the coating was gradually decreased to nothing with the increase in the cathode pulse whereas rutile TiO 2 began to form in the coating. As opposed to the single-polar anode pulse mode, the cathode pulse reduced the thickness of the coatings. However, as the cathode pulse intensity continued to increase, the coating then became thicker regardless of cathode current density or pulse width. In addition, the residual discharging channels were reduced and the density of the coating was increased with the appropriate increase of the cathode pulse.

S-containing copolymer as cathode material in poly(ethylene oxide)-based all-solid-state Li-S batteries

Science.gov (United States)

Gracia, Ismael; Ben Youcef, Hicham; Judez, Xabier; Oteo, Uxue; Zhang, Heng; Li, Chunmei; Rodriguez-Martinez, Lide M.; Armand, Michel

2018-06-01

Inverse vulcanization copolymers (p(S-DVB)) from the radical polymerization of elemental sulfur and divinylbenzene (DVB) have been studied as cathode active materials in poly(ethylene oxide) (PEO)-based all-solid-state Li-S cells. The Li-S cell comprising the optimized p(S-DVB) cathode (80:20 w/w S/DVB ratio) and lithium bis(fluorosulfonyl)imide/PEO (LiFSI/PEO) electrolyte shows high specific capacity (ca. 800 mAh g-1) and high Coulombic efficiency for 50 cycles. Most importantly, polysulfide (PS) shuttle is highly mitigated due to the strong interactions of PS species with polymer backbone in p(S-DVB). This is demonstrated by the stable cycling of the p(S-DVB)-based cell using lithium bis(trifluoromethanesulfonyl)imide (LiTFSI)/PEO electrolyte, where successful charging cannot be achieved even at the first cycle with plain elemental S-based cathode material due to the severe PS shuttle phenomenon. These results suggest that inverse vulcanization copolymers are promising alternatives to elemental sulfur for enhancing the electrochemical performance of PEO-based all-solid-state Li-S cells.

Lanthanum Manganate Based Cathodes for Solid Oxide Fuel Cells

DEFF Research Database (Denmark)

Jørgensen, Mette Juhl

Composite cathodes for solid oxide fuel cells were investigated using electrochemical impedance spectroscopy and scanning electron microscopy. The aim was to study the oxygen reduction process in the electrode in order to minimise the voltage drop in the cathode. The electrodes contained...... five processes were found to affect the impedance of LSM/YSZ composite electrodes. Two high frequency processes were ascribed to transport of oxide ions/oxygen intermediates across LSM/YSZ interfaces and through YSZ in the composite. Several competitive elementary reaction steps, which appear as one...

Synthesis and characterization of high-density LiFePO4/C composites as cathode materials for lithium-ion batteries

International Nuclear Information System (INIS)

Chang Zhaorong; Lv Haojie; Tang Hongwei; Li Huaji; Yuan Xiaozi; Wang Haijiang

2009-01-01

To achieve a high-energy-density lithium electrode, high-density LiFePO 4 /C composite cathode material for a lithium-ion battery was synthesized using self-produced high-density FePO 4 as a precursor, glucose as a C source, and Li 2 CO 3 as a Li source, in a pipe furnace under an atmosphere of 5% H 2 -95% N 2 . The structure of the synthesized material was analyzed and characterized by X-ray diffraction (XRD) and scanning electron microscope (SEM). The electrochemical properties of the synthesized LiFePO 4 /carbon composite were investigated by cyclic voltammetry (CV) and the charge/discharge process. The tap-density of the synthesized LiFePO 4 /carbon composite powder with a carbon content of 7% reached 1.80 g m -3 . The charge/discharge tests show that the cathode material has initial charge/discharge capacities of 190.5 and 167.0 mAh g -1 , respectively, with a volume capacity of 300.6 mAh cm -3 , at a 0.1C rate. At a rate of 5C, the LiFePO 4 /carbon composite shows a high discharge capacity of 98.3 mAh g -1 and a volume capacity of 176.94 mAh cm -3 .

Nano-sized LiFePO4/C composite with core-shell structure as cathode material for lithium ion battery

International Nuclear Information System (INIS)

Liu, Yang; Zhang, Min; Li, Ying; Hu, Yemin; Zhu, Mingyuan; Jin, Hongming; Li, Wenxian

2015-01-01

Graphical abstract: Nano-sized LiFePO4/C composite with core-shell structure was fabricated via a well-designed approach as cathode material forlithium ion battery. The nano-sized LiFePO4/C composite with whole carbon shell coating layer showed an excellent electrical performance. - Abstract: Nano-sized composite with LiFePO 4 -core and carbon-shell was synthesized via a facile route followed by heat treatment at 650 °C. X-ray diffraction (XRD) shows that the core is well crystallized LiFePO 4 . The electron microscopy (SEM and TEM) observations show that the core-shell structured LiFePO 4 /C composite coating with whole carbon shell layer of ∼2.8 nm, possesses a specific surface area of 51 m 2 g −1 . As cathode material for lithium ion battery, the core-shell LiFePO 4 /C composite exhibits high initial capacity of 161 mAh g −1 at 0.1 C, excellent high-rate discharge capacity of 135 mAh g −1 at 5 C and perfect cycling retention of 99.6% at 100 th cycle. All these promising results should be contributed to the core-shell nanostructure which prevents collapse of the particle structure in the long-term charge and discharge cycles, as well as the large surface area of the nano-sized LiFePO 4 /C composite which enhances the electronic conductivity and shortens the distance of lithium ion diffusion

Nickel oxide and carbon nanotube composite (NiO/CNT) as a novel cathode non-precious metal catalyst in microbial fuel cells.

Science.gov (United States)

Huang, Jianjian; Zhu, Nengwu; Yang, Tingting; Zhang, Taiping; Wu, Pingxiao; Dang, Zhi

2015-10-15

Comparing with the precious metal catalysts, non-precious metal catalysts were preferred to use in microbial fuel cells (MFCs) due to the low cost and high oxygen reduction reaction (ORR) efficiency. In this study, the transmission electron microscope and X-ray diffraction as well as Raman investigation revealed that the prepared nanoscale NiO was attached on the surface of CNT. Cyclic voltammogram and rotating ring-disk electrode tests showed that the NiO/CNT composite catalyst had an apparent oxygen reduction peak and 3.5 electron transfer pathway was acquired under oxygen atmosphere. The catalyst performance was highly dependent on the percentage of NiO in the CNT nanocomposites. When 77% NiO/CNT nano-sized composite was applied as cathode catalyst in membrane free single-chamber air cathode MFC, a maximum power density of 670 mW/m(2) and 0.772 V of OCV was obtained. Moreover, the MFC with pure NiO (control) could not achieve more than 0.1 V. All findings suggested that NiO/CNT could be a potential cathode catalyst for ORR in MFCs. Copyright © 2015 Elsevier B.V. All rights reserved.

Cathodic electrogenerated chemiluminescence of aromatic Tb(III) chelates at polystyrene-graphite composite electrodes

International Nuclear Information System (INIS)

Salminen, Kalle; Grönroos, Päivi; Tuomi, Sami; Kulmala, Sakari

2017-01-01

Tb(III) chelates exhibit intense hot electron-induced electrogenerated chemiluminescence during cathodic polarization of metal/polystyrene-graphite (M/PG) electrodes in fully aqueous solutions. The M/PG working electrode provides a sensitive means for the determination of aromatic Tb(III) chelates at nanomolar concentration levels with a linear log-log calibration curve spanning more than five orders of magnitude. The charge transport and other properties of these novel electrodes were studied by electrochemiluminescence measurements and cyclic voltammetry. The present composite electrodes can by utilized both under pulse polarization and DC polarization unlike oxide-coated metal electrodes which do not tolerate cathodic DC polarization. The present cost-effective electrodes could be utilized e.g. in immunoassays where polystyrene is extensively used as a solid phase for various bioaffinity assays by using electrochemiluminescent Tb(III) chelates or e.g. Ru(bpy) 3 2+ as labels. - Highlights: • Generation of hydrated electrons at Polystyrene-graphite electrodes. • The insulating polystyrene layer on the outer electrode surface seems necessary. • Hydrated electrons are able to produce chemiluminescence. • Strongest signal and lowest std. dev. achieved at same graphite weight fraction.

Cu-based metal–organic framework/activated carbon composites for sulfur compounds removal

Energy Technology Data Exchange (ETDEWEB)

Shi, Rui-Hua [State Key Laboratory of Coal Science and Technology, Co-founded by Shanxi Province and the Ministry of Science and Technology, Institute for Chemical Engineering of Coal, Taiyuan University of Technology, West Yingze Street Number 79, Taiyuan 030024 (China); Zhang, Zhen-Rong [Institute of Applied Chemical, Shanxi (China); Fan, Hui-Ling, E-mail: fanhuiling@tyut.edu.cn [State Key Laboratory of Coal Science and Technology, Co-founded by Shanxi Province and the Ministry of Science and Technology, Institute for Chemical Engineering of Coal, Taiyuan University of Technology, West Yingze Street Number 79, Taiyuan 030024 (China); Zhen, Tian [Deparment of Analysis and Service Center Micromertics instrumental Ltd, Shanghai (China); Shangguan, Ju; Mi, Jie [State Key Laboratory of Coal Science and Technology, Co-founded by Shanxi Province and the Ministry of Science and Technology, Institute for Chemical Engineering of Coal, Taiyuan University of Technology, West Yingze Street Number 79, Taiyuan 030024 (China)

2017-02-01

Highlights: • Incorporation of AC less than 2% in MOF-199 can increase micropores and BET surface area, as evidenced by N{sub 2} adsorption. • Lewis acid (unsaturated copper) sites could also be increased in the modified MOF-199, as revealed by Py-IR characterization. • Composite with 2% AC showed highest sulfur capacity with 8.46 and 8.53% for H{sub 2}S and CH{sub 3}SCH{sub 3}, respectively. • The adsorption of CH{sub 3}SCH{sub 3} on composite is reversible, physic-adsorption and weak chemisorption were involved. - Abstract: MOF-199 was modified by incorporating activated carbon (AC) during its synthesis under hydrothermal conditions to improve its performance in the removal of hydrogen sulfide (H{sub 2}S) and dimethyl sulfide (CH{sub 3}SCH{sub 3}). A variety of different characterization techniques including X-ray diffraction (XRD), Fourier transform infrared (FT-IR) spectroscopy, nitrogen adsorption/desorption isotherms, scanning electron microscopy (SEM), pyridine adsorption infrared spectroscopy (Py-IR), thermogravimetric- mass spectroscopy (TG-MS) and X-ray photoelectron spectroscopy (XPS) were used to analyze the fresh and exhausted composites. It was found that the composites, which have an amount of AC of less than 2%, had the same morphology as those of pristine MOF-199, but exhibited a more ordered crystallinity structure as well as higher surface area. The composite with 2% AC incorporation showed highest sulfur capacity of 8.46 and 8.53% for H{sub 2}S and CH{sub 3}SCH{sub 3}, respectively, which increased by 51 and 41% compared to that of MOF-199. This improvement was attributed to the formation of more micropores and especially the increased number of unsaturated copper metal sites, as revealed by Py-IR. It is suggested the chemical reaction was apparent during adsorption of H{sub 2}S, which resulted in the formation of CuS and the collapse of the MOF structure. Whereas reversible chemisorption was found for CH{sub 3}SCH{sub 3} adsorption, as

Experimental Studies of the Effects of Anode Composition and Process Parameters on Anode Slime Adhesion and Cathode Copper Purity by Performing Copper Electrorefining in a Pilot-Scale Cell

Science.gov (United States)

Zeng, Weizhi; Wang, Shijie; Free, Michael L.

2016-10-01

Copper electrorefining tests were conducted in a pilot-scale cell under commercial tankhouse environment to study the effects of anode compositions, current density, cathode blank width, and flow rate on anode slime behavior and cathode copper purity. Three different types of anodes (high, mid, and low impurity levels) were used in the tests and were analyzed under SEM/EDS. The harvested copper cathodes were weighed and analyzed for impurities concentrations using DC Arc. The adhered slimes and released slimes were collected, weighed, and analyzed for compositions using ICP. It was shown that the lead-to-arsenic ratio in the anodes affects the sintering and coalescence of slime particles. High current density condition can improve anode slime adhesion and cathode purity by intensifying slime particles' coalescence and dissolving part of the particles. Wide cathode blanks can raise the anodic current densities significantly and result in massive release of large slime particle aggregates, which are not likely to contaminate the cathode copper. Low flow rate can cause anode passivation and increase local temperatures in front of the anode, which leads to very intense sintering and coalescence of slime particles. The results and analyses of the tests present potential solutions for industrial copper electrorefining process.

Honeycomb-like Nitrogen and Sulfur Dual-Doped Hierarchical Porous Biomass-Derived Carbon for Lithium-Sulfur Batteries.

Science.gov (United States)

Chen, Manfang; Jiang, Shouxin; Huang, Cheng; Wang, Xianyou; Cai, Siyu; Xiang, Kaixiong; Zhang, Yapeng; Xue, Jiaxi

2017-04-22

Honeycomb-like nitrogen and sulfur dual-doped hierarchical porous biomass-derived carbon/sulfur composites (NSHPC/S) are successfully fabricated for high energy density lithium-sulfur batteries. The effects of nitrogen, sulfur dual-doping on the structures and properties of the NSHPC/S composites are investigated in detail by transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS), X-ray diffraction (XRD), and charge/discharge tests. The results show that N, S dual-doping not only introduces strong chemical adsorption and provides more active sites but also significantly enhances the electronic conductivity and hydrophilic properties of hierarchical porous biomass-derived carbon, thereby significantly enhancing the utilization of sulfur and immobilizing the notorious polysulfide shuttle effect. Especially, the as-synthesized NSHPC-7/S exhibits high initial discharge capacity of 1204 mA h g -1 at 1.0 C and large reversible capacity of 952 mA h g -1 after 300 cycles at 0.5 C with an ultralow capacity fading rate of 0.08 % per cycle even at high sulfur content (85 wt %) and high active material areal mass loading (2.8 mg cm -2 ) for the application of high energy density Li-S batteries. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Influence of sulfur, phosphorus, and antimony segregation on the intergranular hydrogen embrittlement of nickel

International Nuclear Information System (INIS)

Bruemmer, S.M.; Baer, D.R.; Jones, R.H.; Thomas, M.T.

1983-01-01

The effectiveness of sulfur, phosphorus, and antimony in promoting the intergranular embrittlement of nickel was investigated using straining electrode tests in 1N H 2 SO 4 at cathodic potentials. Sulfur was found to be the critical grain boundary segregant due to its large enrichment at grain boundaries (10 4 to 10 5 times the bulk content) and the direct relationship between sulfur coverage and hydrogeninduced intergranular failure. Phosphorus was shown to be significantly less effective than sulfur or antimony in inducing the intergranular hydrogen embrittlement of nickel. The addition of phosphoru to nickel reduced the tendency for intergranular fracture and improved ductility because phosphoru segregated strongly to grain interfaces and limited sulfur enrichment. The hydrogen embrittling potency of antimony was also less than that of sulfur while its segregation propensity was considerably less. It was found that the effectiveness of segregated phosphorus and antimony in prompting inter granular embrittlement vs that of sulfur could be expressed in terms of an equivalent grain boundary sulfur coverage. The relative hydrogen embrittling potencies of sulfur, phosphorus, and antimony are discussed in reference to general mechanisms for the effect of impurity segregation on hydrogeninduced intergranular fracture

Composition-Graded MoWSx Hybrids with Tailored Catalytic Activity by Bipolar Electrochemistry.

Science.gov (United States)

Tan, Shu Min; Pumera, Martin

2017-12-06

Among transition metal dichalcogenide (TMD)-based composites, TMD/graphene-related material and bichalcogen TMD composites have been widely studied for application toward energy production via the hydrogen evolution reaction (HER). However, scarcely any literature explored the possibility of bimetallic TMD hybrids as HER electrocatalysts. The use of harmful chemicals and harsh preparation conditions in conventional syntheses also detracts from the objective of sustainable energy production. Herein, we present the conservational alternative synthesis of MoWS x via one-step bipolar electrochemical deposition. Through bipolar electrochemistry, the simultaneous fabrication of composition-graded MoWS x hybrids, i.e., sulfur-deficient Mo x W (1-x) S 2 and Mo x W (1-x) S 3 (MoWS x /BPE cathodic and MoWS x /BPE anodic , respectively) under cathodic and anodic overpotentials, was achieved. The best-performing MoWS x /BPE cathodic and MoWS x /BPE anodic materials exhibited Tafel slopes of 45.7 and 50.5 mV dec -1 , together with corresponding HER overpotentials of 315 and 278 mV at -10 mA cm -2 . The remarkable HER activities of the composite materials were attributed to their small particle sizes, as well as the near-unity value of their surface Mo/W ratios, which resulted in increased exposed HER-active sites and differing active sites for the concurrent adsorption of protons and desorption of hydrogen gas. The excellent electrocatalytic performances achieved via the novel methodology adopted here encourage the empowerment of electrochemical deposition as the foremost fabrication approach toward functional electrocatalysts for sustainable energy generation.

Synthesis of LiFePO4/Graphene Nano composite and Its Electrochemical Properties as Cathode Material for Li-Ion Batteries

International Nuclear Information System (INIS)

Ma, X.; Chen, G.; Liu, Q.; Zeng, G.; Wu, T.

2014-01-01

LiFePO 4 /graphene nano composite was successfully synthesized by rheological phase method and its electrochemical properties as the cathode materials for lithium ion batteries were measured. As the iron source in the synthesis, FeOOH nano rods anchored on graphene were first synthesized. The FeOOH nano rods precursors and the final LiFePO 4 /graphene nano composite products were characterized by XRD, SEM, and TEM. While the FeOOH precursors were nano rods with 5-10 nm in diameter and 10-50 nm in length, the LiFePO 4 were nanoparticles with 20-100 nm in size. Compared with the electrochemical properties of LiFePO 4 particles without graphene nano sheets, it is clear that the graphene nano sheets can improve the performances of LiFePO 4 as the cathode material for lithium ion batteries. The as-synthesized LiFePO 4 /graphene nano composite showed high capacities and good cyclabilities. When measured at room temperature and at the rate of 0.1 C (1 C = 170 mA g -1 ), the composite showed a discharge capacity of 156 mA h g -1 in the first cycle and a capacity retention of 96% after 15 cycles. The improved performances of the composite are believed to be the result of the three-dimensional conducting network formed by the flexible and planar graphene nano sheets.

Synthesis and electrochemical characterization of mesoporous Li2FeSiO4/C composite cathode material for Li-ion batteries

Science.gov (United States)

Kumar, Ajay; Jayakumar, O. D.; Bazzi, Khadije; Nazri, Gholam-Abbas; Naik, Vaman M.; Naik, Ratna

2015-03-01

Lithium iron silicate (Li2FeSiO4) has the potential as cathode for Li ion batteries due to its high theoretical capacity (~ 330 mAh/g) and improved safety. The application of Li2FeSiO4 as cathode material has been challenged by its poor electronic conductivity and slow lithium ion diffusion in the solid phase. In order to solve these problems, we have synthesized mesoporous Li2FeSiO4/C composites by sol-gel method using the tri-block copolymer (P123) as carbon source. The phase purity and morphology of the composite materials were characterized by x-ray diffraction, SEM and TEM. The XRD pattern confirmed the formation of ~ 12 nm size Li2FeSiO4 crystallites in composites annealed at 600 °C for 6 h under argon atmosphere. The electrochemical properties are measured using the composite material as positive electrode in a standard coin cell configuration with lithium as the active anode and the cells were tested using AC impedance spectroscopy, cyclic voltammetry, and galvanostatic charge/discharge cycling. The Li2FeSiO4/C composites showed a discharge capacity of ~ 240 mAh/g at a rate of C/30 at room temperature. The effect of different annealing temperature and synthesis time on the electrochemical performance of Li2FeSiO4/C will be presented.

The influence of reduced graphene oxide on electrical conductivity of LiFePO{sub 4}-based composite as cathode material

Energy Technology Data Exchange (ETDEWEB)

Arifin, Muhammad; Aimon, Akfiny Hasdi; Winata, Toto; Abdullah, Mikrajuddin [Physics of Electronic Materials Research Division, Department of Physics, Institut Teknologi Bandung, Bandung 40132 Indonesia (Indonesia); Iskandar, Ferry, E-mail: ferry@fi.itb.ac.id [Physics of Electronic Materials Research Division, Department of Physics, Institut Teknologi Bandung, Bandung 40132 Indonesia (Indonesia); Research Center for Nanoscience and Nanotechnology Institut Teknologi Bandung, Bandung 40132 Indonesia (Indonesia)

2016-02-08

LiFePO{sub 4} is fascinating cathode active materials for Li-ion batteries application because of their high electrochemical performance such as a stable voltage at 3.45 V and high specific capacity at 170 mAh.g{sup −1}. However, their low intrinsic electronic conductivity and low ionic diffusion are still the hindrance for their further application on Li-ion batteries. Therefore, the efforts to improve their conductivity are very important to elevate their prospecting application as cathode materials. Herein, we reported preparation of additional of reduced Graphene Oxide (rGO) into LiFePO{sub 4}-based composite via hydrothermal method and the influence of rGO on electrical conductivity of LiFePO{sub 4}−based composite by varying mass of rGO in composition. Vibration of LiFePO{sub 4}-based composite was detected on Fourier Transform Infrared Spectroscopy (FTIR) spectra, while single phase of LiFePO{sub 4} nanocrystal was observed on X-Ray Diffraction (XRD) pattern, it furthermore, Scanning Electron Microscopy (SEM) images showed that rGO was distributed around LiFePO4-based composite. Finally, the 4-point probe measurement result confirmed that the optimum electrical conductivity is in additional 2 wt% rGO for range 1 to 2 wt% rGO.

Tailored Core Shell Cathode Powders for Solid Oxide Fuel Cells

Energy Technology Data Exchange (ETDEWEB)

Swartz, Scott [NexTech Materials, Ltd.,Lewis Center, OH (United States)

2015-03-23

In this Phase I SBIR project, a “core-shell” composite cathode approach was evaluated for improving SOFC performance and reducing degradation of lanthanum strontium cobalt ferrite (LSCF) cathode materials, following previous successful demonstrations of infiltration approaches for achieving the same goals. The intent was to establish core-shell cathode powders that enabled high performance to be obtained with “drop-in” process capability for SOFC manufacturing (i.e., rather than adding an infiltration step to the SOFC manufacturing process). Milling, precipitation and hetero-coagulation methods were evaluated for making core-shell composite cathode powders comprised of coarse LSCF “core” particles and nanoscale “shell” particles of lanthanum strontium manganite (LSM) or praseodymium strontium manganite (PSM). Precipitation and hetero-coagulation methods were successful for obtaining the targeted core-shell morphology, although perfect coverage of the LSCF core particles by the LSM and PSM particles was not obtained. Electrochemical characterization of core-shell cathode powders and conventional (baseline) cathode powders was performed via electrochemical impedance spectroscopy (EIS) half-cell measurements and single-cell SOFC testing. Reliable EIS testing methods were established, which enabled comparative area-specific resistance measurements to be obtained. A single-cell SOFC testing approach also was established that enabled cathode resistance to be separated from overall cell resistance, and for cathode degradation to be separated from overall cell degradation. The results of these EIS and SOFC tests conclusively determined that the core-shell cathode powders resulted in significant lowering of performance, compared to the baseline cathodes. Based on the results of this project, it was concluded that the core-shell cathode approach did not warrant further investigation.

Isotopic composition of reduced and oxidized sulfur in the Canary Islands: implications for the mantle S cycle

Science.gov (United States)

Beaudry, P.; Longpre, M. A.; Wing, B. A.; Bui, T. H.; Stix, J.

2017-12-01

The Earth's mantle contains distinct sulfur reservoirs, which can be probed by sulfur isotope analyses of volcanic rocks and gases. We analyzed the isotopic composition of reduced and oxidized sulfur in a diverse range of volcanically derived materials spanning historical volcanism in the Canary Islands. Our sample set consists of subaerial volcanic tephras from three different islands, mantle and sedimentary xenoliths, as well as lava balloon samples from the 2011-2012 submarine El Hierro eruption and associated crystal separates. This large sample set allows us to differentiate between the various processes responsible for sulfur isotope heterogeneity in the Canary archipelago. Our results define an array in triple S isotope space between the compositions of the MORB and seawater sulfate reservoirs. Specifically, the sulfide values are remarkably homogeneous around d34S = -1 ‰ and D33S = -0.01 ‰, while sulfate values peak at d34S = +4 ‰ and D33S = +0.01 ‰. Lava balloons from the El Hierro eruption have highly enriched sulfate d34S values up to +19.3 ‰, reflecting direct interaction between seawater sulfate and the erupting magma. Several sulfate data points from the island of Lanzarote also trend towards more positive d34S up to +13.8 ‰, suggesting interaction with seawater sulfate-enriched lithologies or infiltration of seawater within the magmatic system. On the other hand, the modal values and relative abundances of S2- and S6+ in crystal separates suggest that the Canary Island mantle source has a d34S around +3 ‰, similar to the S-isotopic composition of a peridotite xenolith from Lanzarote. We infer that the S2- and S6+ modes reflect isotopic equilibrium between those species in the magmatic source, which requires 80 % of the sulfide to become oxidized after melting, consistent with measured S speciation. This 34S enrichment of the source could be due to the recycling of hydrothermally-altered oceanic crust, which has been previously suggested

Influence of carbon black distribution on performance of oxide cathodes for Li ion batteries

International Nuclear Information System (INIS)

Dominko, Robert; Gaberscek, Miran; Drofenik, Jernej; Bele, Marjan; Jamnik, Janez

2003-01-01

The influence of carbon black content and carbon black distribution on performance of oxide-based cathodes, such as LiCoO 2 and LiMn 2 O 4 , is investigated. The electronic conductivity of oxide material/carbon black composites is compared with electrochemical characteristics of the same composites. Uniformity of carbon black distribution in cathode composites is achieved using novel coating technology in cathode preparation. In this technology, the active particles are first pretreated in a gelatin solution. The adsorbed gelatin then controls the deposition of carbon black so that carbon black particles are uniformly distributed in the final composite. The influence of various parameters, such as pH of gelatin, amount of gelatin and concentration of carbon black on the uniformity of carbon black distribution is investigated. It is shown that the conventional technology of cathode preparation yields quite non-uniform distribution of carbon black in cathode material. At the end, we demonstrate that uniformity of carbon black distribution has a crucial impact on reversible capacity, especially at high current densities

Dynamics of a Novel Class of Polymers: Polymerized Sulfur

Science.gov (United States)

Masser, Kevin; Kim, Jenny; Oleshko, Vladimir; Griebel, Jared; Chung, Woo; Simmons, Adam; Pyun, Jeff; Soles, Christopher

2013-03-01

In this study we investigate the dynamics of a new type of polymer, consisting mainly of sulfur. Room-temperature stable polymerized sulfur samples were prepared by crosslinking the well-known living sulfur polymers formed at elevated temperatures by the addition of a crosslinking agent. This reverse vulcanization process was used to create a series of samples with different amounts of crosslinking agent. These polymers show great promise for use in advanced batteries as cathode materials. Each system exhibits a glassy-state beta relaxation, with the intensity of this relaxation proportional to the crosslinking content. A dynamic glass transition is also observed for each system, and the glass transition temperature/segmental relaxation moves to higher temperatures with increased crosslink content as is typically observed in crosslinked systems. As is typical of polymers, ion motion in these systems is closely coupled to the backbone motion of the host polymer. National Research Council Postdoctoral Fellowship

Effect of sulfur dioxide partial pressure on the reaction of iodine, sulfur dioxide and water

International Nuclear Information System (INIS)

Nakajima, Hayato; Imai, Yoshiyuki; Kasahara, Seiji; Kubo, Shinji; Onuki, Kaoru

2007-01-01

Effect of sulfur dioxide partial pressure on the reaction of iodine, sulfur dioxide and water, which is a unit reaction in the IS process for thermochemical hydrogen production, was studied experimentally at 323 K under iodine saturation. Quasi-equilibrium state was observed in the presence of sulfur dioxide gas at constant pressure. The composition of the poly-hydriodic acid solution formed was discussed assuming an ideal desulfurization by the reverse reaction of the Bunsen reaction. The value of HI/(HI+H 2 O) of the desulfurized solution was large at high sulfur dioxide pressure and reached the maximum of 15.7 ± 0.3 mol%. (author)

Elaboration and characterisation of functionally graded cathodes for solid oxide fuel cells

Energy Technology Data Exchange (ETDEWEB)

Simonet, J.; Kapelski, G.; Bouvard, D. [Laboratoire de Genie Physique et Mecanique des Materiaux, Institut National Polytechnique de Grenoble, CNRS UMR 5010, BP 46, 38042 Saint Martin d' Heres cedex (France)

2005-07-01

The industrial development of solid oxide fuel cells (SOFC) requires decreasing their operating temperature from 1000 deg. C to 700 deg. C while keeping acceptable mechanical and electrochemical performances. A solution consists in designing composite bulk cathodes with numerous electro-chemical reaction sites. The fabrication of such cathodes has been investigated with classical materials as lanthanum strontium manganese (LSM) and yttrium stabilized zirconia (YSZ), which is also the constitutive material of the electrolyte. A composite cathode with continuous composition gradient has been obtained by co-sedimentation of the powders in a liquid and subsequent firing. The obtained composition is investigated with Scanning Electron Microscope (SEM) and Electron Dispersive Spectrometry (EDS). It is found to be in good agreement with the prediction of a numerical model of the sedimentation process. (authors)

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

Energy Technology Data Exchange (ETDEWEB)

Yan, Pengfei; Zheng, Jianming; Kuppan, Saravanan; Li, Qiuyan; Lv, Dongping; Xiao, Jie; Chen, Guoying; Zhang, Jiguang; Wang, Chong M.

