锂硫电池安全性问题现状及未来发展态势

doi:10.12028/j.issn.2095-4239.2018.0172

摘要/Abstract

摘要： 锂硫电池由于其原料来源广泛、成本低廉并且具有理论容量高以及环境友好等优点，被认为是最有潜力的新一代高能量密度电池技术之一。近年来，随着固硫化学的发展和硫电极结构设计的优化，锂硫电池技术发展已经取得了长足的进步。但是，锂硫电池的实用化仍然面临着一系列的挑战，如高载量硫正极的设计，少液体系或固态体系中硫的催化活化、稳定的电极/电解液界面、安全性能的提升等。其中，安全性能是阻碍锂硫电池商业化进程的关键问题之一。目前，已有众多的研究者对锂硫电池的安全性能提出了改进策略，包括金属锂负极的保护、阻燃电解液的开发、修饰隔膜乃至固体电解质的使用，以及通过电极结构设计缓解电池体积变化等。本文从锂硫电池的化学特性和影响安全性的关键部件出发，在基础研究方面，从负极锂枝晶生长、充放电过程中电极的体积变化以及电解液体系的问题等几方面总结了锂硫电池安全性问题的来源，针对这些问题提出了解决锂硫电池安全性问题的关键需求，总结了近年来安全性锂硫电池研究工作的进展，并对未来发展态势及方向进行探讨。由于缺乏直接的电芯和模块的数据测试，在大型器件上的安全性测试问题上，亟待其他科研工作者补充总结。

关键词: 锂硫电池, 安全性能, 阻燃电解液, 固体电解质

Abstract: Lithium-sulfur battery (Li-S) has been regarded as one of the most promising energy storage system due to its high energy density, environmental friendly, low cost and abundant resources of sulfur. Recently, the technology development of Li-S battery has been largely improved with the progress of sulfur trapping chemistry and sulfur cathode design. However, the commercialization of Li-S battery is still encountering a series of challenges, such as design of high loading sulfur cathode, activation of sulfur in lean electrolyte or solid electrolyte, stable electrode/electrolyte interface, and safety concerns. In which, the safety issue of Li-S battery is one of the key factors, which impede the commercialization process. In recent years, some strategies have been proposed to address the safety concerns of Li-S battery, including protection of Li metal anode, flame retardant electrolyte, modification of separator, solid electrolyte and accommodation of volume change during discharge and charge. In this review contribution, we summarize the research progress on the safety issue of Li-S battery, and discuss the future development of commercially available high-performance Li-S batteries featuring high energy density, stable cycle and high safety.

Key words: lithium-sulfur battery, safe property, flame retardant electrolyte, solid electrolyte

中图分类号:

TQ028.8

胡策军, 杨积瑾, 王航超, 陈一帆, 张茸茸, 刘文, 孙晓明. 锂硫电池安全性问题现状及未来发展态势[J]. 储能科学与技术, 2018, 7(6): 1082-1093.

HU Cejun, YANG Jijin, WANG Hangchao, CHEN Yifan, ZHANG Rongrong, LIU Wen, SUN Xiaoming. Research progress of safe lithium sulfur batteries[J]. Energy Storage Science and Technology, 2018, 7(6): 1082-1093.

