Dual-Decoration and Mechanism Analysis of Ni-rich LiNi0.83Co0.11Mn0.06O2 Cathodes by Na2PO3F

doi:10.6023/A21100477

Acta Chimica Sinica ›› 2022, Vol. 80 ›› Issue (2): 150-158.DOI: 10.6023/A21100477 Previous Articles Next Articles

Article

Na₂PO₃F对LiNi_0.83Co_0.11Mn_0.06O₂材料的复合改性及机理分析

黄擎^a^,^b, 丁瑞^a^,^b, 陈来^a^,^b^,^*(), 卢赟^a^,^b, 石奇^a^,^b, 张其雨^a^,^b, 聂启军^a^,^b, 苏岳锋^a^,^b^,^*(), 吴锋^a^,^b

a 北京理工大学材料学院环境科学与工程北京市重点实验室北京 100081
b 北京理工大学重庆创新中心重庆 401120

投稿日期:2021-10-26 发布日期:2022-01-18
通讯作者: 陈来, 苏岳锋
基金资助:
国家自然科学基金(2217090605); 国家自然科学基金(21875022); 国家自然科学基金(51802020); 重庆市自然科学基金(cstc2020jcyj-msxmX0654); 重庆市自然科学基金(cstc2020jcyj-msxmX0589); 中国科学技术协会青年人才托举计划(2018QNRC001); 北京理工大学“青年教师学术启动计划”

Dual-Decoration and Mechanism Analysis of Ni-rich LiNi_0.83Co_0.11Mn_0.06O₂ Cathodes by Na₂PO₃F

Qing Huang^a^,^b, Rui Ding^a^,^b, Lai Chen^a^,^b(), Yun Lu^a^,^b, Qi Shi^a^,^b, Qiyu Zhang^a^,^b, Qijun Nie^a^,^b, Yuefeng Su^a^,^b(), Feng Wu^a^,^b

a School of Materials Science and Engineering, Beijing Key Laboratory of Environmental Science and Engineering, Beijing Institute of Technology, Beijing 100081
b Beijing Institute of Technology Chongqing Innovation Center, Chongqing 401120

Received:2021-10-26 Published:2022-01-18
Contact: Lai Chen, Yuefeng Su
Supported by:
National Natural Science Foundation of China(2217090605); National Natural Science Foundation of China(21875022); National Natural Science Foundation of China(51802020); Natural Science Foundation of Chongqing, China(cstc2020jcyj-msxmX0654); Natural Science Foundation of Chongqing, China(cstc2020jcyj-msxmX0589); Young Elite Scientists Sponsorship Program by China Association for Science and Technology, China(2018QNRC001); L. Chen acknowledges the support from Beijing Institute of Technology Research Fund Program for Young Scholars

Since the commercialization of lithium-ion battery in 1991, it has promoted human society development for nearly three decades. Due to its higher energy density, Ni-rich layered oxides currently stand out as the most promising cathode materials to build power batteries for portable electronic devices and new energy electric vehicles. However, the severe side effects on the electrode/electrolyte interface and the structural instability of the material hinder its development, and a lot of research focus on improving the cycling stability and rate capability of nickel-rich cathode material. Here, a facile treatment with Na₂PO₃F was carried out to modify the Ni-rich LiNi_0.83Co_0.11Mn_0.06O₂ material at surface and bulk regions by using wet methods. By virtue of the fact that Na₂PO₃F dissolves in water and releases fluorine ions, a F^– doped and LiF coated Ni-rich LiNi_0.83Co_0.11Mn_0.06O₂ material was obtained. The X-ray diffraction (XRD) results showed that (003) peak shifted to a higher angle due to the replacement of O^2– by smaller F^–. Besides, the XRD Rietveld refinement and X-ray photoelectron spectroscopy (XPS) sputtering data determined that part of F^– ions had been successfully doped into the lattice, and the basic layer structure of the material was still well preserved in the process of modification. Scanning electron microscope (SEM), energy disperse spectroscopy (EDS), and transmission electron microscope (TEM) combined with XPS proved the existence of surface LiF coating layer. The 2~10 nm LiF layer was uniformly covered onto the surface of the cathode material, acting as a physical barrier against direct corrosion from the electrolyte, thus enhancing the cycling stability. In addition, the lithium ion diffusion coefficients (D_Li⁺) for bare and modified samples were calculated from cyclic voltammetry test results, which reveals a better rate capability from the synergistic effect of surface LiF coating and lattice F^– doping. The electrochemical tests also showed a better cycling stability and enhanced rate capability of the modified samples: within 2.75~4.3 V, the capacity retention after 200 cycles at 1 C-rate had been elevated from 32.2% to 65.2%; the discharge capacity under 10 C-rate was also improved from 145.7 to 161.5 mAh/g. To elaborate the improved effect, post-cycling characterizations were conducted. The morphology of modified particles after 200 cycles at 1 C still maintained intact grains, in contrast with the bare samples, exhibiting many micro-cracks. XPS spectra on decorated cathodes after cycling showed weaker signals of by-products including LiF, Li_xPO_yF_z, NiF₂ in the CEI layer, indicating side reaction on the interface was effectively suppressed, thus contributing to enhancing the cycling stability. The applicable method herein demonstrates a promising solution for improvement of Ni-rich cathode materials and their coming commercial application.

