锂离子电池高镍LiNi0.8Mn0.2O2正极材料的微波合成及其Co、Al共改性

doi:10.15541/jim20200522

无机材料学报 ›› 2021, Vol. 36 ›› Issue (7): 718-724.DOI: 10.15541/jim20200522 CSTR: 32189.14.10.15541/jim20200522

锂离子电池高镍LiNi_0.8Mn_0.2O₂正极材料的微波合成及其Co、Al共改性

付宇坤¹(), 曾敏¹, 饶先发¹, 钟盛文¹, 张慧娟², 姚文俐¹()

1.江西理工大学材料冶金化学学部, 赣州 341000
2.上海理工大学材料科学与工程学院, 上海 200240

收稿日期:2020-09-07 修回日期:2021-01-04 出版日期:2021-07-20 网络出版日期:2021-01-25
通讯作者: 姚文俐, 副教授. E-mail:wenliyao@126.com
作者简介:付宇坤(1996-), 男, 硕士研究生. E-mail:475322904@qq.com
基金资助:
江西省自然科学基金(20192BAB206021);江西省教育厅(GJJ190423);江西省教育厅(GJJ200850);赣市财教字([2019] 60);国家自然科学基金(51874151)

Microwave-assisted Synthesis and Co, Al Co-modification of Ni-rich LiNi_0.8Mn_0.2O₂ Materials for Li-ion Battery Electrode

FU Yukun¹(), ZENG Min¹, RAO Xianfa¹, ZHONG Shengwen¹, ZHANG Huijuan², YAO Wenli¹()

1. Faculty of Materials Metallurgy and Chemistry, Jiangxi University of Science and Technology, Ganzhou 341000, China
2. School of Materials Science and Engineering, University of Shanghai for Science and Technology, Shanghai 200240, China

Received:2020-09-07 Revised:2021-01-04 Published:2021-07-20 Online:2021-01-25
Contact: YAO Wenli, associate professor. E-mail:wenliyao@126.com
About author:FU Yukun(1996-), male, Master candidate. E-mail:475322904@qq.com
Supported by:
Natural Science Foundation of Jiangxi Province(20192BAB206021);Foundation of Jiangxi Educational Committee(GJJ190423);Foundation of Jiangxi Educational Committee(GJJ200850);Finance and Education Plan of Ganzhou City([2019] 60);National Natural Science Foundation of China(51874151)

摘要/Abstract

摘要：

高镍正极材料由于较高的比容量和性价比而受到关注, 但在循环过程中稳定性较差且安全性能不佳, 限制了其更广泛的应用。本研究结合微波辅助共沉淀与高温固相法制备高镍正极LiNi_0.8Mn_0.2O₂二元材料, 再掺入不同比例的Co、Al对材料进行改性研究。结果表明, 改性后的材料性能明显改善, 特别是LiNi_0.8Mn_0.1Co_0.08Al_0.02O₂在2.75~4.35 V、1C下循环100次后容量保持率达到91.39%, 在5C下放电比容量仍有160.03 mAh∙g^-1, 并且掺杂后的材料具有较高的热稳定性, 安全性得到提升。其优异的循环保持率归因于Co、Al较好地抑制了循环过程中H2→H3相变的不可逆性对材料结构稳定性的破坏, 以及较弱的电极反应极化, 使电荷转移电阻降低。

关键词: LiNi_0.8Mn_0.2O₂, Co、Al共改性, 微波辅助共沉淀, 循环性能, 倍率性能

Abstract:

Due to high specific capacity and cost performance, high-nickel cathode materials have received much attention. However, its further application is hindered by poor stability and safety performance during cycling. In this work, Ni-rich LiNi_0.8Mn_0.2O₂ materials were prepared through microwave-assisted co-precipitation followed by high-temperature solid-phase method, which can be further modified by doping different proportions of Co and Al. As a result, LiNi_0.8Mn_0.1Co_0.08Al_0.02O₂ (NMCA-2) exhibits the best electrochemical performance, whose capacity retention rate reaches 91.39% after 100 cycles at 1C in the voltage range between 2.75 and 4.35 V, and still owns a specific discharge capacity of 160.03 mAh∙g^-1 at 5C. Its excellent cyclic retention rate can be attributed to the restrained irreversibility of H2→H3 phase transition during cycling with Co and Al doping, and the lower reaction polarization which contributed to the decline of charge transfer resistance, resulting in good cycle and rate performance of the material. Furthermore, high thermal stability of NMCA-2 improves the safety of the material.

Key words: LiNi_0.8Mn_0.2O₂, Co,Al co-modification, microwave-assisted coprecipitation, cycle performance, rate performance

中图分类号:

TQ174

付宇坤, 曾敏, 饶先发, 钟盛文, 张慧娟, 姚文俐. 锂离子电池高镍LiNi_0.8Mn_0.2O₂正极材料的微波合成及其Co、Al共改性[J]. 无机材料学报, 2021, 36(7): 718-724.

FU Yukun, ZENG Min, RAO Xianfa, ZHONG Shengwen, ZHANG Huijuan, YAO Wenli. Microwave-assisted Synthesis and Co, Al Co-modification of Ni-rich LiNi_0.8Mn_0.2O₂ Materials for Li-ion Battery Electrode[J]. Journal of Inorganic Materials, 2021, 36(7): 718-724.