参考文献

[1] GOODENOUGH J B, PARK K S. The Li-ion rechargeable battery:A perspective[J]. J. Am. Chem. Soc., 2013, 135 (4):1167-1176.
[2] WHITTINGHAM M S. Ultimate limits to intercalation reactions for lithium batteries[J]. Chem. Rev., 2014, 114 (23):11414-11443.
[3] CHENG X B, ZHANG R, ZHAO C Z, et al. Toward safe lithium metal anode in rechargeable batteries:A review[J]. Chem. Rev., 2017, 117 (15):10403-10473.
[4] CAO R, XU W, LV D, et al. Anodes for rechargeable lithium-sulfur batteries[J]. Adv. Energy Mater., 2015, 5 (16):1402273.
[5] BRUCE P G, FREUNBERGER S A, HARDWICK L J, et al. Li-O₂ and Li-S batteries with high energy storage[J]. Nat. Mater., 2011, 11 (1):19-29.
[6] SCROSATI B, GARCHE J. Lithium batteries:Status, prospects and future[J]. J. Power Sources, 2010, 195 (9):2419-2430.
[7] NITTA N, WU F, LEE J T, et al. Li-ion battery materials:Present and future[J]. Materials Today, 2015, 18 (5):252-264.
[8] LIU X, HUANG J Q, ZHANG Q, et al. Nanostructured metal oxides and sulfides for lithium-sulfur batteries[J]. Adv. Mater., 2017, 29 (20):doi:10.1002/adma.201601759.
[9] YANG Y, ZHENG G, CUI Y. Nanostructured sulfur cathodes[J]. Chem. Soc. Rev., 2013, 42 (7):3018.
[10] MA L, HENDRICKSON K E, WEI S, et al. Nanomaterials:Science and applications in the lithium-sulfur battery[J]. Nano Today, 2015, 10 (3):315-338.
[11] YIN Y X, XIN S, GUO Y G, et al. Lithium-sulfur batteries:Electrochemistry, materials, and prospects[J]. Angew. Chem. Int. Ed. Engl., 2013, 52 (50):13186-13200.
[12] ADELHELM P, HARTMANN P, BENDER C L, et al. From lithium to sodium:Cell chemistry of room temperature sodium-air and sodium-sulfur batteries[J]. Beilstein. J. Nanotechnol., 2015, 6:1016-1055.
[13] LI M, CHEN Z, WU T, et al. Li₂S-or S-based lithium-ion batteries[J]. Adv. Mater., 2018, e1801190.
[14] CHIANG Y M. Materials science. Building a better battery[J]. Science, 2010, 330 (6010):1485-1486.
[15] LEI T, CHEN W, HUANG J, et al. Multi-functional layered WS2 nanosheets for enhancing the performance of lithium-sulfur batteries[J]. Advanced Energy Materials, 2017, 7 (4):1601843.
[16] CHUNG S H, CHANG C H, MANTHIRAM A. Progress on the critical parameters for lithium-sulfur batteries to be practically viable[J]. Advanced Functional Materials, 2018, doi:10.1002/adfm. 20180118.
[17] PENG H J, HUANG J Q, CHENG X B, et al. Review on high-loading and high-energy lithium-sulfur batteries[J]. Advanced Energy Materials, 2017, 7 (24):doi:10.1002/aenm.201700260.
[18] CHENG Z, PAN H, ZHONG H, et al. Porous organic polymers for polysulfide trapping in lithium-sulfur batteries[J]. Advanced Functional Materials, 2018, doi:10.1002/adfm.201707597.
[19] LI G, WANG S, ZHANG Y, et al. Revisiting the role of polysulfides in lithium-sulfur batteries[J]. Adv. Mater., 2018, 30 (22):e1705590.
[20] FANG R, ZHAO S, SUN Z, et al. More reliable lithium-sulfur batteries:status, solutions and prospects[J]. Adv. Mater., 2017, 29 (48):doi:10.1002/adma.201606823.
[21] ZHANG S, UENO K, DOKKO K, et al. Recent advances in electrolytes for lithium-sulfur batteries[J]. Advanced Energy Materials, 2015, 5 (16):doi:10.1002/aenm.201500117.
[22] ROSENMAN A, MARKEVICH E, SALITRA G, et al. Review on Li-sulfur battery systems:An integral perspective[J]. Advanced Energy Materials, 2015, 5 (16):doi:10.1002/aenm.201500212.
