硅基负极材料的研究进展

doi:10.11949/0438-1157.20241425

摘要/Abstract

摘要：

近年来，随着新能源汽车的高速发展，对电池的比容量、循环效率以及安全性提出了更高的要求。硅基负极材料因超高理论比容量（4200 mAh/g）和丰富储量成为突破锂离子电池能量密度瓶颈的核心方向，但其产业化进程受制于锂化过程中>300%的体积膨胀及SEI膜动态破裂引发的结构失效。综述了国内外在硅材料与其他物质的材料制备、复合工艺、元素掺杂、结构设计、纳米化硅材料以及SEI膜研究等方面的前沿研究成果，并阐述了硅负极产业化方向的未来发展，为硅基负极的发展提供了重要参考。

关键词: 硅负极, 碳包覆, 电化学, 负极材料, SEI膜, 产业化

Abstract:

In recent years, the rapid development of new energy vehicles has imposed increasingly stringent requirements on batteries in terms of high specific capacity, long-term cycling stability, and operational safety. Si-based anode materials have become the core direction to break through the bottleneck of lithium-ion battery energy density due to their ultra-high theoretical specific capacity (4200 mAh/g) and abundant reserves, but their industrialization process is restricted by the volume expansion of >300% during the lithiation process and the structural failure caused by the dynamic rupture of the SEI film. This review systematically examines recent advancements in silicon-based anode technologies, encompassing innovative material synthesis approaches, advanced composite engineering, strategic element doping, nanostructural design optimization, and interfacial modification strategies targeting SEI stabilization. Furthermore, it critically analyzes emerging trends in industrial-scale manufacturing processes and proposes a multidisciplinary roadmap for overcoming existing technical barriers, thereby establishing a comprehensive framework to guide the development of next-generation high-performance silicon anodes. By integrating fundamental mechanistic insights with scalable engineering solutions, this work provides critical perspectives on balancing electrochemical performance enhancement with cost-effective production methodologies, ultimately advancing the commercialization of silicon-based anodes in high-energy-density energy storage systems.

Key words: silicon negative electrode, carbon capping, electrochemistry, anode materials, SEI membrane, industrialization

中图分类号:

TM 912

孙国庆, 李海波, 丁志阳, 郭文辉, 徐浩, 赵艳侠. 硅基负极材料的研究进展[J]. 化工学报, 2025, 76(7): 3197-3211.

Guoqing SUN, Haibo LI, Zhiyang DING, Wenhui GUO, Hao XU, Yanxia ZHAO. Research progress of silicon based anode materials[J]. CIESC Journal, 2025, 76(7): 3197-3211.

图/表 8

表1 各类负极材料的理论质量比容量和理论体积比容量［4，17-19］

Table 1 Theoretical specific capacity and volumetric specific capacity of various anode materials［4，17-19］

负极材料类型	嵌锂相	理论质量比容量/(mAh/g)	理论体积比容量/(mAh/cm³)
C	LiC₆	372	837
Li₄Ti₅O₁₂	Li₇Ti₅O₁₂	175	613
Si	Li_4.4Si	4200	9786
Sb	Li_4.4Sb	660	4422
Sn	Li₃Sn	994	7246
Mg	Li₃Mg	3350	4355
Al	LiAl	993	2681

图1 (a)电极材料膨胀导致粉化；(b) SEI膜不断产生与破碎；(c)多次循环后材料与集流体丧失电接触[8]

Fig.1 (a) Expansion of the electrode material leading to pulverisation; (b) Continuous generation and fragmentation of the SEI film; (c) Loss of electrical contact between the material and the collector after multiple cycles[8]

图2 (a)海滩沙石制纳米硅流程图；(b)废旧玻璃制硅材料流程图；(c)稻壳材料处理后的宏观形貌；(d)、(e)稻壳材料处理后的微观形貌；(f)、(g)海滩沙石处理后碳包覆[35,38-39]

Fig.2 (a) Flow chart of beach sand and gravel to make nanosilica; (b) Flow chart of waste glass to make silicon material; (c) Macroscopic morphology after treatment of rice husk material; (d），（e) Microscopic morphology after treatment of rice husk material; (f），（g) Carbon encapsulation after treatment of beach sand and gravel[35,38-39]

