Synthesis of single-crystal LiNi0.8Co0.1Mn0.1O2 by flux method

doi:10.19799/j.cnki.2095-4239.2020.0149

Abstract

Abstract:

The nickel-rich ternary material LiNi_0.8Co_0.1Mn_0.1O₂ (NCM811) is one of the cathode material candidates for new-generation high-energy density lithium-ion batteries due to its advantages of high specific capacity, low cost, and high safety. However, the inter-granular fracture cannot be avoided in polycrystalline NCM811 materials due to the contraction and expansion of the lattice volume during the charge and discharge processes, which causes an unsatisfied cycling life of the materials. Compared to polycrystalline materials, single-crystal materials have better mechanical property and thermal and cycle stabilities. In this work, the LiNO₃-LiOH mixed flux with a low-melting point is applied to prepare the single-crystal LiNi_0.8Co0.1Mn_0.1O₂ (NCM811) material. The influence of the synthesis conditions on the structure, morphology, and electrochemical performances of the final products (e.g., flux dosage) and the sintering temperature are systematically investigated through X-ray diffraction, scanning electron microscopy, transmission electron microscopy, and electrochemical measurements. The results show that the molar ratio of flux in the mixture of the precursors and the flux is optimized to be 90 mol%, and the optimized sintering temperature is 800 °C. The as-prepared NCM811 material measuring 1-2 μm exhibits an excellent electrochemical performance. Furthermore, the Mg-doped single-crystal NCM 811 material achieves a large discharge specific capacity of 165.4 mA·h/g and a capacity retention of 97.7% after 100 cycles at 1 °C. For comparison, the discharge specific capacity of the polycrystalline NCM811 material synthesized from the commodity precursors is only 132.9 mA·h/g, and the capacity retention is 75.0% after 100 cycles at 1 °C. In conclusion, the electrochemical performance and the cycling capability of the single-crystal NCM811 material are superior to those of the polycrystalline NCM811 material.

Key words: single crystal nickel-rich ternary material, flux method, element doping, lithium-ion batteries

CLC Number:

TM 911

Sijia REN, Leiwu TIAN, Qinjun SHAO, Jian CHEN. Synthesis of single-crystal LiNi_0.8Co_0.1Mn_0.1O₂ by flux method[J]. Energy Storage Science and Technology, 2020, 9(6): 1702-1713.