[23] SEH Z W, YU J H, LI W, et al. Two-dimensional layered transition metal disulphides for effective encapsulation of high-capacity lithium sulphide cathodes[J]. Nat. Commun., 2014, 5:5017.
[24] PENG H J, ZHANG G, CHEN X, et al. Enhanced electrochemical kinetics on conductive polar mediators for lithium-sulfur batteries[J]. Angewandte Chemie International Edition, 2016, 55 (42):12990-12995.
[25] LIU W, LIN D C, PEI A, et al. Stabilizing lithium metal anodes by uniform Li-ion flux distribution in nanochannel confinement[J]. Journal of the American Chemical Society, 2016, 138 (47):15443-15450.
[26] LIANG X, PANG Q, KOCHETKOV I R, et al. A facile surface chemistry route to a stabilized lithium metal anode[J]. Nature Energy, 2017, 6:doi:10.1038/nenergy.2017.119.
[27] CHENG X B, ZHANG R, ZHAO C Z, et al. Toward safe lithium metal anode in rechargeable batteries:A review[J]. Chem. Rev., 2017, 117 (15):10403-10473.
[28] ZHENG G, LEE S W, LIANG Z, et al. Interconnected hollow carbon nanospheres for stable lithium metal anodes[J]. Nature Nanotech, 2014, 9 (8):618-623.
[29] LIU Y Y, LIN D C, YUEN P Y, et al. An artificial solid electrolyte interphase with high Li-ion conductivity, mechanical strength, and flexibility for stable lithium metal anodes[J]. Advanced Materials, 2017, 29 (10):doi:10.1002/adma.201605531.
[30] LIU K, PEI A, LEE H R, et al. Lithium metal anodes with an adaptive "solid-liquid" interfacial protective layer[J]. Journal of the American Chemical Society, 2017, 139 (13):4815-4820.
[31] ZHAO J, LIAO L, SHI F, et al. Surface fluorination of reactive battery anode materials for enhanced stability[J]. Journal of the American Chemical Society, 2017, 139 (33):11550-11558.
[32] LIN D C, LIU Y Y, CHEN W, et al. Conformal lithium fluoride protection layer on three-dimensional lithium by nonhazardous gaseous reagent freon[J]. Nano Lett., 2017, 17 (6):3731-3737.
[33] ZHAO J, ZHOU G, YAN K, et al. Air-stable and freestanding lithium alloy/graphene foil as an alternative to lithium metal anodes[J]. Nature Nanotechnology, 2017, 12 (10):993-999.
[34] XU R, ZHANG X Q, CHENG X B, et al. Artificial soft-rigid protective layer for dendrite-free lithium metal anode[J]. Advanced Functional Materials, 2018, doi:10.1002/adfm.201705838.
[35] ZHANG X Q, CHENG X B, CHEN X, et al. Fluoroethylene carbonate additives to render uniform Li deposits in lithium metal batteries[J]. Advanced Functional Materials, 2017, 27 (10):doi:10.1002/adfm.201605989.
[36] LI G, GAO Y, HE X, et al. Organosulfide-plasticized solid-electrolyte interphase layer enables stable lithium metal anodes for long-cycle lithium-sulfur batteries[J]. Nature Communications, 2017, 8 (1):850.
[37] ELAZARI R, SALITRA G, TALYOSEF Y, et al. Morphological and structural studies of composite sulfur electrodes upon cycling by hrtem, afm and raman spectroscopy[J]. Journal of the Electrochemical Society, 2010, 157 (10):A1131.
[38] MIKHAYLIK Y V, AKRIDGE J R. Polysulfide shuttle study in the Li/S battery system[J]. Journal of the Electrochemical Society, 2004, 151 (11):A1969.
