锂离子电池石墨负极材料的包覆改性及电化学性能研究

doi:10.19964/j.issn.1006-4990.2025-0021

摘要/Abstract

摘要：

石墨是重要的锂离子电池负极材料，但天然石墨的初始库伦效率低、循环稳定性和倍率性能较差等缺点限制其应用。为了提高石墨结构稳定性及其电化学性能，以Al（NO₃）₃·9H₂O为铝源，利用氨水调节pH，采用沉淀法在石墨表面均匀包覆一层Al（OH）₃，并进一步热处理制备Al₂O₃包覆石墨负极材料。此方法与原子层沉积法相比，具有过程简单和成本低廉的优点，比溶胶-凝胶法反应进程更好控制且能耗更低。当Al₂O₃包覆质量分数为1.03%时，获得表面光滑的改性石墨，Al₂O₃包覆层可起到预成型固态电解质界面（SEI）的作用，降低SEI膜的再生及锂离子的损耗。电化学性能试验表明，该材料在充放电过程中表现出优异的倍率性能及循环稳定性，将原料石墨和1.03%（质量分数）Al₂O₃包覆改性的石墨负极材料分别与锂片组装成锂离子电池，在0.1C（1.0C=372 mA∙h/g）的电流密度下，充放电循环100次后，其比容量分别为212.59 mA∙h/g和354.37 mA∙h/g，容量保持率分别为67.99%和98.59%。

关键词: 锂离子电池, 氧化铝, 表面改性, 负极材料

Abstract:

Graphite is an important anode material for lithium-ion batteries，but the low initial coulombic efficiency，short cycle life，and poor rate performance of natural graphite limit its application.In order to improve the stability of its graphite structure and electrochemical performance，Al（NO₃）₃·9H₂O was used as the aluminum source with adjusting the pH with ammonia water and uniformly coating a layer of Al（OH）₃ on the surface of graphite by precipitation method，and Al₂O₃ coated graphite anode material was further prepared by heat treatment.Compared with the atomic layer deposition method，this method had the advantages of simple process and low cost，better control of the reaction process and lower energy consumption than the sol gel method.When the Al₂O₃ coating mass was 1.03%，the modified graphite surface was smooth.The Al₂O₃ coating layer could serve as a preformed solid electrolyte interface（SEI），reducing the regeneration of SEI and the consumption of lithium ions during subsequent cycling processes.Electrochemical performance tests showed that the materials exhibited excellent rate performance and cycling stability during charge and discharge processes.Graphite and Al₂O₃ coated graphite anode materials with a modification amount of 1.03% were assembled with lithium sheets to form lithium-ion batteries.After 100 cycles of charge and discharge at a current density of 0.1C（1.0C=372 mA∙h/g），the specific capacities were 212.59 mA∙h/g and 354.37 mA∙h/g，with capacity retention rates of 67.99% and 98.59%，respectively.

Key words: lithium-ion batteries, alumina, surface modification, anode material

中图分类号:

TQ131.11

凌政, 孙陆, 田朋, 叶俊伟. 锂离子电池石墨负极材料的包覆改性及电化学性能研究[J]. 无机盐工业, 2025, 57(12): 18-25.

LING Zheng, SUN Lu, TIAN Peng, YE Junwei. Study on coating modification and electrochemical performance investigation of graphite anode materials for lithium-ion batteries[J]. Inorganic Chemicals Industry, 2025, 57(12): 18-25.

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负极材料	改性方法	首次库伦效率/%	循环后比容量/（mA·h·g^-1）	循环容量保持率/%
MCMB-1^［20］	双水解法	90.73	295.00 （0.2C，100次）	98.57（0.2C，100次）
G05U^［22］	溶胶-凝胶法	90.70	290.00（0.33C，50次）	91.33（0.33C，50次）
1% Al₂O₃（质量分数）^［25］	溶胶-凝胶法	94.60	334.00（1.1C，100次）	94.83（1.1C，100次）
0.7%-Al-A（质量分数）^［26］	溶胶浸渍-包覆法		385.06（0.1C，45次）	93.45（0.1C，45次）
BG/Al₂O₃-1.8^［34］	高能球磨法	84.21	344.00（2.7C，500次）	84.00（2.7C，500次）
AN-1^［35］	溶胶-凝胶法	93.40		84.95（1C，200次）
C-Al₂O₃-2（本工作）	沉淀法	91.64	354.37（0.1C，100次）	98.59（0.1C，100次）

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