配锂量对LiNi0.90Mn0.07Al0.03O2正极材料电化学性能影响的研究

doi:10.19964/j.issn.1006-4990.2024-0238

摘要/Abstract

摘要：

随着现代社会对电池能量密度需求的日益增长，研究者的关注重点放到了高比容量的高镍层状正极材料上，但高镍材料的煅烧条件十分苛刻，材料合成复杂，因此需要探究其合成条件。采用共沉淀法成功制备了3种不同配锂量（1.02、1.04、1.06）的LiNi_0.90Mn_0.07Al_0.03O₂（NMA973）正极材料，探究了不同配锂量对正极材料NMA973的结构形貌、电化学性能的影响。通过XRD、SEM表征得出NMA973-1.04正极材料具有良好的层状结构。通过XPS测试得出NMA973-1.04正极材料的Ni³⁺含量较高，进一步证明Li⁺/Ni²⁺混排程度较低。ICP测试证实了NMA973-1.04正极材料的Li含量是最接近设计值的。电化学测试表明，NMA973-1.04正极材料在不同倍率下都显示出较高的放电比容量，小倍率0.2C的放电比容量可以达到199.00 mA·h/g，从大倍率5.0C再回到小倍率0.2C放电比容量仍为198.60 mA·h/g，容量保持率高达99.0%；在1.0C倍率循环100次后容量保持率为89.0%，这展示了NMA973-1.04正极材料的优异循环性能和结构稳定性。结果说明，配锂量为1.04的NMA973正极材料具有优异的性能。

关键词: 锂离子电池, 高镍三元正极, 配锂量, 共沉淀法

Abstract:

With the increasing demand for battery energy density in modern society，researchers have focused on high-nickel layered cathode materials with high specific capacity.However，the calcination conditions of high-nickel materials are very harsh and the material synthesis is complicated，so it is necessary to explore their synthesis conditions.Three kinds of LiNi_0.90Mn_0.07Al_0.03O₂（NMA973） cathode materials with different lithium contents（1.02，1.04，1.06） were successfully prepared by the coprecipitation method，and the effects of different lithium contents on the structural morphology and electrochemical properties of the cathode material NMA973 were investigated.NMA973-1.04 cathode material had a good layered structure as determined by XRD and SEM characterization.The XPS test showed that the Ni³⁺ of NMA973-1.04 cathode material was high，which further proved that the Li⁺/Ni²⁺ mixing degree was low.The ICP test confirmed that the Li content of NMA973-1.04 cathode material was the closest to the design value.The electrochemical tests showed that NMA973-1.04 cathode material had high discharge specific capacity at different rates，the discharge specific capacity of small rate 0.2C could reach 199.00 mA·h/g，and the discharge specific capacity from large rate 5.0C and back to small rate 0.2C could reach 198.60 mA·h/g，with a capacity retention rate of 99.0%.The capacity retention of 89.0% after 100 cycles at 1.0C demonstrated the excellent cycling performance and structural stability of NMA973-1.04 cathode material.The results indicated that the NMA973 cathode material with a lithium distribution of 1.04 had excellent performance.

Key words: lithium-ion battery, Ni-rich ternary cathodes, lithium content, coprecipitation method

中图分类号:

TQ131.11

申琦荣欣, 艾登登, 金生萍, 席儒恒, 后小毅. 配锂量对LiNi_0.90Mn_0.07Al_0.03O₂正极材料电化学性能影响的研究[J]. 无机盐工业, 2025, 57(7): 50-56.

SHEN Qirongxin, AI Dengdeng, JIN Shengping, XI Ruheng, HOU Xiaoyi. Study on effect of lithium concent on electrochemical performance of LiNi_0.90Mn_0.07Al_0.03O₂ cathode materials[J]. Inorganic Chemicals Industry, 2025, 57(7): 50-56.

