超高镍LiNi0.91Co0.06Al0.03O2@Ca3(PO4)2正极材料的储锂稳定性的提升机制

doi:10.15541/jim20210769

无机材料学报 ›› 2022, Vol. 37 ›› Issue (9): 1030-1036.DOI: 10.15541/jim20210769

• 研究论文 • 上一篇

超高镍LiNi_0.91Co_0.06Al_0.03O₂@Ca₃(PO₄)₂正极材料的储锂稳定性的提升机制

朱河圳¹(), 王选朋²^,³(), 韩康¹, 杨晨¹, 万睿哲², 吴黎明¹, 麦立强¹^,³()

1.武汉理工大学材料科学与工程学院, 武汉 430700
2.武汉理工大学理学院, 武汉 430700
3.先进能源科学与技术广东省实验室佛山分中心(佛山仙湖实验室), 佛山 528200

收稿日期:2021-12-17 修回日期:2022-02-26 出版日期:2022-09-20 网络出版日期:2022-03-10
通讯作者: 王选朋, 讲师. E-mail: wxp122525691@whut.edu.cn;
麦立强, 教授. E-mail: mlq518@whut.edu.cn
作者简介:朱河圳(1995-), 男, 硕士研究生. E-mail: 290761@whut.edu.cn
基金资助:
国家重点研发计划(2020YFA0715000);国家自然科学基金(51832004);国家自然科学基金(21905218);武汉理工大学自主创新研究基金项目

Enhanced Lithium Storage Stability Mechanism of Ultra-high Nickel LiNi_0.91Co_0.06Al_0.03O₂@Ca₃(PO₄)₂ Cathode Materials

ZHU Hezhen¹(), WANG Xuanpeng²^,³(), HAN Kang¹, YANG Chen¹, WAN Ruizhe², WU Liming¹, MAI Liqiang¹^,³()

1. School of Material Science and Engineering, Wuhan University of Technology, Wuhan 430070, China
2. School of Science, Wuhan University of Technology, Wuhan 430070, China
3. Foshan Xianhu Laboratory of the Advanced Energy Science and Technology Guangdong Laboratory, Foshan 528200, China

Received:2021-12-17 Revised:2022-02-26 Published:2022-09-20 Online:2022-03-10
Contact: WANG Xuanpeng, lecturer. E-mail: wxp122525691@whut.edu.cn;
MAI Liqiang, professor. E-mail: mlq518@whut.edu.cn
About author:ZHU Hezhen (1995-), male, Master candidate. E-mail: 290761@whut.edu.cn
Supported by:
National Key Research and Development Program of China(2020YFA0715000);National Natural Science Foundation of China(51832004);National Natural Science Foundation of China(21905218);Independent Innovation Research Fund Project of Wuhan University of Technology WUT:2021-LX-B1-04

摘要/Abstract

摘要：

超高镍正极材料具有高比能、高电压和低成本等特点, 在新一代锂离子电池中备受关注, 但在电池的长循环过程中会出现微裂纹、机械粉化和不可逆相变, 导致差的循环性能。本研究采用简便的湿化学法制备了一系列Ca₃(PO₄)₂包覆的超高镍LiNi_0.91Co_0.06Al_0.03O₂材料(NCA@nCP)。其中, NCA@1CP在1C (1C=200 mA/g)、2.7~4.3 V下可获得204.8 mAh/g的放电比容量, 100圈循环后容量保持率为91.5%, 甚至在2C的倍率下循环300圈后仍保留153.4 mAh/g的放电比容量。表征结果证实该包覆层可抑制材料的Li/Ni混排、不可逆相变和机械粉化, 从而大幅提升了循环稳定性。本研究表明Ca₃(PO₄)₂包覆策略在提升超高镍正极材料储锂稳定性方面具有较大的应用潜力。

关键词: 锂离子电池, 超高镍正极, Ca₃(PO₄)₂, 表面包覆

Abstract:

