锂硫电池结构设计研究现状及展望

doi:10.13208/j.electrochem.180544

摘要/Abstract

摘要： 锂硫电池体系由于理论能量密度高和硫材料资源丰富，成为了极具发展潜力的二次电池之一. 但由于放电过程中间产物多硫化物溶于有机电解液，产生穿梭效应，导致活性物质利用率低，造成电池容量损失和循环性能下降，而锂金属枝晶和界面问题同样限制了锂硫电池的进一步发展和利用. 研究表明，电池结构设计和改造，如隔膜结构设计、正极夹层设计、正极载硫结构设计以及负极结构设计等方面，有效地缓解了上述问题. 本文整理总结了近年来国内外在锂硫电池结构设计上研究思路和进展，并对今后的发展趋势做了进一步展望.

关键词: 锂硫电池, 结构设计, 穿梭效应, 锂负极保护

Abstract: Commercial lithium-ion batteries (LIBs) are incapable of satisfying the increasing demand for emerging electronic devices due to their limited energy density. Among the next-generation batteries, lithium-sulfur (Li-S) batteries are becoming a promising energy-storage system due to their high theoretical energy density and natural abundance of sulfur. However, the shuttle of soluble polysulfide intermediates between two electrodes, as well as the problem on Li metal anode，lower the utilization of active material and lead to the loss of specific capacity and rapid capacity fading. All the above challenges limit the further application of Li-S batteries. Recently, various novel battery configurations have been reported in Li-S system, such as the construction design of multi-functional separator, cathode interlayer, brand sulfur hosts, as well as hybrid anode. The novel structure designs have been proved effective to relieve the intrinsic problems of Li-S batteries. Herein, we summarize the developments in separator modification and carbon-based interlayer in Li-S batteries. In the end, a perspective for future research direction of Li-S batteries is also presented.

Key words: lithium-sulfur batteries, battery configuration, shuttle effect, lithium anode protection

中图分类号:

O646

陈加航, 杨慧军, 郭城, 王久林. 锂硫电池结构设计研究现状及展望[J]. 电化学（中英文）, 2019, 25(1): 3-16.

CHEN Jia-hang, YANG Hui-jun, GUO Cheng, WANG Jiu-lin. Current Status and Prospect of Battery Configuration in Li-S System[J]. Journal of Electrochemistry, 2019, 25(1): 3-16.

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链接本文: https://electrochem.xmu.edu.cn/CN/10.13208/j.electrochem.180544

