Anionic redox reaction in layered NaCr2/3Ti1/3S2 through electron holes formation and dimerization of S–S

Tian Wang; Guo Xi Ren; Zulipiya Shadike; Ji Li Yue; Ming Hui Cao; Jie Nan Zhang; Ming Wei Chen; Xiao Qing Yang; Seong Min Bak; Paul Northrup; Pan Liu; Xiao Song Liu; Zheng Wen Fu

doi:10.1038/s41467-019-12310-6

Anionic redox reaction in layered NaCr_2/3Ti_1/3S₂ through electron holes formation and dimerization of S–S

Tian Wang, Guo Xi Ren, Zulipiya Shadike, Ji Li Yue, Ming Hui Cao, Jie Nan Zhang, Ming Wei Chen, Xiao Qing Yang, Seong Min Bak, Paul Northrup, Pan Liu, Xiao Song Liu, Zheng Wen Fu

Department of Materials Science and Engineering

Research output: Contribution to journal › Article › peer-review

Abstract

The use of anion redox reactions is gaining interest for increasing rechargeable capacities in alkaline ion batteries. Although anion redox coupling of S²⁻ and (S₂)²⁻ through dimerization of S–S in sulfides have been studied and reported, an anion redox process through electron hole formation has not been investigated to the best of our knowledge. Here, we report an O3-NaCr_2/3Ti_1/3S₂ cathode that delivers a high reversible capacity of ~186 mAh g⁻¹ (0.95 Na) based on the cation and anion redox process. Various charge compensation mechanisms of the sulfur anionic redox process in layered NaCr_2/3Ti_1/3S₂, which occur through the formation of disulfide-like species, the precipitation of elemental sulfur, S–S dimerization, and especially through the formation of electron holes, are investigated. Direct structural evidence for formation of electron holes and (S₂)ⁿ⁻ species with shortened S–S distances is obtained. These results provide valuable information for the development of materials based on the anionic redox reaction.

Original language	English
Article number	4458
Journal	Nature communications
Volume	10
Issue number	1
DOIs	https://doi.org/10.1038/s41467-019-12310-6
Publication status	Published - 2019 Dec 1

Bibliographical note

Funding Information:
This work was financially supported by the National Natural Science Foundation of China (Grant No. 21773037, 21473235, 11227902, 11704245 and U1632269); the National Key Scientific Research Project (Grant No. 2016YFB090150); Shanghai Pujiang Program (17PJ1403700). The work at Taiwan Light Source (beamline 16A1) was supported by National Synchrotron Radiation Research Center. The work at Brookhaven National Laboratory was supported by the Assistant Secretary for Energy Efficiency and Renewable Energy, Vehicle Technology Office of the U.S. Department of Energy through the Advanced Battery Materials Research (BMR) Program, including Battery500 Consortium under contract DE-SC0012704. This research used resources at beamlines 7-BM (QAS), 8-BM (TES) of the National Synchrotron Light Source II, a U.S. Department of Energy (DOE) Office of Science User Facility operated for the DOE Office of Science by Brookhaven National Laboratory under Contract no. DE-SC0012704. DFT calculation was performed in National Supercomputing Center in Shenzhen (Shenzhen Cloud Computing Center). P.L. is supported by the Program for Professor of Special Appointment (Eastern Scholar) at Shanghai Institutions of Higher Learning. The authors also thank beamline BL14B1 of the Shanghai Synchrotron Radiation Facility (SSRF). G.-X.R. also acknowledges the support from the UCAS Joint Ph.D. Training Program. The authors gratefully acknowledge the help by Prof. Xi-Qian Yu for his help on in situ XRD measurements, Bo-Yuan Ning, and Hong-Kun Zhu at Fudan University for their help on DFT calculations, Peng-Fei Yu, Xin-Yang Yue, Qin-Chao Wang, Ding-Ren Shi, Jing-Ke Meng, Wei-Wen Wang, Si-Yu Yang and He-Yi Xia for their help on experiments.

Publisher Copyright:
© 2019, The Author(s).