[39] HAGEN M, HANSELMANN D, AHLBRECHT K, et al. Lithium-sulfur cells:The gap between the state-of-the-art and the requirements for high energy battery cells[J]. Advanced Energy Materials, 2015, 5 (16):doi:10.1002/aenm.201401986.
[40] SUN Y Z, HUANG J Q, ZHAO C Z, et al. A review of solid electrolytes for safe lithium-sulfur batteries[J]. Science China Chemistry, 2017, 60 (12):1508-1526.
[41] YU X, JOSEPH J, MANTHIRAM A. Polymer lithium-sulfur batteries with a Nafion membrane and an advanced sulfur electrode[J]. Journal of Materials Chemistry A, 2015, 3 (30):15683-15691.
[42] BAUER I, THIEME S, BR CKNER J, et al. Reduced polysulfide shuttle in lithium-sulfur batteries using Nafion-based separators[J]. Journal of Power Sources, 2014, 251:417-422.
[43] HUANG J Q, ZHUANG T Z, ZHANG Q, et al. Permselective graphene oxide membrane for highly stable and anti-self-discharge lithium-sulfur batteries[J]. ACS Nano, 2015, 9 (3):3002-3011.
[44] ZHOU G, LI L, WANG D W, et al. A flexible sulfur-graphene-polypropylene separator integrated electrode for advanced Li-S batteries[J]. Advanced Materials, 2015, 27 (4):641-647.
[45] LI W, HICKS-GARNER J, WANG J, et al. V₂O₅ polysulfide anion barrier for long-lived Li-S batteries[J]. Chemistry of Materials, 2014, 26 (11):3403-3410.
[46] ZHUANG T Z, HUANG J Q, PENG H J, et al. Rational integration of polypropylene/graphene oxide/nafion as ternary-layered separator to retard the shuttle of polysulfides for lithium-sulfur batteries[J]. Small, 2016, 12 (3):381-389.
[47] CHENG X B, HOU T Z, ZHANG R, et al. Dendrite-free lithium deposition induced by uniformly distributed lithium ions for efficient lithium metal batteries[J]. Advanced Materials, 2016, 28 (15):2888-2895.
[48] XU K. Electrolytes and interphases in Li-ion batteries and beyond[J]. Chem. Rev., 2014, 114 (23):11503-11618.
[49] XU R C, XIA X H, WANG X L, et al. Tailored Li₂S-P₂S₅ glass-ceramic electrolyte by MoS₂ doping, possessing high ionic conductivity for all-solid-state lithium-sulfur batteries[J]. Journal of Materials Chemistry A, 2017, 5 (6):2829-2834.
[50] WANG Q, WEN Z, JIN J, et al. A gel-ceramic multi-layer electrolyte for long-life lithium sulfur batteries[J]. Chemical Communications, 2016, 52 (8):1637-1640.
[51] FURUKAWA K, OKAJIMA K, SUDOH M. Structural control and impedance analysis of cathode for direct methanol fuel cell[J]. Journal of Power Sources, 2005, 139 (1/2):9-14.
[52] ZHU S, MA F, WANG Y, et al. New small molecule gel electrolyte with high ionic conductivity for Li-S batteries[J]. Journal of Materials Science, 2016, 52 (7):4086-4095.
[53] YANG W, YANG W, FENG J, et al. High capacity and cycle stability rechargeable lithium-sulfur batteries by sandwiched gel polymer electrolyte[J]. Electrochimica Acta, 2016, 210:71-78.
[54] 王维坤, 王安邦, 金朝庆, 等. 高性能锂硫电池正极材料研究进展及构建策略[J]. 储能科学与技术, 2017, 6 (3):331-344. WANG Weikun, WANG Anbang, JIN Chaoqing, et al. Research development and progress of high performance cathode design for lithium sulfur batteries.[J]. Energy Storage Science and Technology, 2017, 6 (3):331-344
[55] YAN K, LU Z, LEE H W, et al. Selective deposition and stable encapsulation of lithium through heterogeneous seeded growth[J]. Nature Energy, 2016, 1 (3):doi:10.1038/nenergy.2016.10.