https://electrochem.xmu.edu.cn/CN/Y2019/V25/I1/3

参考文献

[1] Van Noorden R. A better battery[J]. Nature, 2014, 507(7490): 26-28.
[2] Jayaprakash N, Shen J, Moganty S S, et al. Porous hollow carbon@sulfur composites for high-power lithium-sulfur batteries[J]. Angewandte Chemie-International Edition, 2011, 50(26): 5904-5908.
[3] Chen L, Shaw L L. Recent advances in lithium-sulfur batteries[J]. Journal of Power Sources, 2014, 267: 770-783.
[4] Yuan S Y(袁守怡), Pang Y(庞莹), Wang L N(王丽娜), et al. Advances and prospects of lithium-sulfur batteries[J]. Journal of Electrochemistry(电化学), 2016, 22(5): 453-463.
[5] Yin Y X, Xin S, Guo Y G, et al. Lithium-sulfur batteries: electrochemistry, materials, and prospects[J]. Angewandte Chemie International Edition, 2013, 52(50): 13186-13200.
[6] Wang J L, Yang J, Xie J Y, et al. Sulfur-carbon nano-composite as cathode for rechargeable lithium battery based on gel electrolyte[J]. Electrochemistry Communications, 2002, 4(6): 499-502.
[7] Ji X, Lee K T, Nazar L F. A highly ordered nanostructured carbon-sulphur cathode for lithium-sulphur batteries[J]. Nature Materials, 2009, 8(6): 500-506.
[8] Arora P, Zhang Z. Battery separators[J]. Chemical Reviews, 2004, 104(10): 4419-4462.
[9] Cheon S E, Choi S S, Han J S, et al. Capacity fading mechanisms on cycling a high-capacity secondary sulfur cathode[J]. Journal of The Electrochemical Society, 2004, 151(12): A2067-A2073.
[10] Jin Z Q, Xie K, Hong X B, et al. Application of lithiated Nafion ionomer film as functional separator for lithium sulfur cells[J]. Journal of Power Sources, 2012, 218: 163-167.
[11] Huang J Q, Zhang Q, Peng H J, et al. Ionic shield for polysulfides towards highly-stable lithium-sulfur batteries[J]. Energy & Environmental Science, 2014, 7(1): 347-353.
[12] Yao H B, Yan K, Li W Y, et al. Improved lithium-sulfur batteries with a conductive coating on the separator to prevent the accumulation of inactive S-related species at the cathode-separator interface[J]. Energy & Environmental Science, 2014, 7(10): 3381-3390.
[13] Chung S H, Manthiram A. Carbonized eggshell membrane as a natural polysulfide reservoir for highly reversible Li-S batteries[J]. Advanced Materials, 2014, 26(9): 1360-1365.
[14] Balach J, Jaumann T, Klose M, et al. Functional mesoporous carbon-coated separator for long-life, high-energy lithium-sulfur batteries[J]. Advanced Functional Materials, 2015, 25(33): 5285-5291.
[15] Peng H J, Wang D W, Huang J Q, et al. Janus Separator of polypropylene-supported cellular graphene framework for sulfur cathodes with high utilization in lithium-sulfur batteries[J]. Advanced Science, 2016, 3(1): 1500268.
[16] Walther A, Müller A H E. Janus particles: synthesis, selfassembly, physical properties, and applications[J]. Chemical Reviews, 2013, 113(7): 5194-5261.
[17] Pang Q, Tang J T, Huang H, et al. A nitrogen and sulfur dual-doped carbon derived from polyrhodanine@cellulose for advanced lithium-sulfur batteries[J]. Advanced Materials, 2015, 27(39): 6021-6028.
[18] Pei F, Lin L L, Fu A, et al. A two-dimensional porous carbon-modified separator for high-energy-density Li-S batteries[J]. Joule, 2018, 2 (2): 323-336.
[19] Wang H Q, Zhang W C, Liu H K, et al. A strategy for configuration of an integrated flexible sulfur cathode for high-performance lithium-sulfur batteries[J]. Angewandte Chemie International Edition, 2016, 55(12): 3992-3996.
[20] Kang H S, Sun Y K. Freestanding bilayer carbon-sulfur cathode with function of entrapping polysulfide for high performance Li-S batteries[J]. Advanced Functional Materials, 2016, 26(8): 1225-1232.
