A quantum-chemical study on the discharge reaction mechanism of lithium-sulfur batteries

能源化学(英文) ›› 2013, Vol. 22 ›› Issue (1): 72-77.

A quantum-chemical study on the discharge reaction mechanism of lithium-sulfur batteries

Lijiang Wang, Tianran Zhang, Siqi Yang, Fangyi Cheng, Jing Liang, Jun Chen*

Key Laboratory of Advanced Energy Materials Chemistry (Ministry of Education), College of Chemistry, Nankai University, Tianjin 300071, China

收稿日期:2012-11-20 修回日期:2013-01-10 出版日期:2013-01-20 发布日期:2013-02-06
通讯作者: Jun Chen

A quantum-chemical study on the discharge reaction mechanism of lithium-sulfur batteries

Lijiang Wang, Tianran Zhang, Siqi Yang, Fangyi Cheng, Jing Liang, Jun Chen*

Key Laboratory of Advanced Energy Materials Chemistry (Ministry of Education), College of Chemistry, Nankai University, Tianjin 300071, China

Received:2012-11-20 Revised:2013-01-10 Online:2013-01-20 Published:2013-02-06
Contact: Jun Chen

摘要/Abstract

摘要： Lithium-sulfur batteries have attracted a great interest in electrochemical energy conversion and storage, but their discharge mechanism remains not well understood up to now. Here, we report density functional theory (DFT) calculation study of the discharge mechanism for lithium-sulfur batteries which are based on the structure of S₈ and Li₂S_x (1≤x≤8) clusters. The results show that for Li₂S_x (1≤x≤8) clusters, the most stable geometry is chainlike when x = 1 and 6, while the minimal-energy structure is found to be cyclic when x = 2-5, 7, 8. The stability of Li₂S_x (1≤x≤8) clusters increases with the decreasing x value, indicating a favorable thermodynamic tendency of transition from S₈ to Li₂S. A three-step reaction route has been proposed during the discharge process, that is, S₈→Li₂S₄ at about 2.30 V, Li₂S₄→Li₂S₂ at around 2.22 V, and Li₂S₂ →Li₂S at 2.18 V. Furthermore, the effect of the electrolyte on the potential platform has been also investigated. The discharge potential is found to increase with the decrease of dielectric constant of the electrolyte. The computational results could provide insights into further understanding the discharge mechanism of lithium-sulfur batteries.

关键词: lithium-sulfur battery, density functional theory, discharge mechanism, lithium polysulfide, discharge potential

Abstract: Lithium-sulfur batteries have attracted a great interest in electrochemical energy conversion and storage, but their discharge mechanism remains not well understood up to now. Here, we report density functional theory (DFT) calculation study of the discharge mechanism for lithium-sulfur batteries which are based on the structure of S₈ and Li₂S_x (1≤x≤8) clusters. The results show that for Li₂S_x (1≤x≤8) clusters, the most stable geometry is chainlike when x = 1 and 6, while the minimal-energy structure is found to be cyclic when x = 2-5, 7, 8. The stability of Li₂S_x (1≤x≤8) clusters increases with the decreasing x value, indicating a favorable thermodynamic tendency of transition from S₈ to Li₂S. A three-step reaction route has been proposed during the discharge process, that is, S₈→Li₂S₄ at about 2.30 V, Li₂S₄→Li₂S₂ at around 2.22 V, and Li₂S₂ →Li₂S at 2.18 V. Furthermore, the effect of the electrolyte on the potential platform has been also investigated. The discharge potential is found to increase with the decrease of dielectric constant of the electrolyte. The computational results could provide insights into further understanding the discharge mechanism of lithium-sulfur batteries.

Key words: lithium-sulfur battery, density functional theory, discharge mechanism, lithium polysulfide, discharge potential

Lijiang Wang, Tianran Zhang, Siqi Yang, Fangyi Cheng, Jing Liang, Jun Chen* . A quantum-chemical study on the discharge reaction mechanism of lithium-sulfur batteries[J]. 能源化学(英文), 2013, 22(1): 72-77.

Lijiang Wang, Tianran Zhang, Siqi Yang, Fangyi Cheng, Jing Liang, Jun Chen* . A quantum-chemical study on the discharge reaction mechanism of lithium-sulfur batteries[J]. Journal of Energy Chemistry, 2013, 22(1): 72-77.

