特殊结构前驱体对锂电池三元正极材料性能的提升

doi:10.19799/j.cnki.2095-4239.2021.0471

摘要/Abstract

摘要：

前驱体制备过程中通过控制不同的反应条件可以得到形貌各异的材料，而其中氨值对于前驱体的微观形貌影响颇大。本文在不同氨值条件下制备得到形貌各异的高镍三元前驱体材料，发现低氨值条件下制备得到的前驱体表面晶须细致，内部结构密实且外部呈树杈状结构。这种条件下制备得到的前驱体材料经烧结后，一次颗粒仍呈放射状生长，且颗粒更为细长。该材料制成扣式电池后，0.2 C放电条件下比容量可达210.3 mA·h/g，首次充放电效率可达93.05%，且倍率及循环性能优异。与市面所售相同配比产品相比，放电容量提升3%。该形貌控制方法为高比容量三元正极材料的规模化制备提供了一种新思路。

关键词: 锂电池, 前驱体, 正极, 氨值, 形貌, 比容量

Abstract:

When preparing precursors, materials with various morphologies can be obtained by controlling different reaction conditions. Notably, the ammonia condition significantly affects morphology. Herein, high-nickel ternary precursor materials with different morphologies were prepared under different ammonia conditions. It was found that the precursor prepared under low-ammonia condition had fine whiskers on the surface, dense internal structure, and branching-like external structure. After sintering the precursor material, the primary particles still grew radially, and more slender than in other conditions. After fabricating the button battery, the capacity reached 210.3 mA·h/g at 0.2 C discharge, and the first charge-discharge efficiency reached 93.05%, with excellent cycle and rate performance. Herein, the discharge capacity of the device increased by 3% compared with the same ratio of commercial devices. The morphology control method provides a new idea for the large-scale preparation of high specific capacity ternary cathode materials.

Key words: lithium-ion battery, precursor, cathode, ammonia value, morphology, specific capacity

中图分类号:

TM 912

余春林, 陈旭东, 宫川敏夫, 孙辉, 张兴旺, 童莉葛. 特殊结构前驱体对锂电池三元正极材料性能的提升[J]. 储能科学与技术, 2022, 11(3): 1000-1007.

Chunlin YU, Xudong CHEN, Toshio MIYAGAWA, Hui SUN, Xingwang ZHANG, Lige TONG. Precursor with special structure for improving the performance of the ternary cathode material of Li-ion batteries[J]. Energy Storage Science and Technology, 2022, 11(3): 1000-1007.

图/表 12

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样品	D_min/μm	D₁₀/μm	D₅₀/μm	D₉₀/μm	D_max/μm
NCM-PL	3.43	5.14	6.83	11.90	14.00
NCM-PM	3.39	5.32	7.03	12.39	14.10
NCM-PH	4.20	5.68	7.59	13.39	21.32

指标	NCM-L	NCM-M	NCM-H	市售产品
BET/(m²/g)	1.29	0.86	0.58	0.53
D₅₀/μm	6.97	6.88	7.03	7.02
Li/%	1.03	1.03	1.03	1.02
Ni/%	0.827	0.828	0.825	0.825
Co/%	0.121	0.118	0.12	0.12
Mn/%	0.052	0.054	0.055	0.055
松装/(g/cm³)	1.64	1.72	1.79	1.77
H₂O/10^-6	586	562	514	534
自由Li⁺/%	1140	1433	1362	1450

产品	0.2 C放电容量/(mA·h/g)	首效/%	300圈循环保持率/%	4.5 C倍率容量保持率/%
NCM-L	210.3	93.05	92	74.4
市售产品	204	92	92	65.5

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