Figures/Tables 13

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References 38

1	CHIANG Y M. Building a better battery[J]. Science, 2010, 330(6010): 1485-1486.
2	FERGUS J W. Recent developments in cathode materials for lithium ion batteries[J]. Journal of Power Sources, 2010, 195(4): 939-954.
3	KIM Junhyeok, Hyomyung LEE, Hyungyeon CHA, et al. Prospect and reality of Ni-rich cathode for commercialization[J]. Advanced Energy Materials, 2018, 8(6): doi: 10.1002/aenm.201702028.
4	KIM Yongseon, KIM Doyu. Synthesis of high-density nickel cobalt aluminum hydroxide by continuous coprecipitation method[J]. ACS Applied Materials & Interfaces, 2012, 4(2): 586-589.
5	MA Fei, WU Yinghong, WEI Guangye, et al. Comparative study of simple and concentration gradient shell coatings with Li_1.2Ni_0.13Mn_0.54Co_0.13O₂ on LiNi_0.8Mn_0.1Co_0.1O₂ cathodes for lithium-ion batteries[J]. Solid State Ionics, 2019, 341: doi: 10.1016/j.ssi.2019.115034.
6	SHIM Jae Hyun, KIM Chang Yeon, Sang Woo CHO, et al. Effects of heat-treatment atmosphere on electrochemical performances of Ni-rich mixed-metal oxide (LiNi_0.80Co_0.15Mn_0.05O₂) as a cathode material for lithium ion battery[J]. Electrochimica Acta, 2014, 138: 15-21.
7	WATANABE S, KINOSHITA M, HOSOKAWA T, et al. Capacity fade of LiAl_yNi_1-_x_-_yCo_xO₂ cathode for lithium-ion batteries during accelerated calendar and cycle life tests[J]. Journal of Power Sources, 2014, 258: 210-217.
8	DOKKO K, NISHIZAWA M, HORIKOSHI S, et al. In situ observation of LiNiO₂ single-particle fracture during Li-ion extraction and insertion[J]. Electrochemical and Solid-State Letters, 2000, 3(3): 125-127.
9	AURBACH D. Review of selected electrode-solution interactions which determine the performance of Li and Li ion batteries[J]. Journal of Power Sources, 2000, 89(2): 206-218.
10	LI Hongyang, LI Jing, MA Xiaowei, et al. Synthesis of single crystal LiNi_0.6Mn_0.2Co_0.2O₂ with enhanced electrochemical performance for lithium ion batteries[J]. Journal of the Electrochemical Society, 2018, 165(5): A1038-A1045.
11	LI Jing, CAMERON A R, LI Hongyang, et al. Comparison of single crystal and polycrystalline LiNi_0.5Mn_0.3Co_0.2O₂ positive electrode materials for high voltage Li-ion cells[J]. Journal of The Electrochemical Society, 2017, 164(7): A1534-A1544.
12	KIM Yongseon. Lithium nickel cobalt manganese oxide synthesized using alkali chloride flux: morphology and performance as a cathode material for lithium ion batteries[J]. ACS Applied Materials & Interfaces, 2012, 4(5): 2329-2333.
13	WU Kang, LI Qi, DANG Rongbin, et al. A novel synthesis strategy to improve cycle stability of LiNi_0.8Mn_0.1Co_0.1O₂ at high cut-off voltages through core-shell structuring[J]. Nano Research, 2019, 12(10): 2460-2467.
14	LI Xiangqun, XIONG Xunhui, WANG Zhixing, et al. Effect of sintering temperature on cycling performance and rate performance of LiNi_0.8Co_0.1Mn_0.1O₂[J]. Transactions of Nonferrous Metals Society of China, 2014, 24(12): 4023-4029.
15	LI Yan, XU Rui, REN Yang, et al. Synthesis of full concentration gradient cathode studied by high energy X-ray diffraction[J]. Nano Energy, 2016, 19: 522-531.
16	JIANG Xuyin, CHU Shiyong, CHEN Yubo, et al. LiNi_0.29Co_0.33Mn_0.38O₂ polyhedrons with reduced cation mixing as a high-performance cathode material for Li-ion batteries synthesized via a combined co-precipitation and molten salt heating technique[J]. Journal of Alloys and Compounds, 2017, 691: 206-214.
17	SATYANARAYANA M, JAMES J, VARADARAJU U. Electrochemical performance of LiNi_0.4Co_0.2Mn_0.4O₂ prepared by different molten salt flux: LiNO₃-LiCl and LiNO₃-KNO₃[J]. Applied Surface Science, 2017, 418: 72-78.
18	ZHAO Xuan, REDDY M, LIU Hanxing, et al. Layered Li(Ni_0.2Mn_0.2Co_0.6)O₂ synthesized by a molten salt method for lithium-ion batteries[J]. RSC Advances, 2014, 4(47): 24538-24543.
19	LACMANN R, HERDEN A, MAYER C. Kinetics of nucleation and crystal growth[J]. Chemical Engineering & Technology, 1999, 22(4): 279-289.
20	OHZUKU T, BRODD R J. An overview of positive-electrode materials for advanced lithium-ion batteries[J]. Journal of Power Sources, 2007, 174(2): 449-456.
21	DING Yin, WANG Rui, WANG Lei, et al. A short review on layered LiNi_0.8Co_0.1Mn_0.1O₂ positive electrode material for lithium-ion batteries[J]. Energy Procedia, 2017, 105: 2941-2952.