[21] Yim T, Han S H, Park N H, et al. Effective polysulfide rejection by dipole-aligned BaTiO₃ coated separator in lithium-sulfur batteries[J]. Advanced Functional Materials, 2016, 26(43): 7817-7823.
[22] Su Y S, Manthiram A. Lithium-sulphur batteries with a microporous carbon paper as a bifunctional interlayer[J]. Nature Communications, 2012, 3: 1166.
[23] Zheng Z M, Guo H C, Pei F, et al. High sulfur loading in hierarchical porous carbon rods constructed by vertically oriented porous graphene-like nanosheets for Li-S batteries[J]. Advanced Functional Materials, 2016, 26(48): 8952-8959.
[24] Bai S Y, Liu X Z, Zhu K, et al. Metal-organic framework-based separator for lithium-sulfur batteries[J]. Nature Energy, 2016, 1(7): 16094.
[25] Dikin D A, Stankovich S, Zimney E J, et al. Preparation and characterization of graphene oxide paper[J]. Nature, 2007, 448(7152): 457-460.
[26] Joshi R K, Carbone P, Wang F C, et al. Precise and ultrafast molecular sieving through graphene oxide membranes[J]. Science, 2014, 343(6172): 752-754.
[27] Bai S Y, Sheng T L, Tan C H, et al. Distinct anion sensing by a 2D self-assembled Cu(I)-based metal-organic polymer with versatile visual colorimetric responses and efficient selective separations via anion exchange[J]. Journal of Materials Chemistry A, 2013, 1(9): 2970-2973.
[28] Stavila V, Talin A A, Allendorf M D. MOF-based electronic and opto-electronic devices[J]. Chemical Society Reviews, 2014, 43(16): 5994-6010.
[29] Bai S Y, Zhu K, Wu S C, et al. A long-life lithium-sulphur battery by integrating zinc-organic framework based separator[J]. Journal of Materials Chemistry A, 2016, 4(43): 16812-16817.
[30] Ghazi Z A, He X, Khattak A M, et al. MoS₂/celgard separator as efficient polysulfide barrier for long-life lithium-sulfur batteries[J]. Advanced Materials, 2017, 29(21): 1606817.
[31] Su Y S, Manthiram A. A new approach to improve cycle performance of rechargeable lithium-sulfur batteries by inserting a free-standing MWCNT interlayer[J]. Chemical Communications, 2012, 48(70): 8817-8819.
[32] Manthiram A, Fu Y, Chung S H, et al. Rechargeable lithium-sulfur batteries[J]. Chemical Reviews, 2014, 114(23): 11751-11787.
[33] Su Y S, Fu Y Z, Guo B K, et al. Fast, reversible lithium storage with a sulfur/long-chain-polysulfide redox couple[J]. Chemistry-A European Journal, 2013, 19(26): 8621-8626.
[34] Su Y S, Fu Y, Cochell T, et al. A strategic approach to recharging lithium-sulphur batteries for long cycle life[J]. Nature Communications, 2013, 4: 2985.
[35] Fu Y, Su Y S, Manthiram A. Li₂S-carbon sandwiched electrodes with superior performance for lithium-sulfur batteries[J]. Advanced Energy Materials, 2014, 4(1): 1300655.
[36] Zu C X, Su Y S, Fu Y Z, et al. Improved lithium-sulfur cells with a treated carbon paper interlayer[J]. Physical Chemistry Chemical Physics, 2013, 15(7): 2291-2297.
[37] Chung S H, Manthiram A. A hierarchical carbonized paper with controllable thickness as a modulable interlayer system for high performance Li-S batteries[J]. Chemical Communications, 2014, 50(32): 4184-4187.
[38] Zhang K, Qin F R, Fang J, et al. Nickel foam as interlayer to improve the performance of lithium-sulfur battery[J]. Journal of Solid State Electrochemistry, 2014, 18(4): 1025-1029.
[39] Chung S H, Manthiram A. A natural carbonized leaf as polysulfide diffusion inhibitor for high-performance lithium-sulfur battery cells[J]. ChemSusChem, 2014, 7(6): 1655-1661.
[40] He X M, Ren J G, Wang L, et al. Expansion and shrinkage of the sulfur composite electrode in rechargeable lithium batteries[J]. Journal of Power Sources, 2009, 190(1): 154-156.
[41] Yuan L X, Yuan H P, Qiu X P, et al. Improvement of cycle property of sulfur-coated multi-walled carbon nanotubes composite cathode for lithium/sulfur batteries[J]. Journal of Power Sources, 2009, 189(2): 1141-1146.