[56] LIU Y, LIN D, LIANG Z, et al. Lithium-coated polymeric matrix as a minimum volume-change and dendrite-free lithium metal anode[J]. Nature Communications, 2016, 7:doi:10.1038/ncomms10992.
[57] ZUO T T, WU X W, YANG C P, et al. Graphitized carbon fibers as multifunctional 3D current collectors for high areal capacity Li anodes[J]. Advanced Materials, 2017, 29 (29):doi:10.1002/adma.201700389.
[58] WANG Q, YANG C, YANG J, et al. Stable Li metal anode with protected interface for high-performance Li metal batteries[J]. Energy Storage Materials, 2018, 15:249-256.
[59] WANG M, WANG W, WANG A, et al. A multi-core-shell structured composite cathode material with a conductive polymer network for Li-S batteries[J]. Chemical Communications, 2013, 49 (87):10263-10265.
[60] JI X, LEE K T, NAZAR L F. A highly ordered nanostructured carbon-sulphur cathode for lithium-sulphur batteries[J]. Nat. Mater., 2009, 8 (6):500-506.
[61] TAO X, WANG J, YING Z, et al. Strong sulfur binding with conducting Magneli-phase Ti_nO_2n-1 nanomaterials for improving lithium-sulfur batteries[J]. Nano Letters, 2014, 14 (9):5288-5294.
[62] WEI SEH Z, LI W, CHA J J, et al. Sulphur-TiO₂ yolk-shell nanoarchitecture with internal void space for long-cycle lithium-sulphur batteries[J]. Nat. Commun., 2013, 4:1331.
[63] YIN Y X, XIN S, WAN L J, et al. SnO hollow spheres:Polymer bead-templated hydrothermal synthesis and their electrochemical properties for lithium storage[J]. Science China Chemistry, 2012, 55 (7):1314-1318.
[64] QIU Y, LI W, ZHAO W, et al. High-rate, ultralong cycle-life lithium/sulfur batteries enabled by nitrogen-doped graphene[J]. Nano Lett., 2014, 14 (8):4821-4827.
[65] XIAO L, CAO Y, XIAO J, et al. A soft approach to encapsulate sulfur:polyaniline nanotubes for lithium-sulfur batteries with long cycle life[J]. Advanced Materials, 2012, 24 (9):1176-1181.
[66] QU C, CHEN Y, YANG X, et al. LiNO₃-free electrolyte for Li-S battery:A solvent of choice with low K sp of polysulfide and low dendrite of lithium[J]. Nano Energy, 2017, 39:262-272.
[67] WANG J, LIN F, JIA H, et al. Towards a safe lithium-sulfur battery with a flame-inhibiting electrolyte and a sulfur-based composite cathode[J]. Angewandte Chemie, 2014, 53 (38):10099-10104.
[68] JIA H, WANG J, LIN F, et al. TPPi as a flame retardant for rechargeable lithium batteries with sulfur composite cathodes[J]. Chemical Communications, 2014, 50 (53):7011-7013.
[69] SHI P, ZHENG H, LIANG X, et al. A highly concentrated phosphate-based electrolyte for high-safety rechargeable lithium batteries[J]. Chemical Communications, 2018, 54 (35):4453.
[70] CHEN S, ZHENG J, YU L, et al. High-efficiency lithium metal batteries with fire-retardant electrolytes[J]. Joule, 2018, 2 (8):1548-1558.
[71] PENG H J, HUANG J Q, ZHANG Q. A review of flexible lithium-sulfur and analogous alkali metal-chalcogen rechargeable batteries[J]. Chemical Society Reviews, 2017, 46 (17):5237-5288.
[72] XIAO J. Understanding the lithium sulfur battery system at relevant scales[J]. Advanced Energy Materials, 2015, 5 (16):doi:10.1002/aenm.201501102.
[73] ZHANG S S. Liquid electrolyte lithium/sulfur battery:Fundamental chemistry, problems, and solutions[J]. Journal of Power Sources, 2013, 231:153-162.