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 coupled 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.

Modeling and Predicting the Electrical Conductivity of Composite Cathode for Solid Oxide Fuel Cell by Using Support Vector Regression

Science.gov (United States)

Tang, J. L.; Cai, C. Z.; Xiao, T. T.; Huang, S. J.

2012-07-01

The electrical conductivity of solid oxide fuel cell (SOFC) cathode is one of the most important indices affecting the efficiency of SOFC. In order to improve the performance of fuel cell system, it is advantageous to have accurate model with which one can predict the electrical conductivity. In this paper, a model utilizing support vector regression (SVR) approach combined with particle swarm optimization (PSO) algorithm for its parameter optimization was established to modeling and predicting the electrical conductivity of Ba0.5Sr0.5Co0.8Fe0.2 O3-δ-xSm0.5Sr0.5CoO3-δ (BSCF-xSSC) composite cathode under two influence factors, including operating temperature (T) and SSC content (x) in BSCF-xSSC composite cathode. The leave-one-out cross validation (LOOCV) test result by SVR strongly supports that the generalization ability of SVR model is high enough. The absolute percentage error (APE) of 27 samples does not exceed 0.05%. The mean absolute percentage error (MAPE) of all 30 samples is only 0.09% and the correlation coefficient (R2) as high as 0.999. This investigation suggests that the hybrid PSO-SVR approach may be not only a promising and practical methodology to simulate the properties of fuel cell system, but also a powerful tool to be used for optimal designing or controlling the operating process of a SOFC system.

High energy density layered-spinel hybrid cathodes for lithium ion rechargeable batteries

Energy Technology Data Exchange (ETDEWEB)

Basu, S., E-mail: sbasumajumder@yahoo.com [Department of Physics, Indian Institute of Technology Kharagpur, Kharagpur 721 302 (India); Dahiya, P.P.; Akhtar, Mainul [Materials Science Center, Indian Institute of Technology Kharagpur, Kharagpur 721 302 (India); Ray, S.K. [Department of Physics, Indian Institute of Technology Kharagpur, Kharagpur 721 302 (India); Chang, J.K. [Institute of Materials Science and Engineering, National Central University, Taiwan (China); Majumder, S.B. [Materials Science Center, Indian Institute of Technology Kharagpur, Kharagpur 721 302 (India)

2016-11-15

Highlights: • Structural integration of layered domains in spinel matrix of the composite particles. • Highest discharge capacity (275 mAh g{sup −1}) in composite with 30.0 mole% Li{sub 2}MnO{sub 3}. • Reasonably good rate capability of layered-spinel composite cathode. • Capacity fading with cycling is related to cubic to tetragonal structural phase transition. - Abstract: High energy density Li{sub 2}MnO{sub 3} (layered)–LiMn{sub 1.5}Ni{sub 0.5}O{sub 4} (spinel) composite cathodes have been synthesized using auto-combustion route. Rietveld refinements together with the analyses of high resolution transmission electron micrographs confirm the structural integration of Li{sub 2}MnO{sub 3} nano-domains into the LiMn{sub 1.5}Ni{sub 0.5}O{sub 4} matrix of the composite cathodes. The discharge capacity of the composite cathodes are due to the intercalation of Li{sup +} ion in the tetrahedral (8a) and octahedral (16c) sites of the spinel component and also the insertion of Li{sup +} in the freshly prepared MnO{sub 2} lattice, formed after Li{sub 2}O extraction from the Li{sub 2}MnO{sub 3} domains. The capacity fading of the composite cathodes are explained to be due to the layered to spinel transition of the Li{sub 2}MnO{sub 3} component and Li{sup +} insertion into the octahedral site of the spinel lattices which trigger cubic to tetragonal phase transition resulting volume expansion which eventually retard the Li{sup +} intercalation with cycling.

High Performance Fe-Co Based SOFC Cathodes

DEFF Research Database (Denmark)

Kammer Hansen, Kent; Hansen, Karin Vels; Mogensen, Mogens Bjerg

2010-01-01

With the aim of reducing the temperature of the solid oxide fuel cell (SOFC), a new high-performance perovskite cathode has been developed. An area-specific resistance (ASR) as low as 0.12 Ωcm2 at 600 °C was measured by electrochemical impedance spectroscopy (EIS) on symmetrical cells. The cathode...... is a composite between (Gd0.6Sr0.4)0.99Fe0.8Co0.2O3-δ (GSFC) and Ce0.9Gd0.1O1.95 (CGO10). Examination of the microstructure of the cathodes by scanning electron microscopy (SEM) revealed a possibility of further optimisation of the microstructure in order to increase the performance of the cathodes. It also...... seems that an adjustment of the sintering temperature will make a lowering of the ASR value possible. The cathodes were compatible with ceria-based electrolytes but reacted to some extent with zirconia-based electrolytes depending on the sintering temperature....

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

Energy Technology Data Exchange (ETDEWEB)

Chen, Yu [Georgia Inst. of Technology, Atlanta, GA (United States); Ding, Dong [Georgia Inst. of Technology, Atlanta, GA (United States); Wei, Tao [Georgia Inst. of Technology, Atlanta, GA (United States); Liu, Meilin [Georgia Inst. of Technology, Atlanta, GA (United States)

2016-03-31

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 contaminants 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, CO₂, 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

Toward High-Performance Lithium-Sulfur Batteries: Upcycling of LDPE Plastic into Sulfonated Carbon Scaffold via Microwave-Promoted Sulfonation.

Science.gov (United States)

Kim, Patrick J; Fontecha, Harif D; Kim, Kyungho; Pol, Vilas G

2018-05-02

Lithium-sulfur batteries were intensively explored during the last few decades as next-generation batteries owing to their high energy density (2600 Wh kg -1 ) and effective cost benefit. However, systemic challenges, mainly associated with polysulfide shuttling effect and low Coulombic efficiency, plague the practical utilization of sulfur cathode electrodes in the battery market. To address the aforementioned issues, many approaches have been investigated by tailoring the surface characteristics and porosities of carbon scaffold. In this study, we first present an effective strategy of preparing porous sulfonated carbon (PSC) from low-density polyethylene (LDPE) plastic via microwave-promoted sulfonation. Microwave process not only boosts the sulfonation reaction of LDPE but also induces huge amounts of pores within the sulfonated LDPE plastic. When a PSC layer was utilized as an interlayer in lithium-sulfur batteries, the sulfur cathode delivered an improved capacity of 776 mAh g -1 at 0.5C and an excellent cycle retention of 79% over 200 cycles. These are mainly attributed to two materialistic benefits of PSC: (a) porous structure with high surface area and (b) negatively charged conductive scaffold. These two characteristics not only facilitate the improved electrochemical kinetics but also effectively block the diffusion of polysulfides via Coulomb interaction.

Electrospun LiFePO₄/C Composite Fiber Membrane as a Binder-Free, Self-Standing Cathode for Power Lithium-Ion Battery.

Science.gov (United States)

Chen, Li-Li; Shen, Xiang-Qian; Jing, Mao-Xiang; Zhu, Sheng-Wen; Pi, Zhi-Chao; Li, Jing-Quan; Zhai, Hong-Ai; Xiao, Ke-Song

2018-07-01

A LiFePO4/C composite fiber membrane was fabricated by the electrospinning method and subsequent thermal treatment. The thermal decomposition process was analyzed by TG/DSC, the morphology, microstructure and composition were studied using SEM, TEM, XRD, Raman, respectively. The results indicated that the prepared LiFePO4/C composite fibers were composed of nanosized LiFePO4 crystals and amorphous carbon coatings, which formed a three dimensional (3D) long-range networks, greatly enhanced the electronic conductivity of LiFePO4 electrode up to 3.59× 10-2 S · cm-2. The 3D LiFePO4/C fiber membrane could be directly used as a binder-free, self-standing cathode for lithium-ion battery, and exhibited an improved capacity and rate performance. The LiFePO4/C composite electrode delivered a discharge capacity of 116 mAh·g-1, 109 mAh·g-1, 103 mAh·g-1, 91 mAh·g-1, 80 mAh·g-1 at 0.1 C, 0.5 C, 1 C, 3 C, 5 C, respectively. And a stable cycling performance was also achieved that the specific capacity could retain 75 mA·g-1 after 500 cycles at 5 C. Therefore, this LiFePO4/C composite fiber membrane was promising to be used as a cathode for power lithium ion battery.

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

Science.gov (United States)

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

2014-10-01

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

Performance Enhancement of Small Molecular Solar Cells by Bilayer Cathode Buffer.

Science.gov (United States)

Sun, Qinjun; Zhao, Huanbin; Zhou, Miao; Gao, Liyan; Hao, Yuying

2016-04-01

An effective composite bilayer cathode buffer structure is proposed for use in small molecular solar cells. CsF was doped in Alq3 to form the first cathode buffer, leading to small serial resistances. BCP was used as the second cathode buffer to block the holes to the electrode. The optimized bilayer cathode buffer significantly increased the short circuit and fill factor of devices. By integrating this bilayer cathode buffer, the CuPc/C60 small molecular heterojunction cell exhibited a power conversion efficiency of up to 0.8%, which was an improvement of 56% compared to a device with only the Alq3 cathode buffer. Meanwhile, the bilayer cathode buffer still has a good protective effect on the performance of the device.

Synthesis and characterization of high-density LiFePO{sub 4}/C composites as cathode materials for lithium-ion batteries

Energy Technology Data Exchange (ETDEWEB)

Chang Zhaorong [College of Chemistry and Environmental Science, Henan Normal University, Xinxiang 453007 (China)], E-mail: czr_56@163.com; Lv Haojie; Tang Hongwei; Li Huaji [College of Chemistry and Environmental Science, Henan Normal University, Xinxiang 453007 (China); Yuan Xiaozi; Wang Haijiang [Institute for Fuel Cell Innovation, National Research Council of Canada, Vancouver, BC, V6T 1W5 (Canada)

2009-08-01

To achieve a high-energy-density lithium electrode, high-density LiFePO{sub 4}/C composite cathode material for a lithium-ion battery was synthesized using self-produced high-density FePO{sub 4} as a precursor, glucose as a C source, and Li{sub 2}CO{sub 3} as a Li source, in a pipe furnace under an atmosphere of 5% H{sub 2}-95% N{sub 2}. The structure of the synthesized material was analyzed and characterized by X-ray diffraction (XRD) and scanning electron microscope (SEM). The electrochemical properties of the synthesized LiFePO{sub 4}/carbon composite were investigated by cyclic voltammetry (CV) and the charge/discharge process. The tap-density of the synthesized LiFePO{sub 4}/carbon composite powder with a carbon content of 7% reached 1.80 g m{sup -3}. The charge/discharge tests show that the cathode material has initial charge/discharge capacities of 190.5 and 167.0 mAh g{sup -1}, respectively, with a volume capacity of 300.6 mAh cm{sup -3}, at a 0.1C rate. At a rate of 5C, the LiFePO{sub 4}/carbon composite shows a high discharge capacity of 98.3 mAh g{sup -1} and a volume capacity of 176.94 mAh cm{sup -3}.

Silver-coated LiVPO4F composite with improved electrochemical performance as cathode material for lithium-ion batteries

Science.gov (United States)

Yang, Bo; Yang, Lin

2015-12-01

Nano-structured LiVPO4F/Ag composite cathode material has been successfully synthesized via a sol-gel route. The structural and physical properties, as well as the electrochemical performance of the material are compared with those of the pristine LiVPO4F. X-ray diffraction (XRD) and scanning electron microscopy (SEM) reveal that Ag particles are uniformly dispersed on the surface of LiVPO4F without destroying the crystal structure of the bulk material. An analysis of the electrochemical measurements show that the Ag-modified LiVPO4F material exhibits high discharge capacity, good cycle performance (108.5 mAh g-1 after 50th cycles at 0.1 C, 93% of initial discharge capacity) and excellent rate behavior (81.8 mAh g-1 for initial discharge capacity at 5 C). The electrochemical impedance spectroscopy (EIS) results reveal that the adding of Ag decreases the charge-transfer resistance (Rct) of LiVPO4F cathode. This study demonstrates that Ag-coating is a promising way to improve the electrochemical performance of the pristine LiVPO4F for lithium-ion batteries cathode material.

Influence of the radial spacing between cathodes on the surface composition of iron samples sintered by hollow cathode electric discharge

Directory of Open Access Journals (Sweden)

Brunatto S.F.

2001-01-01

Full Text Available The present work reports an investigation of the influence of the radial spacing between cathodes on the iron sintering process by hollow cathode electrical discharge, with surface enrichment of the alloying elements Cr and Ni. Pressed cylindrical samples of 9.5 mm diameter and density of 7.0 ± 0.1 g/cm³ were prepared by compaction of Ancorsteel 1000C iron powder. These samples, constituting the central cathode, were positioned concentrically in the interior of an external cathode machined from a tube of stainless steel AISI 310 (containing: 25% Cr, 16% Ni, 1.5% Mn, 1.5% Si, 0.03% C and the remainder Fe. Sintering was done at 1150 °C, for 120 min, utilizing radial spacings between the central and hollow cathodes of 3, 6 and 9 mm and a gas mixture of 80% Ar and 20% H2, with a flow rate of 5 cm³/s at a pressure of 3 Torr. The electric discharge was generated using a pulsed voltage power source, with a period of 200 mus. The radial spacing had only a slight influence on the quantity of atoms of alloying elements deposited and diffused on the surface of the sample. Analysis with a microprobe showed the presence of chrome (up to 4.0% and nickel (up to 3.0%, in at. % at the surface of the samples. This surface enrichment can be attributed to the mechanism of sputtering of the metallic atoms present in the external cathode, with the deposition of these elements on the sample surface and consequent diffusion within the sample.

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

Science.gov (United States)

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

2016-11-23

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

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

Science.gov (United States)

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

2018-04-01

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

Study of Poly (3,4-ethylenedioxythiophene)/MnO2 as Composite Cathode Materials for Aluminum-Air Battery

International Nuclear Information System (INIS)

Kuo, Yu-Lin; Wu, Ching-Chen; Chang, Wen-Sheng; Yang, Ching-Ru; Chou, Hung-Lung

2015-01-01

Highlights: • Open-tunnel structure of MnO 2 catalysts were prepared by the hydrothermal method. • PEDOT was deposited on MnO 2 /carbon paper by oxidative chemical vapor deposition. • PEDOT/α-MnO 2 /10AA composite cathode shows the highest discharge performance. • The enhancement on discharge performance was due to the clear charge transfer. - Abstract: This study focuses on the development of the composite electrode materials for an aluminum-air battery and improving the oxygen reduction reaction (ORR) of the air electrode by matching alpha- and beta- manganese dioxide (MnO 2 ) with poly-(3,4-ethylenedioxythiophene) (PEDOT) conducting polymer. The catalyst powders of α-MnO 2 and β-MnO 2 are prepared by hydrothermal method with different precursors, while PEDOT conducting polymer is subsequently deposited on the screen-printed electrodes (MnO 2 /carbon paper) by oxidative chemical vapor deposition (oCVD). Material characteristics of prepared MnO 2 powder and PEDOT layer are investigated by X-ray diffraction (XRD), scanning electron microscopy (SEM) and Raman scattering spectroscopy. The half-cell polarization curve test is found to be strongly depended on the crystalline phases of MnO 2 . From experimental observations and a density functional theory (DFT) study, the conductivity of PEDOT/α-MnO 2 is found to be higher than PEDOT/β-MnO 2 contributed to structural effect mediated improvements in charge transfer. As a result, integrating the deposition of PEDOT on α-MnO 2 /carbon paper as composite cathode is suitable for the use in aluminum-air battery

Biomass carbon composited FeS2 as cathode materials for high-rate rechargeable lithium-ion battery

Science.gov (United States)

Xu, Xin; Meng, Zhen; Zhu, Xueling; Zhang, Shunlong; Han, Wei-Qiang

2018-03-01

Pyrite FeS2 has long been used as commercial primary lithium batteries at room temperature. To achieve rechargeable FeS2 battery, biomass-carbon@FeS2 composites are prepared using green and renewable auricularia auricula as carbon source through the process of carbonization and sulfuration. The auricularia auricula has strong swelling characteristics to absorb aqueous solution which can effectively absorb Fe ions into its body. FeS2 homogeneously distributed in biomass carbon matrix performs high electronic and ionic conductivity. The specific capacity of biomass-carbon@FeS2 composites remains 850 mAh g-1 after 80 cycles at 0.5C and 700 mAh g-1 at the rate of 2C after 150 cycles. Biomass-carbon@FeS2 composites exhibit high-rate capacity in lithium-ion battery.

Coulometric titration of niobium in 1F sulfuric acid

International Nuclear Information System (INIS)

Pannu, S.S.

1975-01-01

A coulometric titration at constant current has been devised for Nb in 1F sulfuric acid. The titration was based on the oxidation of Nb(III) to Nb(V) by Fe(III) electrogenerated at a graphite anode. Both potentiometric and amperometric end points were used. The Nb(V) was prior reduced at a mercury cathode by exhaustive electrolysis at a current density of 15 ma/mc 2 for at least 10 hr. Ta,V,Ti and a working platinum anode interfered, but the separation of the potentials of Nb(V)/Nb(III) and Ti(IV)/Ti(III) permitted the titration of first Nb and then Ti. The average error for the titration of 0.30 to 13.00 mg of niobium in 100 ml of 1F sulfuric acid was + 0.57%. (author)

Synthesis of selenium/EDTA-derived porous carbon composite as a Li–Se battery cathode

Energy Technology Data Exchange (ETDEWEB)

Zhao, Chenhao, E-mail: zhaochenhao123456@163.com; Fang, Shuzhen; Hu, Zhibiao, E-mail: zhibiaohu@163.com; Qiu, Sheng’en; Liu, Kaiyu [LongYan University, College of Chemistry & Materials Science (China)

2016-07-15

The carbon substrate with unique 3D macroporous structure has been prepared through the immediate carbonization of ethylenediaminetetraacetic acid (EDTA) and KOH mixture. The porous carbon composed of micro- and small mesoporous (2–5 nm) structure has a BET specific surface area of 1824.8 m{sup 2} g{sup −1}. The amorphous and nanosized Se is uniformly encapsulated into the porous structure of porous carbon using melting diffusion route, and the weight content of Se in target Se/C composite can be as high as ~50 %. As an Li–Se battery cathode, the Se/C composite delivers a reversible (2nd) discharge capacity of 597.4 mAh g{sup −1} at 0.24C and retains a discharge capacity of 538.4 mAh g{sup −1} at 0.24C after 100 cycles. Furthermore, the composite also has a stable capacity of 291.0 mAh g{sup −1} at a high current of 4.8C. The high specific area and good porous size of EDTA-derived carbon substrate may a be responsibility for the excellent electrochemical performances of Se/C composite.

Core-shell Li2S@Li3PS4 nanoparticles incorporated into graphene aerogel for lithium-sulfur batteries with low potential barrier and overpotential

Science.gov (United States)

Jiao, Zheng; Chen, Lu; Si, Jian; Xu, Chuxiong; Jiang, Yong; Zhu, Ying; Yang, Yaqing; Zhao, Bing

2017-06-01

Lithium sulfide as a promising cathode material not only have a high theoretical specific capacity, but also can be paired with Li-free anode material to avoid potential safety issues. However, how to prepare high electrochemical performance material is still challenge. Herein, we present a facile way to obtain high crystal quality Li2S nanomaterials with average particle size of about 55 nm and coated with Li3PS4 to form the nano-scaled core-shell Li2S@Li3PS4 composite. Then nano-Li2S@Li3PS4/graphene aerogel is prepared by a simple liquid infiltration-evaporation coating process and used directly as a composite cathode without metal substrate for lithium-sulfur batteries. Electrochemical tests demonstrate that the composite delivers a high discharge capacity of 934.4 mAh g-1 in the initial cycle and retains 485.5 mAh g-1 after 100 cycles at 0.1 C rate. In addition, the composite exhibits much lower potential barrier (∼2.40 V) and overpotential compared with previous reports, indicating that Li2S needs only a little energy to be activated. The excellent electrochemical performances could be attributed to the tiny particle size of Li2S and the superionic conducting Li3PS4 coating layer, which can shorten Li-ion and electron diffusion paths, improve the ionic conductivity, as well as retarding polysulfides dissolution into the electrolyte to some extent.

Enhanced microbial electrosynthesis with three-dimensional graphene functionalized cathodes fabricated via solvothermal synthesis

DEFF Research Database (Denmark)

Aryal, Nabin; Halder, Arnab; Tremblay, Pier-Luc

2016-01-01

by 6.8 fold. It also significantly improved biofilm density and current consumption. A 2-fold increase in specific surface area of the 3D-graphene/carbon felt composite cathode explained in part the formation of more substantial biofilms compared to untreated control. Furthermore, in cyclic voltammetry...... must be implemented. Here, we report the development of a 3D-graphene functionalized carbon felt composite cathode enabling faster electron transfer to the microbial catalyst Sporomusa ovata in a MES reactor. Modification with 3D-graphene network increased the electrosynthesis rate of acetate from CO2...... analysis, 3D-graphene/carbon felt composite cathode exhibited higher current response. The results indicate that the development of a 3D-network cathode is an effective approach to improve microbe-electrode interactions leading to productive MES systems....

Unique aqueous Li-ion/sulfur chemistry with high energy density and reversibility.

Science.gov (United States)

Yang, Chongyin; Suo, Liumin; Borodin, Oleg; Wang, Fei; Sun, Wei; Gao, Tao; Fan, Xiulin; Hou, Singyuk; Ma, Zhaohui; Amine, Khalil; Xu, Kang; Wang, Chunsheng

2017-06-13

Leveraging the most recent success in expanding the electrochemical stability window of aqueous electrolytes, in this work we create a unique Li-ion/sulfur chemistry of both high energy density and safety. We show that in the superconcentrated aqueous electrolyte, lithiation of sulfur experiences phase change from a high-order polysulfide to low-order polysulfides through solid-liquid two-phase reaction pathway, where the liquid polysulfide phase in the sulfide electrode is thermodynamically phase-separated from the superconcentrated aqueous electrolyte. The sulfur with solid-liquid two-phase exhibits a reversible capacity of 1,327 mAh/(g of S), along with fast reaction kinetics and negligible polysulfide dissolution. By coupling a sulfur anode with different Li-ion cathode materials, the aqueous Li-ion/sulfur full cell delivers record-high energy densities up to 200 Wh/(kg of total electrode mass) for >1,000 cycles at ∼100% coulombic efficiency. These performances already approach that of commercial lithium-ion batteries (LIBs) using a nonaqueous electrolyte, along with intrinsic safety not possessed by the latter. The excellent performance of this aqueous battery chemistry significantly promotes the practical possibility of aqueous LIBs in large-format applications.

Ultra-high Rates and Reversible Capacity of Li-S Battery with a Nitrogen-doping Conductive Lewis Base Matrix

International Nuclear Information System (INIS)

Cao, Yong; Li, Xi-long; Zheng, Ming-sen; Yang, Mao-ping; Yang, Xu-lai; Dong, Quan-feng

2016-01-01

Highlights: • A polypyrrole/reduced graphene oxide (PPy/rGO) composite was prepared from in-situ hybridization of graphene oxide and pyrrole without additional oxidant. • Nitrogen doped graphene (NG) was obtained from the calcination of the PPy/rGO composite under 1500 °C and was confirmed with abundant pyridinic type nitrogen doping. • NG was employed as a conductive Lewis base matrix of sulfur cathode and the obtained composite cathode exhibited ultra-high rates and reversible capacity. • The excellent electrochemical performance can be attributed to the efficient adsorption of Li 2 S n (n=4-8) on the pyridinic-N enriched NG surface. - Abstract: To improve the electrochemical performance of lithium sulfur batteries, a conductive Lewis base matrix, nitrogen doped graphene (NG), was prepared here through a facile strategy of annealing a polypyrrole/reduced graphene oxide composite. The obtained NG was demonstrated with enriched pyridinic-N doping and was employed as the matrix of sulfur cathode with ultra-high rates, reversible capacity and high coulombic efficiency. The improved performance can be attributed to the high conductivity of the NG and the enhanced adsorption energy of Li 2 S n (n=4-8) on the NG surface. The NG can act not only as an electronic conductive network but also as a Lewis base “catalyst” matrix that promotes the higher Li 2 S n to be further oxidized completely to S 8 as demonstrated in the cyclic voltammetry curve, which can thus significantly improve the sulfur utilization and cyclic stability even at a high sulfur loading of 75% (w/w) in the S@NG composite.