×
扫码分享

导出引用管理器 EndNote|Ris|BibTeX

链接本文: https://www.jenergychem.com/CN/

https://www.jenergychem.com/CN/Y2013/V22/I1/72

参考文献

[1] Ji L W, Rao M M, Zheng H M, Zhang L, Li Y C, Duan W H, Guo J H, Cairns E J, Zhang Y G. J Am Chem Soc, 2011, 133: 18522
[2] Chen J, Cheng F Y. Acc Chem Res, 2009, 42: 713
[3] Ji X L, Lee K T, Nazar L F. Nat Mater, 2009, 8: 500
[4] Ellis B L, Lee K T, Nazar L F. Chem Mater, 2010, 22: 691
[5] Jayaprakash N, Shen J, Moganty S S, Corona A, Archer L A. Angew Chem Int Ed, 2011, 50: 5904
[6] Yamin H, Gorenshtein A, Penciner J, Sternberg Y, Peled E. J Electrochem Soc, 1988, 135: 1045
[7] Kumaresan K, Mikhaylik Y, White R E. J Electrochem Soc, 2008, 155: A576
[8] Scrosati B, Hassoun J, Sun Y K. Energy Environ Sci, 2011, 4: 3287
[9] Bruce P G, Freunberger S A, Hardwick L J, Tarascon J M. Nat Mater, 2012, 11: 19
[10] Barchasz C, Molton F, Duboc C, Lepr\^etre J C, Patoux S, Alloin F. Anal Chem, 2012, 84: 3973
[11] Fu Y Z, Manthiram A. J Phys Chem C, 2012, 116: 8910
[12] He G, Ji X L, Nazar L. Energy Environ Sci, 2011, 4: 2878
[13] Yang Y, Yu G H, Cha J J, Wu H, Vosgueritchian M, Yao Y, Bao Z N, Cui Y. ACS Nano, 2011, 11: 9187
[14] Ji L W, Rao M M, Aloni S, Wang L, Cairns E J, Zhang Y G. Energy Environ Sci, 2011, 4: 5053
[15] Bichat M P, Gillot F, Monconduit L, Favier F, Morcrette M, Lemoigno F, Doublet M L. Chem Mater, 2004, 16: 1002
[16] Maxisch T, Zhou F, Ceder G. Phys Rev B, 2006, 73: 104301
[17] Van der Ven A, Thomas J C, Xu Q C, Swoboda B, Morgan D. Phys Rev B, 2008, 78: 104306
[18] Peng B, Cheng F Y, Tao Z L, Chen J. J Chem Phys, 2010, 133: 034701
[19] Frisch M J, Trucks G W, Schlegel H B, Frisch M J, Trucks G W et al., GAUSSIAN03, Revision C02, Gaussian, Inc, Pittsburgh, PA 2004
[20] Li L L, Peng B, Ji W Q, Chen J. J Phys Chem C, 2009, 113: 3007
[21] Peng B, Li L L, Ji W Q, Cheng F Y, Chen J. J Alloy Compd, 2009, 484: 308
[22] Tomasi J, Mennucci B, Cammi R. Chem Rev, 2005, 105: 2999
[23] Yang X, Wang G C, Shang Z F, Pan Y M, Cai Z S, Zhao X Z. Phys Chem Chem Phys, 2002, 4: 2546
[24] Bogatko S, Geerlings P. Phys Chem Chem Phys, 2012, 14: 8058
[25] Meyer B. Chem Rev, 1976, 76: 367
[26] Gao J, Lowe M A, Kiya Y, Abru\{n}a H D. J Phys Chem C, 2011, 115: 25132
[27] Zhang S S. Electrochim Acta, 2012, 70: 344
[28] Elazari R, Salitra G, Garsuch A, Panchenko A, Aurbach D. Adv Mater, 2011, 23: 5641
[29] He X M, Ren J G, Wang L, Pu W H, Jiang C Y, Wan C R. J Power Sources, 2009, 190: 154

A quantum-chemical study on the discharge reaction mechanism of lithium-sulfur batteries

A quantum-chemical study on the discharge reaction mechanism of lithium-sulfur batteries