图/表 17

图1 (a, b) NM-82、(c~l) NMCA-n (n=0, 1, 2, 3, 5)的SEM照片

Fig. 1 SEM images of (a, b) NM-82, (c-l) NMCA-n (n=0, 1, 2, 3, 5) (c, d) n=0; (e, f) n=1; (g, h) n=2; (i, j) n=3; (k, l) n=5

图2 NM-82和NMCA-n(n=0, 1, 2, 3, 5)的XRD图谱

Fig. 2 XRD patterns of NM-82 and NMCA-n (n=0, 1, 2, 3, 5)

图3 NM-82和NMCA-2的(a)XPS全谱和(b)Ni2p、(c)Co2p、(d)Al2p XPS分谱

Fig. 3 (a) Total survey and (b) Ni2p, (c) Co2p, (d) Al2p XPS spectra of NM-82 and NMCA-2

图4 NM-82和NMCA-2的(a, c)TEM照片、(b, d)HR-TEM照片和((b, d)中插图)相应的FFT图片

Fig. 4 (a,c) TEM images, (b,d)HR-TEM images and (insets in (b, d)) the corresponding FFT graphs of NM-82 and NMCA-2 (a, c) Magnified images of the square areas in the corresponding insets

图5 NM-82、NMCA-0和NMCA-2的(a~c)充电/放电曲线和(d~f)相应的dQ/dV曲线

Fig. 5 (a-c) Charge/discharge curves and (d-f) corresponding dQ/dV plots of NM-82, NMCA-0 and NMCA-2

图6 不同材料的电化学循环性能曲线和(插图)相应的容量保持率

Fig. 6 Cycling performance and corresponding capacity retention rate (inset) of different materials

图7 NM-82、NMCA-0和NMCA-2的(a~c)CV曲线、(d~f)EIS图谱及((d)中插图)对应的等效电路图

Fig. 7 (a-c) CV curves, (d-f) EIS plots and (insert in (d)) corresponding equivalent electrical circuit of NM-82, NMCA-0 and NMCA-2

图S1 微波辅助共沉淀示意图

Fig. S1 Schematic diagram of microwave assisted coprecipitation

图S2 NMCA-2的SEM照片和TEM-EDS元素分布图

Fig. S2 SEM image and TEM-EDS elemental mappings of NMCA-2

图S3 NM-82和NMCA-2的(a, b)粒径分布、(c)氮气吸附-解吸等温线和(d)孔径分布图

Fig. S3 (a, b) Particle size distributions, (c) nitrogen adsorption-desorption isotherms and (d) pore size distributions of NM-82 and NMCA-2

图S4 材料的层状结构示意图

Fig. S4 Schematic diagram of layered material structure

图S5 (a)NM-82、(b)NMCA-0和(c)NMCA-2的XRD精修结果

Fig. S5 Rietveld refinement results of (a) NM-82, (b) NMCA-0 and (c) NMCA-2

图S6 不同正极材料的倍率性能

Fig. S6 Rate performances of different cathode materials

图S7 NM-82、NMCA-0和NMCA-2的DSC曲线

Fig. S7 DSC curves of NM-82, NMCA-0 and NMCA-2

表S1 NM-82、NMCA-0和NMCA-2的XRD精修结果

Table S1 Parameters of Rietveld refinement for NM-82, NMCA-0 and NMCA-2

Sample	a/nm	c/nm	c/a	I₍₀₀₃₎/I₍₁₀₄₎
NM-82	0.2875	1.4232	4.9507	1.3197
NMCA-0	0.2877	1.4229	4.9457	1.3945
NMCA-2	0.2872	1.4243	4.9593	1.5888

表S2 材料在不同倍率下的放电比容量

Table S2 Specific discharge capacities of materials at different rates/(mAh·g-1)

Sample	0.2C	0.5C	1C	2C	3C	4C	5C	0.2C
NM-82	195.57	183.52	175.03	164.59	157.33	149.26	141.49	185.66
NMCA-0	192.45	182.66	176.69	166.91	160.88	157.05	153.17	183.80
NMCA-1	189.79	182.60	177.43	169.72	165.24	162.25	158.83	187.36
NMCA-2	189.70	183.05	177.84	172.80	169.08	164.76	160.03	189.25
NMCA-3	187.28	180.32	174.85	168.60	162.63	158.61	156.14	187.50
NMCA-5	186.04	178.28	173.83	167.08	163.41	157.97	150.84	181.33

表S3 NM-82、NMCA-0和NMCA-2的EIS拟合数据

Table S3 EIS fitting data of NM-82, NMCA-0 and NMCA-2

Sample	Cycle number	R_s/Ω	R_sf/Ω	R_ct/Ω
NM-82	5	3.85	20.20	46.65
	50	3.09	49.32	64.95
	100	7.27	94.06	138.40
NMCA-0	5	1.89	29.24	20.19
	50	2.01	58.13	72.25
	100	4.04	82.55	114.90
NMCA-2	5	5.11	31.85	19.80
	50	3.30	51.78	72.70
	100	4.08	67.32	67.88

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锂离子电池高镍LiNi_0.8Mn_0.2O₂正极材料的微波合成及其Co、Al共改性

Microwave-assisted Synthesis and Co, Al Co-modification of Ni-rich LiNi_0.8Mn_0.2O₂ Materials for Li-ion Battery Electrode

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