Improvement of (La{sub 0.74}Bi{sub 0.10}Sr{sub 0.16})MnO{sub 3}-Bi{sub 1.4}Er{sub 0.6}O{sub 3} composite cathodes for intermediate-temperature solid oxide fuel cells

Energy Technology Data Exchange (ETDEWEB)

Li, Junliang; Wang, Shaorong; Sun, Xiufu; Liu, Renzhu; Ye, Xiaofeng; Wen, Zhaoyin [Shanghai Institute of Ceramics, Chinese Academy of Sciences, 1295 Dingxi Road, Shanghai 200050 (China)

2008-12-01

Porous composite cathodes including (La{sub 0.74}Bi{sub 0.10}Sr{sub 0.16})MnO{sub 3-{delta}} (LBSM) and Bi{sub 1.4}Er{sub 0.6}O{sub 3} (ESB) were fabricated and characterized using AC impedance spectroscopy. In our earlier work, the growth and aggregation of ESB particles were found in LBSM-ESB composite cathodes. In this study, therefore, two approaches were used to restrain the growth and aggregation of ESB particles. First, the sintering temperature of the composite cathode was reduced by introducing a sintering function layer, which caused a 22% reduction in the initial polarization resistance (R), but the cathode polarization resistance decreased at a rate of 2.15 x 10{sup -4} {omega} cm{sup 2} h{sup -1} at 700 C during a period of 100 h. Second, nano-sized Gd-doped ceria powder (CGO) was added to the composite cathode system. Stability improvement was achieved at 10 vol% CGO, and the degradation rate at 700 C was 4.01 x 10{sup -5} {omega} cm{sup 2} h{sup -1} during a period of 100 h. (author)

Effect of cathode gas humidification on performance and durability of Solid Oxide Fuel Cells

DEFF Research Database (Denmark)

Nielsen, Jimmi; Hagen, Anke; Liu, Yi-Lin

2010-01-01

The effect of cathode inlet gas humidification was studied on single anode supported Solid Oxide Fuel Cells (SOFC's). The studied cells were Risø 2 G and 2.5 G. The former consists of a LSM:YSZ composite cathode, while the latter consists of a LSCF:CGO composite cathode on a CGO protection layer....... The humidification effect was found to be dependent on both the degree of humidification and the cathode polarization. No significant effect of humidification was found at OCV which rules out the possibility of a traditional poisoning effect with a blocking of active sites. Post-mortem high resolution FEG......-SEM analysis showed clear changes at and around the cathode/electrolyte contact area. In contrast to Risø 2 G cells, a very high tolerance towards humidification of cathode gas air was observed for Risø 2.5 G cells with no detectable effect of humidification even when the humidification was as high as 12.8 mol%...

New doped tungsten cathodes. Applications to power grid tubes

International Nuclear Information System (INIS)

Cachard, J. de; Cadoret, K; Martinez, L.; Veillet, D.; Millot, F.

2001-01-01

Thermionic emission behavior of tungsten/tungsten carbide modified with rare earth (La, Ce, Y) oxides is examined on account of suitability to deliver important current densities in a thermo-emissive set up and for long lifetime. Work functions of potential cathodes have been determined from Richardson plots for La 2 O 3 doped tungsten and for tungsten covered with variable compositions rare earth tungstates. The role of platinum layers covering the cathode was also examined. Given all cathodes containing mainly lanthanum oxides were good emitters, emphasis was put on service lifetime. Comparisons of lifetime in tungsten doped with rare earth oxides and with rare earth tungstates show that microstructure of the operating cathodes may play the major role in the research of very long lifetime cathodes. Based on these results, tests still running show lifetime compatible with power grid tubes applications. (author)

Short, intermediate and mesoscopic range order in sulfur-rich binary glasses

International Nuclear Information System (INIS)

Bychkov, E.; Miloshova, M.; Price, D.L.; Benmore, C.J.; Lorriaux, A.

2006-01-01

Pulsed neutron and high-energy X-ray diffraction, small-angle neutron scattering, Raman spectroscopy and DSC were used to study structural changes on the short, intermediate and mesoscopic range scale for sulfur-rich AsS x (x (ge) 1.5) and GeS x (x (ge) 2) glasses. Two structural regions were found in the both systems. (1) Between stoichiometric (As 2 S 3 and GeS 2 ) and 'saturated' (AsS 2.2 and GeS 2.7 ) compositions, excessive sulfur atoms form sulfur dimers and/or short chains, replacing bridging sulfur in corner-sharing AsS 3/2 and GeS 4/2 units. (2) Above the 'saturated' compositions at (As) x system) appear in the glass network. The glasses become phase separated with the domains of 20-50 (angstrom), presumably enriched with sulfur rings. The longer chains Sn are not stable and crystallize to c-S 8 on ageing of a few days to several months, depending on composition.

Corrosion evaluation of materials in sulfur compound environments

International Nuclear Information System (INIS)

Maoying Teng; Iuanjou Yang

1993-01-01

The para-toluene sulfonic acid (PTSA) serves as a catalyst in producing diethylene glycol dibenzoate (DEGDB) and decomposes with increasing time at elevated temperature. Due to the presence of bisulfite ion, it is important to evaluate the corrosion properties of materials in this metastable environments. A potentiodynamic method was used to screen materials' properties in a PTSA solution. A surface analysis technique was also performed to investigate the oxide films. The critical current density and passive current density were substantially reduced when Fe alloyed with Cr and/or Ni. With the addition of Mo in Fe-Ni-Cr alloys, the critical current density was lowered further to show the beneficial effect of alloyed Mo. A plot of the corrosion rate of materials in DEGDB as a function of Ni/Cr ratio shows the linearity with increasing Ni/Cr ratio, disregard the type of materials. The corrosion rate of pure chromium can be estimated as ∼ 2.0 mpy by extrapolation of the linearity to Ni/Cr = 0. This is also the minimum corrosion rate that even Fe-Ni-Cr alloys were alloyed with Mo. Surface analysis results showed that the dissolution of Fe and/or Ni leads to a higher surface chromium content and results in the formation of chromium oxide on metal surface. This chromium oxide then prevents metal from corrosion. It is concluded that the higher the nickel content the higher the corrosion rate of materials. The composition potential-pH diagrams for Fe-S-H 2 O and Ni-S-H 2 O show that the stability fields of FeS and NiS cover a wide range of pH. The effect of sulfur or sulfide ions in promoting dissolution of Fe and/or Ni are highly possible. The activating influence of sulfur compounds on Ni is stronger than that of Fe, although the highly electronic conductivity of iron sulfides can catalyze the cathodic reaction. Undoubtedly, sulfur compound strongly depassivates high Ni contents materials

Large sulfur isotope fractionations in Martian sediments at Gale crater

Science.gov (United States)

Franz, H. B.; McAdam, A. C.; Ming, D. W.; Freissinet, C.; Mahaffy, P. R.; Eldridge, D. L.; Fischer, W. W.; Grotzinger, J. P.; House, C. H.; Hurowitz, J. A.; McLennan, S. M.; Schwenzer, S. P.; Vaniman, D. T.; Archer, P. D., Jr.; Atreya, S. K.; Conrad, P. G.; Dottin, J. W., III; Eigenbrode, J. L.; Farley, K. A.; Glavin, D. P.; Johnson, S. S.; Knudson, C. A.; Morris, R. V.; Navarro-González, R.; Pavlov, A. A.; Plummer, R.; Rampe, E. B.; Stern, J. C.; Steele, A.; Summons, R. E.; Sutter, B.

2017-09-01

Variability in the sulfur isotopic composition in sediments can reflect atmospheric, geologic and biological processes. Evidence for ancient fluvio-lacustrine environments at Gale crater on Mars and a lack of efficient crustal recycling mechanisms on the planet suggests a surface environment that was once warm enough to allow the presence of liquid water, at least for discrete periods of time, and implies a greenhouse effect that may have been influenced by sulfur-bearing volcanic gases. Here we report in situ analyses of the sulfur isotopic compositions of SO2 volatilized from ten sediment samples acquired by NASA’s Curiosity rover along a 13 km traverse of Gale crater. We find large variations in sulfur isotopic composition that exceed those measured for Martian meteorites and show both depletion and enrichment in 34S. Measured values of δ34S range from -47 +/- 14‰ to 28 +/- 7‰, similar to the range typical of terrestrial environments. Although limited geochronological constraints on the stratigraphy traversed by Curiosity are available, we propose that the observed sulfur isotopic signatures at Gale crater can be explained by equilibrium fractionation between sulfate and sulfide in an impact-driven hydrothermal system and atmospheric processing of sulfur-bearing gases during transient warm periods.

Sulfur and Oxygen Isotopic Composition of Sulfate in the Fresh Water, King Sejong Station, King George Island, Antarctica

Science.gov (United States)

Kim, M.; Lee, I.; Lee, J.; Park, B.; Mayer, B.; Kaufman, A. J.; Park, S.; Kim, G.; Lee, K.

2008-12-01

Isotopic compositions of sulfur (δ34S) and oxygen (δ18O) were measured for the sulfate of the fresh water near the King Sejong Station, King George Island, Antarctica. Sejong station is located in the Barton peninsular of the King George Island. The geology around King Sejong station mainly composed of basalt-andesite, quart monzodiorite, and granodiorite. Lapilli tuff, conglomerate, sandstone, and siltstone occur along the southern and eastern shore of the Barton peninsula. Lapilli tuff also occurs on the highland located on southeastern part of the Barton peninsula. The δ34S values of sulfate extracted from fresh water samples at King Sejong Station range from 13.7 to 16.3 per mil excluding 1 sample. These sulfur values are very narrow in their range compared with those from anthropogenic sources. These sulfur values are 5 to 7 per mil lower than those of typical present seawater. Considering the rocks occurring near the King Sejong station, these sulfur isotopic values do not seem to be related to any evaporites of certain age. In Antarctic region the natural source of sulfate dissolved in water could be originated from marine biogenic source (DMS), sea-salt, volcanic source, or other continental sources. Most of the δ34S values of sulfate at King Sejong station seems to indicate the dominance of marine biogenic origin for the source of sulfur. The δ18O values of sulfate extracted from fresh water samples at King Sejong Station range from 1.9 to 6.4 per mil excluding 1 sample. These oxygen isotope values are lower than those of the sulfate in the present seawater by 6 per mil. However, both sulfur and oxygen isotope values strongly represent the influence of the seawater sulfate. One sample have 2.6 and -1.1 per mil in its δ34S and δ18O values, respectively, that are quite different from the isotopic values of other samples. This sample was collected in the highland far from the King Sejong station. Therefore this sample might reflect the composition of

Predicting Alkylate Yield and its Hydrocarbon Composition for Sulfuric Acid Catalyzed Isobutane Alkylation with Olefins Using the Method of Mathematical Modeling

OpenAIRE

Nurmakanova, А. Е.; Ivashkina, Elena Nikolaevna; Ivanchina, Emilia Dmitrievna; Dolganov, I. A.; Boychenko, S. S.

2015-01-01

The article provides the results of applied mathematical model of isobutane alkylation with olefins catalyzed by sulfuric acid to predict yield and hydrocarbon composition of alkylate caused by the changes in the feedstock composition and process parameters. It is shown that the alkylate produced from feedstock with less mass fraction of isobutane has lower octane value. Wherein the difference in composition of the feedstock contributes to antiknock index by the amount of 1.0-2.0 points.

A review of flexible lithium-sulfur and analogous alkali metal-chalcogen rechargeable batteries.

Science.gov (United States)

Peng, Hong-Jie; Huang, Jia-Qi; Zhang, Qiang

2017-08-29

Flexible energy storage systems are imperative for emerging flexible devices that are revolutionizing our life. Lithium-ion batteries, the current main power sources, are gradually approaching their theoretical limitation in terms of energy density. Therefore, alternative battery chemistries are urgently required for next-generation flexible power sources with high energy densities, low cost, and inherent safety. Flexible lithium-sulfur (Li-S) batteries and analogous flexible alkali metal-chalcogen batteries are of paramount interest owing to their high energy densities endowed by multielectron chemistry. In this review, we summarized the recent progress of flexible Li-S and analogous batteries. A brief introduction to flexible energy storage systems and general Li-S batteries has been provided first. Progress in flexible materials for flexible Li-S batteries are reviewed subsequently, with a detailed classification of flexible sulfur cathodes as those based on carbonaceous (e.g., carbon nanotubes, graphene, and carbonized polymers) and composite (polymers and inorganics) materials and an overview of flexible lithium anodes and flexible solid-state electrolytes. Advancements in other flexible alkali metal-chalcogen batteries are then introduced. In the next part, we emphasize the importance of cell packaging and flexibility evaluation, and two special flexible battery prototypes of foldable and cable-type Li-S batteries are highlighted. In the end, existing challenges and future development of flexible Li-S and analogous alkali metal-chalcogen batteries are summarized and prospected.

submitter On the composition of ammonia–sulfuric-acid ion clusters during aerosol particle formation

CERN Document Server

Schobesberger, S; Bianchi, F; Rondo, L; Duplissy, J; Kürten, A; Ortega, I K; Metzger, A; Schnitzhofer, R; Almeida, J; Amorim, A; Dommen, J; Dunne, E M; Ehn, M; Gagné, S; Ickes, L; Junninen, H; Hansel, A; Kerminen, V -M; Kirkby, J; Kupc, A; Laaksonen, A; Lehtipalo, K; Mathot, S; Onnela, A; Petäjä, T; Riccobono, F; Santos, F D; Sipilä, M; Tomé, A; Tsagkogeorgas, G; Viisanen, Y; Wagner, P E; Wimmer, D; Curtius, J; Donahue, N M; Baltensperger, U; Kulmala, M; Worsnop, D R

2015-01-01

The formation of particles from precursor vapors is an important source of atmospheric aerosol. Research at the Cosmics Leaving OUtdoor Droplets (CLOUD) facility at CERN tries to elucidate which vapors are responsible for this new-particle formation, and how in detail it proceeds. Initial measurement campaigns at the CLOUD stainless-steel aerosol chamber focused on investigating particle formation from ammonia $(NH_3)$ and sulfuric acid $(H-2SO_4)$. Experiments were conducted in the presence of water, ozone and sulfur dioxide. Contaminant trace gases were suppressed at the technological limit. For this study, we mapped out the compositions of small $NH_3–H_2SO_4$ clusters over a wide range of atmospherically relevant environmental conditions. We covered [NH3] in the range from 10. Positively charged clusters grew on average by Δm/Δn = 1.05 and were only observed at sufficiently high $[NH_3]$ / $[H_2SO_4]$. The $H_2SO_4$ molecules of these clusters are partially neutralized by $NH_3$, in close resemblance...

(La{sub 0.74}Bi{sub 0.10}Sr{sub 0.16})MnO{sub 3-{delta}}-(Bi{sub 2}O{sub 3}){sub 0.7}(Er{sub 2}O{sub 3}){sub 0.} {sub 3} composite cathodes for intermediate temperature solid oxide fuel cells

Energy Technology Data Exchange (ETDEWEB)

Li, Junliang; Wang, Shaorong; Wang, Zhengrong; Liu, Renzhu; Wen, Tinglian; Wen, Zhaoyin [Shanghai Institute of Ceramics, Chinese Academy of Sciences, 1295 Dingxi Road, Shanghai 200050 (China)

2008-05-01

(La{sub 0.74}Bi{sub 0.10}Sr{sub 0.16})MnO{sub 3-{delta}} (LBSM)-(Bi{sub 2}O{sub 3}){sub 0.7}(Er{sub 2}O{sub 3}){sub 0.3}(ESB) composite cathodes were fabricated for intermediate-temperature solid oxide fuel cells with Sc-stabilized zirconia as the electrolyte. The performance of these cathodes was investigated at temperatures below 750 C by AC impedance spectroscopy and the results indicated that LBSM-ESB had a better performance than traditional composite electrodes such as LSM-GDC and LSM-YSZ. At 750 C, the lowest interfacial polarization resistance was only 0.11 {omega} cm{sup 2} for the LBSM-ESB cathode, 0.49 {omega} cm{sup 2} for the LSM-GDC cathode, and 1.31 {omega} cm{sup 2} for the LSM-YSZ cathode. The performance of the cathode was improved gradually by increasing the ESB content, and the performance was optimal when the amounts of LBSM and ESB were equal in composite cathodes. This study shows that the sintering temperature of the cathode affected performance, and the optimum sintering temperature for LBSM-ESB was 900 C. (author)

Microstructural characterization of composite cobaltite and lanthanum-based ceria for use as fuel cell cathodes; Caracterizacao microestrutural de compositos a base de cobaltita de lantanio e ceria para aplicacao como catodos de celulas a combustivel

Energy Technology Data Exchange (ETDEWEB)

Rodrigues, E.R.T.; Nascimento, R.M.; Miranda, A.C. de; Lima, A.M. de, E-mail: erickssonrtr@gmail.com [Universidade Federal do Rio Grande do Norte (UFRN), RN (Brazil); Macedo, D.A. [Universidade Federal da Paraiba (UFPB), PB (brazil)

2016-07-01

Fuel cells are devices that convert chemical energy into electricity via redox reactions. In this work, the lanthanum cobaltite doped with strontium and iron (La{sub 0,6}Sr{sub 0,4}Co{sub 0,2}Fe{sub 0,8}O{sub 3} - LSCF) a traditional cathodes material of the fuel cell was mixed with an electrolyte material (composite) to the base ceria doped with gadolinia and a eutectic mixture of lithium carbonates and sodium (CGO-NLC). The powders of LSCF and CGO-NLC were obtained by the citrate method and mixed to obtain a composite cathode. Samples obtained by uniaxial pressure between 5 and 10 MPa were sintered at 1100°C and investigated by X-ray diffraction, scanning electron microscopy and micro hardness test. A symmetric cell cathode / electrolyte / cathode, obtained by co-pressing and co-sintering was investigated by electron microscopy. The results indicated that the composite is chemically stable up to the sintering temperature used. The hardness ranged between 51 and 227 HV. (author)

Biogeochemical conversion of sulfur species in saline lakes of Steppe Altai

Science.gov (United States)

Borzenko, Svetlana V.; Kolpakova, Marina N.; Shvartsev, Stepan L.; Isupov, Vitaly P.

2017-08-01

The aim of the present research is to identify the main mechanisms of sulfur behavior in saline lakes in the course of time and followed transformations in their chemical composition. The influence of water on chemical composition of biochemical processes involved in decomposition of organic matter was determined by the study of behavior of reduced forms of sulfur in lakes. The determination of reduced forms of sulfur was carried out by successive transfer of each form of sulfur to hydrogen sulfide followed by photometric measurements. The other chemical components were determined by standard methods (atomic absorption, potentiometric method, titration method and others). The salt lakes of the Altai steppe were studied in summer season 2013-2015. Analysis of the chemical composition of the saline lakes of Altai Krai has shown that carbonate-, hydrocarbonate- and chloride ions dominate among anions; sodium is main cation; sulfates are found in subordinate amounts. Reduced forms of sulfur occur everywhere: hydrogen and hydrosulfide sulfur S2- prevail in the bottom sediments; its derivative—elemental S0—prevails in the lakes water. The second important species in water of soda lakes is hydrosulfide sulfur S2-, and in chloride lakes is thiosulfate sulfur S2O3 2- . The lag in the accumulation of sulfates in soda lakes in comparison to chloride lakes can be explained by their bacterial reduction, followed by the formation and deposition of iron sulfides in sediments. In chloride lakes gypsum is a predominantly barrier for sulfates.

Sulfur isotopes in coal constrain the evolution of the Phanerozoic sulfur cycle

DEFF Research Database (Denmark)

Canfield, Donald Eugene

2013-01-01

Sulfate is the second most abundant anion (behind chloride) in modern seawater, and its cycling is intimately coupled to the cycling of organic matter and oxygen at the Earth’s surface. For example, the reduction of sulfide by microbes oxidizes vast amounts of organic carbon and the subsequent......, these compositions do not deviate substantially from the modern surface-water input to the oceans. When applied to mass balance models, these results support previous interpretations of sulfur cycle operation and counter recent suggestions that sulfate has been a minor player in sulfur cycling through...... reaction of sulfide with iron produces pyrite whose burial in sediments is an important oxygen source to the atmosphere. The concentrations of seawater sulfate and the operation of sulfur cycle have experienced dynamic changes through Earth’s history, and our understanding of this history is based mainly...

Nitrogen-doped porous “green carbon” derived from shrimp shell: Combined effects of pore sizes and nitrogen doping on the performance of lithium sulfur battery

Energy Technology Data Exchange (ETDEWEB)

Qu, Jiangying, E-mail: qujy@lnnu.edu.cn [Faculty of Chemistry and Chemical Engineering, Liaoning Normal University, Dalian, 116029 (China); Carbon Research Laboratory, Center for Nano Materials and Science, School of Chemical Engineering, State Key Lab of Fine Chemicals, Dalian University of Technology, Dalian, 116024 (China); Lv, Siyuan; Peng, Xiyue; Tian, Shuo; Wang, Jia [Faculty of Chemistry and Chemical Engineering, Liaoning Normal University, Dalian, 116029 (China); Gao, Feng, E-mail: fenggao2003@163.com [Faculty of Chemistry and Chemical Engineering, Liaoning Normal University, Dalian, 116029 (China); Carbon Research Laboratory, Center for Nano Materials and Science, School of Chemical Engineering, State Key Lab of Fine Chemicals, Dalian University of Technology, Dalian, 116024 (China)

2016-06-25

Nitrogen-rich porous “green carbons” derived from abundant shrimp shell shows good performance for Li–S batteries. The strategy in this work is highlighted to selective removal of intrinsic CaCO{sub 3} in shrimp shell followed by KOH activation to tune the pore sizes of the obtained carbons. On the basis of the different porous structures, the discharge capacity of the obtained carbons as Li–S cathodes follows the order of micro-mesoporous carbon>mesoporous carbon>microporous carbon. The high capacity of the micro-mesoporous carbon is attributed to its positive characters such as the coexistence of micro-mesoporous structure, the large pore volume and the high specific surface area. Furthermore, well-dispersed nitrogen in the porous carbons is naturally doped and inherited from shrimp shell, and can help to enhance cycle stability when used as cathodes. As a result, all carbon cathodes exhibit the good cycle stability (>78%) due to their nitrogen doping induced chemical adsorption of sulfur on the surface areas of the porous carbons. Among them, mesoporous carbon cathode shows the best cycle stability with 90% retention within 100 cycles, which is mainly attributed to the synergistic effects of its both large pore size (5.12 nm) and high nitrogen content (6.67 wt %). - Highlights: • Nitrogen-rich porous “green carbons” derived from abundant shrimp shell shows good performance for Li–S batteries. • Intrinsic CaCO{sub 3} in shrimp shell as the natural template plays an important role on tailoring of the pore sizes of the porous carbons. • Nitrogen containing polysaccharide in shrimp shell benefits to produce nitrogen-rich carbons. • The effects of pore sizes on the electrochemical performance are investigated in detail. • The carbon-sulfur cathodes exhibit the good cycle stability because of nitrogen doping induced chemical adsorption of sulfur.

Nitrogen-doped porous “green carbon” derived from shrimp shell: Combined effects of pore sizes and nitrogen doping on the performance of lithium sulfur battery

International Nuclear Information System (INIS)

Qu, Jiangying; Lv, Siyuan; Peng, Xiyue; Tian, Shuo; Wang, Jia; Gao, Feng

2016-01-01

Nitrogen-rich porous “green carbons” derived from abundant shrimp shell shows good performance for Li–S batteries. The strategy in this work is highlighted to selective removal of intrinsic CaCO_3 in shrimp shell followed by KOH activation to tune the pore sizes of the obtained carbons. On the basis of the different porous structures, the discharge capacity of the obtained carbons as Li–S cathodes follows the order of micro-mesoporous carbon>mesoporous carbon>microporous carbon. The high capacity of the micro-mesoporous carbon is attributed to its positive characters such as the coexistence of micro-mesoporous structure, the large pore volume and the high specific surface area. Furthermore, well-dispersed nitrogen in the porous carbons is naturally doped and inherited from shrimp shell, and can help to enhance cycle stability when used as cathodes. As a result, all carbon cathodes exhibit the good cycle stability (>78%) due to their nitrogen doping induced chemical adsorption of sulfur on the surface areas of the porous carbons. Among them, mesoporous carbon cathode shows the best cycle stability with 90% retention within 100 cycles, which is mainly attributed to the synergistic effects of its both large pore size (5.12 nm) and high nitrogen content (6.67 wt %). - Highlights: • Nitrogen-rich porous “green carbons” derived from abundant shrimp shell shows good performance for Li–S batteries. • Intrinsic CaCO_3 in shrimp shell as the natural template plays an important role on tailoring of the pore sizes of the porous carbons. • Nitrogen containing polysaccharide in shrimp shell benefits to produce nitrogen-rich carbons. • The effects of pore sizes on the electrochemical performance are investigated in detail. • The carbon-sulfur cathodes exhibit the good cycle stability because of nitrogen doping induced chemical adsorption of sulfur.

Theory, Investigation and Stability of Cathode Electrocatalytic Activity

Energy Technology Data Exchange (ETDEWEB)

Ding, Dong; Liu, Mingfei; Lai, Samson; Blinn, Kevin; Liu, Meilin

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 and 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

Performance Improvement of an Inhomogeneous Cathode by Infiltration

DEFF Research Database (Denmark)

Seyed-Vakili, S. V.; Graves, Christopher R.; Babaei, A.

2017-01-01

The performance of solid oxide fuel cells (SOFCs) is considerably influenced by the microstructure and chemical composition of cathode materials. Porous La0.85Sr0.15FeO3– Ce0.9Gd0.1O2 composite electrodes were infiltrated by La0.6Sr0.4CoO3 and La0.6Sr0.4FeO3. The effects of infiltration loading...... performance of the electrodes. The electrochemical results revealed that the polarization resistance of the cathodes significantly was decreased by infiltration from 2.59 to 0.034 Ω cm2 measured at 670 °C. The best electrode performance was achieved at a calcination temperature of 770 °C. It was also found...

Lithium secondary batteries: Role of polymer cathode morphology

Science.gov (United States)

Naoi, Katsuhiko; Osaka, Tetsuya; Owens, Boone B.

1988-06-01

Electrically conducting polymers have been utilized both as the cathode and as the electrolyte element of Li secondary cells. Polymer cathodes were limited in their suitability for batteries because of the low energy content associated with low levels of doping and the inclusion of complex ionic species in the cathode. Recent studies have indicated that doping levels up to 100 percent can be achieved in polyanilene. High doping levels in combination with controlled morphologies have been found to improve the energy and rate capabilities of polymer cathodes. A morphology-modifying technique was utilized to enhance the charge/discharge characteristics of Li/liquid electrolyte polypyrrole cells. The polymer is electropolymerized in a preferred orientation morphology when the substrate is first precoated with an insulating film of nitrile butadiene rubber (NBR). Modification of the kinetic behavior of the electrode results from variations in the chemical composition of the NBR.

Methods and apparatuses for making cathodes for high-temperature, rechargeable batteries

Science.gov (United States)

Meinhardt, Kerry D; Sprenkle, Vincent L; Coffey, Gregory W

2014-05-20

The approaches for fabricating cathodes can be adapted to improve control over cathode composition and to better accommodate batteries of any shape and their assembly. For example, a first solid having an alkali metal halide, a second solid having a transition metal, and a third solid having an alkali metal aluminum halide are combined into a mixture. The mixture can be heated in a vacuum to a temperature that is greater than or equal to the melting point of the third solid. When the third solid is substantially molten liquid, the mixture is compressed into a desired cathode shape and then cooled to solidify the mixture in the desired cathode shape.

