Constructing Uniform Ionic Conductor Coatings on LiCoO₂ Cathode to Realize 4.6 V High-Voltage All-Solid-State Lithium Batteries

Abstract

All solid-state lithium batteries (ASSLBs) are identified as the next-generation energy storage technology due to their prospects of nonflammability and improved energy density. Elevating the charging cutoff voltage of cathode materials is an effective strategy to improve the energy density of ASSLBs. However, the limited oxidative stability of solid-state electrolytes (SEs) and structural and chemically irreversible changes in the cathode active material result in inferior electrochemical performance. Here, we synthesized nano-Li_1.2Al_0.1Ta_1.9PO₈ (LATPO) coatings on the surface of lithium cobalt oxide (LCO) by a facile ball-milling method combined with heat treatments. This artificial intermediate phase effectively enhances the structural stability and interfacial transport kinetics of the cathode and mitigates continuous side reactions at the cathode/solid electrolyte interface. As a result, the ASSLBs with modified LCO cathode exhibit a reversible capacity of 203.5 mAh g⁻¹ at 0.1 C and 4.0 V (corresponding to the potential of 4.6 V vs. Li⁺/Li), superior cycling stability (85.4% capacity retention after 500 cycles), a high areal capacity (4.6 mAh cm⁻²), and a good rate capability (62 mAh g⁻¹ at 3 C). This study emphasizes the importance of cathode surface modification in achieving stable cycling of halide-based ASSLBs at high voltages.

Keywords

all-solid-state lithium batteries / coating materials / halide electrolyte / high voltage stability

References

[1] B. Dunn, H. Kamath, and J.-M. Tarascon, “Electrical Energy Storage for the Grid: A Battery of Choices,” Science 334, no. 6058 (2011): 928-935.

[2] L.-Z. Fan, H. He, and C.-W. Nan, “Tailoring Inorganic-Polymer Composites for the Mass Production of Solid-State Batteries,” Nature Reviews Materials 6 (2021): 1003-1019.

[3] A. Manthiram, X. Yu, and S. Wang, “Lithium Battery Chemistries Enabled by Solid-State Electrolytes,” Nature Reviews Materials 2, no. 4 (2017): 16103.

[4] G. Wang, Y. Liang, H. Liu, C. Wang, D. Li, and L.-Z. Fan, “Scalable, Thin Asymmetric Composite Solid Electrolyte for High-Performance All-Solid-State Lithium Metal Batteries,” Interdisciplinary Materials 1, no. 3 (2022): 434-444.

[5] C. Lin, J. Li, Z. W. Yin, et al., “Structural Understanding for High-Voltage Stabilization of Lithium Cobalt Oxide,” Advanced Materials 36, no. 6 (2023): 2307404.

[6] S. Kalluri, M. Yoon, M. Jo, et al., “Surface Engineering Strategies of Layered LiCoO₂ Cathode Material to Realize High-Energy and High-Voltage Li-Ion Cells,” Advanced Energy Materials 7, no. 1 (2016): 1601507.

[7] J. N. Reimers and J. R. Dahn, “Electrochemical and In Situ X-Ray Diffraction Studies of Lithium Intercalation in Li_xCoO₂,” Journal of the Electrochemical Society 139, no. 8 (1992): 2091-2097.

[8] Q. Liu, X. Su, D. Lei, et al., “Approaching the Capacity Limit of Lithium Cobalt Oxide in Lithium Ion Batteries via Lanthanum and Aluminium Doping,” Nature Energy 3, no. 11 (2018): 936-943.

[9] S. Zhang, F. Zhao, S. Wang, et al., “Advanced High-Voltage All-Solid-State Li-Ion Batteries Enabled by a Dual-Halogen Solid Electrolyte,” Advanced Energy Materials 11, no. 32 (2021): 2100836.

[10] L. Wang, X. Sun, J. Ma, et al., “Bidirectionally Compatible Buffering Layer Enables Highly Stable and Conductive Interface for 4.5 V Sulfide-Based All-Solid-State Lithium Batteries,” Advanced Energy Materials 11, no. 32 (2021): 2100881.

[11] H.-S. Zhang, X.-C. Lei, D. Su, et al., “Surface Lattice Modulation Enables Stable Cycling of High-Loading All-Solid-State Batteries at High Voltages,” Angewandte Chemie International Edition 63, no. 16 (2024): e202400562.

[12] H.-J. Deiseroth, S.-T. Kong, H. Eckert, et al., “Li₆PS₅X: A Class of Crystalline Li-Rich Solids With an Unusually High Li⁺ Mobility,” Angewandte Chemie International Edition 47, no. 4 (2008): 755-758.

