Preparation and Electrochemical Performance of Macroporous Ni-rich LiNi0.8Co0.1Mn0.1O2 Cathode Material

doi:10.6023/A21010019

Abstract

High-performance rechargeable lithium-ion batteries (LIBs) have been widely applied in electrochemical energy storage fields. In recent years, Ni-rich ternary cathode materials have received considerable attention due to their low cost and high theoretical specific capacity, and they are regarded as promising candidates for the next-generation lithium-ion batteries. In this paper, macroporous Ni-rich LiNi_0.8Co_0.1Mn_0.1O₂(NCM811) cathode material has been successfully prepared by using a poly(methyl methacrylate) (PMMA) colloidal crystal template and sol-gel method. The typical experimental procedure for the synthesis of macroporous LiNi_0.8Co_0.1Mn_0.1O₂ is as follows: Firstly, a stoichiometric mixture of LiNO₃, (CH₃COO)₂Mn∙4H₂O, (CH₃COO)₂Co∙4H₂O, and (CH₃COO)₂Ni∙4H₂O were dissolved together in ethanol for 1 h. Acetylacetone was then drop by drop into the prepared solution under continuous stirring for 1.5 h (a molar ratio of acetylacetone to transition metal ions was 1∶1). Then, the LiNi_0.8Co_0.1Mn_0.1O₂sol was infiltrated completely into PMMA template under vacuum. After that, the as-prepared product was filtrated and dried at 50 ℃, followed by a heat treatment at 450 ℃ for 2 h for removing the PMMA template, and then calcined at 700 ℃ under a flowing oxygen atmosphere. These results suggest that the macroporous architecture stacked by the 100 nm particles is obtained by using the pore-forming agent PMMA, and this structure is beneficial to improve the rate capability and cycling stability of the Ni-rich cathode materials. Specifically, macroporous NCM811 delivers an initial discharge capacity of 190.3 mAh∙g^-1 between 2.7 V and 4.3 V at 0.1C rate. The discharge specific capacity of the nanoparticle NCM811 is only 129.3 mAh∙g^-1 at 2C rate, whereas the macroporous NCM811 is 149.8 mAh∙g^-1 at the same rate. In addition, macroporous NCM811 can still delivers a high discharge specific capacity of 111.7 mAh∙g^-1 at 10C rate. Macroporous NCM811 also exhibits superior capacity retention of 83.02% after 400 cycles at 0.5C rate, surpassing the 38.59% of nanoparticle NCM811 obviously. The macroporous architecture is conducive to shorten the transport distance of lithium ions and electrons, suppress the phase transition and structural deterioration resulting from the frequent Li⁺ insertion/deinsertion, reduce polarization, and thus improving the electrochemical performances, which provides new insights for the development of high-energy-density lithium-ion batteries.

Key words: lithium-ion batteries, cathode material, colloidal crystal template, macroporous, LiNi_0.8Co_0.1Mn_0.1O₂

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Tongxin Li, Donglin Li, Qingbo Zhang, Jianhang Gao, Xiangze Kong, Xiaoyong Fan, Lei Gou. Preparation and Electrochemical Performance of Macroporous Ni-rich LiNi_0.8Co_0.1Mn_0.1O₂ Cathode Material[J]. Acta Chimica Sinica, 2021, 79(5): 678-684.

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Fig. & Tab. 11

Figure 1. XRD patterns of (a) the precursor of NCM811 after calcination at 450 ℃ and (b) nanoparticle and macroporous NCM811 samples; XRD Rietveld refinement results of (c) nanoparticle and (d) macroporous NCM811 samples

样品	a/nm	c/nm	c/a	I₍₀₀₃₎/I₍₁₀₄₎
NCM811纳米颗粒	0.28735	1.42109	4.9455	1.227
大孔NCM811	0.28741	1.42237	4.9489	1.426

Table 1. The lattice parameters of nanoparticle and macroporous NCM811 samples

Parameter	NCM811纳米颗粒	大孔NCM811
Li1(3a)	0.9468	0.9611
Ni1(3a)	0.0532	0.0389
Li2(3b)	0.0532	0.0389
Ni2(3b)	0.7468	0.7611
Co1(3b)	0.1000	0.1000
Mn1(3b)	0.1000	0.1000
O1(6c)	1.0000	1.0000
Ni在Li位的占比/%	5.32	3.89
R_p/%	6.21	6.25
R_wp/%	7.94	7.92
χ²	1.144	1.130

Table 2. XRD Rietveld refinement results of nanoparticle and macroporous NCM811 samples

Figure 2. SEM images of (a, b) nanoparticle and (c, d) macroporous NCM811 material at different magnifications

