Cation-doped LiNi0.8Co0.1Mn0.1O2 cathode with high rate performance

doi:10.1016/j.cjche.2024.02.009

中国化学工程学报 ›› 2024, Vol. 70 ›› Issue (6): 139-148.DOI: 10.1016/j.cjche.2024.02.009

Cation-doped LiNi_0.8Co_0.1Mn_0.1O₂ cathode with high rate performance

Long Zhang^1,2, Dongsheng Yang³, Lilei Miao³, Chunmeng Zhang^1,2, Jiexiang Li^1,2, Jiawei Wen^1,2, Chunxia Wang^1,2, Tiantian Cao^4,5, Guoyong Huang^1,2, Shengming Xu^6,7

1. College of New Energy and Materials, China University of Petroleum, Beijing 102249, China;
2. State Key Laboratory of Heavy Oil Processing, College of Chemical Engineering, China University of Petroleum, Beijing 102249, China;
3. Beijing Spacecrafts, Beijing 100094, China;
4. SINOPEC Sales Co., Ltd., Beijing 100728, China;
5. SINOPEC Research Institute of Petroleum Processing Co., Ltd, Beijing 100083, China;
6. Institute of Nuclear and New Energy Technology, Tsinghua University, Beijing 100084, China;
7. Beijing Key Laboratary of Fine Ceramics, Tsinghua University, Beijing 100084, China

收稿日期:2023-11-15 修回日期:2024-01-16 出版日期:2024-06-28 发布日期:2024-08-05
通讯作者: Tiantian Cao,E-mail:aott65855@sinopec.com;Guoyong Huang,E-mail:huanggy@cup.edu.cn
基金资助:
This project was supported by the National Natural Science Foundation of China (52274307), National Key Research and Development Program of China (2021YFC2901100), Science Foundation of China University of Petroleum, Beijing (2462022QZDX008, 2462021QNX2010), State Key Laboratory of Heavy Oil Processing (HON-KFKT2022-10).

Cation-doped LiNi_0.8Co_0.1Mn_0.1O₂ cathode with high rate performance

Long Zhang^1,2, Dongsheng Yang³, Lilei Miao³, Chunmeng Zhang^1,2, Jiexiang Li^1,2, Jiawei Wen^1,2, Chunxia Wang^1,2, Tiantian Cao^4,5, Guoyong Huang^1,2, Shengming Xu^6,7

1. College of New Energy and Materials, China University of Petroleum, Beijing 102249, China;
2. State Key Laboratory of Heavy Oil Processing, College of Chemical Engineering, China University of Petroleum, Beijing 102249, China;
3. Beijing Spacecrafts, Beijing 100094, China;
4. SINOPEC Sales Co., Ltd., Beijing 100728, China;
5. SINOPEC Research Institute of Petroleum Processing Co., Ltd, Beijing 100083, China;
6. Institute of Nuclear and New Energy Technology, Tsinghua University, Beijing 100084, China;
7. Beijing Key Laboratary of Fine Ceramics, Tsinghua University, Beijing 100084, China

Received:2023-11-15 Revised:2024-01-16 Online:2024-06-28 Published:2024-08-05
Contact: Tiantian Cao,E-mail:aott65855@sinopec.com;Guoyong Huang,E-mail:huanggy@cup.edu.cn
Supported by:
This project was supported by the National Natural Science Foundation of China (52274307), National Key Research and Development Program of China (2021YFC2901100), Science Foundation of China University of Petroleum, Beijing (2462022QZDX008, 2462021QNX2010), State Key Laboratory of Heavy Oil Processing (HON-KFKT2022-10).

摘要/Abstract

摘要： The nickel-rich layered cathode material LiNi_0.8Co_0.1Mn_0.1O₂ (NCM811) has high energy density, lower cost and is a promising cathode material currently under development. However, its electrochemical and structural stability is poor during cycling. Among the many modification methods, cation doping has been consistently proven to be an effective strategy for enhancing electrochemical performance. Herein, the NCM811 cathode material was modified by solid-phase reactions with Mg and Al doped. In addition, the corresponding mechanism of NCM811 cathode material-doped modification is explored by density functional theory (DFT) calculations, and we have extended this approach to other ternary cathode materials with different ratios and obtained universal laws. Combined with DFT calculations, the results show that Mg²⁺ occupies the Li⁺ site and reduces the degree of Li⁺/Ni²⁺ mixture; Al³⁺ acts as a structural support during charging and discharging to prevent structural collapse. The electrochemical properties were tested by an electrochemical workstation and the LAND system, and the results showed that the capacity retention rate increased to varying degrees from 63.66% to 69.87% and 89.05% for NCM811-Mg and NCM811-Al at room temperature after 300 cycles, respectively. This study provides a theoretical basis and design strategy for commercializing cationic-doped modification of nickel-rich cathode materials.

