NCM622正极材料结构形态和储锂特性的同步演变

doi:10.11949/0438-1157.20240983

摘要/Abstract

摘要：

当前以锂离子电池为主的二次电池已经步入主流。而LiNi_1-x-yCo_xMn_yO₂（NCM）材料在锂离子电池之中也具有相当大的商业市场，是一种具备极大应用价值的正极材料。根据镍的含量不同具备不同的性能。镍比例的增加能使得比容量提高，但也会导致热稳定性下降，因此对于高镍材料需要对制备工艺有更高的要求来确保其性能。相对于Li［Ni_0.8Co_0.1Mn_0.1］O₂（NCM811），Li［Ni_0.6Co_0.2Mn_0.2］O₂（NCM622）在具备较高比容量的同时热稳性更优秀。对纯相NCM622材料使用水热法进行制备，通过控制煅烧温度和煅烧时间来得出最佳制备方案。所制备的NCM622材料在最佳条件下能够达到最高191.3 mAh·g^-1的放电比容量，充放电循环也能有最高88.74%的容量保持率。

关键词: 锂离子电池, 正极材料, 层状氧化物, 电化学

Abstract:

The secondary battery based on lithium-ion battery has entered the mainstream. LiNi_1-x-yCo_xMn_yO₂ (NCM) material also has a considerable commercial market in lithium-ion batteries, and is a cathode material with great application value. According to the different content of nickel, they have different properties. The increase of nickel ratio can increase the specific capacity, but it will also lead to the decrease of thermal stability. Therefore, higher requirements for the preparation process of high nickel materials are needed to ensure their performance. Compared with Li[Ni_0.8Co_0.1Mn_0.1]O₂ (NCM811), Li[Ni_0.6Co_0.2Mn_0.2]O₂ (NCM622) has higher specific capacity and better thermal stability. In this work, the pure phase materials NCM622 are prepared by hydrother、mal method, and the best preparation scheme is obtained by controlling the calcination temperature and calcination time. The prepared NCM622 material can achieve a discharge specific capacity of up to 191.3 mAh·g^-1 under optimal conditions, and the charge-discharge cycle can also have a capacity retention rate of up to 88.74%.

Key words: lithium ion battery, cathode materials, layered oxides, electrochemistry

中图分类号:

TQ 028.8

李坤, 黄锐, 丛君, 马海涛, 常龙娇, 罗绍华. NCM622正极材料结构形态和储锂特性的同步演变[J]. 化工学报, DOI: 10.11949/0438-1157.20240983.

Kun LI, Rui HUANG, Jun CONG, Haitao MA, Longjiao CHANG, Shaohua LUO. Simultaneous evolution of structural morphology and lithium storage properties in NCM622 cathode material[J]. CIESC Journal, DOI: 10.11949/0438-1157.20240983.

图/表 10

图1 实验流程图

Fig.1 Flow chart of experiment

图2 (a)不同煅烧温度制备NCM622的XRD；(b~d)不同煅烧温度制备NCM622的SEM

Fig.2 (a) XRD of NCM622 prepared at different calcination temperatures; (b~d) SEM of NCM622 prepared at different calcination temperatures

图3 不同煅烧温度制备NCM622的XRD精修: (a) 800 ℃, (b) 850 ℃ and (c) 900 ℃；(d)不同煅烧温度制备NCM622的形成能

Fig.3 Rietveld XRD of NCM622 prepared at different calcination temperatures: (a) 800 ℃, (b) 850 ℃ (c) 900 ℃; (d) formation energy of NCM622 prepared at different calcination temperatures

图4 (a)不同煅烧温度制备NCM622的首次充放电曲线；(b)长循环性能；(c)倍率性能；(d)电化学阻抗

Fig.4 (a) first charge-discharge curve; (b) long cycle performance; (c) rate performance and (d) electrochemical impedance of NCM622 prepared at different calcination temperatures

图5 (a~b) 850 ℃制备NCM622的循环后XRD和SEM；

Fig.5 (a~b) XRD and SEM of NCM622 prepared at 850 ℃ after cycling

图6 不同煅烧时间制备NCM622的(a)XRD和(b~d)SEM

Fig.6 (a) XRD and (b~d) SEM of NCM622 prepared at different calcination time

图7 不同煅烧温度制备NCM622的XRD精修: (a) 6 h, (b) 8 h and (c) 10 h；(d)不同煅烧时间制备NCM622的形成能

Fig.7 Rietveld XRD of NCM622 prepared at different calcination temperatures: (a) 6 h, (b) 8 h and (c) 10 h; (d) formation energy of NCM622 prepared at different calcination time