22	DUAN Jianguo, WU Ceng, CAO Yanbing, et al. Enhanced compacting density and cycling performance of Ni-riched electrode via building mono dispersed micron scaled morphology[J]. Journal of Alloys and Compounds, 2017, 695: 91-99.
23	FU Chaochao, LI Guangshe, LUO Dong, et al. Nickel-rich layered microspheres cathodes: lithium/nickel disordering and electrochemical performance[J]. ACS Applied Materials & Interfaces, 2014, 6(18): 15822-15831.
24	LI Xing, ZHANG Kangjia, WANG Siyuan, et al. Optimal synthetic conditions for a novel and high performance Ni-rich cathode material of LiNi_0.68Co_0.10Mn_0.22O₂[J]. Sustainable Energy & Fuels, 2018, 2(8): 1772-1780.
25	HWANG Bing Joe, SANTHANAM R, CHEN Chinh Hsiang. Effect of synthesis conditions on electrochemical properties of LiNi_1-_yCo_yO₂ cathode for lithium rechargeable batteries[J]. Journal of Power Sources, 2003, 114(2): 244-252.
26	ZHU Xinhua, ZHOU Jun, JIANG Mengchao, et al. Molten salt synthesis of bismuth ferrite nano and microcrystals and their structural characterization[J]. Journal of the American Ceramic Society, 2014, 97(7): 2223-2232.
27	YANG Chaofan, HUANG Junjie, HUANG Liangai, et al. Electrochemical performance of LiCo_1/3Mn_1/3Ni_1/3O₂ hollow spheres as cathode material for lithium ion batteries[J]. Journal of Power Sources, 2013, 226: 219-222.
28	KWON Soon Gu, HYEON Taeghwan. Formation mechanisms of uniform nanocrystals via hot-injection and heat-up methods[J]. Small, 2011, 7(19): 2685-2702.
29	WANG Lei, WU Borong, MU Daobin, et al. Single-crystal LiNi_0.6Co_0.2Mn_0.2O₂ as high performance cathode materials for Li-ion batteries[J]. Journal of Alloys and Compounds, 2016, 674: 360-367.
30	Duc Luong VU, Jae Won LEE. Properties of LiNi_0.8Co_0.1Mn_0.1O₂ as a high energy cathode material for lithium-ion batteries[J]. Korean Journal of Chemical Engineering, 2016, 33(2): 514-526.
31	KANG Jian, TAKAI S, YABUTSUKA T, et al. Structural relaxation of Li_x(Ni_0.874Co_0.090Al_0.036)O₂ after lithium extraction down to x= 0.12[J]. Materials, 2018, 11(8): doi: 10.1149/2.0211903jes.
32	HUANG Bin, LI Xinhai, WANG Zhixing, et al. Synthesis of Mg-doped LiNi_0.8Co_0.15Al_0.05O₂ oxide and its electrochemical behavior in high-voltage lithium-ion batteries[J]. Ceramics International, 2014, 40(8): 13223-13230.
33	LIANG Longwei, JIANG Feng, CAO Yanbing, et al. One strategy to enhance electrochemical properties of Ni-based cathode materials under high cut-off voltage for Li-ion batteries[J]. Journal of Power Sources, 2016, 328: 422-432.
34	YANG Xinhe, SHEN Lanyao, WU Bin, et al. Improvement of the cycling performance of LiCoO₂ with assistance of cross-linked PAN for lithium ion batteries[J]. Journal of Alloys and Compounds, 2015, 639: 458-464.
35	DU Ke, GUO Hongwei, HU Guorong, et al. Na₃V(PO₄)₃ as cathode material for hybrid lithium ion batteries[J]. Journal of Power Sources, 2013, 223: 284-288.
36	XIAO Biwei, WANG Kuan, XU Guiliang, et al. Revealing the atomic origin of heterogeneous Li-ion diffusion by probing Na[J]. Advanced Materials, 2019, 31(29): doi: 10.1002/adma.201805889.
37	MIAO Xiaowei, NI Huan, ZHANG Han, et al. Li₂ZrO₃-coated 0.4Li₂MnO₃·0.6LiNi_1/3Co_1/3Mn_1/3O₂ for high performance cathode material in lithium-ion battery[J]. Journal of Power Sources, 2014, 264: 147-154.
38	LV Yeting, CHENG Xu, QIANG Wenjiang, et al. Improved electrochemical performances of Ni-rich LiNi_0.83Co_0.12Mn_0.5O₂ by Mg-doping[J]. Journal of Power Sources, 2020, 450: doi: 10.1016/j.jpowsour.2020.227718.

样品	a/?	c/?	R_wp/%	R_p/%	阳离子混排程度/%
NCM-800-1	2.87	14.21	1.61	1.18	5.42
NCM-800-2	2.87	14.20	1.74	1.25	2.21
NCM-800-3	2.87	14.21	1.46	1.11	2.95
NCM-800-4	2.87	14.22	1.40	1.09	3.97

样品	摩尔比 (ref. O = 2.0000)
样品	Li	Ni	Co	Mn	O
理想值	1.0000	0.8000	0.1000	0.1000	2.0000
NCM-800-2	0.9740	0.8010	0.0985	0.1000	2.0000

参数	循环前		循环100圈后
参数	NCM-S0	NCM-800-2	NCM-S0	NCM-800-2
R_s /Ω	1.65	1.67	2.35	2.04
R_SEI /Ω	15.39	4.06	36.48	34.00
R_ct /Ω	222.70	101.90	318.80	99.91
D_Li⁺(×10^-12)/cm²·s^-1	0.622	1.04	49.6	423

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Synthesis of single-crystal LiNi_0.8Co_0.1Mn_0.1O₂ by flux method

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