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Title: Catalytic oxidation of Li 2 S on the surface of metal sulfides for Li−S batteries

Authors:
; ; ; ; ; ; ; ; ; ; ; ; ; ;
Publication Date:
Sponsoring Org.:
USDOE
OSTI Identifier:
1339582
Grant/Contract Number:
Battery Materials Research Program
Resource Type:
Journal Article: Published Article
Journal Name:
Proceedings of the National Academy of Sciences of the United States of America
Additional Journal Information:
Journal Volume: 114; Journal Issue: 5; Related Information: CHORUS Timestamp: 2017-06-25 04:29:15; Journal ID: ISSN 0027-8424
Publisher:
Proceedings of the National Academy of Sciences
Country of Publication:
United States
Language:
English

Citation Formats

Zhou, Guangmin, Tian, Hongzhen, Jin, Yang, Tao, Xinyong, Liu, Bofei, Zhang, Rufan, Seh, Zhi Wei, Zhuo, Denys, Liu, Yayuan, Sun, Jie, Zhao, Jie, Zu, Chenxi, Wu, David Sichen, Zhang, Qianfan, and Cui, Yi. Catalytic oxidation of Li 2 S on the surface of metal sulfides for Li−S batteries. United States: N. p., 2017. Web. doi:10.1073/pnas.1615837114.
Zhou, Guangmin, Tian, Hongzhen, Jin, Yang, Tao, Xinyong, Liu, Bofei, Zhang, Rufan, Seh, Zhi Wei, Zhuo, Denys, Liu, Yayuan, Sun, Jie, Zhao, Jie, Zu, Chenxi, Wu, David Sichen, Zhang, Qianfan, & Cui, Yi. Catalytic oxidation of Li 2 S on the surface of metal sulfides for Li−S batteries. United States. doi:10.1073/pnas.1615837114.
Zhou, Guangmin, Tian, Hongzhen, Jin, Yang, Tao, Xinyong, Liu, Bofei, Zhang, Rufan, Seh, Zhi Wei, Zhuo, Denys, Liu, Yayuan, Sun, Jie, Zhao, Jie, Zu, Chenxi, Wu, David Sichen, Zhang, Qianfan, and Cui, Yi. Tue . "Catalytic oxidation of Li 2 S on the surface of metal sulfides for Li−S batteries". United States. doi:10.1073/pnas.1615837114.
@article{osti_1339582,
title = {Catalytic oxidation of Li 2 S on the surface of metal sulfides for Li−S batteries},
author = {Zhou, Guangmin and Tian, Hongzhen and Jin, Yang and Tao, Xinyong and Liu, Bofei and Zhang, Rufan and Seh, Zhi Wei and Zhuo, Denys and Liu, Yayuan and Sun, Jie and Zhao, Jie and Zu, Chenxi and Wu, David Sichen and Zhang, Qianfan and Cui, Yi},
abstractNote = {},
doi = {10.1073/pnas.1615837114},
journal = {Proceedings of the National Academy of Sciences of the United States of America},
number = 5,
volume = 114,
place = {United States},
year = {Tue Jan 17 00:00:00 EST 2017},
month = {Tue Jan 17 00:00:00 EST 2017}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record at 10.1073/pnas.1615837114