Electrochemical properties of composite cathodes using Sm doped layered perovskite for intermediate temperature-operating solid oxide fuel cell

Science.gov (United States)

Baek, Seung-Wook; Azad, Abul K.; Irvine, John T. S.; Choi, Won Seok; Kang, Hyunil; Kim, Jung Hyun

2018-02-01

SmBaCo2O5+d (SBCO) showed the lowest observed Area Specific Resistance (ASR) value in the LnBaCo2O5+d (Ln: Pr, Nd, Sm, and Gd) oxide system for the overall temperature ranges tested. The ASR of a composite cathode (mixture of SBCO and Ce0.9Gd0.1O2-d) on a Ce0.9Gd0.1O2-d (CGO91) electrolyte decreased with respect to the CGO91 content; the percolation limit was also achieved for a 50 wt% SBCO and 50 wt% CGO91 (SBCO50) composite cathode. The ASRs of SBCO50 on the dense CGO91 electrolyte in the overall temperature range of 500-750 °C were relatively lower than those of SBCO50 on the CGO91 coated dense 8 mol% yttria-stabilized zirconia (8YSZ) electrolyte for the same temperature range. From 750 °C and for all higher temperatures tested, however, the ASRs of SBCO50 on the CGO91 coated dense 8YSZ electrolyte were lower than those of the CGO91 electrolyte. The maximum power densities of SBCO50 on the Ni-8YSZ/8YSZ/CGO91 buffer layer were 1.034 W cm-2 and 0.611 W cm-2 at 800 °C and 700 °C.

Design of a neutral electro-Fenton system with Fe-Fe2O3/ACF composite cathode for wastewater treatment

International Nuclear Information System (INIS)

Li Jinpo; Ai Zhihui; Zhang Lizhi

2009-01-01

The narrow pH range limits the wide application of Fenton reaction in the wastewater treatment. It is of great importance to widen working pH range of Fenton reaction from strong acidic condition to neutral, even basic ones. In this study, for the first time nanostructured Fe-Fe 2 O 3 was loaded on active carbon fiber (ACF) as an oxygen diffusion cathode to be used in a heterogeneous electro-Fenton (E-Fenton) oxidation system. This novel Fe-Fe 2 O 3 /ACF composite cathode was characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), energy dispersive X-ray (EDX) analysis, transmission electron microscopy (TEM), and element mapping. On the degradation of dye pollutant rhodamine B in water, this heterogeneous E-Fenton system with the Fe-Fe 2 O 3 /ACF cathode showed much higher activity than other E-Fenton systems with commercial zero valent iron powders (Fe 0 ) and ferrous ions (Fe 2+ ) under neutral pH. On the basis of experimental results, we proposed a possible pathway of rhodamine B degradation in this heterogeneous Fe-Fe 2 O 3 /ACF E-Fenton process. This heterogeneous E-Fenton system is very promising to remove organic pollutants in water at neutral pH

Improving lithium-ion battery performances by adding fly ash from coal combustion on cathode film

Energy Technology Data Exchange (ETDEWEB)

Dyartanti, Endah Retno; Jumari, Arif, E-mail: arifjumari@yahoo.com; Nur, Adrian; Purwanto, Agus [Research Group of Battery & Advanced Material, Department of Chemical Engineering, Sebelas Maret University, Jl. Ir. Sutami 36 A Kentingan, Surakarta Indonesia 57126 (Indonesia)

2016-02-08

A lithium battery is composed of anode, cathode and a separator. The performance of lithium battery is also influenced by the conductive material of cathode film. In this research, the use of fly ash from coal combustion as conductive enhancer for increasing the performances of lithium battery was investigated. Lithium iron phosphate (LiFePO{sub 4}) was used as the active material of cathode. The dry fly ash passed through 200 mesh screen, LiFePO{sub 4} and acethylene black (AB), polyvinylidene fluoride (PVDF) as a binder and N-methyl-2-pyrrolidone (NMP) as a solvent were mixed to form slurry. The slurry was then coated, dried and hot pressed to obtain the cathode film. The ratio of fly ash and AB were varied at the values of 1%, 2%, 3%, 4% and 5% while the other components were at constant. The anode film was casted with certain thickness and composition. The performance of battery lithium was examined by Eight Channel Battery Analyzer, the composition of the cathode film was examined by XRD (X-Ray Diffraction), and the structure and morphology of the anode film was analyzed by SEM (Scanning Electron Microscope). The composition, structure and morphology of cathode film was only different when fly ash added was 4% of AB or more. The addition of 2% of AB on cathode film gave the best performance of 81.712 mAh/g on charging and 79.412 mAh/g on discharging.

Impedance of SOFC electrodes: A review and a comprehensive case study on the impedance of LSM:YSZ cathodes

DEFF Research Database (Denmark)

Nielsen, Jimmi; Hjelm, Johan

2014-01-01

It was shown through a comprehensive impedance spectroscopy study that the impedance of the classic composite LSM:YSZ (lanthanum strontium manganite and yttria stabilized zirconia) solid oxide fuel cell (SOFC) cathode can be described well with porous electrode theory. Furthermore, it was illustr......It was shown through a comprehensive impedance spectroscopy study that the impedance of the classic composite LSM:YSZ (lanthanum strontium manganite and yttria stabilized zirconia) solid oxide fuel cell (SOFC) cathode can be described well with porous electrode theory. Furthermore......, it was illustrated through a literature review on SOFC electrodes that porous electrode theory not only describes the classic LSM:YSZ SOFC cathode well, but SOFC electrodes in general. The extensive impedance spectroscopy study of LSM:YSZ cathodes consisted of measurements on cathodes with three different sintering...... temperatures and hence different microstructures and varying degrees of LSM/YSZ solid state interactions. LSM based composite cathodes, where YSZ was replaced with CGO was also studied in order to acquire further knowledge on the chemical compatibility between LSM and YSZ. All impedance measurements were...

Properties of sulfur-extended asphalt concrete

Directory of Open Access Journals (Sweden)

Gladkikh Vitaliy

2016-01-01

Full Text Available Currently, increased functional reliability of asphalt concrete coatings associated with various modifying additives that improve the durability of pavements. Promising builder is a technical sulfur. Asphalt concrete, made using a complex binder consisting of petroleum bitumen and technical sulfur, were calledsSulfur-Extended Asphalt Concrete. Such asphalt concrete, due to changes in the chemical composition of particulate and bitumen, changes the intensity of the interaction at the interface have increased rates of physical and mechanical properties. There was a lack of essential knowledge concerning mechanical properties of the sulfur-bituminous concrete with such an admixture; therefore, we had carried out the necessary examination. It is revealed that a new material satisfies local regulations in terms of compressive and tensile strength, shear resistance, and internal friction.

Development of enhanced sulfur rejection processes

Energy Technology Data Exchange (ETDEWEB)

Yoon, R.H.; Luttrell, G.H.; Adel, G.T.; Richardson, P.E.

1996-03-01

Research at Virginia Tech led to the development of two complementary concepts for improving the removal of inorganic sulfur from many eastern U.S. coals. These concepts are referred to as Electrochemically Enhanced Sulfur Rejection (EESR) and Polymer Enhanced Sulfur Rejection (PESR) processes. The EESR process uses electrochemical techniques to suppress the formation of hydrophobic oxidation products believed to be responsible for the floatability of coal pyrite. The PESR process uses polymeric reagents that react with pyrite and convert floatable middlings, i.e., composite particles composed of pyrite with coal inclusions, into hydrophilic particles. These new pyritic-sulfur rejection processes do not require significant modifications to existing coal preparation facilities, thereby enhancing their adoptability by the coal industry. It is believed that these processes can be used simultaneously to maximize the rejection of both well-liberated pyrite and composite coal-pyrite particles. The project was initiated on October 1, 1992 and all technical work has been completed. This report is based on the research carried out under Tasks 2-7 described in the project proposal. These tasks include Characterization, Electrochemical Studies, In Situ Monitoring of Reagent Adsorption on Pyrite, Bench Scale Testing of the EESR Process, Bench Scale Testing of the PESR Process, and Modeling and Simulation.

Synthesis and electrochemical performance of Li2FeSiO4/C/carbon nanosphere composite cathode materials for lithium ion batteries

International Nuclear Information System (INIS)

Yang, Jinlong; Kang, Xiaochun; Hu, Lin; Gong, Xue; He, Daping; Peng, Tao; Mu, Shichun

2013-01-01

Highlights: •The Li 2 FeSiO 4 /C/CNS was prepared by effective double-carbon composite route. •The CNS as the conductivity belt connects the Li 2 FeSiO 4 /C particles. •The samples have a high capacity and excellent cyclic and rate performance. -- Abstract: Li 2 FeSiO 4 /C/carbon nanosphere (CNS) composites as cathode materials for lithium-ion batteries were synthesized by a simple hydro-chemical method. The double-carbon structural design of glucose pyrolysis-carbon (C) and CNS improved electrochemical performance of the composite where the CNS can build conductivity belts to connect the Li 2 FeSiO 4 /C particles and to favor electronic transmission. The exchange current density and the diffusion coefficient of lithium ions with the composite were 0.208 mA cm −2 and 1.06E−11 cm 2 S −1 , respectively, which were much larger than that of conventional Li 2 FeSiO 4 /C composite cathode materials (i = 0.131 mA cm −2 , D Li = 4.69E−12 cm 2 S −1 ). The electrochemical test results showed that the discharge capacity of 164.7 mA h g −1 could be obtained, and especially, after 60 cycles, 98.4% of the initial discharge capacity remained at 0.1 C of galvanostatic discharge in the potential range of 1.5–4.8 V (vs. Li/Li + ). In addition, the discharge capacity of 92.4 mA h g −1 at 5 C was easily recovered to 159.8 mA h g −1 at 0.1 C

Durability and Performance of High Performance Infiltration Cathodes

DEFF Research Database (Denmark)

Samson, Alfred Junio; Søgaard, Martin; Hjalmarsson, Per

2013-01-01

The performance and durability of solid oxide fuel cell (SOFC) cathodes consisting of a porous Ce0.9Gd0.1O1.95 (CGO) infiltrated with nitrates corresponding to the nominal compositions La0.6Sr0.4Co1.05O3-δ (LSC), LaCoO3-δ (LC), and Co3O4 are discussed. At 600°C, the polarization resistance, Rp......, varied as: LSC (0.062Ωcm2)cathode was found to depend on the infiltrate firing temperature and is suggested to originate...... of the infiltrate but also from a better surface exchange property. A 450h test of an LSC-infiltrated CGO cathode showed an Rp with final degradation rate of only 11mΩcm2kh-1. An SOFC with an LSC-infiltrated CGO cathode tested for 1,500h at 700°C and 0.5Acm-2 (60% fuel, 20% air utilization) revealed no measurable...

Electrochemical characterization of a LiV3O8-polypyrrole composite as a cathode material for lithium ion batteries

International Nuclear Information System (INIS)

Tian Fanghua; Liu Li; Yang Zhenhua; Wang Xingyan; Chen Quanqi; Wang Xianyou

2011-01-01

Research highlights: → LiV 3 O 8 -PPy composite has been synthesized successfully. → LiV 3 O 8 -PPy composite shows better cycling behavior and rate capability than LiV 3 O 8 . → LiV 3 O 8 -PPy composite shows lower electrochemical resistance than LiV 3 O 8 . - Abstract: LiV 3 O 8 -Polypyrrole (LiV 3 O 8 -PPy) composite has been chemically synthesized by an oxidative polymerization of pyrrole monomer on the surface of LiV 3 O 8 using ferric chloride as oxidizing agent. The electrochemical properties of LiV 3 O 8 -PPy composite were systematically investigated using a variety of electrochemical methods. The LiV 3 O 8 -PPy composite electrode exhibited better cycling behavior and superior rate capability as compared with the bare LiV 3 O 8 electrode. Cyclic voltammetry corroborated the galvanostatic cycling tests, with the composite cathode material showing better reversibility than bare material. Finally, fitting the impedance results to an equivalent circuit indicated that the enhanced electrochemical performances of LiV 3 O 8 -PPy composite resulted from a facilitated kinetics of interfacial charge transfer in the presence of PPy.

Understanding the role of lithium polysulfide solubility in limiting lithium-sulfur cell capacity

International Nuclear Information System (INIS)

Shen, Chao; Xie, Jianxin; Zhang, Mei; Andrei, Petru; Hendrickson, Mary; Plichta, Edward J.; Zheng, Jim P.

2017-01-01

Highlights: •At normal rate, LiPS soluble reaction pathway dominates the discharge process. •Reduction of sulfur to Li 2 S 8 is not inhibited by high Li 2 S 8 concentration. •Subsequent LiPS electrochemical reactions are restricted by LiPS solubility. •Specific energy of the Li-S cell was reevaluated considering LiPS solubility. -- Abstract: Although the cathode of lithium-sulfur (Li-S) batteries has a theoretical specific capacity of 1,672 mAh g −1 , its practical capacity is much smaller than this value and depends on the electrolyte/sulfur ratio. The operation of Li-S batteries under lean electrolyte conditions can be challenging, especially in the case when the solubility of lithium polysulfide (LiPS) sets an upper bound for polysulfide dissolution. In this work, specially designed cathode structures and electrolyte configurations were built in order to analyze the effects of LiPS solubility on cell capacity. Two reaction pathways involving the reduction of LiPS in liquid and solid phase are proposed and analyzed. We show that at discharge rates above 0.4 mA cm −2 the reaction in the liquid phase dominates the discharge process. Once the electrolyte becomes saturated, the solid phase LiPS cannot be further reduced and does not contribute to the capacity of the cells. This phenomenon prevents Li-S batteries from achieving their high theoretical specific capacity. Finally, the specific energy of the Li-S cell is reevaluated and discussed considering the limitation imposed by LiPS solubility.

Cathode architectures for alkali metal / oxygen batteries

Science.gov (United States)

Visco, Steven J; Nimon, Vitaliy; De Jonghe, Lutgard C; Volfkovich, Yury; Bograchev, Daniil

2015-01-13

Electrochemical energy storage devices, such as alkali metal-oxygen battery cells (e.g., non-aqueous lithium-air cells), have a cathode architecture with a porous structure and pore composition that is tailored to improve cell performance, especially as it pertains to one or more of the discharge/charge rate, cycle life, and delivered ampere-hour capacity. A porous cathode architecture having a pore volume that is derived from pores of varying radii wherein the pore size distribution is tailored as a function of the architecture thickness is one way to achieve one or more of the aforementioned cell performance improvements.

Selective catalytic reduction of sulfur dioxide to elemental sulfur. Final report

Energy Technology Data Exchange (ETDEWEB)

Liu, W.; Flytzani-Stephanopoulos, M.; Sarofim, A.F.

1995-06-01

This project has investigated new metal oxide catalysts for the single stage selective reduction of SO{sub 2} to elemental sulfur by a reductant, such as CO. Significant progress in catalyst development has been made during the course of the project. We have found that fluorite oxides, CeO{sub 2} and ZrO{sub 2}, and rare earth zirconates such as Gd{sub 2}Zr{sub 2}O{sub 7} are active and stable catalysts for reduction Of SO{sub 2} by CO. More than 95% sulfur yield was achieved at reaction temperatures about 450{degrees}C or higher with the feed gas of stoichiometric composition. Reaction of SO{sub 2} and CO over these catalysts demonstrated a strong correlation of catalytic activity with the catalyst oxygen mobility. Furthermore, the catalytic activity and resistance to H{sub 2}O and CO{sub 2} poisoning of these catalysts were significantly enhanced by adding small amounts of transition metals, such as Co, Ni, Co, etc. The resulting transition metal-fluorite oxide composite catalyst has superior activity and stability, and shows promise in long use for the development of a greatly simplified single-step sulfur recovery process to treat variable and dilute SO{sub 2} concentration gas streams. Among various active composite catalyst systems the Cu-CeO{sub 2} system has been extensively studied. XRD, XPS, and STEM analyses of the used Cu-CeO{sub 2} catalyst found that the fluorite crystal structure of ceria was stable at the present reaction conditions, small amounts of copper was dispersed and stabilized on the ceria matrix, and excess copper oxide particles formed copper sulfide crystals of little contribution to catalytic activity. A working catalyst consisted of partially sulfated cerium oxide surface and partially sulfided copper clusters. The overall reaction kinetics were approximately represented by a first order equation.

High performance Li2MnO3/rGO composite cathode for lithium ion batteries

Science.gov (United States)

Zhao, Wei; Xiong, Lilong; Xu, Youlong; Li, Houli; Ren, Zaihuang

2017-05-01

The novel composite Li2MnO3 (LMO)/reduced graphene oxide (rGO) has been synthesized successfully. Based on the scanning electron microscopy and transmission electron microscopy, LMO is found to distribute separately on the rGO sheets by forming a laminated structure, which is in favor of good electrical contact between the cathode active materials and the rGO matrix, and also facilitates the separation of LMO secondary particles with reduced size. Cyclic voltammetry and electrochemical impedance spectroscopy tests show that the charge transfer resistance decreases from 81.2 Ω for LMO to 29.6 Ω for LMO/rGO composite. The Li-ion diffusion coefficient of LMO/rGO composite is almost triple that of LMO. As a result, the LMO/rGO composite delivers an initial discharge capacity of 284.9 mAh g-1 with a capacity retention of 86.6% after 45 cycles at 0.1 C between 2.0 and 4.6 V. Cycle performance is even better at a higher current density 0.2 C while the retention ratio is up to 97.1% after 45 cycles. The rate capability is also significantly enhanced, and the LMO/rGO composite could exhibit a large discharge capacity of 123.7 mAh g-1 which is more than three times larger than that of LMO (40.8 mAh g-1) at a high rate of 8 C.

The partitioning of sulfur between multicomponent aqueous fluids and felsic melts

Science.gov (United States)

Binder, Bernd; Wenzel, Thomas; Keppler, Hans

2018-02-01

Sulfur partitioning between melt and fluid phase largely controls the environmental impact of volcanic eruptions. Fluid/melt partitioning data also provide the physical basis for interpreting changes in volcanic gas compositions that are used in eruption forecasts. To better constrain some variables that control the behavior of sulfur in felsic systems, in particular the interaction between different volatiles, we studied the partitioning of sulfur between aqueous fluids and haplogranitic melts at 200 MPa and 750-850 °C as a function of oxygen fugacity (Ni-NiO or Re-ReO2 buffer), melt composition (Al/(Na + K) ratio), and fluid composition (NaCl and CO2 content). The data confirm a first-order influence of oxygen fugacity on the partitioning of sulfur. Under "reducing conditions" (Ni-NiO buffer), D fluid/melt is nearly one order of magnitude larger (323 ± 14 for a metaluminous melt) than under "oxidizing conditions" (Re-ReO2 buffer; 74 ± 5 for a metaluminous melt). This effect is likely related to a major change in sulfur speciation in both melt and fluid. Raman spectra of the quenched fluids show the presence of H2S and HS- under reducing conditions and of SO4 2- and HSO4 - under oxidizing conditions, while SO2 is undetectable. The latter observation suggests that already at the Re-ReO2 buffer, sulfur in the fluid is almost completely in the S6+ state and, therefore, more oxidized than expected according to current models. CO2 in the fluid (up to x CO2 = 0.3) has no effect on the fluid/melt partitioning of sulfur, neither under oxidizing nor under reducing conditions. However, the effect of NaCl depends on redox state. While at oxidizing conditions, D fluid/melt is independent of x NaCl, the fluid/melt partition coefficient strongly decreases with NaCl content under reducing conditions, probably due to a change from H2S to NaSH as dominant sulfur species in the fluid. A decrease of D fluid/melt with alkali content in the melt is observed over the entire

Coralline-Like N-Doped Hierarchically Porous Carbon Derived from Enteromorpha as a Host Matrix for Lithium-Sulfur Battery.

Science.gov (United States)

Ji, Shengnan; Imtiaz, Sumair; Sun, Dan; Xin, Ying; Li, Qian; Huang, Taizhong; Zhang, Zhaoliang; Huang, Yunhui

2017-12-22

Coralline-like N-doped hierarchically porous carbon (CNHPC) was prepared through a hydrothermal carbonization process using a sea pollutant enteromorpha as the starting material. The addition of a small amount of glucose during carbonization improved the yield of carbon, and the inherent N contents, especially for pyrrolic N and pyridinic N atoms. After loading 40 wt. % sulfur, the CNHPC/S composite, as a cathode in a Li-S battery, exhibited an initial discharge capacity of 1617 mAh g -1 (96.5 % of theoretical capacity) at 0.1 C and a capacity loss of 0.05 % per charge-discharge cycle after 500 cycles at 0.5 C with a stable Coulombic efficiency of 100 % in carbonate based electrolyte. Such a great performance can be attributed to the coralline-like hierarchically porous infrastructure and inherently abundant N doping. Given the conversion of waste pollutants into valuable energy-storage materials and the easy process, this work features a promising approach to prepare C/S cathodes for Li-S batteries. The special structural and textural characteristics of CNHPC might be attractive to other practical applications such as supercapacitors and catalysis. © 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Steep spatial gradients of volcanic and marine sulfur in Hawaiian rainfall and ecosystems

Energy Technology Data Exchange (ETDEWEB)

Bern, Carleton R., E-mail: cbern@usgs.gov [U.S. Geological Survey, Denver Federal Center, Denver, CO 80225 (United States); Department of Geography University of California, Santa Barbara, CA 93106-4060 (United States); Chadwick, Oliver A. [Department of Geography University of California, Santa Barbara, CA 93106-4060 (United States); Kendall, Carol [U.S. Geological Survey, Menlo Park, CA (United States); Pribil, Michael J. [U.S. Geological Survey, Denver Federal Center, Denver, CO 80225 (United States)

2015-05-01

Sulfur, a nutrient required by terrestrial ecosystems, is likely to be regulated by atmospheric processes in well-drained, upland settings because of its low concentration in most bedrock and generally poor retention by inorganic reactions within soils. Environmental controls on sulfur sources in unpolluted ecosystems have seldom been investigated in detail, even though the possibility of sulfur limiting primary production is much greater where atmospheric deposition of anthropogenic sulfur is low. Here we measure sulfur isotopic compositions of soils, vegetation and bulk atmospheric deposition from the Hawaiian Islands for the purpose of tracing sources of ecosystem sulfur. Hawaiian lava has a mantle-derived sulfur isotopic composition (δ{sup 34}S VCDT) of − 0.8‰. Bulk deposition on the island of Maui had a δ{sup 34}S VCDT that varied temporally, spanned a range from + 8.2 to + 19.7‰, and reflected isotopic mixing from three sources: sea-salt (+ 21.1‰), marine biogenic emissions (+ 15.6‰), and volcanic emissions from active vents on Kilauea Volcano (+ 0.8‰). A straightforward, weathering-driven transition in ecosystem sulfur sources could be interpreted in the shift from relatively low (0.0 to + 2.7‰) to relatively high (+ 17.8 to + 19.3‰) soil δ{sup 34}S values along a 0.3 to 4100 ka soil age-gradient, and similar patterns in associated vegetation. However, sub-kilometer scale spatial variation in soil sulfur isotopic composition was found along soil transects assumed by age and mass balance to be dominated by atmospheric sulfur inputs. Soil sulfur isotopic compositions ranged from + 8.1 to + 20.3‰ and generally decreased with increasing elevation (0–2000 m), distance from the coast (0–12 km), and annual rainfall (180–5000 mm). Such trends reflect the spatial variation in marine versus volcanic inputs from atmospheric deposition. Broadly, these results illustrate how the sources and magnitude of atmospheric deposition can exert controls

Steep spatial gradients of volcanic and marine sulfur in Hawaiian rainfall and ecosystems

International Nuclear Information System (INIS)

Bern, Carleton R.; Chadwick, Oliver A.; Kendall, Carol; Pribil, Michael J.

2015-01-01

Sulfur, a nutrient required by terrestrial ecosystems, is likely to be regulated by atmospheric processes in well-drained, upland settings because of its low concentration in most bedrock and generally poor retention by inorganic reactions within soils. Environmental controls on sulfur sources in unpolluted ecosystems have seldom been investigated in detail, even though the possibility of sulfur limiting primary production is much greater where atmospheric deposition of anthropogenic sulfur is low. Here we measure sulfur isotopic compositions of soils, vegetation and bulk atmospheric deposition from the Hawaiian Islands for the purpose of tracing sources of ecosystem sulfur. Hawaiian lava has a mantle-derived sulfur isotopic composition (δ 34 S VCDT) of − 0.8‰. Bulk deposition on the island of Maui had a δ 34 S VCDT that varied temporally, spanned a range from + 8.2 to + 19.7‰, and reflected isotopic mixing from three sources: sea-salt (+ 21.1‰), marine biogenic emissions (+ 15.6‰), and volcanic emissions from active vents on Kilauea Volcano (+ 0.8‰). A straightforward, weathering-driven transition in ecosystem sulfur sources could be interpreted in the shift from relatively low (0.0 to + 2.7‰) to relatively high (+ 17.8 to + 19.3‰) soil δ 34 S values along a 0.3 to 4100 ka soil age-gradient, and similar patterns in associated vegetation. However, sub-kilometer scale spatial variation in soil sulfur isotopic composition was found along soil transects assumed by age and mass balance to be dominated by atmospheric sulfur inputs. Soil sulfur isotopic compositions ranged from + 8.1 to + 20.3‰ and generally decreased with increasing elevation (0–2000 m), distance from the coast (0–12 km), and annual rainfall (180–5000 mm). Such trends reflect the spatial variation in marine versus volcanic inputs from atmospheric deposition. Broadly, these results illustrate how the sources and magnitude of atmospheric deposition can exert controls over

The Effect of Humidity and Oxygen Partial Pressure on LSM–YSZ Cathode

DEFF Research Database (Denmark)

Knöfel, Christina; Chen, Ming; Mogensen, Mogens Bjerg

2011-01-01

Two series of anode supported solid oxide fuel cells (SOFC) were prepared, one with a composite cathode layer of lanthanum strontium manganite (LSM) and yttria stabilized zirconia (YSZ) on top and the other further has a LSM current collector layer on top. The fuel cells were heat treated at 1...... of manganese concentration and strontium enrichment on the surface of the materials. Formation of monoclinic zirconia and zirconate phases was also observed. These results give a closer insight into possible degradation mechanisms of SOFC composite cathode materials in dependence of humidity and oxygen partial...

Organic sulfur metabolisms in hydrothermal environments.

