固定床法制备锂离子电池硅碳负极材料及其储锂性能研究

doi:10.11949/0438-1157.20240331

摘要/Abstract

摘要：

以导电炭黑为碳基底，以SiH₄为硅源前体，采用固定床CVD反应器制备锂离子电池硅碳复合负极材料。分别考察了SiH₄单独沉积及其与C₂H₄共沉积两种方案，并研究了以C₂H₄为碳源碳包覆对样品储锂性能的影响。实验结果表明，SiH₄单独沉积会形成尺寸较小的Si纳米颗粒，且随沉积温度提高，Si的负载量降低。SiH₄和C₂H₄共沉积过程会形成C@SiC复合结构，且随C₂H₄比例增加，单质硅的结晶度和晶粒尺寸降低。在硅碳共沉积和碳包覆条件下，则会形成Si、SiC和C三种晶体共存复合结构，有助于提高样品材料的循环性能，但比容量明显下降。

关键词: 固定床, 气相沉积法, 锂离子电池, 硅碳负极, 复合材料, 电化学

Abstract:

Utilizing conductive carbon black as the substrate and SiH₄ as the silicon source precursor, silicon-carbon composite anode material were prepared for lithium-ion batteries via a fixed bed CVD reactor. Two schemes were studied: sole deposition of SiH₄ and its co-deposition with C₂H₄. Additionally, the impact of carbon encapsulation using C₂H₄ as the carbon source on the lithium storage performance was investigated. The experimental results reveal that sole SiH₄ deposition yields smaller Si nanoparticles, with a reduction in Si loading as the deposition temperature increases.During the co-deposition of SiH₄ and C₂H₄, C@SiC composite structure is formed, and the crystallinity and grain size of elemental silicon decrease with the increase of C₂H₄ proportion. Under the co-deposition of SiH₄/C₂H₄ and C₂H₄ carbon coating conditions, a composite structure featuring coexistent Si, SiC, and C crystals is observed, enhancing sample material cycling performance albeit with a notable decrease in capacity.

Key words: fixed bed, vapor deposition method, lithium-ion batteries, silicon carbon anode, composite material, electrochemistry

中图分类号:

TQ 152

吴德威, 汪郑鹏, 周玥, 李晓宁, 陈招, 李卓, 刘成伟, 李学刚, 肖文德. 固定床法制备锂离子电池硅碳负极材料及其储锂性能研究[J]. 化工学报, 2024, 75(S1): 300-308.

Dewei WU, Zhengpeng WANG, Yue ZHOU, Xiaoning LI, Zhao CHEN, Zhuo LI, Chengwei LIU, Xuegang LI, Wende XIAO. Preparation of silicon carbon anode for lithium-ion batteries by fixed bed and lithium storage properties[J]. CIESC Journal, 2024, 75(S1): 300-308.

图/表 13

图1 固定床CVD反应装置图

Fig.1 Diagram of fixed bed CVD reaction equipment

图2 炭黑材料及C@Si-480硅碳材料的实物图和SEM图

Fig.2 Physical and SEM image of carbon-black and C@Si-480 material

图3 CVD温度对SiH4出口浓度的影响

Fig.3 Effect of CVD temperature on SiH4 concentration

图4 反应温度对Si负载量的影响

Fig.4 Effect of reaction temperature on Si deposition loading

图5 四种硅碳材料的电化学表征结果

Fig.5 Electrochemistry characterization of the four C@Si materials

图6 电池负极片的SEM表征

Fig.6 SEM characterization of battery anode

图7 C@SiC材料的气体出口浓度(a)， TEM表征图(b)及区域放大图(c)

Fig.7 Gas concentrations (a) and TEM characterization (b) and magnification (c) of C@SiC material

图8 气体出口浓度及C@SiC@C材料的TEM Mapping元素分析、TEM衍射图和晶面间距分析

Fig.8 Curve of gas concentrations and TEM Mapping image, TEM diffraction patterns and crystal plane spacing analysis of C@Si@C material

图9 C@SiC和C@SiC@C材料的XRD谱图

Fig.9 XRD patterns of C@SiC and C@SiC@C material

图10 材料C@SiC和C@SiC@C的首次充放电曲线(a)和电池循环曲线(b)

Fig.10 Curve of (dis)charge at first cycle (a) and battery cycles (b) of C@SiC and C@SiC@C materials

图11 不同SiH4和C2H4比例C@SiC材料的XRD谱图

Fig.11 XRD patterns of C@SiC material at different proportions of SiH4 and C2H4

图12 不同SiH4和C2H4比例C@SiC材料的电池容量和首效曲线(a)以及电池循环曲线(b)

Fig.12 Curve of initial discharge specific capacity and initial coulomb efficiency (a) and curve of battery cycles of C@SiC at different proportions of SiH4 and C2H4 (b)

图13 不同SiH4浓度下C@SiC材料的电池容量和首效以及电池循环曲线

Fig.13 Curve of initial discharge specific capacity and initial coulomb efficiency and curve of battery cycles of C@SiC at different concentrations of SiH4

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