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实用化条件下金属锂负极失效的研究

王鑫萌 石鹏 张学强 陈爱兵 张强

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实用化条件下金属锂负极失效的研究

王鑫萌, 石鹏, 张学强, 陈爱兵, 张强

Failure mechanism of lithium metal anode under practical conditions

Wang Xin-Meng, Shi Peng, Zhang Xue-Qiang, Chen Ai-Bing, Zhang Qiang
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  • 金属锂因其高理论比容量和低电极电势, 被视为下一代高比能二次电池理想的负极材料之一. 然而, 其表面不稳定的固液界面膜及不均匀锂沉积等问题严重限制着其实际应用. 目前, 金属锂负极的研究大多采用温和的实验条件, 这对于理解负极表界面的物理化学性质和揭示锂沉积规律等基础研究具有重要意义. 但是, 超薄锂负极(< 50 μm), 低负极/正极面容量比(< 3.0), 低电解液量(< 3.0 g·Ah–1)等实用化条件是实现高比能金属锂电池(> 350 W·h·kg–1)的前提. 本文对金属锂负极在温和及实用化条件下的循环稳定性和负极表面形貌等进行比较, 分析造成差异的原因, 揭示金属锂负极在实用化条件下面临的挑战, 并提出潜在的实用化金属锂负极的研究策略, 以望促进高比能金属锂电池的发展.
    Lithium (Li) metal is regarded as one of the most promising anodes in the next-generation high-energy-density rechargeable batteries due to its ultrahigh theoretical specific capacity and low reduction potential. Nevertheless, the unstable solid electrolyte interphase on the surface of Li metal anode and the nonuniform Li deposition seriously hinder its practical applications. Currently, mild conditions are employed in the researches of Li metal anode, which is of great significance for fundamentally understanding the physicochemical features of the anode interface and the mechanisms of Li deposition. However, practical conditions including ultrathin Li metal anode (< 50 μm), low negative/positive electrode areal capacity ratio (< 3.0), and lean electrolyte (< 3.0 g·Ah–1) are the premise to realize high energy density of Li metal batteries (> 350 W·h·kg–1). Herein, the gaps of Li metal anode under mild and practical conditions in terms of the cycling stability and surface morphology are compared and the reasons for the gaps are analyzed carefully. The total quantity of active Li metal decreases and the utilization depth of Li per cycle has been greatly improved under practical conditions. Therefore, the huge volume fluctuation and uneven Li deposition result in ceaseless destruction and regeneration of solid electrolyte interphase, and thus consuming the lean electrolyte and generating a large quantity of dead Li rapidly. Consequently, the polarization voltage of Li metal anode increases rapidly and the cycling stability of Li metal batteries deteriorates evidently under practical conditions. Moreover, the electrochemical reaction of Li metal anode is accelerated while fast charge/discharge process is employed, which further aggravates the stability of Li metal anode. This work reveals the challenges of Li metal anode under practical conditions and present the perspectives for the further researches in practical Li metal anode, which conduces to the solid development of high-energy-density Li metal batteries.
      通信作者: 陈爱兵, chen_ab@163.com ; 张强, zhang-qiang@mails.tsinghua.edu.cn
    • 基金项目: 国家重点研发计划项目(批准号: 2016YFA0202500, 2016YFA0200102)、国家自然科学基金(批准号: 21676160)、国家杰出青年科学基金(批准号: 21825501)、国家自然科学基金地区联合基金项目(批准号: U1801257)和清华大学自主科研基金资助的课题
      Corresponding author: Chen Ai-Bing, chen_ab@163.com ; Zhang Qiang, zhang-qiang@mails.tsinghua.edu.cn
    • Funds: Project supported by the National Key Research and Development Program (Grant Nos. 2016YFA0202500, 2016YFA0200102), the National Natural Scientific Foundation of China (Grant No. 21676160), the National Science Fund for Distinguished Young Scholars of China (Grant No. 21825501), the Fund for Less Developed Regions of the National Natural Science Foundation of China (Grant No. U1801257), and the Tsinghua University Initiative Scientific Research Program of China
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  • 图 1  金属锂负极厚度对电池循环的影响 (a)不同锂负极厚度条件下电池结构示意图; (b) Li | NCM523全电池的循环性能; (c) Li | NCM523全电池第3圈和第60圈对应的充放电曲线

    Fig. 1.  The effect of the thickness of Li metal anode on the cycling of batteries: (a) The schematics of batteries with Li metal anode in different thicknesses; (b) the cycling performance of Li | NCM523 batteries; (c) the corresponding charge and discharge curves of Li | NCM523 batteries at the 3rd and 60th cycle.

    图 2  金属锂厚度对锂负极沉积形貌的影响 (a) 锂负极厚度为600 μm, 电流密度为1.0 mA·cm–2, 循环容量为1.0 mA·h·cm–2条件下, Li | Li对称电池的沉积形貌; (b) 锂负极厚度为50 μm, 电流密度为1.0 mA· cm–2, 循环容量为1.0 mA·h·cm–2条件下, Li | Li对称电池的沉积形貌; (c) 锂负极厚度为600 μm, 电流密度为3.0 mA·cm–2, 循环容量为3.0 mA·h·cm–2条件下, Li | Li对称电池的沉积形貌; (d)锂负极厚度为50 μm, 电流密度为3.0 mA·cm–2, 循环容量为3.0 mA·h·cm–2条件下, Li | Li对称电池的沉积形貌

    Fig. 2.  The effect of the thickness of Li metal anode on the morphology of Li deposition: The morphology of the deposited Li in Li | Li symmetrical cells at (a, b) a current density of 1.0 mA·cm–2 and a capacity of 1.0 mA·h·cm–2, and (c, d) a current density of 3.0 mA·cm–2 and a capacity of 3.0 mA·h·cm–2. The thickness of the Li anode is 600 μm in (a, c) and 50 μm in (b, d).

    图 3  N/P比对电池循环的影响 (a)不同N/P比条件下的电池示意图; (b) Li | NCM523全电池循环性能; (c) Li | NCM523全电池第3圈和第50圈对应的充放电曲线

    Fig. 3.  The effect of the N/P ratio on the cycling of batteries: (a) The schematics of batteries with different N/P ratios; (b) the cycling performance of Li | NCM523 batteries; (c) the corresponding charge and discharge curves of Li | NCM523 batteries at the 3rd and 50th cycle.

    图 4  电解液量对电池循环的影响 (a)不同电解液量下的电池示意图; (b) Li | NCM523全电池的循环性能; (c) Li | NCM523电池第3圈和第40圈对应的充放电曲线

    Fig. 4.  The effect of the amount of electrolyte on the cycling of batteries: (a) The schematics of batteries with different amounts of electrolyte; (b) the cycling performance of Li | NCM523 batteries; (c) the corresponding charge and discharge curves of Li | NCM523 batteries at the 3rd and 40th cycle.

    图 5  循环倍率对电池循环的影响 (a)不同循环倍率下的电池示意图; (b) Li | NCM523全电池的循环性能; (c) Li | NCM523电池第3圈和第70圈对应的充放电曲线

    Fig. 5.  The effect of the rate on the cycling of batteries: (a) The schematics of batteries with different rates; (b) the cycling performance of Li | NCM523 batteries; (c) the corresponding charge and discharge curves of Li | NCM523 batteries at the 3rd and 70th cycle.

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出版历程
  • 收稿日期:  2020-06-14
  • 修回日期:  2020-07-15
  • 上网日期:  2020-11-10
  • 刊出日期:  2020-11-20

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