图/表 6

图1

表1

图2

图3

图4

图5

参考文献 27

[1]	CHU Binbin， GUO Yujie， SHI Jilei，et al.Cobalt in high-energy-density layered cathode materials for lithium ion batteries［J］.Journal of Power Sources，2022，544：231873.
[2]	刘培松，宋利君，黄朝连，等.锰源对尖晶石LiMn₂O₄高温性能的影响［J］.无机化学学报，2023，39（1）：55-62.
	LIU Peisong， SONG Lijun， HUANG Chaolian，et al.Effects of manganese sources on the high temperature performance of spinel LiMn₂O₄ ［J］.Chinese Journal of Inorganic Chemistry，2023，39（1）：55-62.
[3]	HU Jiangtao， HUANG Weiyuan， YANG Luyi，et al.Structure and performance of the LiFePO₄ cathode material：From the bulk to the surface［J］.Nanoscale，2020，12（28）：15036-15044.
[4]	王峰，赵桓，吴红峰，等.镍酸锂系正极材料倍率性能的研究进展［J］.中国稀土学报，2023，41（3）：497-519.
	WANG Feng， ZHAO Huan， WU Hongfeng，et al.Research progress on C-rate performance of LiNiO₂ series cathode materials［J］.Journal of the Chinese Society of Rare Earths，2023，41（3）：497- 519.
[5]	CHENG Yong， ZHANG Xiaozhen， LENG Qianyi，et al.Boosting electrochemical performance of Co-free Ni-rich cathodes by combination of Al and high-valence elements［J］.Chemical Engineering Journal，2023，474：145869.
[6]	LIU Zhedong， WANG Chunying， ZHANG Jingchao，et al.Co-free/Co-poor high-Ni cathode for high energy，stable and low-cost lithium-ion batteries［J］.Rare Metals，2023，42（7）：2214-2225.
[7]	LI Wangda， LEE S， MANTHIRAM A.High-nickel NMA：A cobalt-free alternative to NMC and NCA cathodes for lithium-ion batteries［J］.Advanced Materials，2020，32（33）：2002718.
[8]	RYU H H， SUN H H， MYUNG S T，et al.Reducing cobalt from lithium-ion batteries for the electric vehicle era［J］.Energy & Environmental Science，2021，14（2）：844-852.
[9]	CHENG Fangyuan， ZHANG Wen， QIN Daomin，et al.Reinterpreting the correlation between cycling stability of Ni-rich layered oxide cathode and the charging cut-off voltage in Li-ion batteries［J］.Nano Energy，2023，115：108699.
[10]	黄丽颖，陆冬楚，宁玉雪，等.锂离子电池正极材料铌掺杂LiNiO₂的制备与电化学性能［J］.无机盐工业，2022，54（11）：52-58.
	HUANG Liying， LU Dongchu， NING Yuxue，et al.Preparation and electrochemical performance of Nb-doped LiNiO₂ cathode material for lithium-ion batteries［J］.Inorganic Chemicals Industry，2022，54（11）：52-58.
[11]	SONG Yijun， CUI Yongpeng， GENG Lin，et al.Li/Ni intermixing：The real origin of lattice oxygen stability in Co-free Ni-rich cathode materials［J］.Advanced Energy Materials，2024，14（7）：2303207.
[12]	MA Mingyuan， YANG Dan， JI Yongsheng，et al.Achieving enhanced electrochemical performance for cobalt-free layered cathode material by aluminum doping［J］.Batteries & Supercaps，2023，6（6）：e202300103.
[13]	CUI Zehao， GUO Zezhou， MANTHIRAM A.Assessing the intrinsic roles of key dopant elements in high-nickel layered oxide cathodes in lithium-based batteries［J］.Advanced Energy Materials，2023，13（12）：2203853.
[14]	YAO Meng， TAO Zemin， LIU Guobiao，et al.A novel calcination method towards layered Ni-rich cathode with enhanced electrochemical performances and regulated oxygen vacancies［J］.Che- mical Engineering Journal，2023，473：145090.