[42] Xiao Z B, Yang Z, Wang L, et al. A lightweight TiO₂/graphene interlayer, applied as a highly effective polysulfide absorbent for fast, long-life lithium-sulfur batteries[J]. Advanced Materials, 2015, 27(18): 2891-2898.
[43] Zhao T, Ye Y, Peng X, et al. Advanced lithium-sulfur batteries enabled by a bio-inspired polysulfide adsorptive brush[J]. Advanced Functional Materials, 2016, 26(46): 8418-8426.
[44] Balach J, Jaumann T, Mühlenhoff S, et al. Enhanced polysulphide redox reaction using a RuO₂ nanoparticle-decorated mesoporous carbon as functional separator coating for advanced lithium-sulphur batteries[J]. Chemical Communications, 2016, 52(52): 8134-8137.
[45] Li Q, Liu M, Qin X Y, et al. Cyclized-polyacrylonitrile modified carbon nanofiber interlayers enabling strong trapping of polysulfides in lithium-sulfur batteries[J]. Journal of Materials Chemistry A, 2016, 4(33): 12973-12980.
[46] Xing L B, Xi K, Li Q, et al. Nitrogen, sulfur-codoped graphene sponge as electroactive carbon interlayer for high-energy and-power lithium-sulfur batteries[J]. Journal of Power Sources, 2016, 303: 22-28.
[47] Wu K S, Hu Y, Shen Z, et al. Highly efficient and green fabrication of a modified C nanofiber interlayer for high-performance Li-S batteries[J]. Journal of Materials Chemistry A, 2018, 6 (6): 2693-2699.
[48] Chung S H, Manthiram A. A polyethylene glycol-supported microporous carbon coating as a polysulfide trap for utilizing pure sulfur cathodes in lithium-sulfur batteries[J]. Advanced Materials, 2014, 26(43): 7352-7357.
[49] Seh Z W, Wang H T, Liu N, et al. High-capacity Li₂S-graphene oxide composite cathodes with stable cycling performance[J]. Chemical Science, 2014, 5(4): 1396-1400.
[50] Seh Z W, Zhang Q F, Li W Y, et al. Stable cycling of lithium sulfide cathodes through strong affinity with a bifunctional binder[J]. Chemical Science, 2013, 4(9): 3673-3677.
[51] Kim J, Cote L J, Huang J X. Two dimensional soft material: new faces of graphene oxide[J]. Accounts of Chemical Research, 2012, 45(8): 1356-1364.
[52] Lightcap I V, Kamat P V. Graphitic design: prospects of graphene-based nanocomposites for solar energy conversion, storage, and sensing[J]. Accounts of Chemical Research, 2012, 46(10): 2235-2243.
[53] Wang X F, Wang Z X, Chen L Q. Reduced graphene oxide film as a shuttle-inhibiting interlayer in a lithium-sulfur battery[J]. Journal of Power Sources, 2013, 242: 65-69.
[54] Chung S H, Manthiram A. Lithium-sulfur batteries with superior cycle stability by employing porous current collectors[J]. Electrochimica Acta, 2013, 107: 569-576.
[55] Barchasz C, Mesguich F, Dijon J, et al. Novel positive electrode architecture for rechargeable lithium/sulfur batteries[J]. Journal of Power Sources, 2012, 211: 19-26.
[56] Yu J P(余劲鹏), Zhang M(张明), Ding F(丁飞), et al. Effects of carbon interlayer on electrochemical performance of lithium-sulfur cell[J]. Journal of Electrochemistry (电化学), 2014, 20(2): 105-109.
[57] Chen S Q, Sun B, Xie X Q, et al. Multi-chambered micro/mesoporous carbon nanocubes as new polysulfides reserviors for lithium-sulfur batteries with long cycle life[J]. Nano Energy, 2015, 16: 268-280.
[58] Lu S T, Cheng Y W, Wu X H, et al. Significantly improved long-cycle stability in high-rate Li-S batteries enabled by coaxial graphene wrapping over sulfur-coated carbon nanofibers[J]. Nano Letters, 2013, 13(6): 2485-2489.
[59] Wang H L, Yang Y, Liang Y Y, et al. Graphene-wrapped sulfur particles as a rechargeable lithium-sulfur battery cathode material with high capacity and cycling stability[J]. Nano Letters, 2011, 11(7): 2644-2647.