Ultra-high nickel material as a new lithium-ion battery cathode has attracted much attention due to its high specific capacity, high voltage and low cost. However, the generated microcracks, mechanical pulverization and irreversible phase transformation during cycling, result in poor cycling stability. Herein, a series of Ca₃(PO₄)₂- coated ultra-high nickel LiNi_0.91Co_0.06Al_0.03O₂ materials with different thicknesses (NCA@nCP) were prepared through a facile wet-chemistry strategy. Among them, NCA@1CP manifested specific discharge capacity of 204.8 mAh/g under 2.7-4.3 V at 1C (1C=200 mA/g), with a capacity retention rate of 91.5% after 100 cycles. Even after 300 cycles at 2C, the specific discharge capacity retained 153.4 mAh/g. Material characterization results further confirm that the coating shell inhibits the Li/Ni mixing, irreversible phase transformation and mechanical pulverization of the NCA@1CP, greatly improving the cycling stability. This work shows that the Ca₃(PO₄)₂ coating strategy has great application potential in improving the lithium storage stability of ultra-high nickel cathode materials.

Key words: lithium-ion battery, ultra-high nickel cathode, Ca₃(PO₄)₂, surface coating

中图分类号:

TQ174

朱河圳, 王选朋, 韩康, 杨晨, 万睿哲, 吴黎明, 麦立强. 超高镍LiNi_0.91Co_0.06Al_0.03O₂@Ca₃(PO₄)₂正极材料的储锂稳定性的提升机制[J]. 无机材料学报, 2022, 37(9): 1030-1036.

ZHU Hezhen, WANG Xuanpeng, HAN Kang, YANG Chen, WAN Ruizhe, WU Liming, MAI Liqiang. Enhanced Lithium Storage Stability Mechanism of Ultra-high Nickel LiNi_0.91Co_0.06Al_0.03O₂@Ca₃(PO₄)₂ Cathode Materials[J]. Journal of Inorganic Materials, 2022, 37(9): 1030-1036.

图/表 14

图1 (a)NCA和NCA@nCP(n=0.5, 1, 3)的XRD图谱; (b)NCA@1CP的精修结果

Fig. 1 (a) XRD patterns of NCA and NCA@nCP (n=0.5, 1, 3), and (b) Rietveld refinement results of NCA@1CP Colourful figures are available on website

图2 (a)NCA@1CP的SEM照片; (b)NCA和(c)NCA@1CP的高分辨TEM照片; (d)NCA@1CP的EDS元素分布图

Fig. 2 (a) SEM image of NCA@1CP, high-resolution TEM images of (b) NCA and (c) NCA@1CP, and (d) EDS elemental mappings of NCA@1CP

图3 NCA和NCA@1CP的(a)XPS全谱, (b)Ni2p、(c)Co2p、(d)Al2p、(e)P2p和(f)Ca2p XPS分谱图

Fig. 3 (a) Full survey, (b) Ni2p, (c) Co2p, (d) Al2p, (e) P2p and (f) Ca2p XPS spectra for NCA and NCA@1CP Colourful figures are available on website

图4 (a)NCA和(b)NCA@1CP的CV曲线; NCA和NCA@nCP在(c)0.2C及2.7~4.3 V条件下的初始充电/放电曲线和(d)1C及2.7~4.3 V条件下的循环性能; NCA和NCA@1CP在(e)1C及2.7~4.5 V和(f)2C及2.7~4.3 V条件下的循环性能

Fig. 4 CV curves for (a) NCA and (b) NCA@1CP; (c) Initial charge-discharge curves under 2.7-4.3 V at 0.2C and (d) cycling properties under 2.7-4.3 V at 1C for NCA and NCA@nCP; Cycling properties for NCA and NCA@1CP (e) under 2.7-4.5 V at 1C and (f) under 2.7-4.3 V at 2C Colourful figures are available on website