Science.gov (United States)

Rogers, Karyn L; Schulte, Mitchell D

2012-07-01

Sulfur is central to the metabolisms of many organisms that inhabit extreme environments. While biotic and abiotic cycling of organic sulfur compounds has been well documented in low-temperature anaerobic environments, cycling of organic sulfur in hydrothermal environments has received less attention. Recently published thermodynamic data have been used to estimate aqueous alkyl thiol and sulfide activities in deep-sea hydrothermal systems. Here we use geochemical mixing models to predict fluid compositions that result from mixing end-member hydrothermal fluid from the East Pacific Rise with bottom seawater. These fluid compositions are combined with estimates of methanethiol and dimethylsulfide activities to evaluate energy yields for potential organic sulfur-based metabolisms under hydrothermal conditions. Aerobic respiration has the highest energy yields (over -240 kJ/mol e⁻) at lower temperature; however, oxygen is unlikely to persist at high temperatures, restricting aerobic respiration to mesophilic communities. Nitrite reduction to N₂ has the highest energy yields at higher temperatures (greater than ∼40 °C). Nitrate and nitrite reduction to ammonium also yield significant energy (up to -70 kJ/mol e⁻). Much lower, but still feasible energy yields are calculated for sulfate reduction, disproportionation, and reduction with H₂. Organic compound family and the activity of methanethiol and dimethylsulfide were less important than metabolic strategy in determining overall energy yields. All metabolic strategies considered were exergonic within some portion of the mixing regime suggesting that organic sulfur-based metabolisms may be prevalent within deep-sea hydrothermal vent microbial communities. © 2012 Blackwell Publishing Ltd.

Silver/iron oxide/graphitic carbon composites as bacteriostatic catalysts for enhancing oxygen reduction in microbial fuel cells

Science.gov (United States)

Ma, Ming; You, Shijie; Gong, Xiaobo; Dai, Ying; Zou, Jinlong; Fu, Honggang

2015-06-01

Biofilms from anode heterotrophic bacteria are inevitably formed over cathodic catalytic sites, limiting the performances of single-chamber microbial fuel cells (MFCs). Graphitic carbon (GC) - based nano silver/iron oxide (AgNPs/Fe3O4/GC) composites are prepared from waste pomelo skin and used as antibacterial oxygen reduction catalysts for MFCs. AgNPs and Fe3O4 are introduced in situ into the composites by one-step carbothermal reduction, enhancing their conductivity and catalytic activity. To investigate the effects of Fe species on the antibacterial and catalytic properties, AgNPs/Fe3O4/GC is washed with sulfuric acid (1 mol L-1) for 0.5 h, 1 h, and 5 h and marked as AgNPs/Fe3O4/GC-x (x = 0.5 h, 1 h and 5 h, respectively). A maximum power density of 1712 ± 35 mW m-2 is obtained by AgNPs/Fe3O4/GC-1 h, which declines by 4.12% after 17 cycles. Under catalysis of all AgNP-containing catalysts, oxygen reduction reaction (ORR) proceeds via the 4e- pathway, and no toxic effects to anode microorganisms result from inhibiting the cathodic biofilm overgrowth. With the exception of AgNPs/Fe3O4/GC-5 h, the AgNPs-containing composites exhibit remarkable power output and coulombic efficiency through lowering proton transfer resistance and air-cathode biofouling. This study provides a perspective for the practical application of MFCs using these efficient antibacterial ORR catalysts.

Sputter deposition of BSCCO films from a hollow cathode

International Nuclear Information System (INIS)

Lanagan, M.T.; Kampwirth, R.T.; Doyle, K.; Kowalski, S.; Miller, D.; Gray, K.E.

1991-01-01

High-T c superconducting thin films were deposited onto MgO single crystal substrates from a hollow cathode onto ceramic targets with the nominal composition of Bi 2 Sr 2 CaCu 2 O x . Films similar in composition to those used for the targets were deposited on MgO substrates by rf sputtering. The effects of sputtering time, rf power, and post-annealing on film microstructure and properties were studied in detail. Substrate temperature was found to have a significant influence on the film characteristics. Initial results show that deposition rates from a hollow cathode are an order of magnitude higher than those of a planar magnetron source at equivalent power levels. Large deposition rates allow for the coating of long lengths of wire

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

Science.gov (United States)

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.

Copper-Sulfate Pentahydrate as a Product of the Waste Sulfuric Acid Solution Treatment

Science.gov (United States)

Marković, Radmila; Stevanović, Jasmina; Avramović, Ljiljana; Nedeljković, Dragutin; Jugović, Branimir; Stajić-Trošić, Jasna; Gvozdenović, Milica

2012-12-01

The aim of this study is synthesis of copper-sulfate pentahydrate from the waste sulfuric acid solution-mother liquor generated during the regeneration process of copper bleed solution. Copper is removed from the mother liquor solution in the process of the electrolytic treatment using the insoluble lead anodes alloyed with 6 mass pct of antimony on the industrial-scale equipment. As the result of the decopperization process, copper is removed in the form of the cathode sludge and is precipitated at the bottom of the electrolytic cell. By this procedure, the content of copper could be reduced to the 20 mass pct of the initial value. Chemical characterization of the sludge has shown that it contains about 90 mass pct of copper. During the decopperization process, the very strong poison, arsine, can be formed, and the process is in that case terminated. The copper leaching degree of 82 mass pct is obtained using H2SO4 aqueous solution with the oxygen addition during the cathode sludge chemical treatment at 80 °C ± 5 °C. Obtained copper salt satisfies the requirements of the Serbian Standard for Pesticide, SRPS H.P1. 058. Therefore, the treatment of waste sulfuric acid solutions is of great economic and environmental interest.

A primer on sulfur for the planetary geologist

Science.gov (United States)

Theilig, E.

1982-01-01

Sulfur has been proposed as the dominant composition for the volcanic material on Io. Sulfur is a complex element which forms many intramolecular and intermolecular allotropes exhibiting a variety of physical properties. Cyclo-S8 sulfur is the most abundant and stable molecular form. The important molecular species within liquid sulfur change in concentration with temperature. Concentrations of the allotropes control the physical properties of the melt. Discontinuities in density, viscosity, and thermal properties reflect the polymerization process within liquid sulfur. Variations in the melting point are related to autodissociation of the liquid. Many solids forms of sulfur have been identified but only orthorhombic alpha and monoclinic beta sulfur, both composed of cyclo-S8 sulfur, are stable under terrestrial conditions. Physical properties of solid sulfur are dependent on the allotrope and, in some cases, the thermal history. Three natural terrestrial sulfur flows are described: (1) Siretoko-Iosan, Japan; (2) Volcan Azufre, Galapagos Islands; and (3) Mauna Loa, Hawaii. All of the flows are associated with fumarolic areas and are considered to have formed by the melting and mobilization of sulfur deposits. Surface textures of the flows indicate a behavior of molten sulfur similar to that of silicate lava. Channels, rivulets, and lobate edges were described for the flows. The solidification of man-made sulfur flows formed as part of the Frasch mining process by which sulfur is removed from the subsurface in a liquid state is described.

Multiphysics Modelling of Sodium Sulfur Battery

Science.gov (United States)

Mason, Jerry Hunter

Due to global climate change and the desire to decrease greenhouse gas emissions, large scale energy storage has become a critical issue. Renewable energy sources such as wind and solar will not be a viable energy source unless the storage problem is solved. One of the practical and cost effective solutions for this problem is sodium sulfur batteries. These batteries are comprised of liquid electrode materials suspended in porous media and operate at relatively high temperatures (>300°C). The sodium anode and the sulfur/sodium-polysulfide cathode are separated by a solid electrolyte made of beta-alumina or NASICON material. Due to the use of porous materials in the electrodes, capillary pressure and the combination of capillary action and gravity become important. Capillary pressure has a strong dependence on the wetting phase (liquid electrode material) saturation; therefore sharp concentration gradients can occur between the inert gas and the electrode liquid, especially within the cathode. These concentration gradients can have direct impacts on the electrodynamics of the battery as they may produce areas of high electrical potential variation, which can decrease efficiency and even cause failures. Then, thermal management also becomes vital since the electrochemistry and material properties are sensitive to temperature gradients. To investigate these phenomena in detail and to attempt to improve upon battery design a multi-dimensional, multi-phase code has been developed and validated in this study. Then a porous media flow model is implemented. Transport equations for charge, mass and heat are solved in a time marching fashion using finite volume method. Material properties are calculated and updated as a function of time. The porous media model is coupled with the continuity equation and a separate diffusion equation for the liquid sodium in the melt. The total mass transport model is coupled with charge transport via Faraday's law. Results show that

Sulfur metabolism in phototrophic sulfur bacteria

DEFF Research Database (Denmark)

Frigaard, Niels-Ulrik; Dahl, Christiane

2008-01-01

Phototrophic sulfur bacteria are characterized by oxidizing various inorganic sulfur compounds for use as electron donors in carbon dioxide fixation during anoxygenic photosynthetic growth. These bacteria are divided into the purple sulfur bacteria (PSB) and the green sulfur bacteria (GSB......). They utilize various combinations of sulfide, elemental sulfur, and thiosulfate and sometimes also ferrous iron and hydrogen as electron donors. This review focuses on the dissimilatory and assimilatory metabolism of inorganic sulfur compounds in these bacteria and also briefly discusses these metabolisms...... in other types of anoxygenic phototrophic bacteria. The biochemistry and genetics of sulfur compound oxidation in PSB and GSB are described in detail. A variety of enzymes catalyzing sulfur oxidation reactions have been isolated from GSB and PSB (especially Allochromatium vinosum, a representative...

Electrotransport of Uranium from a Liquid Cadmium Anode to a Solid Cathode

International Nuclear Information System (INIS)

Ahluwalia, Rajesh K.; Hua, Thanh Q.

2002-01-01

During anodic dissolution of irradiated binary Experimental Breeder Reactor-II fuel, a portion of the electrorefined uranium collects in the underlying cadmium pool. It is periodically recovered by setting up a cell configuration in which the pool is made the anode and uranium is electrodeposited on a solid cathode mandrel. A theoretical model is used to determine the current structure of the liquid cadmium anode. The model is validated by comparing against the measured composition of the cathode deposits. Multinodal simulations are conducted to explain the bell shape of deposits observed with this mode of electrotransport. The simulations also determine the dependence of collection efficiency on the electrical charge passed that is functionally consistent with the experimental data. Finally, a simplified operating map of the electrorefiner is presented that can be used to determine the conditions for growing cathode deposits of target composition

Extraction of sulfuric acid with TOPO

International Nuclear Information System (INIS)

Shuyun, Xue; Yonghui, Yang; Yanzhao, Yang; Sixiu, Sun; Borong, Bao

1998-01-01

A study on solvent extraction of sulfuric acid by tri-octylphosphine oxide (TOPO) in n-heptane has been made. Extraction coefficients of H 2 SO 4 as a function of H 2 SO 4 concentration in aqueous phase, and extractant concentrations in organic phase have been studied. The composition of extracted species, equilibrium constants of extraction reaction have been evaluated. These results are important for interpreting extraction equilibrium data of uranium(VI) or other metal ions with TOPO in sulfuric acid media. (author)

Sulfur analysis by inductively coupled plasma-mass spectrometry: A review

Energy Technology Data Exchange (ETDEWEB)

Giner Martínez-Sierra, J.; Galilea San Blas, O.; Marchante Gayón, J.M.; García Alonso, J.I., E-mail: jiga@uniovi.es

2015-06-01

In recent years the number of applications of sulfur (S) analysis using inductively coupled plasma mass spectrometry (ICP-MS) as detector has increased significantly. In this article we describe in some depth the application of ICP-MS for S analysis with emphasis placed on the sulfur-specific detection by hyphenated techniques such as LC, GC, CE and LA coupled on-line to ICP-MS. The different approaches available for sulfur isotope ratio measurements by ICP-MS are also detailed. Particular attention has been paid to the quantification of peptides/proteins and the analysis of metallopeptides/metalloproteins via sulfur by LC–ICP-MS. Likewise, the speciation analysis of metal-based pharmaceuticals and metallodrugs and non-metal selective detection of pharmaceuticals via S are highlighted. Labeling procedures for metabolic applications are also included. Finally, the measurement of natural variations in S isotope composition with multicollector ICP-MS instruments is also covered in this review. - Highlights: • Emphasis placed on the sulfur-specific detection by chromatographic techniques coupled on-line to ICP-MS. • Different instrumental approaches available for sulfur measurements by ICP-MS. • Quantification of proteins and the analysis of metalloproteins via sulfur by LC-ICP-MS. • Labelling procedures for metabolic applications are also included. • The measurement of natural variations in S isotope composition with multicollector ICP-MS.

Composite harm to plants by sulfurous acid gas and oxidant

Energy Technology Data Exchange (ETDEWEB)

Matsushima, J

1971-01-01

The composite effects on plants of sulfur dioxide and ozone, SO/sub 2/ and PAN, SO/sub 2/ and nitrogen dioxide, and NO/sub 2/ and ozone were studied. Pinto bean plants were exposed to SO/sub 2/ or O/sub 3/ only, to each gas alternately, and to a mixture of the two. The degree of injury by the gas or gases was indicated in percentage by area of the leaves damaged. In cases where no geometric effect occurred the damage to the plant by the individual gas had been great; damage from the individual gas had been slight in these cases where such an effect was observed. The geometric effect is produced when the density of SO/sub 2/ is rather low, generally 0.05-0.25 ppm. A mixture of SO/sub 2/ and O/sub 3/ was applied to a tabacco plant; it affected fully grown leaves. In experiments on the composite effects of SO/sub 2/ and PAN on bean, tomato and pepper plants, PAN affected mainly young leaves while SO/sub 2/ affected mature ones. These effects were arithmetric rather then geometric. The SO/sub 2/ and NO/sub 2/ were also studied in the same manner. When SO/sub 2/ and NO/sub 2/ were mixed, a geometric effect was conspicuous in damage to vegetables, the symptoms of damage by either of the two appeared about the same, younger leaves being affected less. When treated with the two gases alternately, the damage was greater if the plants were first treated with NO/sub 2/; possible causes for this effect are discussed. No significant composite effect of NO/sub 2/ and O/sub 3/ was observed.

Electrochemical evaluation of La{sub 0.6}Sr{sub 0.4}CoO{sub 3}-La{sub 0.45}Ce{sub 0.55}O{sub 2} composite cathodes for anode-supported La{sub 0.45}Ce{sub 0.55}O{sub 2}-La{sub 0.9}Sr{sub 0.1}Ga{sub 0.8}Mg{sub 0.2}O{sub 2.85} bilayer electrolyte solid oxide fuel cells

Energy Technology Data Exchange (ETDEWEB)

Bi, Zhonghe; Cheng, Mojie; Dong, Yonglai; Wu, Hejin; She, Yunchuan; Yi, Baolian [Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023 (China)

2005-02-28

The electrochemical properties of porous composite cathodes of La{sub 0.6}Sr{sub 0.4}CoO{sub 3} (LSC) and La{sub 0.45}Ce{sub 0.55}O{sub 2} (LDC) in anode supported lanthanum-doped ceria (LDC)/lanthanum gallate (LSGM) bilayer electrolyte single cells have been investigated. The composite cathodes with different LDC and LSC contents were in contact with the LSGM layer in the single cells. Comparing with the pure LSC cathode, the interfacial resistance decreased upon the addition of LDC and the optimum content of LDC was 50 wt.%. The variation in ohmic resistance suggests that the composite cathode can suppress Co diffusion from the cathode into the LSGM electrolyte during the firing of the composite cathode onto the electrolyte. The composite cathode with 50 wt.% LDC showed an ohmic resistance near to the calculated resistance of an electrolyte film. For the pure LSC cathode, the optimum firing temperature was about 1150 {sup o}C, at which both the electrolyte resistance and interface resistance were the smallest. The cathodic interfacial resistance was effectively reduced for the composite cathodes, especially for the cathode with 50 wt.% LDC, which might be due to the suppressing of sintering and the growth of LSC particles from LDC particles during the firing onto the electrolyte. The complicated effects of the composite cathode on the interfacial resistance and ohmic resistance resulted in the best single cell performance at 650 {sup o}C with a 50 wt.% LDC composite cathode, and the best cell performance above 700 {sup o}C on the single cell with pure LSC cathode.

Io's theothermal (sulfur) - Lithosphere cycle inferred from sulfur solubility modeling of Pele's magma supply

Science.gov (United States)

Battaglia, Steven M.; Stewart, Michael A.; Kieffer, Susan W.

2014-06-01

Surface deposits of volatile compounds such as water (Earth) or sulfur (Io) on volcanically active bodies suggest that a magmatic distillation process works to concentrate volatiles in surface reservoirs. On Earth, this is the combined hydrologic and tectonic cycle. On Io, sulfurous compounds are transferred from the interior to the surface reservoirs through a combination of a mantle-sourced magmatic system, vertical cycling of the lithosphere, and a sulfur-dominated crustal thermal system that we here call the "theothermal" system. We present a geochemical analysis of this process using previously inferred temperature and oxygen fugacity constraints of Pele's basaltic magma to determine the behavior of sulfur in the ionian magmas. Sulfate to sulfide ratios of Pele's magma are -4.084 ± 0.6 and -6.442 ± 0.7 log10 units, comparable to or lower than those of mid-ocean ridge basalts. This reflects the similarity of Io's oxidation state with Earth's depleted mantle as previously suggested by Zolotov and Fegley (Zolotov, M.Y., Fegley, B. [2000]. Geophys. Res. Lett. 27, 2789-2792). Our calculated limits of sulfur solubility in melts from Pele's patera (˜1100-1140 ppm) are also comparable to terrestrial mid-ocean ridge basalts, reflecting a compositional similarity of mantle sources. We propose that the excess sulfur obvious on Io's surface comes from two sources: (1) an insoluble sulfide liquid phase in the magma and (2) theothermal near-surface recycling.

How a gel polymer electrolyte affects performance of lithium/sulfur batteries

International Nuclear Information System (INIS)

Zhang, Sheng S.; Tran, Dat T.

2013-01-01

Highlights: •Conventional separator is coated with a 50PEO-50SiO 2 (wt.%) composite layer. •Composite coating increases tensile strength and electrolyte wettability. •Coated separator offers an alternative approach for making gel polymer Li/S battery. •Li/S battery takes benefits of gel polymer electrolyte at the expense of capacity. -- Abstract: Gel polymer electrolyte (GPE) and composite gel polymer electrolyte (CGPE) have been widely employed to improve the safety and cycling performance of rechargeable lithium and lithium-ion batteries. In order to determine whether this approach is applicable to lithium/sulfur (Li/S) battery, we examine the effect of CGPE on the cycling and storage performances of Li/S cells by comparing a 50PEO-50SiO 2 (wt.%) composite coated separator (C-separator) with a pristine separator (P-separator). Results show that the composite coating significantly enhances the wettability of liquid electrolyte on the separator and that resulting CGPE can tightly glue the separator and electrode together. In comparison with the P-separator, the C-separator offers Li/S cells similar capacity retention and rate capability; however it greatly affects the specific capacity of sulfur. The analysis on the impedance spectrum of a lithium polysulfide (PS) solution reveal that the reduction of sulfur specific capacity is due to the high viscosity of the CGPE and the strong adsorption of SiO 2 filler to the PS species, which trap PS species in the separator and hence reduce the utilization of sulfur active material. Therefore, the benefits of the GPE and CGPE to the Li/S batteries can be taken only at the expense of sulfur specific capacity

Microstructure and emission ability of rare earth oxides doped molybdenum cathodes

International Nuclear Information System (INIS)

Yang Jiancan; Nie Zuoren; Wang Yiman

2003-01-01

We adopted high-resolution transmission electron microscopy (TEM) and scanning electron microscopy (SAM) to observe and analyze the microstructure of rare earth oxide (La 2 O 3 , Sc 2 O 3 ) doped molybdenum cathodes. The results show that there are many nanometer particles in the molybdenum matrix besides some sub-micrometer particles in the crystal interfaces. All these particles are rare earth oxides as determined through calculating the electron diffraction pattern. Then we determined the electron work function and the zero-field emission current of molybdenum cathodes by the electron emission measurement. To correlate the emission data with surface composition, we use Auger electron spectroscopy (AES) to analyze the elements on the activated cathode surface and their depth profiles. We found that there were about 20 nm thick layers on an activated cathode surface, which have a high content of rare earth elements. We also use AES to analyze the elements diffusion to the cathode surface from cathode body during heating up to its operating temperature to find out which element positively affects the electron emission

A Nacre-Like Carbon Nanotube Sheet for High Performance Li-Polysulfide Batteries with High Sulfur Loading.

Science.gov (United States)

Pan, Zheng-Ze; Lv, Wei; He, Yan-Bing; Zhao, Yan; Zhou, Guangmin; Dong, Liubing; Niu, Shuzhang; Zhang, Chen; Lyu, Ruiyang; Wang, Cong; Shi, Huifa; Zhang, Wenjie; Kang, Feiyu; Nishihara, Hirotomo; Yang, Quan-Hong

2018-06-01

Lithium-sulfur (Li-S) batteries are considered as one of the most promising energy storage systems for next-generation electric vehicles because of their high-energy density. However, the poor cyclic stability, especially at a high sulfur loading, is the major obstacles retarding their practical use. Inspired by the nacre structure of an abalone, a similar configuration consisting of layered carbon nanotube (CNT) matrix and compactly embedded sulfur is designed as the cathode for Li-S batteries, which are realized by a well-designed unidirectional freeze-drying approach. The compact and lamellar configuration with closely contacted neighboring CNT layers and the strong interaction between the highly conductive network and polysulfides have realized a high sulfur loading with significantly restrained polysulfide shuttling, resulting in a superior cyclic stability and an excellent rate performance for the produced Li-S batteries. Typically, with a sulfur loading of 5 mg cm -2 , the assembled batteries demonstrate discharge capacities of 1236 mAh g -1 at 0.1 C, 498 mAh g -1 at 2 C and moreover, when the sulfur loading is further increased to 10 mg cm -2 coupling with a carbon-coated separator, a superhigh areal capacity of 11.0 mAh cm -2 is achieved.

Hydrogen pressure dependence of the fracture mode transition in nickel

International Nuclear Information System (INIS)

Jones, R.H.; Baer, D.R.; Bruemmer, S.M.; Thomas, M.T.

1983-01-01

A relationship between fracture mode, grain boundary composition, and hydrogen pressure has been determined for nickel straining electrode samples tested at cathodic potentials. This relationship can be expressed as C /SUB S/ α P /SUP -n/ /SUB H2/ where C /SUB S/ is the critical grain boundary sulfur concentration corresponding to 50% transgranular and 50% intergranular fracture and P /SUB H2/ is the hydrogen pressure. The value of n was found to be between 0.34 and 0.9. This expression was derived by relating C /SUB S/ to the hydrogen overpotential with the Nernst equation. At a cathodic test potential of -0.3 V (SCE), C /SUB S/ was equal to 0.20 monolayers of sulfur and at higher cathodic potentials or higher hydrogen pressures, C /SUB S/ decreased such that at -0.72 V (SCE) C /SUB S/ was equal to 0.045 monolayers of sulfur. The inverse hydrogen pressure dependence observed with cathodic hydrogen is similar to that for the hydrogen permeation rate or a critical hydrogen concentration derived by Gerberich et al. for gaseous hydrogen. This similarity between gaseous and cathodic hydrogen suggests that grain boundary impurities contribute to the hydrogen embrittlement process without altering the embrittlement process although this result does not indicate whether decohesion or plasticity dependent processes are responsible for the combined sulfur-hydrogen effect on the intergranular fracture of nickel

Crystalline structure and microstructural characteristics of the cathode/electrolyte solid oxide half-cells

International Nuclear Information System (INIS)

Chiba, Rubens; Vargas, Reinaldo Azevedo; Andreoli, Marco; Santoro, Thais Aranha de Barros; Seo, Emilia Satoshi Miyamaru

2009-01-01

The solid oxide fuel cell (SOFC) is an electrochemical device generating of electric energy, constituted of cathode, electrolyte and anode; that together they form a unity cell. The study of the solid oxide half-cells consisting of cathode and electrolyte it is very important, in way that is the responsible interface for the reduction reaction of the oxygen. These half-cells are ceramic materials constituted of strontium-doped lanthanum manganite (LSM) for the cathode and yttria-stabilized zirconia (YSZ) for the electrolyte. In this work, two solid oxide half-cells have been manufactured, one constituted of LSM cathode thin film on YSZ electrolyte substrate (LSM - YSZ half-cell), and another constituted of LSM cathode and LSM/YSZ composite cathode thin films on YSZ electrolyte substrate (LSM - LSM/YSZ - YSZ half cell). The cathode/electrolyte solid oxide half-cells were characterized by X-ray diffractometry (XRD), scanning electron microscopy (SEM) and energy dispersive X-ray spectroscopy (EDS). The results have been presented with good adherence between cathode and electrolyte and, LSM and YSZ phases were identified. (author)

Powering Lithium-Sulfur Battery Performance by Propelling Polysulfide Redox at Sulfiphilic Hosts.

Science.gov (United States)

Yuan, Zhe; Peng, Hong-Jie; Hou, Ting-Zheng; Huang, Jia-Qi; Chen, Cheng-Meng; Wang, Dai-Wei; Cheng, Xin-Bing; Wei, Fei; Zhang, Qiang

2016-01-13

Lithium-sulfur (Li-S) battery system is endowed with tremendous energy density, resulting from the complex sulfur electrochemistry involving multielectron redox reactions and phase transformations. Originated from the slow redox kinetics of polysulfide intermediates, the flood of polysulfides in the batteries during cycling induced low sulfur utilization, severe polarization, low energy efficiency, deteriorated polysulfide shuttle, and short cycling life. Herein, sulfiphilic cobalt disulfide (CoS2) was incorporated into carbon/sulfur cathodes, introducing strong interaction between lithium polysulfides and CoS2 under working conditions. The interfaces between CoS2 and electrolyte served as strong adsorption and activation sites for polar polysulfides and therefore accelerated redox reactions of polysulfides. The high polysulfide reactivity not only guaranteed effective polarization mitigation and promoted energy efficiency by 10% but also promised high discharge capacity and stable cycling performance during 2000 cycles. A slow capacity decay rate of 0.034%/cycle at 2.0 C and a high initial capacity of 1368 mAh g(-1) at 0.5 C were achieved. Since the propelling redox reaction is not limited to Li-S system, we foresee the reported strategy herein can be applied in other high-power devices through the systems with controllable redox reactions.

Redox?Reversible Iron Orthovanadate Cathode for Solid Oxide Steam Electrolyzer

OpenAIRE

Gan, Lizhen; Ye, Lingting; Ruan, Cong; Chen, Shigang; Xie, Kui

2015-01-01

A redox?reversible iron orthovanadate cathode is demonstrated for a solid oxide electrolyser with up to 100% current efficiency for steam electrolysis. The iron catalyst is grown on spinel?type electronic conductor FeV2O4 by in situ tailoring the reversible phase change of FeVO4 to Fe+FeV2O4 in a reducing atmosphere. Promising electrode performances have been obtained for a solid oxide steam electrolyser based on this composite cathode.

Effect of Si on DC arc plasma generation from Al-Cr and Al-Cr-Si cathodes used in oxygen

Science.gov (United States)

Zhirkov, I.; Landälv, L.; Göthelid, E.; Ahlgren, M.; Eklund, P.; Rosen, J.