Key words: lithium-ion batteries, nickel-rich cathode, LiF coating, F^– doping, cycling stability, rate performance

Cite this article

Qing Huang, Rui Ding, Lai Chen, Yun Lu, Qi Shi, Qiyu Zhang, Qijun Nie, Yuefeng Su, Feng Wu. Dual-Decoration and Mechanism Analysis of Ni-rich LiNi_0.83Co_0.11Mn_0.06O₂ Cathodes by Na₂PO₃F[J]. Acta Chimica Sinica, 2022, 80(2): 150-158.

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Fig. & Tab. 12

Element	F-0	F-1
Li/%	1.0539	1.0192
Ni/%	0.8285	0.8286
Co/%	0.1137	0.1142
Mn/%	0.0577	0.0572
Na/%	—	0.0002
P/%	—

Table 1. Elemental composition of F-0 and F-1

Figure 1. (a) XRD patterns and (b) magnification of the (003) peaks of F-0, F-0.5, F-1 and F-2; XRD Rietveld refinement results of (c) F-0 and (d) F-1

Parameter	F-0	F-1
a/nm	0.28699	0.28718
c/nm	1.41955	1.41949
Unit volume/nm³	0.10125	0.10138
c∶a	4.946	4.943
R_wp/%	1.61	1.62
R_p/%	1.01	1.14

Table 2. The results of rietveld refinement for F-0 and F-1

Figure 2. SEM images of (a) F-0, (b) F-0.5, (c) F-1 and (d) F-2

Figure 3. EDS mapping of F-1

Figure 4. TEM images of (a) F-0 and (b) F-1; (c~g) element mapping of F-1

Figure 5. XPS patterns of F-0 and F-1 samples (a) Ni 2p, (b) O 1s, (c) Li 1s; (d) F 1s of F-1

Figure 6. CV curves of (a) F-0, (b) F-0.5, (c) F-1 and (d) F-2 with a scan rate of 0.2 mV•s–1

Figure 7. (a) Initial charge-discharge curves; (b) cycling performance at 0.2 C rate; (c) cycling performance at 1 C; (d) cycling performance at 1 C, 2.75~4.5 V; (e) capacity retention of 1 C at 2.75~4.5 V; (f) rate performance comparison

Figure 8. CV curves of (a) F-0 and (b) F-1 at various scan rates; (c) fitting diagram of diffusion coefficient of Li+

Figure 9. SEM images of F-0 and F-1 samples after 200 cycles: (a) F-0, (b) F-1

Figure 10. XPS patterns of F-0 and F-1 samples after 200 cycles: (a) F 1s, (b) C 1s, (c) Ni 2p

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Na₂PO₃F对LiNi_0.83Co_0.11Mn_0.06O₂材料的复合改性及机理分析

Dual-Decoration and Mechanism Analysis of Ni-rich LiNi_0.83Co_0.11Mn_0.06O₂ Cathodes by Na₂PO₃F

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