图8 (a)不同煅烧时间制备NCM622的首次充放电曲线；(b)长循环性能；(c)倍率性能；(d)电化学阻抗

Fig.8 (a) first charge-discharge curve; (b) long cycle performance; (c) rate performance and (d) electrochemical impedance of NCM622 prepared at different calcination time

图9 (a~b) 8 h制备NCM622的循环后XRD和SEM

Fig.9 (a~b) XRD and SEM of NCM622 prepared at 8 h after cycling

表1 不同NCM622的电性能比较

Table 1 Comparison of electrical properties of different NCM622

样品	比容量性能	文献
NCM622	191.3 mAh·g^-1	本文
Li_1.2Mn_0.56Ni_0.11Co_0.13O₂	151.4 mAh·g^-1	[5]
LiNi_0.6Mn_0.2Co_0.2O₂	176.3 mAh·g^-1	[11]
LiNi_0.6Mn_0.2Co_0.2O₂	136 mAh·g^-1	[15]
NMC622	176.6 mAh·g^-1	[16]
Ni-rich ternary cathodes	191.1 mAh·g^-1	[23]
NCM523	150 mAh·g^-1	[24]
LiNi_0.8Co_0.1Mn_0.1O₂	186.1 mAh·g^-1	[27]

参考文献 31

1	Liu Z S, Li L J, Chen J, et al. Effects of chelating agents on electrochemical properties of Na_0.9Ni_0.45Mn_0.55O₂ cathode materials[J]. Journal of Alloys and Compounds, 2021, 855: 157485.[LinkOut]
2	Kunduraci M, Buluttekin R, Mutlu R N, et al. Synergistic coupling of high capacity Li_1.2Mn_0.54Ni_0.13Co_0.13O₂ and high voltage LiMn_1.6Ni_0.4O₄ lithium-ion battery cathodes[J]. Journal of Electronic Materials, 2022, 51(2): 769-777.[LinkOut]
3	Zheng Z Y, Zhou J, Zhu Y S. Computational approach inspired advancements of solid-state electrolytes for lithium secondary batteries: from first-principles to machine learning[J]. Chemical Society Reviews, 2024, 53(6): 3134-3166.[LinkOut]
4	Tolganbek N, Yerkinbekova Y, Kalybekkyzy S, et al. Current state of high voltage olivine structured LiMPO4 cathode materials for energy storage applications: a review[J]. Journal of Alloys and Compounds, 2021, 882: 160774.[LinkOut]
5	Cao W P, Yan J T, Zhang P, et al. Cerium-doped lithium-rich Li_1.2Mn_0.56Ni_0.11Co_0.13O₂ as cathode with high performance for lithium-ion batteries[J]. Ionics, 2022, 28(10): 4515-4526.[LinkOut]
6	Jiang P, Van Fan Y, Klemeš J J. Impacts of COVID-19 on energy demand and consumption: challenges, lessons and emerging opportunities[J]. Applied Energy, 2021, 285: 116441.[LinkOut]
7	Li X R, Chen X, Bai Q, et al. From atomistic modeling to materials design: computation-driven material development in lithium-ion batteries[J]. Science China Chemistry, 2024, 67(1): 276-290.[LinkOut]
8	Na S, Park K. Hybrid dual conductor on Ni-rich NCM for superior electrochemical performance in Lithium-ion batteries[J]. International Journal of Energy Research, 2022, 46(6): 7389-7398.[LinkOut]
9	Jia Z H, Liu Y, Li H M, et al. In-situ polymerized PEO-based solid electrolytes contribute better Li metal batteries: challenges, strategies, and perspectives[J]. Journal of Energy Chemistry, 2024, 92: 548-571.[LinkOut]
10	Huang Y H, Mai L Q, Xu H H, et al. Interdisciplinary research of materials and energy in honor of Nobel laureate John B. Goodenough[J]. Interdisciplinary Materials, 2022, 1(3): 321-322.[LinkOut]
11	Chan K H, Liu H T, Azimi G. Synthesis of a nickel-rich LiNi_0.6Mn_0.2Co_0.2O₂ cathode material utilizing the supercritical carbonation process[J]. Industrial & Engineering Chemistry Research, 2023, 62(10): 4271-4280.[LinkOut]
12	Ling J, Karuppiah C, Krishnan S G, et al. Phosphate polyanion materials as high-voltage lithium-ion battery cathode: a review[J]. Energy & Fuels, 2021, 35(13): 10428-10450.[LinkOut]
13	Jiang X, Qin L, Yu H F, et al. All-dry synthesis of single-crystalline LiNi_0.6Mn_0.2Co_0.2O₂ cathodes for high-energy and long-life Li-ion batteries[J]. Industrial & Engineering Chemistry Research, 2024, 63(23): 10291-10298.[LinkOut]
14	Soloy A, Flahaut D, Ledeuil J B, et al. Unraveling the morphological dependency of the LiNi_0.6Mn_0.2Co_0.2O₂ layered oxide reactivity in Li-ion batteries[J]. ACS Applied Energy Materials, 2022, 5(7): 8669-8685.[LinkOut]