Figure 3. EDS elemental mapping of nanoparticle NCM811

Figure 4. Initial charge-discharge curves of nanoparticle and macroporous NCM811 at 0.1C

Figure 5. (a) Rate performance comparison, charge-discharge curves of (b) nanoparticle and (c) macroporous NCM811 at different rates

Figure 6. CV curves of (a) nanoparticle and (b) macroporous NCM811 electrodes

Figure 7. (a) Cycling performance at 0.5C rate, dQ/dV curves of (b) nanoparticle and (c) macroporous NCM811 at different cycles

Figure 8. (a) Nyquist plots after 115 cycles with an equivalent circuit (inset) and (b) the relationship plots between Z′ and ω-1/2 of nanoparticle and macroporous NCM811 electrodes

样品	Cycle	R_s/Ω	R_ct/Ω
NCM811纳米颗粒	115	2.246	66.52
大孔NCM811	115	3.621	10.94

Table 3. Impedance parameters of the nanoparticle and macroporous NCM811 electrodes after fitting

References 42

[1]	Lee, J.; Kitchaev, D.-A.; Kwon, D.-H.; Lee, C.-W.; Papp, J.-K.; Liu, Y.-S.; Lun, Z.-Y.; Clément, R.-J.; Shi, T.; McCloskey, B.-D.; Guo, J.-H.; Balasubramanian, M.; Ceder, G. Nature 2018, 556,185. doi: 10.1038/s41586-018-0015-4
[2]	Qiao, Q.-Q.; Zhang, H.-Z.; Li, G.-R.; Ye, S.-H.; Wang, C.-W.; Gao, X.-P. J. Mater. Chem. A 2013, 1,5262. doi: 10.1039/c3ta00028a
[3]	Liu, J.-D.; Zhang, Y.-D.; Liu, J.-X.; Li, J.-H.; Qiu, X.-G.; Cheng, F.-Y. Acta Chim. Sinica 2020, 78,1426. (in Chinese). doi: 10.6023/A20070330
	( 刘九鼎, 张宇栋, 刘俊祥, 李金瀚, 邱晓光, 程方益, 化学学报, 2020, 78,1426.) doi: 10.6023/A20070330
[4]	Li, Z.; Wang, Z.; Ban, L.-Q.; Wang, J.-T.; Lu, S.-G. Acta Chim. Sinica 2019, 77,1115. (in Chinese). doi: 10.6023/A19070265
	( 李钊, 王忠, 班丽卿, 王建涛, 卢世刚, 化学学报, 2019, 77,1115.) doi: 10.6023/A19070265
[5]	Zheng, J.-C.; Yang, Z.; He, Z.-J.; Tong, H.; Yu, W.-J.; Zhang, J.-F. Nano Energy 2018, 53,613. doi: 10.1016/j.nanoen.2018.09.014
[6]	Liu, Y.-Y.; Yang, Z.; Li, J.-L.; Niu, B.-B.; Yang, K.; Kang, F.-Y. J. Mater. Chem. A 2018, 6,13883. doi: 10.1039/C8TA04568B
[7]	Zhang, X.-D.; Hao, J.-J.; Wu, L.-C.; Guo, Z.-M.; Ji, Z.-H.; Luo, J.; Chen, C.-G.; Shu, J.-F.; Long, H.-M.; Yang, F.; Volinsky, A.-A. Electrochim. Acta 2018, 283,1203. doi: 10.1016/j.electacta.2018.07.057
[8]	Li, Y.-C.; Zhao, W.-M.; Xiang, W.; Wu, Z.-G.; Yang, Z.-G.; Xu, C.-L.; Xu, Y.-D.; Wang, E.-H.; Wu, C.-J.; Guo, X.-D. J. Alloys Compd. 2018, 766,546. doi: 10.1016/j.jallcom.2018.06.364
[9]	Xu, X.; Huo, H.; Jian, J.-Y.; Wang, L.-G.; Zhu, H.; Xu, S.; He, X.-S.; Yin, G.-P.; Du, C.-Y.; Sun, X.-L. Adv. Energy Mater. 2019, 9,1803963. doi: 10.1002/aenm.v9.15
[10]	Zou, P.-J.; Lin, Z.-H.; Fan, M.-N.; Wang, F.; Liu, Y.; Xiong, X.-H. Appl. Surf. Sci. 2020, 504,144506. doi: 10.1016/j.apsusc.2019.144506