All Science Journal Classification (ASJC) codes

Chemistry(all)
Biochemistry, Genetics and Molecular Biology(all)
Physics and Astronomy(all)

Access to Document

10.1038/s41467-019-12310-6

Cite this

@article{43fbf58331734aa19668a67c1c1d239a,

title = "Anionic redox reaction in layered NaCr2/3Ti1/3S2 through electron holes formation and dimerization of S–S",

abstract = "The use of anion redox reactions is gaining interest for increasing rechargeable capacities in alkaline ion batteries. Although anion redox coupling of S2− and (S2)2− through dimerization of S–S in sulfides have been studied and reported, an anion redox process through electron hole formation has not been investigated to the best of our knowledge. Here, we report an O3-NaCr2/3Ti1/3S2 cathode that delivers a high reversible capacity of ~186 mAh g−1 (0.95 Na) based on the cation and anion redox process. Various charge compensation mechanisms of the sulfur anionic redox process in layered NaCr2/3Ti1/3S2, which occur through the formation of disulfide-like species, the precipitation of elemental sulfur, S–S dimerization, and especially through the formation of electron holes, are investigated. Direct structural evidence for formation of electron holes and (S2)n− species with shortened S–S distances is obtained. These results provide valuable information for the development of materials based on the anionic redox reaction.",

author = "Tian Wang and Ren, {Guo Xi} and Zulipiya Shadike and Yue, {Ji Li} and Cao, {Ming Hui} and Zhang, {Jie Nan} and Chen, {Ming Wei} and Yang, {Xiao Qing} and Bak, {Seong Min} and Paul Northrup and Pan Liu and Liu, {Xiao Song} and Fu, {Zheng Wen}",

note = "Funding Information: This work was financially supported by the National Natural Science Foundation of China (Grant No. 21773037, 21473235, 11227902, 11704245 and U1632269); the National Key Scientific Research Project (Grant No. 2016YFB090150); Shanghai Pujiang Program (17PJ1403700). The work at Taiwan Light Source (beamline 16A1) was supported by National Synchrotron Radiation Research Center. The work at Brookhaven National Laboratory was supported by the Assistant Secretary for Energy Efficiency and Renewable Energy, Vehicle Technology Office of the U.S. Department of Energy through the Advanced Battery Materials Research (BMR) Program, including Battery500 Consortium under contract DE-SC0012704. This research used resources at beamlines 7-BM (QAS), 8-BM (TES) of the National Synchrotron Light Source II, a U.S. Department of Energy (DOE) Office of Science User Facility operated for the DOE Office of Science by Brookhaven National Laboratory under Contract no. DE-SC0012704. DFT calculation was performed in National Supercomputing Center in Shenzhen (Shenzhen Cloud Computing Center). P.L. is supported by the Program for Professor of Special Appointment (Eastern Scholar) at Shanghai Institutions of Higher Learning. The authors also thank beamline BL14B1 of the Shanghai Synchrotron Radiation Facility (SSRF). G.-X.R. also acknowledges the support from the UCAS Joint Ph.D. Training Program. The authors gratefully acknowledge the help by Prof. Xi-Qian Yu for his help on in situ XRD measurements, Bo-Yuan Ning, and Hong-Kun Zhu at Fudan University for their help on DFT calculations, Peng-Fei Yu, Xin-Yang Yue, Qin-Chao Wang, Ding-Ren Shi, Jing-Ke Meng, Wei-Wen Wang, Si-Yu Yang and He-Yi Xia for their help on experiments. Publisher Copyright: {\textcopyright} 2019, The Author(s).",

year = "2019",

month = dec,

day = "1",

doi = "10.1038/s41467-019-12310-6",

language = "English",

volume = "10",

journal = "Nature Communications",

issn = "2041-1723",

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TY - JOUR

T1 - Anionic redox reaction in layered NaCr2/3Ti1/3S2 through electron holes formation and dimerization of S–S