[13] N. Kamaya, K. Homma, Y. Yamakawa, et al., “A Lithium Superionic Conductor,” Nature Materials 10, no. 9 (2011): 682-686.

[14] R. Murugan, V. Thangadurai, and W. Weppner, “Fast Lithium Ion Conduction in Garnet-Type Li₇La₃Zr₂O₁₂,” Angewandte Chemie International Edition 46, no. 41 (2007): 7778-7781.

[15] X. Li, J. Liang, N. Chen, et al., “Water-Mediated Synthesis of a Superionic Halide Solid Electrolyte,” Angewandte Chemie International Edition 58, no. 46 (2019): 16427-16432.

[16] T. Asano, A. Sakai, S. Ouchi, M. Sakaida, A. Miyazaki, and S. Hasegawa, “Solid Halide Electrolytes With High Lithium-Ion Conductivity for Application in 4 V Class Bulk-Type All-Solid-State Batteries,” Advanced Materials 30, no. 44 (2018): 1803075.

[17] Y. Tanaka, K. Ueno, K. Mizuno, K. Takeuchi, T. Asano, and A. Sakai, “New Oxyhalide Solid Electrolytes With High Lithium Ionic Conductivity >10 Ms Cm⁻¹ for All-Solid-State Batteries,” Angewandte Chemie International Edition 62, no. 13 (2023): e202217581.

[18] Q. Zhang, D. Cao, Y. Ma, A. Natan, P. Aurora, and H. Zhu, “Sulfide-Based Solid-State Electrolytes: Synthesis, Stability, and Potential for All-Solid-State Batteries,” Advanced Materials 31, no. 44 (2019): 1901131.

[19] F. Han, Y. Zhu, X. He, Y. Mo, and C. Wang, “Electrochemical Stability of Li₁₀GeP₂S₁₂ and Li₇La₃Zr₂O₁₂ Solid Electrolytes,” Advanced Energy Materials 6, no. 8 (2016): 1501590.

[20] J. Jang, Y.-T. Chen, G. Deysher, et al., “Enabling a Co-Free, High-Voltage LiNi_0.5Mn_1.5O₄ Cathode in All-Solid-State Batteries With a Halide Electrolyte,” ACS Energy Letters 7, no. 8 (2022): 2531-2539.

[21] B. Han, T. Paulauskas, B. Key, et al., “Understanding the Role of Temperature and Cathode Composition on Interface and Bulk: Optimizing Aluminum Oxide Coatings for Li-Ion Cathodes,” ACS Applied Materials & Interfaces 9, no. 17 (2017): 14769-14778.

[22] A. Aboulaich, K. Ouzaouit, H. Faqir, A. Kaddami, I. Benzakour, and I. Akalay, “Improving Thermal and Electrochemical Performances of LiCoO₂ Cathode at High Cut-Off Charge Potentials by MF₃ (M = Ce, Al) Coating,” Materials Research Bulletin 73 (2016): 362-368.

[23] N. Ohta, K. Takada, I. Sakaguchi, et al., “LiNbO₃-Coated LiCoO₂ as Cathode Material for all Solid-State Lithium Secondary Batteries,” Electrochemistry Communications 9, no. 7 (2007): 1486-1490.

[24] J. Yao, Y. Li, T. Xiong, et al., “Scalable Precise Nanofilm Coating and Gradient Al Doping Enable Stable Battery Cycling of LiCoO₂ at 4.7 V,” Angewandte Chemie International Edition 63, no. 32 (2024): e202407898.

[25] A. Zhou, J. Xu, X. Dai, et al., “Improved High-Voltage and High-Temperature Electrochemical Performances of LiCoO₂ Cathode by Electrode Sputter-Coating With Li₃PO₄,” Journal of Power Sources 322 (2016): 10-16.

[26] X. Qi, G. Wu, M. Wu, et al., “Deciphering and Overcoming the High-Voltage Limitations of Halide and Sulfide-Based All-Solid-State Lithium Batteries,” Journal of Energy Chemistry 103 (2025): 926-935.

[27] Y. Liang, H. Liu, G. Wang, et al., “Heuristic Design of Cathode Hybrid Coating for Power-Limited Sulfide-Based All-Solid-State Lithium Batteries,” Advanced Energy Materials 12, no. 33 (2022): 2201555.

[28] X. Zhou, C.-Y. Chang, D. Yu, et al., “Li₂ZrF₆ Protective Layer Enabled High-Voltage LiCoO₂ Positive Electrode in Sulfide All-Solid-State Batteries,” Nature Communications 16, no. 1 (2025): 112.