关键词: Li-ion batteries, Cathode materials, Doped, Electrochemical properties, DFT calculation

Abstract: The nickel-rich layered cathode material LiNi_0.8Co_0.1Mn_0.1O₂ (NCM811) has high energy density, lower cost and is a promising cathode material currently under development. However, its electrochemical and structural stability is poor during cycling. Among the many modification methods, cation doping has been consistently proven to be an effective strategy for enhancing electrochemical performance. Herein, the NCM811 cathode material was modified by solid-phase reactions with Mg and Al doped. In addition, the corresponding mechanism of NCM811 cathode material-doped modification is explored by density functional theory (DFT) calculations, and we have extended this approach to other ternary cathode materials with different ratios and obtained universal laws. Combined with DFT calculations, the results show that Mg²⁺ occupies the Li⁺ site and reduces the degree of Li⁺/Ni²⁺ mixture; Al³⁺ acts as a structural support during charging and discharging to prevent structural collapse. The electrochemical properties were tested by an electrochemical workstation and the LAND system, and the results showed that the capacity retention rate increased to varying degrees from 63.66% to 69.87% and 89.05% for NCM811-Mg and NCM811-Al at room temperature after 300 cycles, respectively. This study provides a theoretical basis and design strategy for commercializing cationic-doped modification of nickel-rich cathode materials.

Key words: Li-ion batteries, Cathode materials, Doped, Electrochemical properties, DFT calculation

Long Zhang, Dongsheng Yang, Lilei Miao, Chunmeng Zhang, Jiexiang Li, Jiawei Wen, Chunxia Wang, Tiantian Cao, Guoyong Huang, Shengming Xu. Cation-doped LiNi_0.8Co_0.1Mn_0.1O₂ cathode with high rate performance[J]. 中国化学工程学报, 2024, 70(6): 139-148.