AU - Wang, Tian

AU - Ren, Guo Xi

AU - Shadike, Zulipiya

AU - Yue, Ji Li

AU - Cao, Ming Hui

AU - Zhang, Jie Nan

AU - Chen, Ming Wei

AU - Yang, Xiao Qing

AU - Bak, Seong Min

AU - Northrup, Paul

AU - Liu, Pan

AU - Liu, Xiao Song

AU - Fu, Zheng Wen

N1 - Funding Information: This work was financially supported by the National Natural Science Foundation of China (Grant No. 21773037, 21473235, 11227902, 11704245 and U1632269); the National Key Scientific Research Project (Grant No. 2016YFB090150); Shanghai Pujiang Program (17PJ1403700). The work at Taiwan Light Source (beamline 16A1) was supported by National Synchrotron Radiation Research Center. The work at Brookhaven National Laboratory was supported by the Assistant Secretary for Energy Efficiency and Renewable Energy, Vehicle Technology Office of the U.S. Department of Energy through the Advanced Battery Materials Research (BMR) Program, including Battery500 Consortium under contract DE-SC0012704. This research used resources at beamlines 7-BM (QAS), 8-BM (TES) of the National Synchrotron Light Source II, a U.S. Department of Energy (DOE) Office of Science User Facility operated for the DOE Office of Science by Brookhaven National Laboratory under Contract no. DE-SC0012704. DFT calculation was performed in National Supercomputing Center in Shenzhen (Shenzhen Cloud Computing Center). P.L. is supported by the Program for Professor of Special Appointment (Eastern Scholar) at Shanghai Institutions of Higher Learning. The authors also thank beamline BL14B1 of the Shanghai Synchrotron Radiation Facility (SSRF). G.-X.R. also acknowledges the support from the UCAS Joint Ph.D. Training Program. The authors gratefully acknowledge the help by Prof. Xi-Qian Yu for his help on in situ XRD measurements, Bo-Yuan Ning, and Hong-Kun Zhu at Fudan University for their help on DFT calculations, Peng-Fei Yu, Xin-Yang Yue, Qin-Chao Wang, Ding-Ren Shi, Jing-Ke Meng, Wei-Wen Wang, Si-Yu Yang and He-Yi Xia for their help on experiments. Publisher Copyright: © 2019, The Author(s).

PY - 2019/12/1

Y1 - 2019/12/1

N2 - The use of anion redox reactions is gaining interest for increasing rechargeable capacities in alkaline ion batteries. Although anion redox coupling of S2− and (S2)2− through dimerization of S–S in sulfides have been studied and reported, an anion redox process through electron hole formation has not been investigated to the best of our knowledge. Here, we report an O3-NaCr2/3Ti1/3S2 cathode that delivers a high reversible capacity of ~186 mAh g−1 (0.95 Na) based on the cation and anion redox process. Various charge compensation mechanisms of the sulfur anionic redox process in layered NaCr2/3Ti1/3S2, which occur through the formation of disulfide-like species, the precipitation of elemental sulfur, S–S dimerization, and especially through the formation of electron holes, are investigated. Direct structural evidence for formation of electron holes and (S2)n− species with shortened S–S distances is obtained. These results provide valuable information for the development of materials based on the anionic redox reaction.

AB - The use of anion redox reactions is gaining interest for increasing rechargeable capacities in alkaline ion batteries. Although anion redox coupling of S2− and (S2)2− through dimerization of S–S in sulfides have been studied and reported, an anion redox process through electron hole formation has not been investigated to the best of our knowledge. Here, we report an O3-NaCr2/3Ti1/3S2 cathode that delivers a high reversible capacity of ~186 mAh g−1 (0.95 Na) based on the cation and anion redox process. Various charge compensation mechanisms of the sulfur anionic redox process in layered NaCr2/3Ti1/3S2, which occur through the formation of disulfide-like species, the precipitation of elemental sulfur, S–S dimerization, and especially through the formation of electron holes, are investigated. Direct structural evidence for formation of electron holes and (S2)n− species with shortened S–S distances is obtained. These results provide valuable information for the development of materials based on the anionic redox reaction.

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