Journal Home > Volume 17 , Issue 4
Nano Research 2024, 17(4): 2712-2718 https://doi.org/10.1007/s12274-023-6129-5
Research Article | Issue | Published: 26 September 2023

Influences of chemical reactions on polysulfide reduction reaction process on promotor surface in Li-S batteries

Show Author's Information Yufeng Luo1,§,  Zhenhan Fang1,§,  Zixin Hong1,2,§,  Shaorong Duan2,  Haitao Liu3,  Hengcai Wu1,2,  Qunqing Li1,2,4,  Yuegang Zhang1,2,4,  Shoushan Fan1,2,  Wenhui Duan2,  Jiaping Wang1,2,4( )
Tsinghua-Foxconn Nanotechnology Research Center, Tsinghua University, Beijing 100084, China
Department of Physics, Tsinghua University, Beijing 100084, China
Laboratory of Computational Physics, Institute of Applied Physics and Computational Mathematics, Beijing 100088, China
Frontier Science Center for Quantum Information, Tsinghua University, Beijing 100084, China

§ Yufeng Luo, Zhenhan Fang, and Zixin Hong contributed equally to this work.

Keywords:
polysulfides, promotors, chemical reactions, catalytic ability, in-situ Raman measurements
Topics:
Lithium sulfur batteries
An erratum to this article is available online at https://doi.org/10.1007/s12274-023-6376-5
Cite this article:
Luo Y, Fang Z, Hong Z, et al. Influences of chemical reactions on polysulfide reduction reaction process on promotor surface in Li-S batteries. Nano Research, 2024, 17(4): 2712-2718. https://doi.org/10.1007/s12274-023-6129-5
Download citation
EndNote(RIS)
BibTeX

370

Views

33

Downloads

Citations

1

Crossref

2

WoS

1

Scopus

0

CSCD

Abstract Full text Electronic supplementary material About this article

Polar promotors have been proven effective in catalyzing the polysulfide (PS) reduction reaction (PSRR) process in lithium-sulfur (Li-S) batteries. However, the promotor surface tends to be poisoned due to the accumulation of insoluble discharging products of lithium disulfide (Li2S2) and lithium sulfide (Li2S) during Li-S battery operation. Herein, we investigate the detailed PSRR mechanism on the surface of manganese sulfides (MnS) as a representative promoter by performing in-situ Raman mapping measurements. The catalytic ability of MnS enables thorough electrochemical reduction of PSs to Li2S2 and Li2S on the MnS surface. The generated Li2S2 and Li2S then adsorb the dissolved PSs via chemical reactions among sulfur species during the subsequent PSRR process. This phenomenon mitigates promotor poisoning and continuously improves the reversible capacity. Consequently, the assembled Li-S cell demonstrates excellent electrochemical performance after introducing a conductive interlayer containing a thin piece of carbon nanotube film and MnS promotors.


menu
Abstract
Full text
Outline
Electronic supplementary material
About this article

Influences of chemical reactions on polysulfide reduction reaction process on promotor surface in Li-S batteries

Show Author's information Yufeng Luo1,§, Zhenhan Fang1,§, Zixin Hong1,2,§, Shaorong Duan2, Haitao Liu3, Hengcai Wu1,2, Qunqing Li1,2,4, Yuegang Zhang1,2,4, Shoushan Fan1,2, Wenhui Duan2, Jiaping Wang1,2,4( )
Tsinghua-Foxconn Nanotechnology Research Center, Tsinghua University, Beijing 100084, China
Department of Physics, Tsinghua University, Beijing 100084, China
Laboratory of Computational Physics, Institute of Applied Physics and Computational Mathematics, Beijing 100088, China
Frontier Science Center for Quantum Information, Tsinghua University, Beijing 100084, China

§ Yufeng Luo, Zhenhan Fang, and Zixin Hong contributed equally to this work.

Abstract

Polar promotors have been proven effective in catalyzing the polysulfide (PS) reduction reaction (PSRR) process in lithium-sulfur (Li-S) batteries. However, the promotor surface tends to be poisoned due to the accumulation of insoluble discharging products of lithium disulfide (Li2S2) and lithium sulfide (Li2S) during Li-S battery operation. Herein, we investigate the detailed PSRR mechanism on the surface of manganese sulfides (MnS) as a representative promoter by performing in-situ Raman mapping measurements. The catalytic ability of MnS enables thorough electrochemical reduction of PSs to Li2S2 and Li2S on the MnS surface. The generated Li2S2 and Li2S then adsorb the dissolved PSs via chemical reactions among sulfur species during the subsequent PSRR process. This phenomenon mitigates promotor poisoning and continuously improves the reversible capacity. Consequently, the assembled Li-S cell demonstrates excellent electrochemical performance after introducing a conductive interlayer containing a thin piece of carbon nanotube film and MnS promotors.