图5 (a)NCA和(c)NCA@1CP在原位XRD测试时的电压-时间变化曲线; (b, e)NCA和(d, f)NCA@1CP的原位XRD图谱; (g)NCA和NCA@1CP充电过程中晶格参数c的变化曲线

Fig. 5 Voltage-time variation curves during in-situ XRD for (a) NCA and (c) NCA@1CP; In-situ XRD patterns for (b, e) NCA and (d, f) NCA@1CP; (g) Variation curves of the lattice parameter c during charging for NCA and NCA@1CP

图6 (a)在1C及2.7~4.25 V条件下NCA和NCA@1CP为正极、石墨为负极的全电池循环性能; (b)NCA@1CP全电池第二圈充放电曲线

Fig. 6 (a) Cycling properties of full cells both NCA and NCA@1CP as cathode, graphite as anode under 2.7-4.25 V at 1C, and (b) charge-discharge curves of the second cycle for NCA@1CP in full cell

图S1 (a)NCA、(b)NCA@0.5CP和(c)NCA@3CP的精修结果

Fig. S1 Rietveld refinement results of (a) NCA, (b) NCA@0.5CP and (c) NCA@3CP

图S2 (a, b)NCA、(c, d)NCA@0.5CP和(e, f)NCA@3CP的SEM照片

Fig. S2 SEM images of (a, b) NCA, (c, d) NCA@0.5CP and (e, f) NCA@3CP

图S3 NCA的EDS元素分布图

Fig. S3 EDS elemental mappings of NCA

图S4 (a)NCA@0.5CP和(b)NCA@3CP的CV曲线

Fig. S4 CV curves for (a) NCA@0.5CP and (b)NCA@3CP

图S5 (a)NCA、NCA@0.5CP、NCA@1CP和NCA@3CP的倍率性能; (b)NCA和(c)NCA@1CP倍率测试中相应的放电曲线

Fig. S5 (a) Rate performance for NCA, NCA@0.5CP, NCA@1CP and NCA@3CP; Corresponding discharge curves during rate tests of (b) NCA and (c) NCA@1CP

图S6 NCA和NCA@1CP在1C及2.7~4.3 V条件下循环100圈后的(a, b)SEM照片与(c~f)XRD图谱

Fig. S6 (a, b) SEM images and (c-f) XRD patterns of NCA and NCA@1CP after 100 cycles under 2.7-4.3 V at 1C

表S1 NCA、NCA@0.5CP、NCA@1CP和NCA@3CP的I(003)/I(104)值

Table S1 I(003)/I(104) values for NCA, NCA@0.5CP, NCA@1CP and NCA@3CP

Sample	NCA	NCA@0.5CP	NCA@1CP	NCA@3CP
I₍₀₀₃₎/I₍₁₀₄₎	1.426	2.120	2.261	1.981

表S2 NCA、NCA@0.5CP、NCA@1CP和NCA@3CP的晶格参数

Table S2 Lattice parameters of the NCA, NCA@0.5CP, NCA@1CP and NCA@3CP calculated from XRD Rietveld refinement

Sample	a/nm	c/nm	V/nm³	c/a	R_wp	R_p
NCA	0.287398	1.421071	0.101652	4.944609	7.13	4.18
NCA@0.5CP	0.287296	1.420733	0.101556	4.945188	6.63	4.73
NCA@1CP	0.287286	1.420440	0.101527	4.944341	5.86	4.39
NCA@3CP	0.287305	1.420646	0.101556	4.944731	6.74	4.82

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超高镍LiNi_0.91Co_0.06Al_0.03O₂@Ca₃(PO₄)₂正极材料的储锂稳定性的提升机制

Enhanced Lithium Storage Stability Mechanism of Ultra-high Nickel LiNi_0.91Co_0.06Al_0.03O₂@Ca₃(PO₄)₂ Cathode Materials

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