Issue

Vol. 17 (2025)

Manipulating Interfacial Stability via Preferential Absorption for Highly Stable and Safe 4.6 V LiCoO2 Cathode

https://doi.org/10.1007/s40820-025-01694-4
Long Chen
Key Laboratory of Hydraulic Machinery Transients, Ministry of Education, School of Power and Mechanical Engineering, Wuhan University, Wuhan 430072, People’s Republic of China
Xin He
State Key Laboratory of Advanced Electromagnetic Technology, School of Electrical and Electronic Engineering, Huazhong University of Science and Technology, Wuhan 430074, People’s Republic of China
Yiqing Chen
Key Laboratory of Hydraulic Machinery Transients, Ministry of Education, School of Power and Mechanical Engineering, Wuhan University, Wuhan 430072, People’s Republic of China
Youmin Hou
Key Laboratory of Hydraulic Machinery Transients, Ministry of Education, School of Power and Mechanical Engineering, Wuhan University, Wuhan 430072, People’s Republic of China
Yujie Zhang
State Key Laboratory of Advanced Electromagnetic Technology, School of Electrical and Electronic Engineering, Huazhong University of Science and Technology, Wuhan 430074, People’s Republic of China
Kangli Wang
State Key Laboratory of Advanced Electromagnetic Technology, School of Electrical and Electronic Engineering, Huazhong University of Science and Technology, Wuhan 430074, People’s Republic of China
Xinping Ai
Hubei Key Laboratory of Electrochemical Power Sources, College of Chemistry and Molecular Sciences, Wuhan University, Wuhan 430072, People’s Republic of China
Yuliang Cao
Hubei Key Laboratory of Electrochemical Power Sources, College of Chemistry and Molecular Sciences, Wuhan University, Wuhan 430072, People’s Republic of China
Zhongxue Chen
Key Laboratory of Hydraulic Machinery Transients, Ministry of Education, School of Power and Mechanical Engineering, Wuhan University, Wuhan 430072, People’s Republic of China

Corresponding Author: Zhongxue Chen

zxchen_pmc@whu.edu.cn

Nano-Micro Letters, Vol. 17 (2025), Article Number: 181

Abstract

Elevating the upper cutoff voltage to 4.6 V could effectively increase the reversible capacity of LiCoO2 (LCO) cathode, whereas the irreversible structural transition, unstable electrode/electrolyte interface and potentially induced safety hazards severely hinder its industrial application. Building a robust cathode/electrolyte interface film by electrolyte engineering is one of the efficient approaches to boost the performance of high-voltage LCO (HV-LCO); however, the elusive interfacial chemistry poses substantial challenges to the rational design of highly compatible electrolytes. Herein, we propose a novel electrolyte design strategy and screen proper solvents based on two factors: highest occupied molecular orbital energy level and LCO absorption energy. Tris (2, 2, 2-trifluoroethyl) phosphate is determined as the optimal solvent, whose low defluorination energy barrier significantly promotes the construction of LiF-rich cathode/electrolyte interface layer on the surface of LCO, thereby eventually suppresses the phase transition and enhances Li+ diffusion kinetics. The rationally designed electrolyte endows graphite||HV-LCO pouch cells with long cycle life (85.3% capacity retention after 700 cycles), wide-temperature adaptability (− 60–80 °C) and high safety (pass nail penetration). This work provides new insights into the electrolyte screening and rational design to constructing stable interface for high-energy lithium-ion batteries.


Highlights:
1 A novel electrolyte design strategy for high voltage and high safe LiCoO2 (LCO) cathode based on highest occupied molecular orbital and LCO absorption energy descriptor was proposed.
2 The irreversible phase transformation was restricted by the LiF rich LCO/electrolyte interface.
3 The well designed tris 2, 2, 2-trifluoroethyl phosphate electrolyte endows Ah grade Gr||LCO pouch cell with excellent electrochemical performance (85.3% capacity retention after 700 cycles), low-temperature adaptability (−60 °C retention: 53%) and greatly improved thermal safety (pass nail penetration).