[11]	Su, Y.-F.; Chen, G.; Chen, L.; Li, W.-K.; Zhang, Q.-Y.; Yang, Z.-R.; Lu, Y.; Bao, L.-Y.; Tan, J.; Chen, R.-J.; Chen, S.; Wu, F. ACS Appl. Mater. Interfaces 2018, 10,6407. doi: 10.1021/acsami.7b18933
[12]	Chen, T.; Wang, F.; Li, X.; Yan, X.-X.; Wang, H.; Deng, B.-W.; Xie, Z.-W.; Qu, M.-Z. Appl. Surf. Sci. 2019, 465,863. doi: 10.1016/j.apsusc.2018.09.250
[13]	Huang, B.; Wang, M.; Zhang, X.-W.; Zhao, Z.-Y.; Chen, L.; Gu, Y.-J. J. Alloys Compd. 2020, 830,154619. doi: 10.1016/j.jallcom.2020.154619
[14]	Yang, H.-P.; Wu, H.-H.; Ge, M.-Y.; Li, L.-J.; Yuan, Y.-F.; Yao, Q.; Chen, J.; Xia, L.-F.; Zheng, J.-M.; Chen, Z.-Y.; Duan, J.-F.; Kisslinger, K.; Zeng, X.-C.; Lee, W.-K.; Zhang, Q.-B.; Lu, J. Adv. Funct. Mater. 2019, 29,1808825. doi: 10.1002/adfm.v29.13
[15]	Zhu, H.-W.; Yu, H.-F.; Jiang, H.-B.; Hu, Y.-J.; Jiang, H.; Li, C.-Z. Chem. Eng. Sci. 2020, 217,115518. doi: 10.1016/j.ces.2020.115518
[16]	Ryu, H.-H.; Park, K.-J.; Yoon, D.-R.; Aishova, A.; Yoon, C.-S.; Sun, Y.-K. Adv. Energy Mater. 2019, 9,1902698. doi: 10.1002/aenm.v9.44
[17]	Song, B.-H.; Li, W.-D.; Oh, S.-M.; Manthiram, A. ACS Appl. Mater. Interfaces 2017, 9,9718. doi: 10.1021/acsami.7b00070
[18]	Wang, M.; Zhang, R.; Gong, Y.-Q.; Su, Y.-F.; Xiang, D.-B.; Chen, L.; Chen, Y.-B.; Luo, M.; Chu, M. Solid State Ionics 2017, 312,53. doi: 10.1016/j.ssi.2017.10.017
[19]	Kong, J.-Z.; Zhai, H.-F.; Ren, C.; Gao, M.-Y.; Zhang, X.; Li, H.; Li, J.-X.; Tang, Z.; Zhou, F. J. Alloys Compd. 2013, 577,507. doi: 10.1016/j.jallcom.2013.07.007
[20]	Li, D.-L.; Tian, M.; Xie, R.; Li, Q.; Fan, X.-Y.; Gou, L.; Zhao, P.; Ma, S.-L.; Shi, Y.-X.; Yong, H.-T.-H. Nanoscale 2014, 6,3302. doi: 10.1039/c3nr04927b
[21]	Li, S.; Ma, G.; Guo, B.; Yang, Z.-H.; Fan, X.-M.; Chen, Z.-X.; Zhang, W.-X. Ind. Eng. Chem. Res. 2016, 55,9352. doi: 10.1021/acs.iecr.6b02463
[22]	Li, L.-J.; Xu, M.; Yao, Q.; Chen, Z.-Y.; Song, L.-B.; Zhang, Z.-A.; Gao, C.-H.; Wang, P.; Yu, Z.-Y.; Lai, Y.-Q. ACS Appl. Mater. Interfaces 2016, 8,30879. doi: 10.1021/acsami.6b09197
[23]	Ren, D.; Yang, Y.; Shen, L.-X.; Zeng, R.; Abruña, H.-D. J. Power Sources 2020, 447,227344. doi: 10.1016/j.jpowsour.2019.227344
[24]	Su, Y.-F.; Zhang, Q.-Y.; Chen, L.; Bao, L.-Y.; Lu, Y.; Chen, S.; Wu, F. Acta Phys.-Chim. Sin. 2021, 37,1. (in Chinese).
	( 苏岳锋, 张其雨, 陈来, 包丽颖, 卢赟, 陈实, 吴锋, 物理化学学报, 2021, 37,1.)
[25]	Gao, S.; Cheng, Y.-T.; Shirpour, M. ACS Appl. Mater. Interfaces 2019, 11,982. doi: 10.1021/acsami.8b19349
[26]	Liu, W.; Li, X.-F.; Xiong, D.-B.; Hao, Y.-C.; Li, J.-W.; Kou, H.-R.; Yan, B.; Li, D.-J.; Lu, S.-G.; Koo, A.; Adair, K.; Sun, X.-L. Nano Energy 2018, 44,111. doi: 10.1016/j.nanoen.2017.11.010
