锂硫电池回顾与最新发展

燕绍九 杨晓辰 王超君 陈翔 刘佳让 南文争 刘津

燕绍九, 杨晓辰, 王超君, 陈翔, 刘佳让, 南文争, 刘津. 锂硫电池回顾与最新发展[J]. 航空材料学报, 2022, 42(5): 32-51. doi: 10.11868/j.issn.1005-5053.2022.000024
引用本文: 燕绍九, 杨晓辰, 王超君, 陈翔, 刘佳让, 南文争, 刘津. 锂硫电池回顾与最新发展[J]. 航空材料学报, 2022, 42(5): 32-51. doi: 10.11868/j.issn.1005-5053.2022.000024
YAN Shaojiu, YANG Xiaochen, WANG Chaojun, CHEN Xiang, LIU Jiarang, NAN Wenzheng, LIU Jin. Review and recent development of lithium-sulfur batteries[J]. Journal of Aeronautical Materials, 2022, 42(5): 32-51. doi: 10.11868/j.issn.1005-5053.2022.000024
Citation: YAN Shaojiu, YANG Xiaochen, WANG Chaojun, CHEN Xiang, LIU Jiarang, NAN Wenzheng, LIU Jin. Review and recent development of lithium-sulfur batteries[J]. Journal of Aeronautical Materials, 2022, 42(5): 32-51. doi: 10.11868/j.issn.1005-5053.2022.000024

锂硫电池回顾与最新发展

doi: 10.11868/j.issn.1005-5053.2022.000024
详细信息
    通讯作者:

    燕绍九(1980—),男,博士,研究员,长期从事低维纳米材料制备及应用研究,主要致力于石墨烯储能材料、石墨烯增强金属基纳米材料研究,联系地址:北京市海淀区温泉镇环山村中国航发北京航空材料研究院(100095),E-mail:shaojiuyan@126.com

  • 中图分类号: TM911.1

Review and recent development of lithium-sulfur batteries

  • 摘要: 锂硫电池具有比容量高、生产成本低及环境友好等特点,是一种高能量密度的储能系统,在便携式电子设备储能中有巨大的发展潜力与应用前景。然而,锂硫电池在实际应用中仍面临着库仑效率低和寿命短等问题。这主要归因于多硫化物穿梭效应、S8和Li2S电导率低和锂枝晶生长不可控。抑制锂枝晶生长和阻止可溶性多硫化物与锂之间的反应不仅能增强锂硫电池的安全性和电化学性能,对高容量锂硫电池也至关重要。本文全面回顾了锂硫电池发展,着重介绍了高硫负载锂电池所取得的进展。通过分析机理了解锂硫电池的运作机制进而制定改进方式,包括对阴极使用分级多孔碳并进行元素掺杂以增加活性物质硫负载率,减少多硫化物的穿梭效应。还介绍了液态和固态电解液系统的发展以及增强阳极稳定性的各种策略。深入了解锂硫电池机理能加强对锂硫电池认知,可以指导高硫负载锂硫电池未来的发展。同时,提高各组件之间协同作用可进一步推动锂硫电池技术从纽扣电池和软包电池到随后的商业化规模应用。

     

  • 图  1  锂硫电池工作机理[11]  (a) 电池的充放电过程中电压和电池容量的函数;(b) 基于XANES在充放电过程中推导出的锂硫电池机制

    Figure  1.  Working mechanism of lithium-sulfur battery[11] (a) function of voltage and battery capacity during charge and discharge;(b) mechanism of lithium-sulfur battery deduced by XANES during charge and discharge

    图  2  基于四甲基脲(TMU)电解质的锂硫电池[14] (a)溶剂化介导的自由基路径;(b)多硫化物解聚过程及方程

    Figure  2.  Lithium sulfur batteries based on tetramethyl urea (TMU) electrolyte[14] (a) solvation mediated free radical pathway; (b) process and equation of polysulfide depolymerization

    图  3  制备分级多孔碳纳米片示意图[30]