15	Woodley C P, Cooper R A, Bartlett B M. Cu doping increases capacity retention in LiNi_0.6Mn_0.2Co_0.2O₂ (NMC622) by altering the potential of the Ni-based redox couple and inhibiting particle pulverization[J]. ACS Applied Energy Materials, 2024, 7(18): 7875-7884.[LinkOut]
16	Azad N, Arabi H. Improving electrochemical performance of NMC622 cathode by coating with Cr₂O₃ nanopowders and modified current collector[J]. Journal of Materials Engineering and Performance, 2023, 32(12): 5603-5609.[LinkOut]
17	Nitou M V M, Pang Y S, Wan Z, et al. LiFePO₄ as a dual-functional coating for separators in lithium-ion batteries: a new strategy for improving capacity and safety[J]. Journal of Energy Chemistry, 2023, 86: 490-498.[LinkOut]
18	Cronk A, Chen Y T, Deysher G, et al. Overcoming the interfacial challenges of LiFePO₄ in inorganic all-solid-state batteries[J]. ACS Energy Letters, 2023, 8(1): 827-835.[LinkOut]
19	Sun Y B, Chang C K, Zheng J N. Doping effects on ternary cathode materials for lithium-ion batteries: a review[J]. Chemphyschem, 2024, 25(17): e202300966.[PubMed]
20	Ma R, Zhao Z K, Fu J L, et al. Tuning cobalt-free nickel-rich layered LiNi_0.9Mn_0.1O₂ cathode material for lithium-ion batteries[J]. ChemElectroChem, 2020, 7(12): 2637-2642.[LinkOut]
21	Chu C T, Chang L M, Yin D M, et al. Large-sized nickel–cobalt–manganese composite oxide agglomerate anode material for long-life-span lithium-ion batteries[J]. ACS Applied Energy Materials, 2021, 4(12): 13811-13818.[LinkOut]
22	Liu X R, Wang X L, Yue B, et al. Preparation of hierarchical LiNi _x Co _y Mn _z O₂ from solvothermal[Ni _x Co _y Mn _z ](OH)₂ via regulating the ratio of Ni, Co, and Mn and its excellent properties for lithium-ion battery cathode[J]. Journal of the Chinese Chemical Society, 2020, 67(11): 2062-2070.[LinkOut]
23	Qin L, Yu H F, Jiang X, et al. All-dry solid-phase synthesis of single-crystalline Ni-rich ternary cathodes for lithium-ion batteries[J]. Science China Materials, 2024, 67(2): 650-657.[LinkOut]
24	Wang H, Wu Z J, Wang M M, et al. "Acid + oxidant" treatment enables selective extraction of lithium from spent NCM523 positive electrode[J]. Batteries, 2024, 10(6): 179.[LinkOut]
25	Guo X B, Song C C, Liu D C, et al. Effect of precursor structure transformation on synthesis and performance of LiNi_0.5Co_0.2Mn_0.3O₂ cathode material[J]. Solid State Sciences, 2022, 131: 106954.[LinkOut]
26	Hu Q, He Y F, Ren D S, et al. Targeted masking enables stable cycling of LiNi_0.6Co_0.2Mn_0.2O₂ at 4.6V[J]. Nano Energy, 2022, 96: 107123.[LinkOut]
27	Xiong Y K, Chang S H, Li Y J, et al. Enhancing surface and internal structural stability of LiNi_0.8Co_0.1Mn_0.1O₂ by yttrium phosphate dual effects[J]. Journal of Alloys and Compounds, 2022, 894: 162155.[LinkOut]
28	Reissig F, Lange M A, Haneke L, et al. Synergistic effects of surface coating and bulk doping in Ni-rich lithium nickel cobalt manganese oxide cathode materials for high-energy lithium ion batteries[J]. ChemSusChem, 2022, 15(4): e202102220.[PubMed]
29	Akhilash M, Salini P S, John B, et al. Surface modification on nickel rich cathode materials for lithium-ion cells: a mini review[J]. Chemical Record, 2023, 23(11): e202300132.[PubMed]
30	Soloy A, Flahaut D, Foix D, et al. Reactivity at the electrode–electrolyte interfaces in Li-ion and gel electrolyte lithium batteries for LiNi_0.6Mn_0.2Co_0.2O₂ with different particle sizes[J]. ACS Applied Materials & Interfaces, 2022, 14(25): 28792-28806.[LinkOut]
31	You L Z, Li G X, Huang B, et al. Surface-reinforced NCM811 with enhanced electrochemical performance for Li-ion batteries[J]. Journal of Alloys and Compounds, 2022, 918: 165488.[LinkOut]