Keywords: polysulfides, promotors, chemical reactions, catalytic ability, in-situ Raman measurements

References(40)

[1]

Dörfler, S.; Althues, H.; Härtel, P.; Abendroth, T.; Schumm, B.; Kaskel, S. Challenges and key parameters of lithium-sulfur batteries on pouch cell level. Joule 2020, 4, 539–554.
DOI Google Scholar
[2]

Bhargav, A.; He, J. R.; Gupta, A.; Manthiram, A. Lithium-sulfur batteries: Attaining the critical metrics. Joule 2020, 4, 285–291.
DOI Google Scholar
[3]

Zhang, Q.; Li, F.; Huang, J. Q.; Li, H. Lithium-sulfur batteries: Co-existence of challenges and opportunities. Adv. Funct. Mater. 2018, 28, 1804589.
DOI Google Scholar
[4]

Xu, N.; Qian, T.; Liu, X. J.; Liu, J.; Chen, Y.; Yan, C. L. Greatly suppressed shuttle effect for improved lithium sulfur battery performance through short chain intermediates. Nano Lett. 2017, 17, 538–543.
DOI Google Scholar
[5]

Li, G. R.; Wang, S.; Zhang, Y. N.; Li, M.; Chen, Z. W.; Lu, J. Revisiting the role of polysulfides in lithium-sulfur batteries. Adv. Mater. 2018, 30, 1705590.
DOI Google Scholar
[6]

He, Y. B.; Qiao, Y.; Chang, Z.; Cao, X.; Jia, M.; He, P.; Zhou, H. S. Developing a “polysulfide-phobic” strategy to restrain shuttle effect in lithium-sulfur batteries. Angew. Chem., Int. Ed. 2019, 58, 11774–11778.
DOI Google Scholar
[7]

Wang, Q.; Zheng, J. M.; Walter, E.; Pan, H. L.; Lv, D. P.; Zuo, P. J.; Chen, H. H.; Deng, Z. D.; Liaw, B. Y.; Yu, X. Q. et al. Direct observation of sulfur radicals as reaction media in lithium sulfur batteries. J. Electrochem. Soc. 2015, 162, A474–A478.
DOI Google Scholar
[8]

Xiang, Y. Y.; Li, J. S.; Lei, J. H.; Liu, D.; Xie, Z. H.; Qu, D. Y.; Li, K.; Deng, T. F.; Tang, H. L. Advanced separators for lithium-ion and lithium-sulfur batteries: A review of recent progress. ChemSusChem 2016, 9, 3023–3039.
DOI Google Scholar
[9]

Qin, X. Y.; Wu, J. X.; Xu, Z. L.; Chong, W. G.; Huang, J. Q.; Liang, G. M.; Li, B. H.; Kang, F. Y.; Kim, J. K. Electrosprayed multiscale porous carbon microspheres as sulfur hosts for long-life lithium-sulfur batteries. Carbon 2019, 141, 16–24.
DOI Google Scholar
[10]

Fang, R. P.; Chen, K.; Yin, L. C.; Sun, Z. H.; Li, F.; Cheng, H. M. The regulating role of carbon nanotubes and graphene in lithium-ion and lithium-sulfur batteries. Adv. Mater. 2019, 31, 1800863.
DOI Google Scholar
[11]

Zheng, B. N.; Lin, X. D.; Zhang, X. C.; Wu, D. C.; Matyjaszewski, K. Emerging functional porous polymeric and carbonaceous materials for environmental treatment and energy storage. Adv. Funct. Mater. 2020, 30, 1907006.
DOI Google Scholar
[12]

Mi, K.; Chen, S. W.; Xi, B. J.; Kai, S. S.; Jiang, Y.; Feng, J. K.; Qian, Y. T.; Xiong, S. L. Sole chemical confinement of polysulfides on nonporous nitrogen/oxygen dual-doped carbon at the kilogram scale for lithium-sulfur batteries. Adv. Funct. Mater. 2017, 27, 1604265.
DOI Google Scholar
[13]

Li, H.; Liu, D.; Zhu, X. X.; Qu, D. Y.; Xie, Z. Z.; Li, J. S.; Tang, H. L.; Zheng, D.; Qu, D. Y. Integrated 3D electrodes based on metal-nitrogen-doped graphitic ordered mesoporous carbon and carbon paper for high-loading lithium-sulfur batteries. Nano Energy 2020, 73, 104763.
DOI Google Scholar
[14]

Tao, X. Y.; Wang, J. G.; Liu, C.; Wang, H. T.; Yao, H. B.; Zheng, G. Y.; Seh, Z. W.; Cai, Q. X.; Li, W. Y.; Zhou, G. M. et al. Balancing surface adsorption and diffusion of lithium-polysulfides on nonconductive oxides for lithium-sulfur battery design. Nat. Commun. 2016, 7, 11203.
DOI Google Scholar
[15]