2017-02-01

Al2O3 alloyed with Cr is an important material for the tooling industry. It can be synthesized from an arc discharge using Al-Cr cathodes in an oxygen atmosphere. Due to formation of Al-rich oxide islands on the cathode surface, the arc process stability is highly sensitive to oxygen pressure. For improved stability, the use of Al0.70Cr0.25Si0.05 cathodes has previously been suggested, where Si may reduce island formation. Here, we have investigated the effect of Si by comparing plasma generation and thin film deposition from Al0.7Cr0.3 and Al0.7Cr0.25Si0.05 cathodes. Plasma ion composition, ion energies, ion charge states, neutral species, droplet formation, and film composition have been characterized at different O2 flow rates for arc currents of 60 and 90 A. Si and related compounds are detected in plasma ions and in plasma neutrals. Scanning electron microscopy and energy dispersive X-ray analysis show that the cathode composition and the film composition are the same, with Si present in droplets as well. The effect of Si on the process stability, ion energies, and ion charge states is found to be negligible compared to that of the arc current. The latter is identified as the most relevant parameter for tuning the properties of the reactive discharge. The present work increases the fundamental understanding of plasma generation in a reactive atmosphere, and provides input for the choice of cathode composition and process parameters in reactive DC arc synthesis.

Effects of Different Level and Source of Sulfur Supplement in Close-up diets of Dairy Cows on Blood Metabolites, Colostrums Composition and Liver Performance

Directory of Open Access Journals (Sweden)

E Manidari

2012-01-01

Full Text Available The 24 maltiparous Holstein dairy cows were allocated in a completely randomized design to study the effects of different level and source of sulfur supplement in close-up diets on blood metabolites, colostrums composition and liver performance. The mean body weight of the cows was 687.9 kg and the mean days until expected calving date was 21.8 d. The first treatment (T1 has contained 0.21% sulfur (DM basis, the second treatment (T2 has contained 0.41% sulfur which supplied entirely through magnesium sulfate and the third treatment (T3 has contained 0.41% sulfur which supplied through a combination of magnesium sulfate and an organic source of sulfur (Mepran. The DMI for pre-calving (P < 0.001 was affected by treatments and T2 showed the lowest DMI among treatments. Colostrums yield, protein, DM and ash significantly decreased in inorganic sulfur supplemented treatment (P < 0.05. Among the blood metabolites, calcium, copper and glucose were decreased in T2 compared with two other treatments (P < 0.05. However, BHBA, NEFA and urea were increased in T2 (P < 0.05. Urine pH was affected with different treatments (P < 0.0001. The both liver enzymes (i.e. AST and CPK were increased supplementing inorganic sulfur showing that inorganic sulfur has potential to decrease liver performance in dairy cows. The results of the present study indicate that although magnesium sulfate (inorganic source has negative effect on dairy cow health and performance, a combination of magnesium sulfate and organic source of sulfur could have positive effects on dry matter intake, blood metabolites and liver health in dairy cows.

Cathodes for Solid Oxide Fuel Cells Operating at Low Temperatures

DEFF Research Database (Denmark)

Samson, Alfred Junio

. High performance cathodes were obtained from strontium-doped lanthanum cobaltite (LSC) infiltrated - Ce0.9Gd0.1O1.95 (CGO) ionic conducting backbone. Systematic tuning of the CGO and LSC firing temperatures and LSC loading resulted in a cathode with low polarization resistance, Rp = 0.044 cm2 at 600......This dissertation focuses on the development of nanostructured cathodes for solid oxide fuel cells (SOFCs) and their performance at low operating temperatures. Cathodes were mainly fabricated by the infiltration method, whereby electrocatalysts are introduced onto porous, ionic conducting backbones...... with increasing LSC firing temperature, highlighting the importance of materials compability over higher ionic conductivity. The potential of Ca3Co4O9+delta as an electrocatalyst for SOFCs has also been explored and encouraging results were found i.e., Rp = 0.64 cm2 for a Ca3Co4O9+delta/CGO 50 vol % composite...

A three-dimensional LiFePO4/carbon nanotubes/graphene composite as a cathode material for lithium-ion batteries with superior high-rate performance

International Nuclear Information System (INIS)

Lei, Xingling; Zhang, Haiyan; Chen, Yiming; Wang, Wenguang; Ye, Yipeng; Zheng, Chuchun; Deng, Peng; Shi, Zhicong

2015-01-01

Graphical abstract: The excellent electrochemical performances can be attributed to the synergistic effect of CNTs and graphene. - Highlights: • The LFP–CNT–G composite was successfully prepared by solid station method. • The interlaced CNTs reduced the crumple of graphene and improved tap density of the composite. • The LFP–CNT–G electrode exhibited superior electrochemical performance. - Abstract: A three-dimensional lithium iron phosphate (LiFePO 4 )/carbon nanotubes (CNTs)/graphene composite was successfully synthesized via solid-state reaction. The LiFePO 4 /carbon nanotubes/graphene (LFP–CNT–G) composite used as Li-ions battery cathode material exhibits superior high-rate capability and favorable charge–discharge cycle performance under relative high current density compared with that of LiFePO 4 /carbon nanotubes (LFP–CNT) composite and LiFePO 4 /graphene (LFP–G) composite. Graphene nanosheets and CNTs construct 3D conducting networks are favor for faster electron transfer, higher Li-ions diffusion coefficient and lower resistance during the Li-ions reversible reaction. The synergistic effect of graphene nanosheets and CNTs improves the rate capability and cycling stability of LiFePO 4 -based cathodes. The LFP–CNT–G electrode shows reversible capacity of 168.9 mA h g −1 at 0.2 C and 115.8 mA h g −1 at 20 C. The electrochemical impedance spectroscopy demonstrate that the LFP–CNT–G electrode has the smallest charge-transfer resistance, indicating that the fast electron transfer from the electrolyte to the LFP–CNT–G active materials in the Li-ions intercalation/deintercalation reactions owing to the three-dimensional networks of graphene and carbon nanotubes

Developments of Electrolyte Systems for Lithium–Sulfur Batteries: A Review

International Nuclear Information System (INIS)

Li, Gaoran; Li, Zhoupeng; Zhang, Bin; Lin, Zhan

2015-01-01

With a theoretical specific energy five times higher than that of lithium–ion batteries (2,600 vs. ~500 Wh kg −1 ), lithium–sulfur (Li–S) batteries have been considered as one of the most promising energy storage systems for the electrification of vehicles. However, both the polysulfide shuttle effects of the sulfur cathode and dendrite formation of the lithium anode are still key limitations to practical use of traditional Li–S batteries. In this review, we focus on the recent developments in electrolyte systems. First, we start with a brief discussion on fundamentals of Li–S batteries and key challenges associated with traditional liquid cells. We then introduce the most recent progresses in liquid systems, including ether-based, carbonate-based, and ionic liquid-based electrolytes. And then we move on to the advances in solid systems, including polymer and non-polymer electrolytes. Finally, the opportunities and perspectives for future research in both the liquid and solid Li–S batteries are presented.

Developments of Electrolyte Systems for Lithium–Sulfur Batteries: A Review

Energy Technology Data Exchange (ETDEWEB)

Li, Gaoran; Li, Zhoupeng [College of Chemical and Biological Engineering, Zhejiang University, Hangzhou, Zhejiang (China); Zhang, Bin [Anhui Academy for Environmental Science Research, Hefei, Anhui (China); Lin, Zhan, E-mail: zhanlin@zju.edu.cn [College of Chemical and Biological Engineering, Zhejiang University, Hangzhou, Zhejiang (China)

2015-02-11

With a theoretical specific energy five times higher than that of lithium–ion batteries (2,600 vs. ~500 Wh kg{sup −1}), lithium–sulfur (Li–S) batteries have been considered as one of the most promising energy storage systems for the electrification of vehicles. However, both the polysulfide shuttle effects of the sulfur cathode and dendrite formation of the lithium anode are still key limitations to practical use of traditional Li–S batteries. In this review, we focus on the recent developments in electrolyte systems. First, we start with a brief discussion on fundamentals of Li–S batteries and key challenges associated with traditional liquid cells. We then introduce the most recent progresses in liquid systems, including ether-based, carbonate-based, and ionic liquid-based electrolytes. And then we move on to the advances in solid systems, including polymer and non-polymer electrolytes. Finally, the opportunities and perspectives for future research in both the liquid and solid Li–S batteries are presented.

Developments of Electrolyte Systems for Lithium-Sulfur Batteries: A Review

Directory of Open Access Journals (Sweden)

Zhan eLin

2015-02-01

Full Text Available With a theoretical specific energy 5 times higher than that of lithium-ion (Li-ion batteries (2,600 vs. ~500 Wh kg-1, lithium-sulfur (Li-S batteries have been considered as one of the most promising energy storage systems for the electrification of vehicles. However, both the polysulfide shuttle effects of the sulfur cathode and dendrite formation of the lithium anode are still key limitations to practical use of traditional Li-S batteries. In this review, we focus on the recent developments in electrolyte systems. First we start with a brief discussion on fundamentals of Li-S batteries and key challenges associated with traditional liquid cells. We then introduce the most recent progresses in liquid systems, including ether-based, carbonate-based, and ionic liquid-based electrolytes. And then we move on to the advances in solid systems, including polymer and non-polymer electrolytes. Finally, the opportunities and perspectives for future research in both the liquid and solid Li-S batteries are presented.

Variable sulfur isotope composition of sulfides provide evidence for multiple sources of contamination in the Rustenburg Layered Suite, Bushveld Complex

Science.gov (United States)

Magalhães, Nivea; Penniston-Dorland, Sarah; Farquhar, James; Mathez, Edmond A.

2018-06-01

The Rustenburg Layered Suite (RLS) of the Bushveld Complex (BC) is famous for its platinum group element (PGE) ore, which is hosted in sulfides. The source of sulfur necessary to generate this type of mineralization is inferred to be the host rock of the intrusion. The RLS has a sulfur isotopic signature that indicates the presence of Archean surface-derived material (Δ33 S ≠ 0) in the magma. This signature, with an average value of Δ33 S = 0.112 ± 0.024 ‰, deviates from the expected Δ33 S value of the mantle of 0 ± 0.008 ‰. Previous work suggested that this signature is uniform throughout the RLS, which contrasts with radiogenic isotopes which vary throughout the igneous stratigraphy of the RLS. In this study, samples from key intervals within the igneous stratigraphy were analyzed, showing that Δ33 S values vary in the same stratigraphic levels as Sr and Nd isotopes. However, the variation is not consistent; in some levels there is a positive correlation and in others a negative correlation. This observation suggests that in some cases distinct magma pulses contained assimilated sulfur from different sources. Textural analysis shows no evidence for late addition of sulfur. These results also suggest that it is unlikely that large-scale assimilation and/or efficient mixing of host rock material in a single magma chamber occurred during emplacement. The data do not uniquely identify the source of sulfur in the different layers of the RLS, but the variation in sulfur isotope composition and its relationship to radiogenic isotope data calls for a reevaluation of the models for the formation and evolution of the RLS, which has the potential to impact the knowledge of how PGE deposits form.

La0.99Co0.4Ni0.6O3−δ–Ce0.8Gd0.2O1.95 as composite cathode for solid oxide fuel cells

DEFF Research Database (Denmark)

Hjalmarsson, Per; Mogensen, Mogens Bjerg

2011-01-01

We have studied a new composite SOFC cathode consisting of LaCo0.4Ni0.6O3−δ (LCN60) and Ce0.9Gd0.1O1.95 (CGO). The polarisation resistance (RP) at 750°C and OCV was measured to 0.05±0.01Ωcm2 and the activation energy was determined to be about 1eV. The impedance spectra were modelled with an EQC......-infiltrated LCN60–CGO cathodes is substantially lower than that of LSM–YSZ and comparable with single phase LSC cathodes at low T due to its low EA. RP was also found to be stable at 750°C and OCV. The cathodes were integrated onto ScYSZ based anode supported cells which were measured to have an ASR of 0...

Impregnation of LSM Based Cathodes for Solid Oxide Fuel Cells

DEFF Research Database (Denmark)

Højberg, Jonathan; Søgaard, Martin

2011-01-01

Composites cathodes consisting of strontium doped lanthanum manganite (LSM) and yttria stabilized zirconia have been impregnated with the nitrates corresponding to the nominal compositions: La0.75Sr0.25Mn1.05O3 +/-delta (LSM25), Ce0.8Sm0.2O2 (SDC) and a combination of both (dual). The latter...

Functionally Graded Cathodes for Solid Oxide Fuel Cells

International Nuclear Information System (INIS)

Lei Yang; Ze Liu; Shizhone Wang; Jaewung Lee; Meilin Liu

2008-01-01

The main objective of this DOE project is to demonstrate that the performance and long-term stability of the state-of-the-art LSCF cathode can be enhanced by a catalytically active coating (e.g., LSM or SSC). We have successfully developed a methodology for reliably evaluating the intrinsic surface catalytic properties of cathode materials. One of the key components of the test cell is a dense LSCF film, which will function as the current collector for the electrode material under evaluation to eliminate the effect of ionic and electronic transport. Since it is dense, the effect of geometry would be eliminated as well. From the dependence of the electrode polarization resistance on the thickness of a dense LSCF electrode and on partial pressure of oxygen, we have confirmed that the surface catalytic activity of LSCF limits the performances of LSCF-based cathodes. Further, we have demonstrated, using test cells of different configurations, that the performance of LSCF-based electrodes can be significantly enhanced by infiltration of a thin film of LSM or SSC. In addition, the stability of LSCF-based cathodes was also improved by infiltration of LSM or SSC. While the concept feasibility of the electrode architecture is demonstrated, many details are yet to be determined. For example, it is not clear how the surface morphology, composition, and thickness of the coatings change under operating conditions over time, how these changes influence the electrochemical behavior of the cathodes, and how to control the microscopic details of the coatings in order to optimize the performance. The selection of the catalytic materials as well as the detailed microstructures of the porous LSCF and the catalyst layer may critically impact the performance of the proposed cathodes. Further, other fundamental questions still remain; it is not clear why the degradation rates of LSCF cathodes are relatively high, why a LSM coating improves the stability of LSCF cathodes, which catalysts

Genotypic variation in the sulfur assimilation and metabolism of onion (Allium cepa L.) I. Plant composition and transcript accumulation

KAUST Repository

McCallum, John A.

2011-06-01

Organosulfur compounds are major sinks for assimilated sulfate in onion (Allium cepa L.) and accumulation varies widely due to plant genotype and sulfur nutrition. In order to better characterise sulfur metabolism phenotypes and identify potential control points we compared plant composition and transcript accumulation of the primary sulfur assimilation pathway in the high pungency genotype \\'W202A\\' and the low pungency genotype \\'Texas Grano 438\\' grown hydroponically under S deficient (S-) and S-sufficient (S+) conditions. Accumulation of total S and alk(en)yl cysteine sulfoxide flavour precursors was significantly higher under S+ conditions and in \\'W202A\\' in agreement with previous studies. Leaf sulfate and cysteine levels were significantly higher in \\'W202A\\' and under S+. Glutathione levels were reduced by S- treatment but were not affected by genotype, suggesting that thiol pool sizes are regulated differently in mild and pungent onions. The only significant treatment effect observed on transcript accumulation in leaves was an elevated accumulation of O-acetyl serine thiol-lyase under S-. By contrast, transcript accumulation of all genes in roots was influenced by one or more treatments. APS reductase transcript level was not affected by genotype but was strongly increased by S-. Significant genotype × S treatment effects were observed in a root high affinity-sulfur transporter and ferredoxin-sulfite reductase. ATP sulfurylase transcript levels were significantly higher under S+ and in \\'W202A\\'. © 2011 Elsevier Ltd. All rights reserved.

High-Current Cold Cathode Employing Diamond and Related Materials

Energy Technology Data Exchange (ETDEWEB)

Hirshfield, Jay L. [Omega-P, Inc., New Haven, CT (United States)

2014-10-22

The essence of this project was for diamond films to be deposited on cold cathodes to improve their emission properties. Films with varying morphology, composition, and size of the crystals were deposited and the emission properties of the cathodes that utilize such films were studied. The prototype cathodes fabricated by the methods developed during Phase I were tested and evaluated in an actual high-power RF device during Phase II. These high-power tests used the novel active RF pulse compression system and the X-band magnicon test facility at US Naval Research Laboratory. In earlier tests, plasma switches were employed, while tests under this project utilized electron-beam switching. The intense electron beams required in the switches were supplied from cold cathodes embodying diamond films with varying morphology, including uncoated molybdenum cathodes in the preliminary tests. Tests with uncoated molybdenum cathodes produced compressed X-band RF pulses with a peak power of 91 MW, and a maximum power gain of 16.5:1. Tests were also carried out with switches employing diamond coated cathodes. The pulse compressor was based on use of switches employing electron beam triggering to effect mode conversion. In experimental tests, the compressor produced 165 MW in a ~ 20 ns pulse at ~18× power gain and ~ 140 MW at ~ 16× power gain in a 16 ns pulse with a ~ 7 ns flat-top. In these tests, molybdenum blade cathodes with thin diamond coatings demonstrated good reproducible emission uniformity with a 100 kV, 100 ns high voltage pulse. The new compressor does not have the limitations of earlier types of active pulse compressors and can operate at significantly higher electric fields without breakdown.

Electrodeposited synthesis of self-supported Ni-P cathode for efficient electrocatalytic hydrogen generation

Directory of Open Access Journals (Sweden)

Ruixian Wu

2016-06-01

Full Text Available One of the key challenges for electrochemical water splitting is the development of low-cost and efficient hydrogen evolution cathode. In this work, a self-supported Ni-P cathode was synthesized by a facile electrodeposition method. The composition and morphology were characterized by X-ray diffraction, X-ray photoelectron spectroscopy, scanning electron microscopy and transmission electron microscopy. The Ni-P cathode performed low onset over-potential, good catalytic activity and long-term stability under neutral and alkaline conditions. The mechanism of Ni-P electrode for hydrogen production was discussed by electrochemical impedance spectroscopy. The excellent performance of Ni-P cathode was mainly attributed to the synergistic effect of phosphate anions and the self-supported feature.

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

Science.gov (United States)

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

2016-02-01

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

Enriching Metal-Oxidizing Microbes from Marine Sediment on Cathodic Currents

Science.gov (United States)

Rowe, A. R.; Nealson, K. H.

2013-12-01

The ability of organisms to transfer electrons to and from substrates outside the cell is reshaping the way we look at microbial respiration. While this process, termed extracellular electron transport (EET), has been described in a number of metal reducing organisms, current evidence suggests that this process is widespread in nature and across physiologies. Additionally, it has been speculated that these previously overlooked electrochemical interactions may play an important role in global biogeochemical cycles. Requirements for EET could play a role in why the ';uncultured majority' have so far been resistant to culturing. As such, we are currently developing culturing techniques to target microbes capable of utilizing insoluble electron acceptors utilizing electrochemical techniques. Microbe-electrode interactions are analogous to the reactions that occur between microbes and minerals and may provide an apt way to mimic the environmental conditions (i.e., insoluble electron donor/acceptor at specific redox potentials) required for culturing specialized or EET dependent metabolisms. It has been previously demonstrated that aquatic sediments are capable of utilizing anodes as electron acceptors, thereby generating a current. While, it is known that microbes utilize electrons from a cathode for the reduction of different metals and oxygen in microbial fuel cells, currently there are no reports of environmental enrichments of microbes using cathodes. Replicate microcosms from marine sediments (sampled from Catalina Harbor, California) were incubated with ITO plated glass electrodes. Negative current production at -400mV (vs. Ag/AgCl reference electrodes) potentials was sustained for four weeks. Secondary enrichments were then constructed using the cathode as the primary electron source and a variety of anaerobic terminal electron acceptors--Nitrate, Fe3+, and SO42-. Positive current was maintained in enrichment cultures (compared to abiotic control containing

Long-term cyclability of LiFePO4/carbon composite cathode material for lithium-ion battery applications

International Nuclear Information System (INIS)

Liu Jing; Wang Jiawei; Yan Xuedong; Zhang Xianfa; Yang Guiling; Jalbout, Abraham F.; Wang Rongshun

2009-01-01

A simple high-energy ball milling combined with spray-drying method has been developed to synthesize LiFePO 4 /carbon composite. This material delivers an improved tap density of 1.3 g/cm 3 and a high electronic conductivity of 10 -2 to 10 -3 S/cm. The electrochemical performance, which is especially notable for its high-rate performance, is excellent. The discharge capacities are as high as 109 mAh/g at the current density of 1100 mA/g (about 6.5C rate) and 94 mAh/g at the current density of 1900 mA/g (about 11C rate). At the high current density of 1700 mA/g (10C rate), it exhibits a long-term cyclability, retaining over 92% of its original discharge capacity beyond 2400 cycles. Therefore, the as-prepared LiFePO 4 /carbon composite cathode material is capable of such large-scale applications as hybrid and plug-in hybrid electric vehicles.

Improved analytical techniques of sulfur isotopic composition in nanomole quantities by MC-ICP-MS.

Science.gov (United States)

Yu, Tsai-Luen; Wang, Bo-Shian; Shen, Chuan-Chou; Wang, Pei-Ling; Yang, Tsanyao Frank; Burr, George S; Chen, Yue-Gau

2017-10-02

We propose an improved method for precise sulfur isotopic measurements by multi-collector inductively coupled plasma mass spectrometry (MC-ICP-MS) in conjunction with a membrane desolvation nebulization system. The problems of sulfur loss through the membrane desolvation apparatus are carefully quantified and resolved. The method overcomes low intrinsic sulfur transmission through the instrument, which was initially 1% when operating at a desolvation temperature of 160 °C. Sulfur loss through the membrane desolvation apparatus was resolved by doping with sodium. A Na/S ratio of 2 mol mol -1 produced sulfur transmissions with 98% recovery. Samples of 3 nmol (100 ng) sulfur achieved an external precision of ±0.18‰ (2 SD) for δ 34 S and ±0.10‰ (2 SD) for Δ 33 S (uppercase delta expresses the extent of mass-independent isotopic fractionation). Measurements made on certified reference materials and in-house standards demonstrate analytical accuracy and reproducibility. We applied the method to examine microbial-induced sulfur transformation in marine sediment pore waters from the sulfate-methane transition zone. The technique is quite versatile, and can be applied to a range of materials, including natural waters and minerals. Copyright © 2017 Elsevier B.V. All rights reserved.

New treating processes for sulfur-containing natural gases

Energy Technology Data Exchange (ETDEWEB)

Kislenko, N.; Aphanasiev, A.; Nabokov, S.; Ismailova, H. [VNIIGAS, Moscow (Russian Federation)

1996-12-31

The traditional method of removing H{sub 2}S from sour natural gases is first to treat the gas with a solvent and then to recover the H{sub 2}S from the sour stream in a Claus plant. This method recovers up to 97% of the sulfur when a three-stage Claus unit is employed. Amine/Claus units have operating difficulties for small sulfur capacities (up to 5 tons/day) because the operation of the fired equipment (reaction furnace) is much more difficult. Therefore, for small scale sulfur recovery plants redox processes which exhibit a significant reduction in investment and operating costs are normally used. Many different factors influence the choice of gas desulfurization technology--composition and gas flow, environmental sulfur recovery requirements and CO{sub 2}/H{sub 2}S ratio.

Advanced carbon materials/olivine LiFePO4 composites cathode for lithium ion batteries

Science.gov (United States)

Gong, Chunli; Xue, Zhigang; Wen, Sheng; Ye, Yunsheng; Xie, Xiaolin

2016-06-01

In the past two decades, LiFePO4 has undoubtly become a competitive candidate for the cathode material of the next-generation LIBs due to its abundant resources, low toxicity and excellent thermal stability, etc. However, the poor electronic conductivity as well as low lithium ion diffusion rate are the two major drawbacks for the commercial applications of LiFePO4 especially in the power energy field. The introduction of highly graphitized advanced carbon materials, which also possess high electronic conductivity, superior specific surface area and excellent structural stability, into LiFePO4 offers a better way to resolve the issue of limited rate performance caused by the two obstacles when compared with traditional carbon materials. In this review, we focus on advanced carbon materials such as one-dimensional (1D) carbon (carbon nanotubes and carbon fibers), two-dimensional (2D) carbon (graphene, graphene oxide and reduced graphene oxide) and three-dimensional (3D) carbon (carbon nanotubes array and 3D graphene skeleton), modified LiFePO4 for high power lithium ion batteries. The preparation strategies, structure, and electrochemical performance of advanced carbon/LiFePO4 composite are summarized and discussed in detail. The problems encountered in its application and the future development of this composite are also discussed.

Electrochemically active microorganisms from an acid mine drainage-affected site promote cathode oxidation in microbial fuel cells

KAUST Repository

Rojas, Claudia; Vargas, Ignacio T.; Bruns, Mary Ann; Regan, John M.

2017-01-01

The limited database of acidophilic or acidotolerant electrochemically active microorganisms prevents advancements on microbial fuel cells (MFCs) operated under low pH. In this study, three MFCs were used to enrich cathodic biofilms using acid mine drainage (AMD) sediments as inoculum. Linear sweep voltammetry showed cathodic current plateaus of 5.5 (± 0.7) mA at about − 170 mV vs Ag/AgCl and 8.5 (± 0.9) mA between − 500 mV to − 450 mV vs Ag/AgCl for biofilms developed on small graphite fiber brushes. After gamma irradiation, biocathodes exhibited a decrease in current density approaching that of abiotic controls. Electrochemical impedance spectroscopy showed six-fold lower charge transfer resistance with viable biofilm. Pyrosequencing data showed that Proteobacteria and Firmicutes dominated the biofilms. Acidithiobacillus representatives were enriched in some biocathodes, supporting the potential importance of these known iron and sulfur oxidizers as cathodic biocatalysts. Other acidophilic chemolithoautotrophs identified included Sulfobacillus and Leptospirillum species. The presence of chemoautotrophs was consistent with functional capabilities predicted by PICRUSt related to carbon fixation pathways in prokaryotic microorganisms. Acidophilic or acidotolerant heterotrophs were also abundant; however, their contribution to cathodic performance is unknown. This study directs subsequent research efforts to particular groups of AMD-associated bacteria that are electrochemically active on cathodes.

Electrochemically active microorganisms from an acid mine drainage-affected site promote cathode oxidation in microbial fuel cells

KAUST Repository

Rojas, Claudia

2017-08-03

The limited database of acidophilic or acidotolerant electrochemically active microorganisms prevents advancements on microbial fuel cells (MFCs) operated under low pH. In this study, three MFCs were used to enrich cathodic biofilms using acid mine drainage (AMD) sediments as inoculum. Linear sweep voltammetry showed cathodic current plateaus of 5.5 (± 0.7) mA at about − 170 mV vs Ag/AgCl and 8.5 (± 0.9) mA between − 500 mV to − 450 mV vs Ag/AgCl for biofilms developed on small graphite fiber brushes. After gamma irradiation, biocathodes exhibited a decrease in current density approaching that of abiotic controls. Electrochemical impedance spectroscopy showed six-fold lower charge transfer resistance with viable biofilm. Pyrosequencing data showed that Proteobacteria and Firmicutes dominated the biofilms. Acidithiobacillus representatives were enriched in some biocathodes, supporting the potential importance of these known iron and sulfur oxidizers as cathodic biocatalysts. Other acidophilic chemolithoautotrophs identified included Sulfobacillus and Leptospirillum species. The presence of chemoautotrophs was consistent with functional capabilities predicted by PICRUSt related to carbon fixation pathways in prokaryotic microorganisms. Acidophilic or acidotolerant heterotrophs were also abundant; however, their contribution to cathodic performance is unknown. This study directs subsequent research efforts to particular groups of AMD-associated bacteria that are electrochemically active on cathodes.