[29] J. Kim, J. Kim, M. Avdeev, H. Yun, and S.-J. Kim, “LiTa₂PO₈: A Fast Lithium-Ion Conductor With New Framework Structure,” Journal of Materials Chemistry A 6, no. 45 (2018): 22478-22482.

[30] D. Li, X. Liu, Y. Li, et al., “A Versatile InF₃ Substituted Argyrodite Sulfide Electrolyte Toward Ultrathin Films for All-Solid-State Lithium Batteries,” Advanced Energy Materials 14, no. 47 (2024): 2402929.

[31] X. Li, J. Liang, J. Luo, et al., “Air-Stable Li₃InCl₆ Electrolyte With High Voltage Compatibility for All-Solid-State Batteries,” Energy & Environmental Science 12, no. 9 (2019): 2665-2671.

[32] T. Shi, Q. Tu, Y. Tian, et al., “High Active Material Loading in All-Solid-State Battery Electrode via Particle Size Optimization,” Advanced Energy Materials 10, no. 1 (2019): 1902881.

[33] Y. Wang, H. Hao, K. G. Naik, et al., “Mechanical Milling-Induced Microstructure Changes in Argyrodite Lpscl Solid-State Electrolyte Critically Affect Electrochemical Stability,” Advanced Energy Materials 14, no. 23 (2024): 202304530.

[34] Y.-C. Wu, F. Li, X. Cheng, et al., “Interface Degradation of LaCl₃-Based Solid Electrolytes Coupled With Ultrahigh-Nickel Cathodes,” Nano Letters 24, no. 49 (2024): 15540-15546.

[35] Y. Lu, C.-Z. Zhao, J.-Q. Huang, and Q. Zhang, “The Timescale Identification Decoupling Complicated Kinetic Processes in Lithium Batteries,” Joule 6, no. 6 (2022): 1172-1198.

[36] D. H. S. Tan, E. A. Wu, H. Nguyen, et al., “Elucidating Reversible Electrochemical Redox of Li₆PS₅Cl Solid Electrolyte,” ACS Energy Letters 4, no. 10 (2019): 2418-2427.

[37] J. Auvergniot, A. Cassel, J.-B. Ledeuil, V. Viallet, V. Seznec, and R. Dedryvère, “Interface Stability of Argyrodite Li₆PS₅Cl Toward LiCoO₂, LiNi_1/3Co_1/3Mn_1/3O₂, and LiMn₂O₄ in Bulk All-Solid-State Batteries,” Chemistry of Materials 29, no. 9 (2017): 3883-3890.

[38] J.-F. Wu, Z. Zou, B. Pu, et al., “Liquid-Like Li-Ion Conduction in Oxides Enabling Anomalously Stable Charge Transport Across the Li/Electrolyte Interface in All-Solid-State Batteries,” Advanced Materials 35, no. 40 (2023): 2303730.

[39] Y. Zhu, X. He, and Y. Mo, “First Principles Study on Electrochemical and Chemical Stability of Solid Electrolyte-Electrode Interfaces in All-Solid-State Li-Ion Batteries,” Journal of Materials Chemistry A 4, no. 9 (2016): 3253-3266.

[40] H. B. Lee, T. Dinh Hoang, Y. S. Byeon, H. Jung, J. Moon, and M.-S. Park, “Surface Stabilization of Ni-Rich Layered Cathode Materials via Surface Engineering With LiTaO₃ for Lithium-Ion Batteries,” ACS Applied Materials & Interfaces 14, no. 2 (2022): 2731-2741.

[41] J. Li, C. Lin, M. Weng, et al., “Structural Origin of the High-Voltage Instability of Lithium Cobalt Oxide,” Nature Nanotechnology 16, no. 5 (2021): 599-605.

[42] K. Y. Chung, W.-S. Yoon, H. S. Lee, et al., “In Situ XRD Studies of the Structural Changes of ZrO₂-coated LiCoO₂ During Cycling and Their Effects on Capacity Retention in Lithium Batteries,” Journal of Power Sources 163, no. 1 (2006): 185-190.

[43] Z. Wang, J. Tan, Z. Jia, et al., “Deciphering Chemical/Electrochemical Compatibility of Li₃InCl₆ in 5.2 V High-Voltage LiCoO₂ All-Solid-State Batteries,” ACS Energy Letters 9, no. 9 (2024): 4485-4492.

[44] M. Sathiya, A. M. Abakumov, D. Foix, et al., “Origin of Voltage Decay in High-Capacity Layered Oxide Electrodes,” Nature Materials 14, no. 2 (2015): 230-238.

RIGHTS & PERMISSIONS

2025 The Author(s). Interdisciplinary Materials published by Wuhan University of Technology and John Wiley & Sons Australia, Ltd.