参考文献

[1] W. Xiao, J. Wang, L. Fan, J. Zhang, X. Li, Recent advances in Li_1+xAl_xTi_2-x(PO₄)₃ solid-state electrolyte for safe lithium batteries, Energy Storage Mater. 19 (2019) 379-400.
[2] G. Harper, R. Sommerville, E. Kendrick, L. Driscoll, P. Slater, R. Stolkin, A. Walton, P. Christensen, O. Heidrich, S. Lambert, A. Abbott, K. Ryder, L. Gaines, P. Anderson, Recycling lithium-ion batteries from electric vehicles, Nature 575 (7781) (2019) 75-86.
[3] F. Duffner, N. Kronemeyer, J. Tubke, J. Leker, M. Winter, R. Schmuch, Post-lithium-ion battery cell production and its compatibility with lithium-ion cell production infrastructure, Nat. Energy 6 (2) (2021) 123-134.
[4] T.F. Yi, T.T. Wei, Y. Li, Y.B. He, Z.B. Wang, Efforts on enhancing the Li-ion diffusion coefficient and electronic conductivity of titanate-based anode materials for advanced Li-ion batteries, Energy Storage Mater. 26 (2020) 165-197.
[5] D.D. Liu, C. Chen, X.H. Xiong, Research progress on artificial protective films for lithium metal anodes, Acta Phys. Chim. Sin. 37 (2) (2021) 202008078. (in Chinese).
[6] Q. Wu, B. Zhang, Y.Y. Lu, Progress and perspective of high-voltage lithium cobalt oxide in lithium-ion batteries, J. Energy Chem. 74 (2022) 283-308.
[7] J. Xia, N. Zhang, Y.J. Yang, X. Chen, X. Wang, F. Pan, J.N. Yao, Lanthanide contraction builds better high-voltage LiCoO₂ batteries, Adv. Funct. Mater. 33 (8) (2023) 2212869.
[8] S. Zhang, H.Y. Chen, J. Chen, S.Y. Yin, Y. Mei, L.S. Ni, A.D. Di, W.T. Deng, G.Q. Zou, H.S. Hou, X.B. Ji, Mitigating the Jahn-Teller distortion driven by the spin-orbit coupling of lithium manganate cathode, J. Energy Chem. 72 (2022) 379-387.
[9] L. Hong, L.S. Li, Y.K. Chen-Wiegart, J.J. Wang, K. Xiang, L.Y. Gan, W.J. Li, F. Meng, F. Wang, J. Wang, Y.M. Chiang, S. Jin, M. Tang, Two-dimensional lithium diffusion behavior and probable hybrid phase transformation kinetics in olivine lithium iron phosphate, Nat. Commun. 8 (1) (2017) 1194.
[10] L.Z. Wang, J. Qin, Z.M. Bai, H.M. Qian, Y.Y. Cao, H.M.K. Sari, Y.K. Xi, H. Shan, S. Wang, J.X. Zuo, X.H. Pu, W.B. Li, J.J. Wang, X.F. Li, Surface reconstruction of Ni-rich layered cathodes: in Situ doping versus Ex Situ doping, Small Struct. 3 (7) (2022) 2100233.
[11] Z. Si, B.Z. Shi, J. Huang, Y. Yu, Y. Han, J.L. Zhang, W. Li, Titanium and fluorine synergetic modification improves the electrochemical performance of Li(Ni_0.8Co_0.1Mn_0.1)O₂, J. Mater. Chem. A 9 (14) (2021) 9354-9363.
[12] Z.Z. Yu, Q.L. Tong, G.Q. Zhao, G.S. Zhu, B.B. Tian, Y. Cheng, Combining surface holistic Ge coating and subsurface Mg doping to enhance the electrochemical performance of LiNi_0.8Co_0.1Mn_0.1O₂ cathodes, ACS Appl. Mater. Interfaces 14 (22) (2022) 25490-25500.
[13] F. Schipper, H. Bouzaglo, M. Dixit, E.M. Erickson, T. Weigel, M. Talianker, J. Grinblat, L. Burstein, M. Schmidt, J. Lampert, C. Erk, B. Markovsky, D.T. Major, D. Aurbach, From surface ZrO₂ coating to bulk Zr doping by high temperature annealing of nickel-rich lithiated oxides and their enhanced electrochemical performance in lithium ion batteries, Adv. Energy Mater. 8 (4) (2018) 1701682.
[14] S. Na, K. Park, Hybrid dual conductor on Ni-rich NCM for superior electrochemical performance in Lithium-ion batteries, Int. J. Energy Res. 46 (6) (2022) 7389-7398.
[15] D.F. Kong, J.T. Hu, Z.F. Chen, K.P. Song, C. Li, M.Y. Weng, M.F. Li, R. Wang, T.C. Liu, J.J. Liu, M.J. Zhang, Y.G. Xiao, F. Pan, Ti-gradient doping to stabilize layered surface structure for high performance high-Ni oxide cathode of Li-ion battery, Adv. Energy Mater. 9 (41) (2019) 1901756.
[16] W.L. Yao, Y. Liu, D. Li, Q. Zhang, S.W. Zhong, H.W. Cheng, Z.Q. Yan, Synergistically enhanced electrochemical performance of Ni-rich cathode materials for lithium-ion batteries by K and Ti co-modification, 124 (4) (2020) 2346-2356.
[17] Q. Xie, W.D. Li, A. Manthiram, A Mg-doped high-nickel layered oxide cathode enabling safer, high-energy-density Li-ion batteries, Chem. Mater. 31 (3) (2019) 938-946.
[18] Y. Zhang, H. Li, J. Liu, J. Zhang, F. Cheng, J. Chen, LiNi_0.90Co_0.07Mg_0.03O₂ cathode materials with Mg-concentration gradient for rechargeable lithium-ion batteries, J. Mater. Chem. A. 7 (2019) 20958-20964.
[19] F. Wu, Q. Li, L. Chen, Y. Lu, Y.F. Su, L.Y. Bao, R.J. Chen, S. Chen, Use of Ce to reinforce the interface of Ni-rich LiNi_0.8Co_0.1Mn_0.1O₂ cathode materials for lithium-ion batteries under high operating voltage, ChemSusChem 12 (4) (2019) 935-943.