[60] Zhou G, Yin L C, Wang D W, et al. Fibrous hybrid of graphene and sulfur nanocrystals for high-performance lithium-sulfur batteries[J]. ACS Nano, 2013, 7(6): 5367-5375.
[61] Zhou L(周兰), Yu A S(余爱水). Current status and prospect of cathode materials for lithium sulfur batteries[J]. Journal of Electrochemistry(电化学), 2015, 21(3): 211-220.
[62] Seh Z W, Li W, Cha J J, et al. Sulphur-TiO₂ yolk-shell nanoarchitecture with internal void space for long-cycle lithium-sulphur batteries[J]. Nature Communications, 2013, 4: 1331.
[63] Wang X L, Li G, Li J D, et al. Structural and chemical synergistic encapsulation of polysulfides enables ultralong-life lithium-sulfur batteries[J]. Energy & Environmental Science, 2016, 9(8): 2533-2538.
[64] Li Z, Zhang J T, Lou X W. Hollow carbon nanofibers filled with MnO₂ nanosheets as efficient sulfur hosts for lithium-sulfur batteries[J]. Angewandte Chemie-International Edition, 2015, 54(44): 12886-12890.
[65] Dai C L, Lim J M, Wang M Q, et al. Honeycomb-like spherical cathode host constructed from hollow metallic and polar Co₉S₈ tubules for advanced lithium-sulfur batteries[J]. Advanced Functional Materials, 2018, 28(14): 1704443.
[66] Hu L Y, Dai C L, Liu H, et al. Double-shelled NiO-NiCo₂O₄ heterostructure@carbon hollow nanocages as an efficient sulfur host for advanced lithium-sulfur batteries[J]. Advanced Energy Materials, 2018: 1800709.
[67] Zheng J M, Tian J, Wu D X, et al. Lewis acid-base interactions between polysulfides and metal organic framework in lithium sulfur batteries[J]. Nano Letters, 2014, 14(5): 2345-2352.
[68] Yu L, Zhang G Q, Yuan C Z, et al. Hierarchical NiCo₂O₄@MnO₂ core-shell heterostructured nanowire arrays on Ni foam as high-performance supercapacitor electrodes[J]. Chemical Communications, 2013, 49(2): 137-139.
[69] Li J F, Xiong S L, Liu Y R, et al. High electrochemical performance of monodisperse NiCo₂O₄ mesoporous microspheres as an anode material for Li-ion batteries[J]. ACS Applied Materials&Interfaces, 2013, 5(3): 981-988.
[70] Liang X, Garsuch A, Nazar L F. Sulfur cathodes based on conductive MXene nanosheets for high-performance lithium-sulfur batteries[J]. Angewandte Chemie-International Edition, 2015, 54(13): 3907-3911.
[71] Bao W Z, Liu L, Wang C Y, et al. Facile synthesis of crumpled nitrogen-doped MXene nanosheets as a new sulfur host for lithium-sulfur batteries[J]. Advanced Energy Materials, 2018, 8(13): 1702485.
[72] Aurbach D, Zinigrad E, Teller H, et al. Factors which limit the cycle life of rechargeable lithium (metal) batteries[J]. Journal of The Electrochemical Society, 2000, 147(4): 1274-1279.
[73] Suo L M, Hu Y S, Li H, et al. A new class of solvent-in-salt electrolyte for high-energy rechargeable metallic lithium batteries[J]. Nature Communications, 2013, 4: 1481.
[74] Mikhaylik Y V, Kovalev I, Schock R, et al. High energy rechargeable Li-S cells for EV application: status, remaining problems and solutions[J]. ECS Transactions, 2010, 25(35): 23-34.
[75] Zheng J M, Gu M, Chen H H, et al. Ionic liquid-enhanced solid state electrolyte interface (SEI) for lithium-sulfur batteries[J]. Journal of Materials Chemistry A, 2013, 1(29): 8464-8470.
[76] Aurbach D, Pollak E, Elazari R, et al. On the surface chemical aspects of very high energy density, rechargeable Li-sulfur batteries[J]. Journal of The Electrochemical Society, 2009, 156(8): A694-A702.
[77] Demir-Cakan R, Morcrette M, Guéguen A, et al. Li-S batteries: simple approaches for superior performance[J]. Energy & Environmental Science, 2013, 6(1): 176-182.
[78] Huang C, Xiao J, Shao Y Y, et al. Manipulating surface reactions in lithium-sulphur batteries using hybrid anode structures[J]. Nature Communications, 2014, 5: 3015.