Sulfur in serpentinized oceanic peridotites: Serpentinization processes and microbial sulfate reduction

Science.gov (United States)

Alt, J.C.; Shanks, Wayne C.

1998-01-01

The mineralogy, contents, and isotopic compositions of sulfur in oceanic serpentinites reflect variations in temperatures and fluid fluxes. Serpentinization of serpentinization of Iberian Margin peridotites occurred at low temperatures (???20??-200??C) and high water/rock ratios. Complete serpentinization and consumption of ferrous iron allowed evolution to higher fO2. Microbial reduction of seawater sulfate resulted in addition of low-??34S sulfide (-15 to -43???) and formation of higher-sulfur assemblages that include valleriite and pyrite. The high SO4/total S ratio of Hess Deep serpentinites (0.89) results in an increase of total sulfur and high ??34S of total sulfur (mean ??? 8???). In contrast, Iberian Margin serpentinites gained large amounts of 34S-poor sulfide (mean total S = 3800 ppm), and the high sulfide/total S ratio (0.61) results in a net decrease in ??34S of total sulfur (mean ??? -5???). Thus serpentinization is a net sink for seawater sulfur, but the amount fixed and its isotopic composition vary significantly. Serpentinization may result in uptake of 0.4-14 ?? 1012 g S yr-1 from the oceans, comparable to isotopic exchange in mafic rocks of seafloor hydrothermal systems and approaching global fluxes of riverine sulfate input and sedimentary sulfide output.

Pyrite sulfur isotopes reveal glacial-interglacial environmental changes

Science.gov (United States)

Pasquier, Virgil; Sansjofre, Pierre; Rabineau, Marina; Revillon, Sidonie; Houghton, Jennifer; Fike, David A.

2017-06-01

The sulfur biogeochemical cycle plays a key role in regulating Earth’s surface redox through diverse abiotic and biological reactions that have distinctive stable isotopic fractionations. As such, variations in the sulfur isotopic composition (δ34S) of sedimentary sulfate and sulfide phases over Earth history can be used to infer substantive changes to the Earth’s surface environment, including the rise of atmospheric oxygen. Such inferences assume that individual δ34S records reflect temporal changes in the global sulfur cycle; this assumption may be well grounded for sulfate-bearing minerals but is less well established for pyrite-based records. Here, we investigate alternative controls on the sedimentary sulfur isotopic composition of marine pyrite by examining a 300-m drill core of Mediterranean sediments deposited over the past 500,000 y and spanning the last five glacial-interglacial periods. Because this interval is far shorter than the residence time of marine sulfate, any change in the sulfur isotopic record preserved in pyrite (δ34Spyr) necessarily corresponds to local environmental changes. The stratigraphic variations (>76‰) in the isotopic data reported here are among the largest ever observed in pyrite, and are in phase with glacial-interglacial sea level and temperature changes. In this case, the dominant control appears to be glacial-interglacial variations in sedimentation rates. These results suggest that there exist important but previously overlooked depositional controls on sedimentary sulfur isotope records, especially associated with intervals of substantial sea level change. This work provides an important perspective on the origin of variability in such records and suggests meaningful paleoenvironmental information can be derived from pyrite δ34S records.

From melamine sponge towards 3D sulfur-doping carbon nitride as metal-free electrocatalysts for oxygen reduction reaction

Science.gov (United States)

Xu, Jingjing; Li, Bin; Li, Songmei; Liu, Jianhua

2017-07-01

Development of new and efficient metal-free electrocatalysts for replacing Pt to improve the sluggish kinetics of oxygen reduction reaction (ORR) is of great importance to emerging renewable energy technologies such as metal-air batteries and polymer electrolyte fuel cells. Herein, 3D sulfur-doping carbon nitride (S-CN) as a novel metal-free ORR electrocatalyst was synthesized by exploiting commercial melamine sponge as raw material. The sulfur atoms were doping on CN networks uniformly through numerous S-C bonds which can provide additional active sites. And it was found that the S-CN exhibited high catalytic activity for ORR in term of more positive onset potential, higher electron transfer number and higher cathodic density. This work provides a novel choice of metal-free ORR electrocatalysts and highlights the importance of sulfur-doping CN in metal-free ORR electrocatalysts.

Copper-Sulfate Pentahydrate as a Product of the Waste Sulfuric Acid Solution Treatment

OpenAIRE

Marković, Radmila; Stevanović, Jasmina; Avramović, Ljiljana; Nedeljković, Dragutin; Jugović, Branimir; Stajić Trošić, Jasna; Gvozdenović, Milica M.

2012-01-01

The aim of this study is synthesis of copper-sulfate pentahydrate from the waste sulfuric acid solution-mother liquor generated during the regeneration process of copper bleed solution. Copper is removed from the mother liquor solution in the process of the electrolytic treatment using the insoluble lead anodes alloyed with 6 mass pct of antimony on the industrial-scale equipment. As the result of the decopperization process, copper is removed in the form of the cathode sludge and is precipit...

Advanced chemical strategies for lithium–sulfur batteries: A review

Directory of Open Access Journals (Sweden)

Xiaojing Fan

2018-01-01

Full Text Available Lithium–sulfur (LiS battery has been considered as one of the most promising rechargeable batteries among various energy storage devices owing to the attractive ultrahigh theoretical capacity and low cost. However, the performance of LiS batteries is still far from theoretical prediction because of the inherent insulation of sulfur, shuttling of soluble polysulfides, swelling of cathode volume and the formation of lithium dendrites. Significant efforts have been made to trap polysulfides via physical strategies using carbon based materials, but the interactions between polysulfides and carbon are so weak that the device performance is limited. Chemical strategies provide the relatively complemented routes for improving the batteries' electrochemical properties by introducing strong interactions between functional groups and lithium polysulfides. Therefore, this review mainly discusses the recent advances in chemical absorption for improving the performance of LiS batteries by introducing functional groups (oxygen, nitrogen, and boron, etc. and chemical additives (metal, polymers, etc. to the carbon structures, and how these foreign guests immobilize the dissolved polysulfides.

High performance Li3V2(PO4)3/C composite cathode material for lithium ion batteries studied in pilot scale test

International Nuclear Information System (INIS)

Chen Zhenyu; Dai Changsong; Wu Gang; Nelson, Mark; Hu Xinguo; Zhang Ruoxin; Liu Jiansheng; Xia Jicai

2010-01-01

Li 3 V 2 (PO 4 ) 3 /C composite cathode material was synthesized via carbothermal reduction process in a pilot scale production test using battery grade raw materials with the aim of studying the feasibility for their practical applications. XRD, FT-IR, XPS, CV, EIS and battery charge-discharge tests were used to characterize the as-prepared material. The XRD and FT-IR data suggested that the as-prepared Li 3 V 2 (PO 4 ) 3 /C material exhibits an orderly monoclinic structure based on the connectivity of PO 4 tetrahedra and VO 6 octahedra. Half cell tests indicated that an excellent high-rate cyclic performance was achieved on the Li 3 V 2 (PO 4 ) 3 /C cathodes in the voltage range of 3.0-4.3 V, retaining a capacity of 95% (96 mAh/g) after 100 cycles at 20C discharge rate. The low-temperature performance of the cathode was further evaluated, showing 0.5C discharge capacity of 122 and 119 mAh/g at -25 and -40 o C, respectively. The discharge capacity of graphite//Li 3 V 2 (PO 4 ) 3 batteries with a designed battery capacity of 14 Ah is as high as 109 mAh/g with a capacity retention of 92% after 224 cycles at 2C discharge rates. The promising high-rate and low-temperature performance observed in this work suggests that Li 3 V 2 (PO 4 ) 3 /C is a very strong candidate to be a cathode in a next-generation Li-ion battery for electric vehicle applications.

Solid Oxide Fuel Cell Cathodes. Unraveling the Relationship Between Structure, Surface Chemistry and Oxygen Reduction

Energy Technology Data Exchange (ETDEWEB)

Gopalan, Srikanth [Boston Univ., MA (United States)

2013-03-31

In this work we have considered oxygen reduction reaction on LSM and LSCF cathode materials. In particular we have used various spectroscopic techniques to explore the surface composition, transition metal oxidation state, and the bonding environment of oxygen to understand the changes that occur to the surface during the oxygen reduction process. In a parallel study we have employed patterned cathodes of both LSM and LSCF cathodes to extract transport and kinetic parameters associated with the oxygen reduction process.

Cathodic Protection Design Algorithms for Refineries Aboveground Storage Tanks

Directory of Open Access Journals (Sweden)

Kosay Abdul sattar Majbor

2017-12-01

Full Text Available Storage tanks condition and integrity is maintained by joint application of coating and cathodic protection. Iraq southern region rich in oil and petroleum product refineries need and use plenty of aboveground storage tanks. Iraq went through conflicts over the past thirty five years resulting in holding the oil industry infrastructure behind regarding maintenance and modernization. The primary concern in this work is the design and implementation of cathodic protection systems for the aboveground storage tanks farm in the oil industry. Storage tank external base area and tank internal surface area are to be protected against corrosion using impressed current and sacrificial anode cathodic protection systems. Interactive versatile computer programs are developed to provide the necessary system parameters data including the anode requirements, composition, rating, configuration, etc. Microsoft-Excel datasheet and Visual Basic.Net developed software were used throughout the study in the design of both cathodic protection systems. The case study considered in this work is the eleven aboveground storage tanks farm situated in al-Shauiba refinery in southern IRAQ. The designed cathodic protection systems are to be installed and monitored realistically in the near future. Both systems were designed for a life span of (15-30 years, and all their parameters were within the internationally accepted standards.

Investigation of spinel-related and orthorhombic LiMNO2 cathodes for rechargeable lithium batteries

CSIR Research Space (South Africa)

Gummow, RJ

1994-05-01

Full Text Available ~ and with carbon at 600~ have been evaluated in rechargeable lithium cells. The cathodes which initially have a composition close to LiMnO2 contain structures related to the lithiated-spinel phase Li2\\[Mn2104 and/or orthorhombic Li... the cathode structure to yield an "over-discharged" state which is possible, for example, with a Lix\\[Mn2104 spinel cathode. 7 Lix\\[Mn2\\]O4 operates at approximately 4 V vs. lithium over the range 0 < x -< 1 and has a...

Investigation of electron emission properties of Ba-activated tungsten cathodes

International Nuclear Information System (INIS)

Beck, I; Josepovits, V K; Sneider, J; Toth, Z

2005-01-01

In this work we investigated the electron emission properties of high-pressure discharge lamp cathode tips. The work function (Φ) of the cathode tip was measured by using the Kelvin probe method and by work function spectroscopy (WFS). The Kelvin probe method was used to measure the average work function of tips under atmospheric pressure in air. By WFS we could measure the local work function value of tips in the selected spots under ultra high vacuum conditions. The chemical composition analysis was carried out in the same chamber by Auger electron spectroscopy. The focus of this study is to investigate the influence of sintering temperature of cathodes (1500-1700 deg. C) and lamp operation time (0-12 000 h) on the work function. The comparison of the work function of both cathodes as a function of operation time originating from the two different ends of the ceramic tube is also considered. In order to understand the structure of the layers on the cathode tips we also give results obtained on a flat tungsten foil covered with Ba-containing emission material. The flat samples were measured using x-ray photoelectron spectroscopy and WFS

Phase III Advanced Anodes and Cathodes Utilized in Energy Efficient Aluminum Production Cells; FINAL

International Nuclear Information System (INIS)

Christini, R.A.; Dawless, R.K.; Ray, S.P.; Weirauch, D.A. Jr.

2001-01-01

During Phase I of the present program, Alcoa developed a commercial cell concept that has been estimated to save 30% of the energy required for aluminum smelting. Phase ii involved the construction of a pilot facility and operation of two pilots. Phase iii of the Advanced Anodes and Cathodes Program was aimed at bench experiments to permit the resolution of certain questions to be followed by three pilot cells. All of the milestones related to materials, in particular metal purity, were attained with distinct improvements over work in previous phases of the program. NiO additions to the ceramic phase and Ag additions to the Cu metal phase of the cermet improved corrosion resistance sufficiently that the bench scale pencil anodes met the purity milestones. Some excellent metal purity results have been obtained with anodes of the following composition: Further improvements in anode material composition appear to be dependent on a better understanding of oxide solubilities in molten cryolite. For that reason, work was commissioned with an outside consultant to model the MeO - cryolite systems. That work has led to a better understanding of which oxides can be used to substitute into the NiO-Fe2O3 ceramic phase to stabilize the ferrites and reduce their solubility in molten cryolite. An extensive number of vertical plate bench electrolysis cells were run to try to find conditions where high current efficiencies could be attained. TiB2-G plates were very inconsistent and led to poor wetting and drainage. Pure TiB2 did produce good current efficiencies at small overlaps (shadowing) between the anodes and cathodes. This bench work with vertical plate anodes and cathodes reinforced the importance of good cathode wetting to attain high current efficiencies. Because of those conclusions, new wetting work was commissioned and became a major component of the research during the third year of Phase III. While significant progress was made in several areas, much work needs to be

Hydrogen pressure dependence of the fracture mode transition in nickel

International Nuclear Information System (INIS)

Jones, R.H.; Baer, D.R.; Bruemmer, S.M.; Thomas, M.T.

1983-01-01

A relationship between fracture mode, grain boundary composition, and hydrogen pressure has been determined for nickel straining electrode samples tested at cathodic potentials. This relationship can be expressed as C /SUB s/ α P /SUP -n/ /SUB H2/ where C /SUB s/ is the critical grain boundary sulfur concentration corresponding to 50 pct transgranular and 50 pct intergranular fracture and P /SUB H2/ is the hydrogen pressure. The value of n was found to be between 0.34 and 0.9. This expression was derived by relating C /SUB s/ to th hydrogen overpotential with the Nernst equation. At a cathodic test potential of -0.3 V (SCE). C /SUB s/ was equal to 0.20 monolayers of sulfur and at higher cathodic potentials or higher hydrogen pressures, C /SUB s/ decreased such that at -0.72 V (SCE) C /SUB s/ was equal to 0.045 monolayers of sulfur. The inverse hydrogen pressure dependence observed with cathodic hydrogen is similar to that for the hydrogen permeation rate or a critical hydrogen concentration derived by Gerberich et al. for gaseous hydrogen. This similarity between gaseous and cathodic hydrogen suggests that grain boundary impurities contribute to the hydrogen embrittlement process without altering the embrittlement process although this result does not indicate whether decohesion or plasticity dependent processes are responsible for the combined sulfur-hydrogen effect on the intergranular fracture of nickel

Lanthanum manganate based cathodes for solid oxide fuel cells

Energy Technology Data Exchange (ETDEWEB)

Juhl Joergensen, M.

2001-07-01

Composite cathodes for solid oxide fuel cells were investigated using electrochemical impedance spectroscopy and scanning electron microscopy. The aim was to study the oxygen reduction process in the electrode in order to minimise the voltage drop in the cathode. The electrodes contained a composite layer made from lanthanum strontium manganate (LSM) and yttria stabilised zirconia (YSZ) and a layer of pure LSM aimed for current collection. The performance of the composite electrodes was sensitive to microstructure and thickness. Further, the interface between the composite and the current collecting layer proved to affect the performance. In a durability study severe deg-radation of the composite electrodes was found when passing current through the electrode for 2000 hours at 1000 deg. C. This was ascribed to pore formation along the composite interfaces and densification of the composite and current collector microstructure. An evaluation of the measurement approach indicated that impedance spectroscopy is a very sensitive method. This affects the reproducibility, as small undesirable variations in for instance the microstructure from electrode to electrode may change the impedance. At least five processes were found to affect the impedance of LSM/YSZ composite electrodes. Two high frequency processes were ascribed to transport of oxide ions/oxygen intermediates across LSM/YSZ interfaces and through YSZ in the composite. Several competitive elementary reaction steps, which appear as one medium frequency process in the impedance spectra, were observed. A low frequency arc related to gas diffusion limitation in a stagnant gas layer above the composite structure was detected. Finally, an inductive process, assumed to be connected to an activation process involving segregates at the triple phase boundary between electrode, electrolyte and gas phase, was found. (au)

The effect of oxygen transfer mechanism on the cathode performance based on proton-conducting solid oxide fuel cells

KAUST Repository

Hou, Jie

2015-01-01

Two types of proton-blocking composites, La2NiO4+δ-LaNi0.6Fe0.4O3-δ (LNO-LNF) and Sm0.2Ce0.8O2-δ-LaNi0.6Fe0.4O3-δ (SDC-LNF), were evaluated as cathode materials for proton-conducting solid oxide fuel cells (H-SOFCs) based on the BaZr0.1Ce0.7Y0.2O3-δ (BZCY) electrolyte, in order to compare and investigate the influence of two different oxygen transfer mechanism on the performance of the cathode for H-SOFCs. The X-ray diffraction (XRD) results showed that the chemical compatibility of the components in both compounds was excellent up to 1000°C. Electrochemical studies revealed that LNO-LNF showed lower area specific polarization resistances in symmetrical cells and better electrochemical performance in single cell tests. The single cell with LNO-LNF cathode generated remarkable higher maximum power densities (MPDs) and lower interfacial polarization resistances (Rp) than that with SDC-LNF cathode. Correspondingly, the MPDs of the single cell with the LNO-LNF cathode were 490, 364, 266, 180 mW cm-2 and the Rp were 0.103, 0.279, 0.587, 1.367 Ω cm2 at 700, 650, 600 and 550°C, respectively. Moreover, after the single cell with LNO-LNF cathode optimized with an anode functional layer (AFL) between the anode and electrolyte, the power outputs reached 708 mW cm-2 at 700°C. These results demonstrate that the LNO-LNF composite cathode with the interstitial oxygen transfer mechanism is a more preferable alternative for H-SOFCs than SDC-LNF composite cathode with the oxygen vacancy transfer mechanism.

Lithium battery using sulfur infiltrated in three-dimensional flower-like hierarchical porous carbon electrode

Energy Technology Data Exchange (ETDEWEB)

Moreno, Noelia; Caballero, Alvaro [Dpto.Química Inorgánica, Instituto Universitario de Investigación en Química Fina y Nanoquímica, Universidad de Córdoba, Campus de Rabanales (Spain); Morales, Julián, E-mail: iq1mopaj@uco.es [Dpto.Química Inorgánica, Instituto Universitario de Investigación en Química Fina y Nanoquímica, Universidad de Córdoba, Campus de Rabanales (Spain); Agostini, Marco [Department of Chemistry, SapienzaUniversity, P.zzale Aldo Moro 5, 00185, Rome (Italy); Hassoun, Jusef, E-mail: jusef.hassoun@unife.it [Università di Ferrara, Dipartimento di Scienze Chimiche e Farmaceutiche, Via Fossato di Mortara 17, Ferrara (Italy)

2016-09-01

Three dimensional, flower-like hierarchical porous carbon (FPC) and its CO{sub 2}-activation (AFPC) are reported as sulfur-hosting matrixes in Li/S battery. The composites are characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), nitrogen adsorption-desorption isotherms as well as by galvanostatic cycling and electrochemical impedance spectroscopy (EIS) in lithium-cell. Both samples show well defined micrometric morphology and a sulfur content as high as 66% expected to reflect into rather high practical energy density of the electrode in lithium-sulfur battery. The lithium sulfur cell using the FPC-S composite exhibits at 25 °C a moderate cycling stability with delivered capacity ranging from 1000 to about 610 mAh g{sup −1} upon 50 cycles at 100 mA g{sup −1}. The AFPC-S composite reveals increased cycling stability and delivers a capacity ranging from 1000 to 680 mAh g{sup −1}. Improved capacity is achieved by slightly increasing the temperature, as demonstrated by cycling the FPC-S at 35 °C using a current as high as 500 mA g{sup −1}. The excellent rate capability of the electrode is associated to the carbon texture and morphology that significantly lower the cell resistance, as indeed demonstrated by EIS measurement upon cycling. - Highlights: • Sulfur electrode basing on activated, flower-like hierarchical porous carbon is reported. • Defined micrometric morphology and a sulfur content as high as 66% are obtained. • Lithium sulfur cell using the composite exhibits remarkable performances. • A specific capacity of about 1000 mAh g{sup −1} is obtained at high current rate. • The resulting Li/S battery has relevant energy content.

Effect of ‘A’-site non stoichiometry in strontium doped lanthanum ferrite based solid oxide fuel cell cathodes

Energy Technology Data Exchange (ETDEWEB)

Banerjee, Koyel; Mukhopadhyay, Jayanta, E-mail: jayanta_mu@cgcri.res.in; Barman, Madhurima; Basu, Rajendra N., E-mail: rnbasu@cgcri.res.in

2015-12-15

Highlights: • La{sub 1−x}Sr{sub x}Co{sub y}Fe{sub 1−y}O{sub 3−δ}, x = 0.4; y = 0.2 system varying La-site (0.6–0.54) are studied. • Combustion synthesis technique is used to prepare the powder samples. • Highest electrical conductivity observed with largest A-site deficit composition. • Lowest cathode polarization is found with the same composition (0.02 Ω cm{sup 2}). • Composition with largest A-site deficiency exhibits best performance (2.84 A cm{sup −2}). - Abstract: Effect of A-site non-stoichiometry in strontium doped lanthanum cobalt ferrite (La{sub 1−x}Sr{sub x}Co{sub y}Fe{sub 1−y}O{sub 3−δ}, x = 0.4; y = 0.2) is studied in a systematic manner with variation of ‘A’ site stoichiometry from 1 to 0.94. The perovskite based cathode compositions are synthesized by combustion synthesis. Powder characterizations reveal rhombohedral crystal structure with crystallite size ranging from 29 to 34 nm with minimum lattice spacing of 0.271 nm. Detailed sintering studies along with total DC electrical conductivities are evaluated in the bulk form with variation of sintering temperatures. The electrode polarizations are measured in the symmetric cell configuration by impedance spectroscopy which is found to be the lowest (0.02 Ω cm{sup 2} at 800 °C) for cathode having highest degree of ‘A’-site deficiency. The same cathode composition exhibits a current density of 2.84 A cm{sup −2} (at 0.7 V, 800 °C) in anode-supported single cell. An attempt has been made to correlate the trend of electrical behaviour with increasing ‘A’-site deficiency for such cathode compositions.

New polyanion-based cathode materials for alkali-ion batteries

Science.gov (United States)

Yaghoobnejad Asl, Hooman

A number of new materials have been discovered through exploratory synthesis with the aim to be studied as the positive electrode (cathode) in Li-ion and Na-ion batteries. The focus has been set on the ease of synthesis, cost and availability of active ingredients in the battery, and decent cycle-life performance through a combination of iron and several polyanionic ligands. An emphasis has been placed also on phosphite (HPO32-) as a polyanionic ligand, mainly due to the fact that it has not been studied seriously before as a polyanion for cathode materials. The concept of mixed polyanions, for example, boro-phosphate and phosphate-nitrates were also explored. In each case the material was first made and purified via different synthetic strategies, and the crystal structure, which dominantly controls the performance of the materials, has been extensively studied through Single-Crystal X-ray Diffraction (SCXRD) or synchrotron-based Powder X-ray Diffraction (PXRD). This investigation yielded four new compositions, namely Li3Fe 2(HPO3)3Cl, LiFe(HPO3)2, Li0.8Fe(H2O)2B[P2O8]•H 2O and AFePO4NO3 (A = NH4/Li, K). Furthermore, for each material the electrochemical performance for insertion of Li+ ion has been studied by means of various electrochemical techniques to reveal the nature of alkali ion insertion. In addition Na-ion intercalation has been studied for boro-phosphate and AFePO4NO3. Additionally a novel synthesis procedure has been reported for tavorite LiFePO4F 1-x(OH)x, where 0 ≤ x ≤ 1, an important class of cathode materials. The results obtained clearly demonstrate the importance of crystal structure on the cathode performance through structural and compositional effects. Moreover these findings may contribute to the energy storage community by providing insight into the solid-state science of electrode material synthesis and proposing new alternative compositions based on sustainable materials.

Release of Chlorine and Sulfur during Biomass Torrefaction and Pyrolysis

DEFF Research Database (Denmark)

Saleh, Suriyati Binti; Flensborg, Julie Pauline; Shoulaifar, Tooran Khazraie

2014-01-01

The release of chlorine (Cl) and sulfur (S) during biomass torrefaction and pyrolysis has been investigated via experiments in two laboratory-scale reactors: a rotating reactor and a fixed bed reactor. Six biomasses with different chemical compositions covering a wide range of ash content and ash...... reporting that biomasses with a lower chlorine content release a higher fraction of chlorine during the pyrolysis process. A significant sulfur release (about 60%) was observed from the six biomasses investigated at 350 degrees C. The initial sulfur content in the biomass did not influence the fraction...

Effect of substrate and cathode parameters on the properties of suspension plasma sprayed solid oxide fuel cell electrolytes

Energy Technology Data Exchange (ETDEWEB)

Waldbillig, D.; Tang, Z.; Burgess, A. [British Columbia Univ., Vancouver, BC (Canada); Kesler, O. [Toronto Univ., ON (Canada)

2008-07-01

An axial injection suspension plasma spray system has been used to produce layers of fully stabilized yttriastabilized zirconia (YSZ) that could be used as solid oxide fuel cell (SOFC) electrolytes. Suspension plasma spraying is a promising technique for the rapid production of coatings with fine microstructures and controlled porosity without requiring a post-deposition heat treatment. This new manufacturing technique to produce SOFC active layers requires the build up of a number of different plasma sprayed SOFC functional layers (cathode, electrolyte and anode) sequentially on top of each other. To understand the influence of the substrate and previouslydeposited coating layers on subsequent coating layer properties, YSZ layers were deposited on top of plasma sprayed composite lanthanum strontium manganite (LSM)/YSZ cathode layers that were first deposited on porous ferritic stainless steel substrates. Three layer half cells consisting of the porous steel substrate, composite cathode, and suspension plasma sprayed electrolyte layer were then characterized. A systematic study was performed in order to investigate the effect of parameters such as substrate and cathode layer roughness, substrate surface pore size, and cathode microstructure and thickness on electrolyte deposition efficiency, cathode and electrolyte permeability, and layer microstructure. (orig.)