Park, J.; Yu, B. C.; Park, J. S.; Choi, J. W.; Kim, C.; Sung, Y. E.; Goodenough, J. B. Tungsten disulfide catalysts supported on a carbon cloth interlayer for high performance Li-S battery. Adv. Energy Mater. 2017, 7, 1602567.
DOI Google Scholar
[16]

Zhong, Y.; Chao, D. L.; Deng, S. J.; Zhan, J. Y.; Fang, R. Y.; Xia, Y.; Wang, Y. D.; Wang, X. L.; Xia, X. H.; Tu, J. P. Confining sulfur in integrated composite scaffold with highly porous carbon fibers/vanadium nitride arrays for high-performance lithium-sulfur batteries. Adv. Funct. Mater. 2018, 28, 1706391.
DOI Google Scholar
[17]

He, M. X.; Li, X.; Li, W. H.; Zheng, M.; Wang, J. J.; Ma, S. B.; Ma, Y. L.; Yin, G. P.; Zuo, P. J.; Sun, X. L. Immobilization and kinetic promotion of polysulfides by molybdenum carbide in lithium-sulfur batteries. Chem. Eng. J. 2021, 411, 128563.
DOI Google Scholar
[18]

Li, H.; Song, J. P.; Wu, F. L.; Wang, R.; Liu, D.; Tang, H. L. Metal-nitrogen-doped hybrid ionic/electronic conduction triple-phase interfaces for high-performance all-solid-state lithium-sulfur batteries. Nano Res. 2023, 16, 10956–10965.
DOI Google Scholar
[19]

Zhang, M.; Chen, W.; Xue, L. X.; Jiao, Y.; Lei, T. Y.; Chu, J. W.; Huang, J. W.; Gong, C. H.; Yan, C. Y.; Yan, Y. C. et al. Adsorption-catalysis design in the lithium-sulfur battery. Adv. Energy Mater. 2020, 10, 1903008.
DOI Google Scholar
[20]

Hua, W. X.; Li, H.; Pei, C.; Xia, J. Y.; Sun, Y. F.; Zhang, C.; Lv, W.; Tao, Y.; Jiao, Y.; Zhang, B. S. et al. Selective catalysis remedies polysulfide shuttling in lithium-sulfur batteries. Adv. Mater. 2021, 33, 2101006.
DOI Google Scholar
[21]

Lin, Y. H.; Tang, W. Q.; Wu, S. Y.; Zhang, Y. Z.; Kong, Z. K.; Shen, C. Y.; Wang, Y. L.; Zhan, L.; Ling, L. C. Alleviating the self-discharge and enhancing the polysulphides conversion kinetics with LaCO3OH nanocrystals decorated hierarchical porous carbon. Chem. Eng. J. 2023, 452, 139091.
DOI Google Scholar
[22]

Li, X.; Guan, Q. H.; Zhuang, Z. C.; Zhang, Y. Z.; Lin, Y. H.; Wang, J.; Shen, C. Y.; Lin, H. Z.; Wang, Y. L.; Zhan, L. et al. Ordered mesoporous carbon grafted MXene catalytic heterostructure as Li-ion kinetic pump toward high-efficient sulfur/sulfide conversions for Li-S battery. ACS Nano 2023, 17, 1653–1662.
DOI Google Scholar
[23]

Wu, S. Y.; Li, X., Zhang, Y. Z.; Guan, Q. H.; Wang, J.; Shen, C. Y.; Lin, H. Z.; Wang, J. T.; Wang, Y. L.; Zhan, L.; Ling, L. C. Interface engineering of MXene-based heterostructures for lithium-sulfur batteries. Nano Res. 2023, 16, 9158–9178.
DOI Google Scholar
[24]
Zhang, X.; Li, X. Y.; Zhang, Y. Z.; Li, X.; Guan, Q. H.; Wang, J.; Zhuang, Z. C.; Zhuang, Q.; Cheng, X. M.; Liu, H. T. et al. Accelerated Li+ desolvation for diffusion booster enabling low-temperature sulfur redox kinetics via electrocatalytic carbon-grazfted-CoP porous nanosheets. Adv. Funct. Mater., in press, DOI: 10.1002/adfm.202302624.
[25]
Webb, P. A. Introduction to chemical adsorption analytical techniques and their applications to catalysis [Online]. Micromerit. Inst. Corp. Techn. Publ. 2003; pp 1–12. http://www.micromeritics.com.cn/downloads/Technical-Articles/intro_to_chemical_adsorption.pdf (accessed Sep 20, 2023).
[26]

Xiao, R.; Yu, T.; Yang, S.; Chen, K.; Li, Z. N.; Liu, Z. B.; Hu, T. Z.; Hu, G. J.; Li, J.; Cheng, H. M. et al. Electronic structure adjustment of lithium sulfide by a single-atom copper catalyst toward high-rate lithium-sulfur batteries. Energy Storage Mater. 2022, 51, 890–899.
DOI Google Scholar
[27]

