所属专题: 锂离子电池
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张伟, 齐小鹏, 方升, 张健华, 史碧梦, 杨娟玉. 碳在锂离子电池硅碳复合材料中的作用[J]. 化学进展, 2020, 32(4): 454-466.
Wei Zhang, Xiaopeng Qi, Sheng Fang, Jianhua Zhang, Bimeng Shi, Juanyu Yang. Effects of Carbon on Silicon-Carbon Composites in Lithium-Ion Batteries[J]. Progress in Chemistry, 2020, 32(4): 454-466.
随着低比容量硅碳复合材料(<500 mAh/g)在锂离子电池中的商业化应用,硅基负极材料也从实验室研究走向了产业化发展。近年来的研究工作中,许多方法被用来解决硅在循环过程中体积变化(>300%)所带来的一系列问题。在材料结构方面,从最初的硅材料纳米化、硅与其他材料复合等技术手段转变到了硅碳复合材料二次颗粒的结构设计、表面包覆层设计等方法;在应用性能方面,除了早期文献报道的材料比容量、循环性能等参数外,还增加了材料比表面积、振实密度、首次及循环库仑效率等更符合电池实际应用要求的性能参数研究,从而极大地推动了硅基负极材料的商业化应用进程。本文首先综述了近年来硅碳复合材料组成、结构设计的发展脉络,进一步分析了由石墨、软碳、硬碳、碳纤维和石墨烯等碳源合成的硅碳复合材料的结构特点,并对其电化学性能进行分析对比,总结了碳在硅碳复合材料结构及其性能上发挥的作用。最后,对硅碳复合材料制备过程中的结构设计要求和碳材料的选择进行了分析和展望。
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Silicon | Carbon Source | Silicon Content(%) | Specific Capacity (mAh/g) | Coulomb Efficiency (%) | Specific Surface Area (m2/g) | ref |
---|---|---|---|---|---|---|
50~200 nm | Phenolic Resin | | 902 | | — | |
100~200 nm | Citric acid | 85.5 | 967.4 | 61.9 | 132.8 | |
Silicon powder | Resorcinol + Formaldehyde | | 787 | 66.19 | — | |
100 nm | Phenolic Resin | 86.3 | 1523.2 | 66.7 | — | |
325 mesh SiO | Resorcinol + Formaldehyde | | 1716 | | — | |
30 nm | Phenolic Resin | — | 624.8 | 70.36 | — | |
<100 nm | Citric acid | | 1857 | 71.4 | — | |
<30 nm | Resorcinol + Formaldehyde | | 1083 | | 367 | |
325 mesh Si | Phenolic Resin | 28.5 | 700 | | — | |
80 nm | Resorcinol + Formaldehyde | 81.7 | 2542 | 74.9 | 129.9 | |
Nano-Si | Resorcinol + Formaldehyde | | 2350 | | | |
20 nm | Acetylene | 86.4 | 2242.1 | 75.9 | — | |
80 nm | PVP | 15.4 | 1078.84 | 79.4 | 197.49 | |
70 nm | Citric acid | | 1561.9 | 80.2 | 214 | |
50 nm | Sucrose | 14.6 | 878.6 | 80.5 | — | |
50~100 nm | Sucrose + Acetylene | 16.5 | 569 | | 19.3 | |
Silicon/Carbon | Carbon Source | Silicon/Carbon Content(%) | Specific Capacity (mAh/g) | Coulomb Efficiency (%) | Specific Surface Area (m2/g) | ref |
---|---|---|---|---|---|---|
Artificial graphite | Coal tar pitch | — | — | | 4 | 102 |
Hard carbon | Coal tar pitch | | 300 | | — | |
Hard carbon | Coal tar pitch | | 297.8 | 89.8 | 2.88 | |
Graphite | Coal tar pitch | | 363 | 90.3 | — | |
SiO | Coal tar pitch | | 730 | — | — | 103 |
50 nm Nano-Si | Coal tar pitch | 11.8 | 670 | 75.5 | — | |
126 nm Nano-Si | pitch | 15.7 | 637.7 | 77.9 | — | |
50~100 nm Nano-Si | Coal tar pitch | | 712 | 80.5 | 1.88 | |
<1 μm | petroleum pitch | | 992 | | — | 104 |
80 nm Nano-Si | Coal tar pitch | | 602 | 82.3 | 4.0 | |
SiO | Coal tar pitch | — | 550 | | — | 105 |
100 nm Nano-Si | Coal tar pitch | 17.6 | 700 | | — | |
30~50 nm Nano-Si | Coal tar pitch | | 650 | 90.6 | 4.8 | |
100 nm Nano-Si | Coal tar pitch | 12.32 | 640 | 90.5 | 2 | |
<100 nm Nano-Si | Coal tar pitch | — | 523 | 90.9 | — | |
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