[27]	Tang, Z.-H.; Zheng, H.-H.; Qian, F.-P.; Ma, Y.-H.; Zhao, C.-Y.; Song, L.-B.; Chen, Y.; Xiong, X.; Zhu, X.-X.; Mi, C. Ionics 2018, 24,61. doi: 10.1007/s11581-017-2179-6
[28]	Luo, D.; Li, G.-S.; Fu, C.-C.; Zheng, J.; Fan, J.-M.; Li, Q.; Li, L.-P. Adv. Energy Mater. 2014, 4,1400062. doi: 10.1002/aenm.201400062
[29]	Wang, H.; Ge, W.-J.; Li, W.; Wang, F.; Liu, W.-J.; Qu, M.-Z.; Peng, G.-C. ACS Appl. Mater. Interfaces 2016, 8,18439. doi: 10.1021/acsami.6b04644
[30]	Aishova, A.; Park, G.-T.; Yoon, C.-S.; Sun, Y.-K. Adv. Energy Mater. 2020, 10,1903179. doi: 10.1002/aenm.v10.4
[31]	Song, X.; Liu, G.-X.; Yue, H.-F.; Luo, L.; Yang, S.-Y.; Huang, Y.-Y.; Wang, C.-R. Chem. Eng. J. 2021, 407,126301. doi: 10.1016/j.cej.2020.126301
[32]	Zheng, Z.; Wu, Z.-G.; Xiang, W.; Guo, X.-D. Acta Chim. Sinica 2017, 75,501. (in Chinese). doi: 10.6023/A16110594
	( 郑卓, 吴振国, 向伟, 郭孝东, 化学学报, 2017, 75,501.) doi: 10.6023/A16110594
[33]	Zhu, X.-J.; Chen, H.-H.; Zhan, H.; Liu, H.-X.; Yang, D.-L.; Zhou, Y.-H. Chin. J. Chem. 2005, 23,491. doi: 10.1002/(ISSN)1614-7065
[34]	Song, J.-W.; Kim, J.-Y.; Kang, T.-W.; Kim, D.-C. Sci. Rep. 2017, 7,42521. doi: 10.1038/srep42521
[35]	Ho, V.-C.; Jeong, S.-H.; Yim, T.; Mun, J.-Y. J. Power Sources 2020, 450,227625. doi: 10.1016/j.jpowsour.2019.227625
[36]	Ding, G.-Y.; Gao, Y.; Li, Y.-H.; Zhu, Z.; Wang, Q.-L.; Jing, X.-G.; Yan, F.-Q.; Xu, G.-J.; Yue, Z.-H.; Li, X.-M.; Sun, F.-G. Chin. J. Inorg. Chem. 2020, 36,2307. (in Chinese).
	( 丁国彧, 高远, 李亚辉, 朱振, 王秋琳, 景鑫国, 严奉乾, 徐国军, 岳之浩, 李晓敏, 孙福根, 无机化学学报, 2020, 36,2307.)
[37]	He, Y.-L.; Li, Y.; Liu, Y.; Li, W.-X.; Liu, W.-B. Mater. Chem. Phys. 2020, 251,123085. doi: 10.1016/j.matchemphys.2020.123085
[38]	Yao, W.-L.; Liu, Y.; Li, D.; Zhang, Q.; Zhong, S.-W.; Cheng, H.-W.; Yan, Z.-Q. J. Phys. Chem. C 2020, 124,2346. doi: 10.1021/acs.jpcc.9b10526
[39]	Sim, S.-J.; Lee, S.-H.; Jin, B.-S.; Kim, H.-S. Sci. Rep. 2019, 9,8952. doi: 10.1038/s41598-019-45556-7
[40]	Wu, Z.-Z.; Ji, S.-P.; Liu, T.-C.; Duan, Y.-D.; Xiao, S.; Lin, Y.; Xu, K.; Pan, F. Nano Lett. 2016, 16,6357. doi: 10.1021/acs.nanolett.6b02742
[41]	Zhu, W.; Tai, Z.-G.; Shu, C.-Y.; Chong, S.-K.; Guo, S.-W.; Ji, L.-J.; Chen, Y.-Z.; Liu, Y.-N. J. Mater. Chem. A 2020, 8,7991. doi: 10.1039/D0TA00355G
[42]	Li, L.-J.; Chen, Z.-Y.; Zhang, Q.-B.; Xu, M.; Zhou, X.; Zhu, H.-L.; Zhang, K.-L. J. Mater. Chem. A 2015, 3,894. doi: 10.1039/C4TA05902F

大孔高镍LiNi_0.8Co_0.1Mn_0.1O₂正极材料的制备及其电化学性能研究

Preparation and Electrochemical Performance of Macroporous Ni-rich LiNi_0.8Co_0.1Mn_0.1O₂ Cathode Material

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大孔高镍LiNi0.8Co0.1Mn0.1O2正极材料的制备及其电化学性能研究