In situ synthesized Li2S@porous carbon cathode for graphite/Li2S full cells using ether-based electrolyte

International Nuclear Information System (INIS)

Wang, Ning; Zhao, Naiqin; Shi, Chunsheng; Liu, Enzuo; He, Chunnian; He, Fang; Ma, Liying

2017-01-01

Graphical abstract: A facile method is proposed to prepare lithium sulfide@porous carbon composites (Li 2 S@PC) by in-situ reaction of lithium sulfate (Li 2 SO 4 ) and the pyrolytic carbon from glucose. We assembled graphite-Li 2 S@PC full-cells using the obtained Li 2 S@PC composites as the cathode, graphite as the anode and DOL/DME with LiNO 3 additive as the electrolyte. Display Omitted -- Highlights: •A simple synthesis method was proposed to form Li 2 S@porous carbon composites. •Graphite-Li 2 S full-cells were constructed in DME-based electrolyte. •A novel method was proposed to activate the full cells. -- Abstract: Lithium-sulfur (Li-S) batteries have been recognized as one of the promising next-generation energy storage devices owing to their high energy density, low cost and eco-friendliness. As for cathode’s performance, the main challenges for developing highly-efficient and long-life Li-S batteries are to retard the polysulfides diffusion into electrolyte and the reaction with metallic lithium (Li). Especially, the safety issues, derived from metallic Li in anode, must be overcome. Herein, we fabricated lithium sulfide@porous carbon composites (Li 2 S@PC) by an in-situ reaction between the lithium sulfate (Li 2 SO 4 ) and the pyrolytic carbon from glucose. The nanosized Li 2 S particles were uniformly distributed in the carbon matrix, which not only significantly improve electronic conductivity of the electrode but also effectively trap the dissolved polysulfides. Furthermore, on the basis of the graphite’s electrochemical features in ether-based electrolyte, we assembled graphite-Li 2 S@PC full cells using the obtained Li 2 S@PC composites as the cathode, graphite as the anode and the DOL/DME with LiNO 3 additive as the electrolyte. A unique strategy was proposed to activate the full-cells in descending order using constant voltage and current to charge the cut-off voltage. This Li-S full cell exhibits stable cycling performance at 0.5 C over

Biogeochemistry of sulfur and iron in Thioploca-colonized surface sediments in the upwelling area off central chile

Science.gov (United States)

Zopfi, Jakob; Böttcher, Michael E.; Jørgensen, Bo Barker

2008-02-01

The biogeochemistry of sedimentary sulfur was investigated on the continental shelf off central Chile at water depths between 24 and 88 m under partial influence of an oxygen minimum zone. Dissolved and solid iron and sulfur species, including the sulfur intermediates sulfite, thiosulfate, and elemental sulfur, were analyzed at high resolution in the top 20 cm. All stations were characterized by high rates of sulfate reduction, but only the sediments within the Bay of Concepción contained dissolved sulfide. Due to advection and/or in-situ reoxidation of sulfide, dissolved sulfate was close to bottom water values. Whereas the concentrations of sulfite and thiosulfate were mostly in the submicromolar range, elemental sulfur was by far the dominant sulfur intermediate. Although the large nitrate- and sulfur-storing bacteria Thioploca were abundant, the major part of S 0 was located extracellularly. The distribution of sulfur species and dissolved iron suggests the reaction of sulfide with FeOOH as an important pathway for sulfide oxidation and sulfur intermediate formation. This is in agreement with the sulfur isotope composition of co-existing elemental sulfur and iron monosulfides. In the Bay of Concepción, sulfur isotope data suggest that pyrite formation proceeds via the reaction of FeS with polysulfides or H 2S. At the shelf stations, on the other hand, pyrite was significantly depleted in 34S relative to its potential precursors FeS and S 0. Isotope mass balance considerations suggest further that pyritization at depth includes light sulfide, potentially originating from bacterial sulfur disproportionation. The δ 34S-values of pyrite down to -38‰ vs. V-CDT are among the lightest found in organic-rich marine sediments. Seasonal variations in the sulfur isotope composition of dissolved sulfate indicated a dynamic non-steady-state sulfur cycle in the surface sediments. The 18O content of porewater sulfate increased with depth at all sites compared to the

Nanoscale visualization of redox activity at lithium-ion battery cathodes.

Science.gov (United States)

Takahashi, Yasufumi; Kumatani, Akichika; Munakata, Hirokazu; Inomata, Hirotaka; Ito, Komachi; Ino, Kosuke; Shiku, Hitoshi; Unwin, Patrick R; Korchev, Yuri E; Kanamura, Kiyoshi; Matsue, Tomokazu

2014-11-17

Intercalation and deintercalation of lithium ions at electrode surfaces are central to the operation of lithium-ion batteries. Yet, on the most important composite cathode surfaces, this is a rather complex process involving spatially heterogeneous reactions that have proved difficult to resolve with existing techniques. Here we report a scanning electrochemical cell microscope based approach to define a mobile electrochemical cell that is used to quantitatively visualize electrochemical phenomena at the battery cathode material LiFePO4, with resolution of ~100 nm. The technique measures electrode topography and different electrochemical properties simultaneously, and the information can be combined with complementary microscopic techniques to reveal new perspectives on structure and activity. These electrodes exhibit highly spatially heterogeneous electrochemistry at the nanoscale, both within secondary particles and at individual primary nanoparticles, which is highly dependent on the local structure and composition.

Microbial transformations of nitrogen, sulfur and iron dictate vegetation composition in wetlands: a review

Directory of Open Access Journals (Sweden)

Leon P.M. Lamers

2012-04-01

Full Text Available The majority of studies on rhizospheric interactions between microbial communities and vegetation focus on pathogens, mycorrhizal symbiosis, and/or carbon transformations. Although the biogeochemical transformations of nitrogen (N, sulfur (S and iron (Fe have profound effects on plants, these effects have received far less attention. Firstly, all three elements are plant nutrients, and microbial activity significantly changes their mobility and availability. Secondly, microbial oxidation with oxygen supplied by radial oxygen loss (ROL from roots in wetlands causes acidification, while reduction using alternative electron acceptors leads to generation of alkalinity, affecting pH in the rhizosphere and hence plant composition. Thirdly, reduced species of all three elements may become phytotoxic. In addition, Fe cycling is tightly linked to that of S and phosphorus (P. As water level fluctuations are very common in wetlands, rapid changes in the availability of oxygen and alternative terminal electron acceptors will result in strong changes in the prevalent microbial redox reactions, with significant effects on plant growth. Depending on geological and hydrological settings, these interacting microbial transformations change the conditions and resource availability for plants, which are strong drivers of vegetation development and composition by changing relative competitive strengths. Conversely, microbial composition is strongly driven by vegetation composition. Therefore, the combination of micro- and macroecological knowledge is essential to understand the biogeochemical and biological key factors driving heterogeneity and total (i.e., micro-macro community composition at different spatial and temporal scales. As N and S inputs have drastically increased due to anthropogenic forcing and Fe inputs have decreased at a global scale, this combined approach has become even more urgent.

Analysis of cathode geometry to minimize cathode erosion in direct current microplasma jet

Energy Technology Data Exchange (ETDEWEB)

Causa, Federica [Dipartimento di Scienze dell' Ambiente, della Sicurezza, del Territorio, degli Alimenti e della Salute, Universita degli studi di Messina, 98122 Messina (Italy); Ghezzi, Francesco; Caniello, Roberto; Grosso, Giovanni [Istituto di Fisica del Plasma, Consiglio Nazionale delle Ricerche, EURATOM-ENEA-CNR Association, Via R. Cozzi 53, 20125 Milano (Italy); Dellasega, David [Istituto di Fisica del Plasma, Consiglio Nazionale delle Ricerche, EURATOM-ENEA-CNR Association, Via R. Cozzi 53, 20125 Milano (Italy); Dipartimento di Energia, Politecnico di Milano, Via Ponzio 34/3, 20133 Milano (Italy)

2012-12-15

Microplasma jets are now widely used for deposition, etching, and materials processing. The present study focuses on the investigation of the influence of cathode geometry on deposition quality, for microplasma jet deposition systems in low vacuum. The interest here is understanding the influence of hydrogen on sputtering and/or evaporation of the electrodes. Samples obtained with two cathode geometries with tapered and rectangular cross-sections have been investigated experimentally by scanning electron microscopy and energy dispersion X-ray spectroscopy. Samples obtained with a tapered-geometry cathode present heavy contamination, demonstrating cathode erosion, while samples obtained with a rectangular-cross-section cathode are free from contamination. These experimental characteristics were explained by modelling results showing a larger radial component of the electric field at the cathode inner wall of the tapered cathode. As a result, ion acceleration is larger, explaining the observed cathode erosion in this case. Results from the present investigation also show that the ratio of radial to axial field components is larger for the rectangular geometry case, thus, qualitatively explaining the presence of micro-hollow cathode discharge over a wide range of currents observed in this case. In the light of the above findings, the rectangular cathode geometry is considered to be more effective to achieve cleaner deposition.

Iron and Sulfur Species and Sulfur Isotopic Compositions of Authigenic Pyrite in Gas Hydrate-Bearing Sediments from Hydrate Ridge, Cascadia Margin (ODP Leg 204): A Proposal of Conceptual Models to Indicate the Non-Steady State Depositional and Diagenetic Processes

Science.gov (United States)

Liu, C.; Jiang, S. Y.; Su, X.

2017-12-01

Two accretionary sediment sequences from Sites 1245 and 1252 recovered during Ocean Drilling Program (ODP) Leg 204 at Hydrate Ridge, Cascadia Margin were investigated to explore the non-steady state depositional and diagenetic history. Five iron species and three sulfur species were chemically extracted, and their concentrations and the sulfur isotopic compositions of pyrite were determined. After the mineral recognitions of these species and detailed comparative analyses, the aerobic history of bottom seawater has been determined. The formation of pyrite is thought to be controlled by the limited production of hydrogen sulfide relative to the supply of reactive iron. Also, the intrusion of oxygen by bioturbation would oxidize the reduced sulfur species and further suppress pyritization. To explain the geochemical relationship between pyrite and siderite and the sulfur isotope characteristics of pyrite, we propose seven conceptual models based on the variations in depositional rate and methane flux, and the models succeed in explaining the geochemical results and are validated by the observed non-steady state events. These models may contribute to the reconstruction of the non-steady state processes in other research areas in the future.

Sulfur isotope variability of oceanic DMSP generation and its contributions to marine biogenic sulfur emissions.

Science.gov (United States)

Oduro, Harry; Van Alstyne, Kathryn L; Farquhar, James

2012-06-05

Oceanic dimethylsulfoniopropionate (DMSP) is the precursor to dimethylsulfide (DMS), which plays a role in climate regulation through transformation to methanesulfonic acid (MSA) and non-seasalt sulfate (NSS-SO(4)(2-)) aerosols. Here, we report measurements of the abundance and sulfur isotope compositions of DMSP from one phytoplankton species (Prorocentrum minimum) and five intertidal macroalgal species (Ulva lactuca, Ulva linza, Ulvaria obscura, Ulva prolifera, and Polysiphonia hendryi) in marine waters. We show that the sulfur isotope compositions (δ(34)S) of DMSP are depleted in (34)S relative to the source seawater sulfate by ∼1-3‰ and are correlated with the observed intracellular content of methionine, suggesting a link to metabolic pathways of methionine production. We suggest that this variability of δ(34)S is transferred to atmospheric geochemical products of DMSP degradation (DMS, MSA, and NSS-SO(4)(2-)), carrying implications for the interpretation of variability in δ(34)S of MSA and NSS-SO(4)(2-) that links them to changes in growth conditions and populations of DMSP producers rather than to the contributions of DMS and non-DMS sources.

Thermodynamic evaluation of liquid Cd cathode containing U and Pu

International Nuclear Information System (INIS)

Kurata, Masaki; Uozumi, Koichi; Kato, Tetsuya; Iizuka, Masatoshi

2009-01-01

In our previous study, a mixture of U and Pu was recovered in liquid Cd cathode from molten salt under various conditions of the U:Pu ratio. Two important things were observed. The first was that three kinds of precipitated phase had been detected in the saturated liquid Cd cathode, such as a U metal and two kinds of U-Pu-Cd compound. The compositions of the compounds were roughly (U+Pu):Cd=1:11 and (U+Pu):Cd=1:6. The second was that the U metal had selectively precipitated in the saturated liquid Cd cathode under the condition that the U:Pu ratio is higher than about 0.8 in the liquid Cd phase. In the present study, phase diagrams were evaluated by the CALPHAD method on the liquid Cd cathode containing U and Pu. The U-Pu-Cd compounds were modeled as MCd 11 -type and MCd 6 -type, respectively, based on the reported binary phase diagrams of U-Cd and Pu-Cd. The calculated result reasonably agreed with the experimental observations. The variations in the U and Pu activities were estimated along with the U:Pu ratio, which is related to the precipitation of various phases in the liquid Cd cathode. (author)

Hierarchically structured Ni(3)S(2)/carbon nanotube composites as high performance cathode materials for asymmetric supercapacitors.

Science.gov (United States)

Dai, Chao-Shuan; Chien, Pei-Yi; Lin, Jeng-Yu; Chou, Shu-Wei; Wu, Wen-Kai; Li, Ping-Hsuan; Wu, Kuan-Yi; Lin, Tsung-Wu

2013-11-27

The Ni3S2 nanoparticles with the diameters ranging from 10 to 80 nm are grown on the backbone of conductive multiwalled carbon nanotubes (MWCNTs) using a glucose-assisted hydrothermal method. It is found that the Ni3S2 nanoparticles deposited on MWCNTs disassemble into smaller components after the composite electrode is activated by the consecutive cyclic voltammetry scan in a 2 M KOH solution. Therefore, the active surface area of the Ni3S2 nanoparticles is increased, which further enhances the capacitive performance of the composite electrode. Because the synergistic effect of the Ni3S2 nanoparticles and MWCNTs on the capacitive performance of the composite electrode is pronounced, the composite electrode shows a high specific capacitance of 800 F/g and great cycling stability at a current density of 3.2 A/g. To examine the capacitive performance of the composite electrode in a full-cell configuration, an asymmetric supercapacitor device was fabricated by using the composite of Ni3S2 and MWCNTs as the cathode and activated carbon as the anode. The fabricated device can be operated reversibly between 0 and 1.6 V, and obtain a high specific capacitance of 55.8 F/g at 1 A/g, which delivers a maximum energy density of 19.8 Wh/kg at a power density of 798 W/kg. Furthermore, the asymmetric supercapacitor shows great stability based on the fact that the device retains 90% of its initial capacitance after a consecutive 5000 cycles of galvanostatic charge-discharge performed at a current density of 4 A/g.

CdTe/TiO{sub 2} nanocomposite material for photogenerated cathodic protection of 304 stainless steel

Energy Technology Data Exchange (ETDEWEB)

Wang, Xiu-tong, E-mail: xiutongwang@gmail.com [Institutes of Oceanology, Chinese Academy of Sciences, Qingdao 266071 China (China); Wei, Qin-yi, E-mail: weiqiny200@163.com [Institutes of Oceanology, Chinese Academy of Sciences, Qingdao 266071 China (China); University of Chinese Academy of Sciences, 19 (Jia) Yuquan Road, Beijing 100049 (China); Zhang, Liang, E-mail: zzll20081988@126.com [CNOOC Information Technology co., Ltd. Beijing Branch, Beijing 100029 China (China); Sun, Hao-fen, E-mail: fyqfyx@163.com [School of Environmental and Municipal Engineering Qingdao, Qingdao Technological University, Qingdao 266033 China (China); Li, Hong, E-mail: lhqdio1987@163.com [Institutes of Oceanology, Chinese Academy of Sciences, Qingdao 266071 China (China); Zhang, Qiao-xia, E-mail: qiaoxiazhang1989@163.com [Institutes of Oceanology, Chinese Academy of Sciences, Qingdao 266071 China (China)

2016-06-15

Graphical abstract: - Highlights: • The photoelectric properties of TiO{sub 2} could greatly improve by doping with CdTe. • The cathodic protection property of the CdTe/TiO{sub 2} was superior to that of pure TiO{sub 2}. • The protective action of the CdTe/TiO{sub 2} for 304SS could be maintained in the dark. - Abstract: TiO{sub 2} nanotubes were fabricated by the anodization method, and CdTe was deposited on them via electrochemical deposition method. The optimal performance of the CdTe/TiO{sub 2} composites was achieved via changing the acidity of the electrolyte. Scanning electron microscopy, energy dispersive spectroscopy and X-ray diffraction were used to investigate the surface morphology, elemental analysis and phase characteristics of the composite materials. Some electrochemical tests, such as open-circuit potential, current variation versus time were carried out to investigate the photogenerated cathodic protection of 304 stainless steel by CdTe/TiO{sub 2}. The results indicated that the cathodic protection performance of the CdTe/TiO{sub 2} composite was superior to that of pure TiO{sub 2} in the wavelength of visible light. The CdTe/TiO{sub 2} composite exhibited optimal photogenerated cathodic protection properties under visible light for the corrosion potential of 304 stainless steel shifted negatively to −850 mV when the concentration of HCl in the deposition electrolyte was 1 mol/L.

Depression cathode structure for cathode ray tubes having surface smoothness and method for producing same

International Nuclear Information System (INIS)

Rychlewski, T.V.

1984-01-01

Depression cathode structures for cathode ray tubes are produced by dispensing liquid cathode material into the depression of a metallic supporting substrate, removing excess cathode material by passing a doctor blade across the substrate surface and over the depression, and drying the cathode layer to a substantially immobile state. The cathode layer may optionally be further shaped prior to substantially complete drying thereof

LOW TEMPERATURE CATHODE SUPPORTED ELECTROLYTES

Energy Technology Data Exchange (ETDEWEB)

Harlan U. Anderson; Fatih Dogan; Vladimir Petrovsky

2002-03-31

This project has three main goals: Thin Films Studies, Preparation of Graded Porous Substrates and Basic Electrical Characterization and testing of Planar Single Cells. This period has continued to address the problem of making dense 1/2 to 5 {micro}m thick dense layers on porous substrates (the cathode LSM). Our current status is that we are making structures of 2-5 cm{sup 2} in area, which consist of either dense YSZ or CGO infiltrated into a 2-5 {micro}m thick 50% porous layer made of either nanoncrystalline CGO or YSZ powder. This composite structure coats a macroporous cathode or anode; which serves as the structural element of the bi-layer structure. These structures are being tested as SOFC elements. A number of structures have been evaluated both as symmetrical and as button cell configuration. Results of this testing indicates that the cathodes contribute the most to cell losses for temperatures below 750 C. In this investigation different cathode materials were studied using impedance spectroscopy of symmetric cells and IV characteristics of anode supported fuel cells. Cathode materials studied included La{sub 0.8}Sr{sub 0.2}Co{sub 0.2}Fe{sub 0.8}O{sub 3} (LSCF), La{sub 0.7}Sr{sub 0.2}MnO{sub 3} (LSM), Pr{sub 0.8}Sr{sub 0.2}Fe{sub 0.8}O{sub 3} (PSCF), Sm{sub 0.8}Sr{sub 0.2}Co{sub 0.2}Fe{sub 0.8}O{sub 3} (SSCF), and Yb{sub .8}Sr{sub 0.2}Co{sub 0.2}Fe{sub 0.8}O{sub 3} (SSCF). A new technique for filtering the Fourier transform of impedance data was used to increase the sensitivity of impedance analysis. By creating a filter specifically for impedance spectroscopy the resolution was increased. The filter was tailored to look for specific circuit elements like R//C, Warburg, or constant phase elements. As many as four peaks can be resolved using the filtering technique on symmetric cells. It may be possible to relate the different peaks to material parameters, like the oxygen exchange coefficient. The cathode grouped in order from lowest to highest ASR is

Mechanism of reaction and cycling behavior of nickel felt cathodes in NaAlCl4 molten salt batteries

Energy Technology Data Exchange (ETDEWEB)

Hjuler, H.A.; Knutz, B.C.; Berg, R.W.; Bjerrum, N.J.

1990-11-01

The battery system: Al/NaCl-AlCl3-Al2X3/Ni-felt (X = S, Se, Te) and the corresponding system without chalcogen have been studied at 175 deg. C. Charge/discharge experiments, performed on cells with NaCl saturated melts, show that advantages with regard to rate capability, cyclability and probably energy density can be obtained with systems containing dissolved chalcogen compared with the chalcogen free system. The cells with sulfur added to the electrolyte exhibit the same charge/discharge curves as found for comparable cells prepared with a nickel sulfide cathode. Exchange of chalcogen between cathode and molten salt during cycling was studied by performing gravimetric analysis and Raman spectroscopy of the electrolytes. In the low charge state, formation and decomposition of nickel chalcogenides, associated with uptake/release of chalcogenide from the melt, take place to a large extent during cycling. Cathode reactions were studied by comparing coulometric titrations (performed on cells with slightly acidic NACl-AlCl3 melts containing approx 0.51 mole % AlCl3 and small amounts of chalcogen) with model calculations. The model set up describes equilibrium concentrations of constituent species in the electrolyte and equilibrium potentials of the electrodes versus number of coulombs passed through the cells, assuming probable cathode reactions. (author) 27 refs.

Biogeochemistry of sulfur and iron in Thioploca-colonized surface sediments in the upwelling area off central Chile

DEFF Research Database (Denmark)

Zopfi, Jakob; Michael E., Böttcher; Jørgensen, Bo Barker

2008-01-01

suggest further that pyritization at depth includes light sulfide, potentially originating from bacterial sulfur disproportionation. The δ34S-values of pyrite down to -38‰ vs. V-CDT are among the lightest found in organic-rich marine sediments. Seasonal variations in the sulfur isotope composition...... of dissolved sulfate indicated a dynamic non-steady-state sulfur cycle in the surface sediments. The 18O content of porewater sulfate increased with depth at all sites compared to the bottom water composition due to intracellular isotope exchange reactions during microbial sulfur transformations....

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

Science.gov (United States)

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.

Corrosion of Graphite Aluminum Metal Matrix Composites

Science.gov (United States)

1991-02-01

cathodic protection of G/AI MMCs resulted in overprotection 13. Overprotection resulted from a local increase in pH near cathodic sites during...34Cathodic Overprotection of SiC/6061-T6 and G/6061- T6 Aluminum Alloy Metal Matrix Composites," Scripta Metallurgica, 22 (1988) 413-418. 14. R

Sulfur in zircons: A new window into melt chemistry

Science.gov (United States)

Tang, H.; Bell, E. A.; Boehnke, P.; Barboni, M.; Harrison, T. M.

2017-12-01

The abundance and isotopic composition of sulfur are important tools for exploring the photochemistry of the atmosphere, the thermal history of mantle and igneous rocks, and ancient metabolic processes on the early Earth. Because the oldest terrestrial samples are zircons, we developed a new in-situ procedure to analyze the sulfur content of zircons using the CAMECA ims 1290 at UCLA. We analyzed zircons from three metaluminous/I-type granites (reduced and oxidized Peninsular range and Elba), which exhibit low sulfur abundance with the average of 0.5ppm, and one peraluminous/S-type zircon (Strathbogie Range), which shows an elevated sulfur level with the average of 1.5ppm. Additionally, we found that sulfur content ranges between 0.4 and 2.3 ppm in young volcanic zircons (St. Lucia). Our analyses of zircons from the Jack Hills, Western Australia, whose ages range between 3.4 and 4.1 Ga, show a variety of sulfur contents. Three out of the ten zircons are consistent with the sulfur contents of S-type zircons; the rest have low sulfur contents, which are similar to those of I-type zircons. The high sulfur content in some of these Jack Hills zircons can be interpreted as indicating their origin in either a S-type granite or a volcanic reservoir. We favor the former interpretation since the Ti-in-zircon temperatures of our Jack Hills zircons is lower than those of volcanic zircons. Future work will be undertaken to develop a systematic understanding of the relationship between melt volatile content, melt chemistry, and zircon sulfur content.

Optimization of Liposomal Lipid Composition for a New, Reactive Sulfur Donor, and In Vivo Efficacy Studies on Mice to Antagonize Cyanide Intoxication

Directory of Open Access Journals (Sweden)

Ilona Petrikovics

2011-01-01

Full Text Available Present studies have focused on a novel cyanide antidotal system, on the coencapsulation of a new sulfur donor DTO with rhodanese within sterically stabilized liposomes. The optimal lipid composition for coencapsulation of DTO with rhodanese is the combination of 1-palmitoyl-2-oleoyl-sn-glycero-3-phosphocholine, cholesterol, cationic lipid (DOTAP, and 1,2-dipalmitoyl-sn-glycero-3-phosphoethanolamine-N-[methoxy(polyethylene glycol-2000] ammonium salt (with molar ratios of 82.7 : 9.2 : 3.0 : 5.1. With the optimized compositions, prophylactic and therapeutic in vivo efficacy studies were carried out in a mice model. When DTO was coencapsulated with rhodanese and thiosulfate the prophylactic antidotal protection was 4.9×LD50. Maximum antidotal protection against cyanide intoxication (15×LD50 was achieved with coencapsulated rhodanese and DTO/thiosulfate in combination with sodium nitrite. When applied therapeutically, 100% survival rate (6/6 was achieved at 20 mg/kg cyanide doses with the encapsulated DTO-rhodanese-thiosulfate antidotal systems with and without sodium nitrite. These data are indicating that the appropriately formulated DTO is a promising sulfur donor for cyanide antagonism.

Characterization of Carbon Composite LiMn1-xFexPO4 Cathodes

International Nuclear Information System (INIS)

Mishima, Y; Honda, S; Sadamura, H; Nakayama, N; Moriyoshi, C; Kuroiwa, Y

2011-01-01

The discharge capacities of 148 mAh/g (87 % theoretical value) at C/10 and 114mAh/g at 5C between 2.0 and 4.5 V at 25 deg. C were achieved for the carbon composite LiMn 0.8 Fe 0.2 PO 4 (C-LiMn 0.8 Fe 0.2 PO 4 ) cathode material of lithium-ion batteries (LIB), synthesized by a hydrothermal and annealing process. To improve the battery properties, we investigated the characteristics of C-LiMn 1-x Fe x PO 4 powders (x = 0.2 and 1) and the delithiated compound. While it was easier to form the homogeneous carbon layer on the surface of LiFePO 4 particles from the pyrolysis of sucrose, there was a tendency to form the particulate carbon on the LiMn 0.8 Fe 0.2 PO 4 particles. The lattice distortion of Mn 0.8 Fe 0.2 PO 4 was revealed by electron charge density study because of the Jahn-Teller active Mn 3+ ion associated with the phosphate ion. The surface and size of C- LiMn 0.8 Fe 0.2 PO 4 had to be modified because of these phenomena.

Evaluation of materials for bipolar plates in simulated PEM fuel-cell cathodic environments

Energy Technology Data Exchange (ETDEWEB)

Rivas, S.V.; Belmonte, M.R.; Moron, L.E.; Torres, J.; Orozco, G. [Centro de Investigacion y Desarrollo Technologico en Electroquimica S.C. Parcque Sanfandila, Queretaro (Mexico); Perez-Quiroz, J.T. [Mexican Transport Inst., Queretaro (Mexico); Cortes, M. A. [Mexican Petroleum Inst., Mexico City (Mexico)

2008-04-15

The bipolar plates in proton exchange membrane fuel cells (PEMFC) are exposed to an oxidizing environment on the cathodic side, and therefore are susceptible to corrosion. Corrosion resistant materials are needed for the bipolar plates in order to improve the lifespan of fuel cells. This article described a study in which a molybdenum (Mo) coating was deposited over austenitic stainless steel 316 and carbon steel as substrates in order to evaluate the resulting surfaces with respect to their corrosion resistance in simulated anodic and cathodic PEMFC environments. The molybdenum oxide films were characterized by scanning electron microscopy (SEM) and Raman spectroscopy. The article presented the experiment and discussed the results of the corrosion behaviour of coated stainless steel. In general, the electrochemical characterization of bare materials and coated steel consisted of slow potentiodynamic polarization curves followed by a constant potential polarization test. The test medium was 0.5M sulfuric acid with additional introduction of oxygen to simulate the cathodic environment. All tests were performed at ambient temperature and at 50 degrees Celsius. The potentiostat used was a Gamry instrument. It was concluded that it is possible to deposit Mo-oxides on steel without using another alloying metal. The preferred substrate for corrosion prevention was found to be an alloy with high chromium content. 24 refs., 4 figs.