    Figure  3.  Schematic diagram of the preparation of hierarchical porous carbon nanosheets[30]

    图  4  氧化石墨烯-硫-支链淀粉复合材料合成路线示意图[35]

    Figure  4.  Schematic diagram of GO-sulfur-amylopectin composite synthesis route[35]

    图  5  吸附硫的俯视图[23] (a) 吸附在带有吡啶 N—COOH 官能团的氮掺杂碳上;(b) 吸附在带有—COOH 基团的无氮碳上

    Figure  5.  Top view of adsorbed sulfur[23] (a) adsorbed on nitrogen-doped carbon with pyridine N—COOH functional group; (b) adsorbed on nitrogen-free carbon with —COOH group

    图  6  N,S-CDs/rGO 和 N,S-CDs/rGO@S 复合材料的制备示意图[55]

    Figure  6.  Schematic diagram of preparation of N, S-CDS /rGO and N, S-CDS /rGO@S composites[55]

    图  7  基于 DFT 计算的Li2S6物质在CoSA-NC上吸附的原子构象和结合能[58]

    Figure  7.  Atomic conformation and binding energy of Li2S6 adsorbed on CoSA-NC based on DFT calculation [58]

    图  8  Li2S6在典型醚溶剂中的溶解实验照片[66]

    Figure  8.  Dissolution test photos of Li2S6 in typical ether solvents[66]

    图  9  Li10GeP2S12以及其他锂固态电解液、聚合物电解液、离子电解液和凝胶电解液的离子电导率的热演化[90]

    Figure  9.  Thermal evolution of ionic conductivity of Li10GeP2S12 and other Lithium solid, polymer, ionic liquid and gel electrolytes[90]

    图  10  纯锂和Cu3N+丁苯橡胶人工SEI镀层行为示意图[109]

    Figure  10.  Diagram of artificial SEI coating behavior of pure lithium and Cu3N+ SBR[109]

    表  1  碳质材料掺杂氮元素制备的锂硫电池性能[39]

    Table  1.   Performance of lithium-sulfur battery prepared by carbon material doped with nitrogen element[39]

    MaterialDoping elementElement contentSulphur content
    (mass fraction/%)
    Initial discharge
    capacity/(mAh·g−1
    Cycle indexCapacity retention rate/%
    N-IOPN3.0 a80 a1162(0.2 C)15064
    NPCMsN8.9 a65 a1132(0.1 A/g)10091
    HNCMN12.43 b6 c902(0.5 C)100089
    N-CNTN61 a1267(0.2 C)10064
    NGN3.9 a60 a1030(0.5 C)30073
    3DG@NPCN18 a70 a1280(0.2 C)10081
    Note: a represents mass fraction/%; b represents atom fraction/%; c represents mg/cm2.
    下载: 导出CSV

    表  2  碳质材料进行二元掺杂制备的锂硫电池性能[48]

    Table  2.   Performance of lithium-sulfur batteries prepared by binary doping of carbonaceous material[48]

    MaterialDoping elementElement contentSulphur contentInitial discharge capacity/(mAh·g-1Cycle indexCapacity retention rate/%
    NSHPCN, SN 3.47 a
    S 4.03 a
    80 a1549(0.1 C)10061.14
    SN-PCNFN, S-80 a1133(0.1 C)15075
    N,S-CDs/
    rGO
    N, SN 2.9 a
    S 3.8 a
    76 a1296(0.1 C)15069
    Co-N-CNTAN, CoN 8.6 b40 a1045(1C)100077.89
    CoSA-N-CN, CoN 16.3 b74 a1038(1 C)100065
    Co-N/GN, CoN 7.25 b
    Co 0.77 b
    67 a861(1 C)50079
    Note: a represents mass fraction,%; b represents atom fraction,%.
    下载: 导出CSV
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  • 收稿日期:  2022-02-22
  • 修回日期:  2022-05-02
  • 网络出版日期:  2022-08-10
  • 刊出日期:  2022-10-11

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