Citation Metrics:
Cited by: 34works
Citation information provided by
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  • The techniques used for the preparation of metal-rich chalcides by high-temperature techniques are discussed. The two newest metal-rich compounds, two ternary metal-rich sulfides with novel structures, are described.
  • The new lithium transition-metal sulfides Li{sub 2}M{sub 3}S{sub 4} (M=Pd, Pt) were obtained via multianvil high-pressure/high-temperature syntheses at 8 GPa and 1150 °C starting from a stoichiometric mixture of lithium nitride, sulfur, and palladium or platinum. Single crystal structure analyses indicated the space group P2{sub 1}/c (no. 14) with the following lattice parameters and refinement results: a=492.9(1), b=1005.9(2), c=614.9(2) pm, β=110.9 (1)°, R1=0.0165, wR2=0.0308 (all data) for Li{sub 2}Pd{sub 3}S{sub 4} and a=498.2(1), b=1005.5(2), c=613.0(2) pm, β=110.8(1)°, R1=0.0215, wR2=0.0450 (all data) for Li{sub 2}Pt{sub 3}S{sub 4}. The crystal structures are built up from two distinct Pd/Pt sites, one of whichmore » is a special position (0,0,0), two sulfur sites, and one lithium site. The atoms Pd2/Pt2 form isolated square planar PdS{sub 4}/PtS{sub 4} units, whereas the Pd1/Pt1 atoms form pairs of square planar PdS{sub 4}/PtS{sub 4} units, which are connected via a common edge. These two structural motives built up a three-dimensional network structure by linking through common corners. The lithium atoms are positioned inside of the so formed channels. Li{sub 2}M{sub 3}S{sub 4} (M=Pd, Pt) are isostructural to the minerals jaguéite, Cu{sub 2}Pd{sub 3}Se{sub 4} and chrisstanleyite, Ag{sub 2}Pd{sub 3}Se{sub 4}, which are up to now the only representatives of this structure type. Both compounds were studied with respect to their magnetic properties and can be classified as Pauli paramagnetic or diamagnetic. Regarding the possibility of lithium mobility inside the channels, of the structure, solid state {sup 7}Li NMR and high-temperature single crystal investigations revealed localization of the lithium atoms on their crystallographic sites. - Graphical abstract: The ternary lithium transition-metal sulfides Li{sub 2}M{sub 3}S{sub 4} (M=Pd, Pt) were prepared via multianvil high-pressure/high-temperature syntheses. They are built up from square planar PtS{sub 4}/PdS{sub 4} units with lithium located in the channels of the crystal structure. - Highlights: • Li{sub 2}M{sub 3}S{sub 4} (M=Pd, Pt) are the missing sulfide analogue compounds to Cu{sub 2}Pd{sub 3}Se{sub 4} and Ag{sub 2}Pd{sub 3}Se{sub 4}. • The compounds are the first Pd or Pt containing lithium transition-metal sulfides. • Li mobility was investigated via temp. dependent XRD and solid state {sup 7}Li NMR. • Magnetic properties revealed Pauli paramagnetic or diamagnetic contributions.« less
  • Presently lithium hexafluorophosphate (LiPF 6) is the dominant Li-salt used in commercial rechargeable lithium-ion batteries (LIBs) based on a graphite anode and a 3-4 V cathode material. While LiPF 6 is not the ideal Li-salt for every important electrolyte property, it has a uniquely suitable combination of properties (temperature range, passivation, conductivity, etc.) rendering it the overall best Li-salt for LIBs. However, this may not necessarily be true for other types of Li-based batteries. Indeed, next generation batteries, for example lithium-metal (Li-metal), lithium-oxygen (Li-O 2), and lithium sulphur (Li-S), require a re-evaluation of Li-salts due to the different electrochemical andmore » chemical reactions and conditions within such cells. Furthermore, this review explores the critical role Li-salts play in ensuring in these batteries viability.« less
  • The precipitation of lithium sulfide (Li 2S) on the Li metal anode surface adversely impacts the performance of lithium–sulfur (Li–S) batteries. In this work, a first-principles approach including density functional theory (DFT) and ab initio molecular dynamics (AIMD) simulations is employed to theoretically elucidate the Li 2S/Li metal surface interactions and the nucleation and growth of a Li 2S film on the anode surface due to long-chain polysulfide decomposition during battery operation. DFT analyses of the energetic properties and electronic structures demonstrate that a single molecule adsorption on Li surface releases energy forming chemical bonds between the S atoms andmore » Li atoms from the anode surface. Reaction pathways of the Li 2S film formation on Li metal surfaces are investigated based on DFT calculations. It is found that a distorted Li 2S (111) plane forms on a Li(110) surface and a perfect Li 2S (111) plane forms on a Li(111) surface. The total energy of the system decreases along the reaction pathway; hence Li 2S film formation on the Li anode surface is thermodynamically favorable. Finally, the calculated difference charge density of the Li 2S film/Li surface suggests that the precipitated film would interact with the Li anode via strong chemical bonds. AIMD simulations reveal the role of the anode surface structure and the origin of the Li 2S formation via decomposition of Li 2S 8 polysulfide species formed at the cathode side and dissolved in the electrolyte medium in which they travel to the anode side during battery cycling.« less