编辑推荐 0

Metrics

阅读次数

全文

146

HTML			PDF

最新录用	在线预览	正式出版	最新录用	在线预览	正式出版
3	0	0	143	0	0

来源	本网站	其他网站

次数	14	132
比例	10%	90%

摘要

最新录用	在线预览	正式出版

94	0	0

来源	本网站	其他网站

次数	7	87
比例	7%	93%

[1]	王舒英, 左涛, 石志伟, 范小明, 张卫新. 阳离子交换树脂基介孔石墨化碳合成与储钠性能[J]. 化工学报, 2024, 75(9): 3338-3347.
[2]	彭丹, 卢俊杰, 倪文静, 杨媛, 汪靖伦. 高电压钴酸锂电池电解液研究进展[J]. 化工学报, 2024, 75(9): 3028-3040.
[3]	罗欣怡, 徐强, 佘永璐, 聂腾飞, 郭烈锦. 光电分解水制氢气泡动力学特性及其传质机理研究[J]. 化工学报, 2024, 75(9): 3083-3093.
[4]	王天闻, 闫肃, 赵梦园, 杨天让, 刘建国. 固体氧化物电池空气电极铬中毒机理及抗铬性能研究进展[J]. 化工学报, 2024, 75(6): 2091-2108.
[5]	江洋, 彭长宏, 陈伟, 周豪, 马忠彬, 李洪博, 邱在容, 张国鹏, 周康根. 废旧磷酸铁锂粉料综合回收中试研究[J]. 化工学报, 2024, 75(6): 2353-2361.
[6]	裴欣哲, 孙朱行, 林钰翔, 张朝阳, 钱勇, 吕兴才. 电催化分解液氨阳极材料的研究[J]. 化工学报, 2024, 75(5): 1843-1854.
[7]	吴希, 孙博, 刘银东, 齐传磊, 陈凯毅, 王路海, 许崇, 李永峰. 钠离子电池沥青基碳负极材料制备技术研究进展[J]. 化工学报, 2024, 75(4): 1270-1283.
[8]	孙铭泽, 黄鹤来, 牛志强. 铂基氧还原催化剂：从单晶电极到拓展表面纳米材料[J]. 化工学报, 2024, 75(4): 1256-1269.
[9]	李云璇, 刘新悦, 陈熙, 刘文, 周明月, 蓝兴英. 基于固液氧化还原靶向反应的能量存储技术：材料、器件及动力学[J]. 化工学报, 2024, 75(4): 1222-1240.
[10]	贾旭东, 杨博龙, 程前, 李雪丽, 向中华. 分步负载金属法制备铁钴双金属位点高效氧还原电催化剂[J]. 化工学报, 2024, 75(4): 1578-1593.
[11]	严孝清, 赵瑛, 张宇哲, 欧鸿辉, 黄起中, 胡华贵, 杨贵东. 五重孪晶铜纳米线@聚吡咯制备及其电催化硝酸盐还原制氨[J]. 化工学报, 2024, 75(4): 1519-1532.
[12]	李昂, 赵振宇, 李洪, 高鑫. 微波诱导高分散Pd/FeP催化剂构筑及其电催化性能研究[J]. 化工学报, 2024, 75(4): 1594-1606.
[13]	潘娜, 田昌, 怀兰坤, 刘玉玉, 张芬芬, 高晓梅, 刘伟, 闫良国, 赵艳侠. 聚合铝钛基絮凝剂的合成与应用[J]. 化工学报, 2024, 75(3): 1009-1018.
[14]	郭邦军, 贾理男, 张希. 全固态硫化物锂电池中NCM正极及其界面研究[J]. 化工学报, 2024, 75(3): 743-759.
[15]	吴吉昊, 陈涛, 刘思宇, 刘梦柯, 杨卷. 双功能活化制备沥青基硬炭用于钠离子电池负极[J]. 化工学报, 2024, 75(3): 1019-1027.