[15]	XIAO Peng， LI Wenhao， CHEN Shuai，et al.Effects of oxygen pressurization on Li⁺/Ni²⁺ cation mixing and the oxygen vacancies of LiNi_0.8Co_0.15Al_0.05O₂ cathode materials［J］.ACS Applied Materials & Interfaces，2022，14（28）：31851-31861.
[16]	冯准.B/Al/Zr协同策略改善高镍单晶正极材料高温稳定性［J］.无机盐工业，2023，55（8）：59-64，70.
	FENG Zhun.Improvement of high temperature stability of high nickel single crystal cathode materials by B/Al/Zr synergistic strategy［J］.Inorganic Chemicals Industry，2023，55（8）：59-64， 70.
[17]	LI Yingying， ZHANG Yang， LIU Jie，et al.Inducing favorable dual-substitution reactivity by doping Mo⁶⁺ and F^- to enhance electrochemical performance of LiNi_0.6Co_0.2Mn_0.2O₂ cathode materials［J］.Ceramics International，2022，48（16）：23016-23023.
[18]	孔祥泽，李东林，王子匀，等.钨掺杂对锂离子电池LiNiO₂正极材料性能的影响［J］.无机化学学报，2019，35（7）：1169-1175.
	KONG Xiangze， LI Donglin， WANG Ziyun，et al.Effect of W-doping on electrochemical performance of LiNiO₂ cathode for lithium-ion batteries［J］.Chinese Journal of Inorganic Chemistry，2019，35（7）：1169-1175.
[19]	TAN Xinxin， PENG Wenjie， WANG Meng，et al.Al，Zr dual-doped cobalt-free nickel-rich cathode materials for lithium-ion batteries［J］.Progress in Natural Science：Materials International，2023，33（1）：108-115.
[20]	王征荣，张海朗.过锂量对富锂锰基正极材料Li_1.2+ _x Ni_0.1Co_0.2Mn_0.5O₂结构与电化学性能的影响［J］.稀有金属材料与工程，2019，48（3）：941-946.
	WANG Zhengrong， ZHANG Hailang.Effect of extra lithium amount on the structure and electrochemical properties of Li-rich manganese-based cathode material of Li_1.2+ _x Ni_0.1Co_0.2Mn_0.5O₂ ［J］.Rare Metal Materials and Engineering，2019，48（3）：941-946.
[21]	ESSEHLI R， PAREJIYA A， MURALIDHARAN N，et al.Hydrothermal synthesis of Co-free NMA cathodes for high performance Li-ion batteries［J］.Journal of Power Sources，2022，545：231938.
[22]	ZHONG Shengwen， CHEN Peng， YAO Wenli.Ni-rich layered oxide Li_1.05（Ni_0.7Mn_0.3）O₂ as a highly reversible cathode material for lithium-ion batteries［J］.ECS Electrochemistry Letters，2015，4（6）：A45-A48.
[23]	NOEROCHIM L， GUNAWAN E A， PINTOWANTORO S，et al.High-rate capability of LiNi_0.9Mn_0.1– _x Al _x O₂（NMA）（x=0.01，0.03，0.05） as cathode for lithium-ion batteries［J］.Batteries，2023，9（8）：420.
[24]	YU S A， SEO J K， YUN J M，et al.Hybrid surface coating layers comprising boron and phosphorous compounds on LiNi_0.90Co_0.05Mn_0.05O₂ cathode materials to ensure the reliability of lithium-ion batteries［J］.Materials Today Energy，2023，37：101377.
[25]	BROW R， DONAKOWSKI A， MESNIER A，et al.Mechanical pulverization of Co-free nickel-rich cathodes for improved high-voltage cycling of lithium-ion batteries［J］.ACS Applied Energy Materials，2022，5（6）：6996-7005.
[26]	XI Ruheng， ZHANG Jianru， LAN Ziwei，et al.High-nickel and cobalt-free layered LiNi_0.90Mn_0.06Al_0.04O₂ cathode for lithium-ion batteries［J］.Ceramics International，2022，48（24）：36690-36696.
[27]	SONG Jinshang， ZHU Lingzhi， LI Yudong，et al.W modification of nickel-rich ternary cathode material for efficient lithium-ion batteries［J］.Journal of The Electrochemical Society，2023，170（1）：010523.