可视化

摘要/Abstract

引用本文

使用本文

扫码分享

参考文献

相关文章 15

编辑推荐

Metrics

[1]	Karam Jabbour. Tuning combined steam and dry reforming of methane for "metgas" production: A thermodynamic approach and state-of-the-art catalysts[J]. 能源化学(英文版), 2020, 48(9): 54-91.
[2]	Wenjing Dong, di Wang, Xiaoyun Li, Yuan Yao, Xu Zhao, Zhao Wang, Hong-En Wang, Yu Li, Lihua Chen, dong Qian, bao-Lian Su. Bronze TiO₂ as a cathode host for lithium-sulfur batteries[J]. 能源化学(英文版), 2020, 48(9): 259-266.
[3]	Yan-Qiu Shen, fang-Lei Zeng, Xin-Yu Zhou, An-bang Wang, Wei-kun Wang, Ning-Yi Yuan, Jian-Ning Ding. A novel permselective organo-polysulfides/PVDF gel polymer electrolyte enables stable lithium anode for lithium-sulfur batteries[J]. 能源化学(英文版), 2020, 48(9): 267-276.
[4]	You Li, Xiao Zhang, Guihua Liu, Ashton Gerhardt, Katelyn Evans, Aizhong Jia, Zisheng Zhang. Oxygen-deficient titanium dioxide supported cobalt nano-dots as efficient cathode material for lithium-sulfur batteries[J]. 能源化学(英文版), 2020, 48(9): 390-397.
[5]	Lishun Meng, Yuan Yao, Jing Liu, Zhao Wang,dong Qian, Liuchun Zheng,bao-Lian Su, Hong-En Wang. MoSe₂ nanosheets as a functional host for lithium-sulfur batteries[J]. 能源化学(英文版), 2020, 47(8): 241-247.
[6]	Hongyan Li, Le Yang, Zhongxu Wang, Peng Jin, Jingxiang Zhao, Zhongfang Chen. N-heterocyclic carbene as a promising metal-free electrocatalyst with high efficiency for nitrogen reduction to ammonia[J]. 能源化学(英文版), 2020, 46(7): 78-86.
[7]	Jin-Lei Qin, Meng Zhao, Hong Yuan, Jia-Qi Huang. Ether-compatible lithium sulfur batteries with robust performance via selenium doping[J]. 能源化学(英文版), 2020, 46(7): 199-201.
[8]	Yanxia Ma, Miaomiao Wang, Xin Zhou. First-principles investigation of β-Ge₃N₄ loaded with RuO₂ cocatalyst for photocatalytic overall water splitting[J]. 能源化学(英文版), 2020, 44(5): 24-32.
[9]	Masud Rana, Ming Li, Qiu He, Bin Luo, Lianzhou Wang, Ian Gentle, Ruth Knibbe. Separator coatings as efficient physical and chemical hosts of polysulfides for high-sulfur-loaded rechargeable lithium-sulfur batteries[J]. 能源化学(英文版), 2020, 44(5): 51-60.
[10]	Yuqi Yang, Hao Zhang, Zhaofeng Liang, Yaru Yin, Bingbao Mei, Fei Song, Fanfei Sun, Songqi Gu, Zheng Jiang, Yuen Wu, Zhiyuan Zhu. Role of local coordination in bimetallic sites for oxygen reduction: A theoretical analysis[J]. 能源化学(英文版), 2020, 44(5): 131-137.
[11]	Soochan Kim, Misuk Cho, Chalathorn Chanthad, Youngkwan Lee. New redox-mediating polymer binder for enhancing performance of Li-S batteries[J]. 能源化学(英文版), 2020, 44(5): 154-161.
[12]	Bin Hu, Qiang Lu, Yu-ting Wu, Wen-luan Xie, Min-shu Cui, Ji Liu, Chang-qing Dong, Yong-ping Yang. Insight into the formation mechanism of levoglucosenone in phosphoric acid-catalyzed fast pyrolysis of cellulose[J]. 能源化学(英文版), 2020, 43(4): 78-89.
[13]	Xiaodong Hong, Rui Wang, Yue Liu, Jiawei Fu, Ji Liang, Shixue Dou. Recent advances in chemical adsorption and catalytic conversion materials for Li-S batteries[J]. 能源化学(英文版), 2020, 42(3): 144-168.
[14]	Fanfei Sun, Ruoou Yang, Zhaoming Xia, Yuqi Yang, Ziang Zhao, Songqi Gu, Dongshuang Wu, Yunjie Ding, Zheng Jiang. Effects of cobalt carbide on Fischer-Tropsch synthesis with MnO supported Co-based catalysts[J]. 能源化学(英文版), 2020, 42(3): 227-232.
[15]	Ming Wang, Shunyuan Tan, Shuting Kan, Yufeng Wu, Shangbin Sang, Kaiyu Liu, Hongtao Liu. In-situ assembly of TiO₂ with high exposure of (001) facets on three-dimensional porous graphene aerogel for lithium-sulfur battery[J]. 能源化学(英文版), 2020, 49(10): 316-322.