锂离子电池硅基复合负极制备方法

doi:10.16085/j.issn.1000-6613.2020-1504

摘要/Abstract

摘要：

硅（Si）被视为取代现有商业化石墨负极极具潜力的材料之一，然而硅基材料在充放电过程中巨大的体积变化严重影响电池的电化学性能和使用寿命，因此如何有效克服体积效应以提高其电化学性能成为亟待解决的问题。本文围绕硅基复合负极制备过程，从物理方法、化学方法、多种方法结合三个方面综述了目前在硅基负极改性方面的最新进展，重点对不同的制备方法及过程进行了简介、分类、比较和分析，总结了其优缺点，指出多种方法结合制备硅基复合负极最具优势。最后对未来高性能硅基复合负极的研究和开发进行了展望，以期为硅基负极性能优化及探索新型制备方法提供借鉴。

关键词: 硅基复合负极, 电化学, 制备, 优化, 成本

Abstract:

Silicon (Si) is regarded as one of the most potential substitutes for the existing commercial graphite anode materials. However, the volume change of silicon-based materials during the charging and discharging process has seriously affected the electrochemical performance and lifespan of the battery. Therefore, how to effectively overcome the volume effect for the improvement of the electrochemical performance has become an urgent problem. In this paper, recent progress in the modification of silicon-based anode is reviewed as the following three aspects: physical method, chemical method, and the combination of various methods. Different preparation methods and processes are introduced, classified, compared, and analyzed, meanwhile, their advantages and disadvantages are also summarized. In the end, the future research and development of high-performance silicon-based anode are prospected to provide references for the optimization of silicon-based anode performance and exploration of new preparation methods.

Key words: silicon-based composite anode, electrochemistry, preparation, optimization, cost

中图分类号:

TM911

宋俊, 楚晓婉, 张琦, 陈宇慧, 张学清, 张国帅, 张若琳. 锂离子电池硅基复合负极制备方法[J]. 化工进展, 2021, 40(7): 3664-3678.

SONG Jun, CHU Xiaowan, ZHANG Qi, CHEN Yuhui, ZHANG Xueqing, ZHANG Guoshuai, ZHANG Ruolin. Preparation methods of the silicon-based composite anode of lithium-ion batteries[J]. Chemical Industry and Engineering Progress, 2021, 40(7): 3664-3678.

图/表 20

图1 本文主题概述

图2 负极前体，在ETEM中热处理期间原位形成的GCSi复合材料、所得复合材料的演变、纽扣电池的制造、热安全性研究以及整体安全性结果[8]

图3 多组分层保护的微米硅复合材料的制备过程图解及硅微粒和多组分层保护的微米级硅复合材料200次循环后体积膨胀和粉化的图解说明[10]

图4 掠射角沉积Si纳米弹簧在扫描电子显微镜中化学锂化[15]

图5 Cu-Si/a-C电极的制备过程和实物照片[18]

表1 物理沉积方法比较

项目	沉积方法比较
项目	EBE	MS	PLD
靶材要求	无	与膜成分一致	无
沉积范围	目标表面	目标表面及周边	目标表面
均匀性	好	差	差
膜层特点	低温时密度小，气孔多，附着性差	密度大，气孔少，溅射气体混入较多，附着性好	熔点高，沉积效率高，结构复杂

图6 分离填充电纺丝系统(a)，双孔碳纳米纤维（Si-Sn-DHCNFs）中自纺、稳定和炭化的硅（Si）、锡（Sn）纳米颗粒的预期横截面形貌示意图(b)及Si-DHCNF(c)、Sn-DHCNF(d)、Si-Sn-DHCNF(e)的横截面SEM图[26]

图7 用于沉积镍和铜颗粒的冷喷涂系统示意图[32]

图8 用于制造rGO/Fe-Fe3C的超音速动力学喷涂示意图[34]

图9 用球磨后的锌锡复合材料通过超音速气流在铜箔上沉积形成的复合涂层、炭化后的涂层及其SEM图[35]

图10 Si/CNTs@(S)-C结构设计示意图[39]

图11 无黏结剂的Cu15Si4/a-Si负极材料制备过程示意图[45]

图12 使用SiCl4和SnCl2作为碳酸亚丙酯电解质中硅和锡源的Sn-Si-O-C电沉积示意图[50]

表2 化学沉积方法比较

项目	沉积方法比较
项目	CVD	ALD	ED
吸附方式	物理吸附	化学吸附	无
沉积原理	通过化学反应将气相物质转化成固相物质并沉积于基板上获得高质量及高纯度薄膜	反应气体与基板之间的气-固相反应生成膜	金属或金属化合物在电场作用下通过电解液发生氧化还原反应完成沉积
用材范围	广	窄	广
沉积特点	沉积物随气相组成的变化而变化，从而获得梯度或混合沉积物，附着力强，厚度均匀，污染小	每次反应只沉积一层原子，逐层沉积，沉积速度慢但厚度均匀一致，成本高	可沉积成表面涂层，也可是块状，成本低

图13 Si@HC蛋黄-壳结构合成过程示意图[55]

图14 SiOx@SnO2@C复合材料的制备示意图[61]

图15 从马尾草提取硅纳米颗粒的示意图及Si@N-C复合材料的制备过程[62]

图16 （a）Si/G/C微粒的制造过程示意图；（b）压制过程中粉末变形的示意图；（c）球磨后的Si/G混合物在圆盘上分别经6t、12t、18t机械压制后的照片；（d）相同管子中采用不同力压制前后的Si/G样品[68]

图17 Si p-NS@TNSs复合材料形成过程示意图[71]

图18 合成Si@CNPs电极的示意图[84]

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