图3 (a)弹性包覆示意图；(b)“三明治”结构示意图；(c)、(d)不同精度下弹性包覆SEM图；(e)、(f)三明治结构SEM图；(g)、(h)“呼吸图”法为硅搭建“房子”；(i)循环2000次后DWSiNTs表面均匀覆盖SEI膜；(j)DWSiNTs SEM图；(k)、(l)原位TEM装置示意图以及拍摄TEM图像；(m)DWSiNTs合成示意图[46-48,52-55]

Fig.3 (a) Elastic coating diagram; (b) Schematic diagram of the “sandwich” structure; (c)，(d) SEM images of elastic coating with different accuracy; (e)，(f) SEM images of sandwich structure; (g)，(h) “Breathing map” method was used to build a “house” for silicon； (i) DWSiNTs surface was uniformly covered with SEI film after 2000 cycles; (j)DWSiNTs SEM images; (k)，(l) Schematic diagram of the in-situ TEM device and TEM images； (m) Schematic diagram of DWSiNTs synthesis[46-48,52-55]

表2 各类硅负极结构设计与纯硅负极性能对比［46-48，52-55］

Table 2 Structural design of various types of silicon negative electrode and performance comparison of pure silicon negative electrode［46-48，52-55］

结构设计	活性物质	活性物质含量/%	充放电条件	循环圈数/次	初始比容量/(mAh/g)	剩余可逆容量/(mAh/g)	容量保持率/%
未设计	Si	100	300 mA/g	60	3250	0	0
核壳结构	Si	77	1.86 A/g	1000	1196（第二圈）	1160	97
弹性包覆	SiO₂	22	750 mA/g	500	1500	836	55
“三明治”结构	Si	60	300 mA/g	400	1000	930	93
“呼吸图”蜂窝结构	Si	50	50 mA/g	50	1686	1183	70
DWSiNTs	Si、SiO₂	60	24 A/g	6000	681.9（第二圈）	600	83

表3 缺陷构筑类改性机制的差异［46-48，52-55］

Table 3 The difference of modification mechanism of defect construction type［46-48，52-55］

对比维度	预置空隙	牺牲缓冲层	自支撑框架	原位限制
设计原理	人为预留膨胀空间（孔洞/间隙）	刻蚀牺牲层形成空腔	刚性骨架限制膨胀方向	循环中动态约束膨胀方向
结构特点	夹层空隙、层间间隙	核壳结构（如Si@刻蚀SiO₂@C）	蜂窝状/管状骨架	刚性外壳（如SiO₂）包裹硅内核
功能侧重	被动容纳膨胀	主动预留可控缓冲空间	机械约束膨胀方向	实时抑制膨胀路径
优势	结构简单，应力分散均匀	空间尺寸精准可控	膨胀抑制效果显著	循环中持续稳定约束
局限	空隙利用率低，能量密度损失	刻蚀工艺复杂，可能损伤硅材料	骨架刚性易导致局部应力集中	外壳破裂风险（长期循环）

图4 (a)不同比例N掺杂循环后电极SEM图；(b)Ni元素掺杂与硅氧负极循环比较；(c)QMS的TEM图像以及放大后晶格条纹TEM图像；(d)QMS与Si电极300次循环后膨胀率对比；(e)不同材料负极长循环对比；(f)B元素均匀掺杂[59-66]

Fig.4 (a) SEM images of the electrodes after cycling with different ratios of N doping; (b) Comparison of Ni elemental doping with SiO2 anode cycling; (c) QMS TEM images as well as enlarged lattice fringing TEM images; (d) Comparison of the expansion rate of the QMS versus Si electrodes after 300 cycles; (e) Comparison of the various types of comparative anodes with long cycling; (f) Homogeneous doping with B elements[59-66]

图5 (a)纳米Si QD沉积自组装在石墨烯网表面；(b)3.5 nm碳涂层包覆纳米硅的TEM图；(c)无定形碳包裹的纳米硅的TEM、EDS图[87-90]

Fig.5 (a) Nano-Si QD deposited self-assembled on the surface of graphene mesh; (b) 3.5 nm carbon coating encapsulating nano-Si; (c) TEM, EDS images of amorphous carbon encapsulated nano-Si[87-90]

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