[20] Y. Huang, S. Cao, X. Xie, C. Wu, S. Jamil, Q.L. Zhao, B.B. Chang, Y. Wang, X.Y. Wang, Improving the structure and cycling stability of Ni-rich layered cathodes by dual modification of yttrium doping and surface coating, ACS Appl. Mater. Interfaces 12 (17) (2020) 19483-19494.
[21] Y.C. Li, W. Xiang, Z.G. Wu, C.L. Xu, Y.D. Xu, Y. Xiao, Z.G. Yang, C.J. Wu, G.P. Lv, X.D. Guo, Construction of homogeneously Al³⁺ doped Ni rich Ni-Co-Mn cathode with high stable cycling performance and storage stability via scalable continuous precipitation, Electrochim. Acta 291 (2018) 84-94.
[22] M.Y. Zhang, C.Y. Wang, J.K. Zhang, G. Li, L. Gu, Preparation and electrochemical characterization of La and Al Co-doped NCM811 cathode materials, ACS Omega 6 (25) (2021) 16465-16471.
[23] T.X. Lei, Y.J. Li, Q.Y. Su, G.L. Cao, W. Li, Y.X. Chen, L.L. Xue, S.Y. Deng, High-voltage electrochemical performance of LiNi_0.5Co_0.2Mn_0.3O₂ cathode materials via Al concentration gradient modification, Ceram. Int. 44 (8) (2018) 8809-8817.
[24] Y. Feng, X. Zhang, C. Lin, Q. Wang, Y. Zhang, Improving the electrochemical performance of LiNi 0.8 Co 0.1 Mn 0.1 O 2 cathodes using a simple Ce 4+ -doping and CeO 2 -coating technique, New J. Chem. 45 (2021) 21617-21623.
[25] C. Roitzheim, L.Y. Kuo, Y.J. Sohn, M. Finsterbusch, S. Moller, D. Sebold, H. Valencia, M. Meledina, J. Mayer, U. Breuer, P. Kaghazchi, O. Guillon, D. Fattakhova-Rohlfing, Boron in Ni-rich NCM811 cathode material: impact on atomic and microscale properties, ACS Appl. Energy Mater. 5 (1) (2022) 524-538.
[26] P. Laine, M. Hietaniemi, J. Välikangas, T. Kauppinen, P. Tynjälä, T. Hu, S.B. Wang, H. Singh, L. Ulla, Co-precipitation of Mg-doped Ni_0.8Co_0.1Mn_0.1(OH)₂: effect of magnesium doping and washing on the battery cell performance, Dalton Trans. 52 (5) (2023) 1413-1424.
[27] X.B. Ding, H.Y. Huang, Q.H. Huang, B.R. Hu, X.K. Li, X.D. Ma, X.H. Xiong, Doping sites modulation of T-Nb₂O₅ to achieve ultrafast lithium storage, J. Energy Chem. 77 (2023) 280-289.
[28] C. Chen, J.M. Zhang, B.R. Hu, Q.W. Liang, X.H. Xiong, Dynamic gel as artificial interphase layer for ultrahigh-rate and large-capacity lithium metal anode, Nat. Commun. 14 (1) (2023) 4018.
[29] V.I. Anisimov, A.I. Poteryaev, M.A. Korotin, A.O. Anokhin, G. Kotliar, First-principles calculations of the electronic structure and spectra of strongly correlated systems: dynamical mean-field theory, (1997): arXiv: cond-mat/9704231.10.1088/0953-8984/9/35/010.
[30] P.H. Xiao, Z.Q. Deng, A. Manthiram, G. Henkelman, Calculations of oxygen stability in lithium-rich layered cathodes, J. Phys. Chem. C 116 (44) (2012) 23201-23204.
[31] L. Musuvadhi Babulal, C. Yang, S. Wu, W.-C. Chien, R. Jose, S. Jessie Lue, Enhanced performance of a Ni-rich LiNi_0.8Co_0.1Mn_0.1O₂ cathode material formed through Taylor flow synthesis and surface modification with Li₂MoO₄, Chem. Eng. J. 413 (2021) 127150.
[32] J.R. Zhang, Z.W. Lan, R.H. Xi, Y.Y. Li, C.H. Zhang, The cycle stability and rate performance of LiNi_0.8Mn_0.1Co_0.1O₂ enhanced by Mg doping and LiFePO₄ coating, Chemelectrochem 9 (6) (2022) e202101654.
[33] S. Maiti, H. Sclar, R. Sharma, N. Vishkin, M. Fayena-Greenstein, J. Grinblat, M. Talianker, L. Burstein, N. Solomatin, O. Tiurin, Y. Ein-Eli, M. Noked, B. Markovsky, D. Aurbach, Understanding the role of alumina (Al₂O₃), pentalithium aluminate (Li₅AlO₄), and pentasodium aluminate (Na₅AlO₄) coatings on the Li and Mn-rich NCM cathode material 0.33Li₂MnO₃·0.67Li(Ni_0.4Co_0.2Mn_0.4)O₂ for enhanced electrochemical performance, Adv. Funct. Mater. 31 (8) (2021) 2008083.
[34] L. Xia, K.H. Qiu, Y.Y. Gao, X. He, F.D. Zhou, High potential performance of Cerium-doped LiNi_0.5Co_0.2Mn_0.3O₂ cathode material for Li-ion battery, J. Mater. Sci. 50 (7) (2015) 2914-2920.
[35] D.C. Gao, Y.W. Huang, H.L. Dong, C.Y. Li, C.K. Chang, Atomic horizons interpretation on enhancing electrochemical performance of Ni-rich NCM cathode via W doping: dual improvements in electronic and ionic conductivities from DFT calculations and experimental confirmation, Small 19 (5) (2023) e2205122.

Cation-doped LiNi_0.8Co_0.1Mn_0.1O₂ cathode with high rate performance

Cation-doped LiNi_0.8Co_0.1Mn_0.1O₂ cathode with high rate performance

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