Kresse, G.; Furthmüller, J. Efficiency of ab-initio total energy calculations for metals and semiconductors using a plane-wave basis set. Comput. Mater. Sci. 1996, 6, 15–50.
DOI Google Scholar
[28]

Blöchl, P. E. Projector augmented-wave method. Phys. Rev. B 1994, 50, 17953–17979.
DOI Google Scholar
[29]

Perdew, J. P.; Burke, K.; Ernzerhof, M. Generalized gradient approximation made simple. Phys. Rev. Lett. 1996, 77, 3865–3868.
DOI Google Scholar
[30]

Grimme, S.; Antony, J.; Ehrlich, S.; Krieg, H. A consistent and accurate ab initio parametrization of density functional dispersion correction (DFT-D) for the 94 elements H–Pu. J. Chem. Phys. 2010, 132, 154104.
DOI Google Scholar
[31]

Dhandayuthapani, T.; Girish, M.; Sivakumar, R.; Sanjeeviraja, C.; Gopalakrishnan, R. Metastable MnS films prepared by the addition of EDTA using chemical bath deposition technique. Int. J. ChemTech Res. 2015, 7, 974–978.
Google Scholar
[32]

Babu, G.; Masurkar, N.; Al Salem, H.; Arava, L. M. R. Transition metal dichalcogenide atomic layers for lithium polysulfides electrocatalysis. J. Am. Chem. Soc. 2017, 139, 171–178.
DOI Google Scholar
[33]

Shen, C.; Xie, J. X.; Zhang, M.; Andrei, P.; Zheng, J. P.; Hendrickson, M.; Plichta, E. J. A Li-Li2S4 battery with improved discharge capacity and cycle life at low electrolyte/sulfur ratios. J. Power Sources 2019, 414, 412–419.
DOI Google Scholar
[34]

Pang, Q.; Kwok, C. Y.; Kundu, D.; Liang, X.; Nazar, L. F. Lightweight metallic MgB2 mediates polysulfide redox and promises high-energy-density lithium-sulfur batteries. Joule 2019, 3, 136–148.
DOI Google Scholar
[35]

Chen, J. J., Yuan, R. M.; Feng, J. M.; Zhang, Q.; Huang, J. X.; Fu, G.; Zheng, M. S.; Ren, B.; Dong, Q. F. Conductive lewis base matrix to recover the missing link of Li2S8 during the sulfur redox cycle in Li-S battery. Chem. Mater. 2015, 27, 2048–2055.
DOI Google Scholar
[36]

Wild, M.; O'Neill, L.; Zhang, T.; Purkayastha, R.; Minton, G.; Marinescu, M.; Offer, G. J. Lithium sulfur batteries, a mechanistic review. Energy Environ. Sci. 2015, 8, 3477–3494.
DOI Google Scholar
[37]

Liu, Z. X.; Mistry, A.; Mukherjee, P. P. Mesoscale physicochemical interactions in lithium-sulfur batteries: Progress and perspective. J. Electrochem. En. Conv. Stor. 2018, 15, 010802.
DOI Google Scholar
[38]

Zhong, Y. R.; Wang, Q.; Bak, S. M.; Hwang, S.; Du, Y. H.; Wang, H. L. Identification and catalysis of the potential-limiting step in lithium-sulfur batteries. J. Am. Chem. Soc. 2023, 145, 7390–7396.
DOI Google Scholar
[39]

Deng, Z. F.; Zhang, Z. A.; Lai, Y. Q.; Liu, J.; Li, J.; Liu, Y. X. Electrochemical impedance spectroscopy study of a lithium/sulfur battery: Modeling and analysis of capacity fading. J. Electrochem. Soc. 2013, 160, A553–A558.
DOI Google Scholar
[40]

Cañas, N. A.; Hirose, K.; Pascucci, B.; Wagner, N.; Friedrich, K. A.; Hiesgen, R. Investigations of lithium-sulfur batteries using electrochemical impedance spectroscopy. Electrochim. Acta 2013, 97, 42–51.
DOI Google Scholar
File
12274_2023_6129_MOESM1_ESM.pdf (770 KB)
Publication history
Copyright
Acknowledgements

Publication history

Received: 10 July 2023
Revised: 15 August 2023
Accepted: 25 August 2023
Published: 26 September 2023
Issue date: April 2024

Copyright

© Tsinghua University Press, corrected publication 2023

Acknowledgements

Acknowledgements

This work was supported by the National Basic Research Program of China (2019YFA0705702) and the National Natural Science Foundation of China (51872158). H. T. Liu acknowledges funding from the National Natural Science Foundation of China (No.11734013, 11874089).

Return