首页

全国无机盐信息中心

中国化工学会

无机酸碱盐专业委员会

配锂量对LiNi_0.90Mn_0.07Al_0.03O₂正极材料电化学性能影响的研究

Study on effect of lithium concent on electrochemical performance of LiNi_0.90Mn_0.07Al_0.03O₂ cathode materials

RichHTML

PDF (PC)

可视化

摘要/Abstract

引用本文

使用本文

图/表 6

参考文献 27

相关文章 15

Metrics

本文评价

推荐阅读 0

[1]	付彤彤, 何婷, 周诗雨, 顾帅. 退役锂离子电池正负极片原电池法自驱动浸出研究[J]. 无机盐工业, 2025, 57(7): 35-43.
[2]	党建猛, 张志超, 曹中凯, 李紫萱, 申继学. 提升高镍正极材料快充条件下电化学性能研究进展[J]. 无机盐工业, 2025, 57(7): 14-23.
[3]	郑天新, 杨宇, 霍东兴. 废旧锂离子电池正极金属材料回收工艺研究进展[J]. 无机盐工业, 2025, 57(6): 1-8.
[4]	王一人, 朵兴红. 磷酸三甲酯-混盐阻燃电解液性能研究[J]. 无机盐工业, 2025, 57(6): 85-92.
[5]	张珊珊, 曾雨乐, 张婷, 林森, 刘程琳. 锂离子电池正极预锂化技术研究进展[J]. 无机盐工业, 2025, 57(1): 1-13.
[6]	田朋, 张浩然, 徐金钢, 牟晨曦, 徐前进, 宁桂玲. 氧化铝溶胶改性锂离子电池正负极材料的研究[J]. 无机盐工业, 2024, 56(9): 44-53.
[7]	薛山, 刘璐, 戴建升, 李晴, 冯泽, 李意能. 铕掺杂改善锂离子电池正极材料LiFePO₄电化学性能研究[J]. 无机盐工业, 2024, 56(8): 67-73.
[8]	朱宗将, 王刚, 魏元峰, 唐艳红, 角田诚, 刘承斌. 退役锂离子电池电解液资源化回收技术进展与展望[J]. 无机盐工业, 2024, 56(7): 11-17.
[9]	赵添婷, 朱德伦, 杨林, 周鑫磊. 锂离子电池多孔硅负极材料制备及工艺优化[J]. 无机盐工业, 2024, 56(5): 31-38.
[10]	周海涛, 温承钦, 郑玲, 孙洁. 金属锂电池负极界面氮化硼修饰膜的研究[J]. 无机盐工业, 2024, 56(4): 85-89.
[11]	李亚广, 韩东战, 齐利娟. 废旧锂离子电池预处理及电解液回收技术研究现状[J]. 无机盐工业, 2024, 56(2): 1-10.
[12]	王亿周, 胡晓梅, 王永详, 张维民. 镍铁锰酸钠层状氧化物的制备及性能研究[J]. 无机盐工业, 2024, 56(2): 57-64.
[13]	刘娟, 蒋庆来, 张月异. 4.6 V高电压钴酸锂正极材料Al-Zn共掺杂研究[J]. 无机盐工业, 2024, 56(11): 59-64.
[14]	冯准. B/Al/Zr协同策略改善高镍单晶正极材料高温稳定性[J]. 无机盐工业, 2023, 55(8): 59-64.
[15]	于惠, 王榆彬, 廖折军, 杨云广. 废旧三元锂离子动力电池循环再生利用工艺概述[J]. 无机盐工业, 2023, 55(7): 32-37.

首 页