Keywords

Electrolyte design LiF-rich interface Wide-temperature High-safe 4.6 V LCO
Chen, Long, Xin He, Yiqing Chen, Youmin Hou, Yujie Zhang, Kangli Wang, Xinping Ai, Yuliang Cao, and Zhongxue Chen. 2025. “Manipulating Interfacial Stability via Preferential Absorption for Highly Stable and Safe 4.6 V LiCoO2 Cathode”. Nano-Micro Letters 17 (March):181. https://doi.org/10.1007/s40820-025-01694-4.
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References
  1. W. Huang, J. Li, Q. Zhao, S. Li, M. Ge et al., Mechanochemically robust LiCoO2 with ultrahigh capacity and prolonged cyclability. Adv. Mater. 36, e2405519 (2024). https://doi.org/10.1002/adma.202405519
  2. J. Li, C. Lin, M. Weng, Y. Qiu, P. Chen et al., Structural origin of the high-voltage instability of lithium cobalt oxide. Nat. Nanotechnol. 16, 599–605 (2021). https://doi.org/10.1038/s41565-021-00855-x
  3. X. Pu, S. Zhang, D. Zhao, Z.-L. Xu, Z. Chen et al., Building the robust fluorinated electrode–electrolyte interface in rechargeable batteries: from fundamentals to applications. Electrochem. Energy Rev. 7, 21 (2024). https://doi.org/10.1007/s41918-024-00226-9
  4. Y. Gao, Z. Pan, J. Sun, Z. Liu, J. Wang, High-energy batteries: beyond lithium-ion and their long road to commercialisation. Nano-Micro Lett. 14, 94 (2022). https://doi.org/10.1007/s40820-022-00844-2
  5. M.D. Radin, S. Hy, M. Sina, C. Fang, H. Liu et al., Narrowing the gap between theoretical and practical capacities in Li-ion layered oxide cathode materials. Adv. Energy Mater. 7, 1602888 (2017). https://doi.org/10.1002/aenm.201602888
  6. Z. Lin, K. Fan, T. Liu, Z. Xu, G. Chen et al., Mitigating lattice distortion of high-voltage LiCoO2 via core-shell structure induced by cationic heterogeneous co-doping for lithium-ion batteries. Nano-Micro Lett. 16, 48 (2023). https://doi.org/10.1007/s40820-023-01269-1
  7. H. Zhang, Y. Huang, Y. Wang, L. Wang, Z. Song et al., In-situ constructed protective bilayer enabling stable cycling of LiCoO2 cathode at high-voltage. Energy Storage Mater. 62, 102951 (2023). https://doi.org/10.1016/j.ensm.2023.102951
  8. K. Zhang, J. Chen, W. Feng, C. Wang, Y.-N. Zhou et al., Constructing solid electrode-electrolyte interfaces in high-voltage Li|LiCoO2 batteries under dual-additive electrolyte synergistic effect. J. Power Sources 553, 232311 (2023). https://doi.org/10.1016/j.jpowsour.2022.232311
  9. J.L. Tebbe, T.F. Fuerst, C.B. Musgrave, Degradation of ethylene carbonate electrolytes of lithium ion batteries via ring opening activated by LiCoO2 cathode surfaces and electrolyte species. ACS Appl. Mater. Interfaces 8, 26664–26674 (2016). https://doi.org/10.1021/acsami.6b06157
  10. X. Yang, M. Lin, G. Zheng, J. Wu, X. Wang et al., Enabling stable high-voltage LiCoO2 operation by using synergetic interfacial modification strategy. Adv. Funct. Mater. 30, 2004664 (2020). https://doi.org/10.1002/adfm.202004664
  11. J. Zhang, H. Zhang, S. Weng, R. Li, D. Lu et al., Multifunctional solvent molecule design enables high-voltage Li-ion batteries. Nat. Commun. 14, 2211 (2023). https://doi.org/10.1038/s41467-023-37999-4
  12. G.G. Amatucci, J.M. Tarascon, L.C. Klein, Cobalt dissolution in LiCoO2-based non-aqueous rechargeable batteries. Solid State Ion. 83, 167–173 (1996). https://doi.org/10.1016/0167-2738(95)00231-6
  13. Y. Xu, E. Hu, K. Zhang, X. Wang, V. Borzenets et al., In situ visualization of state-of-charge heterogeneity within a LiCoO2 p that evolves upon cycling at different rates. ACS Energy Lett. 2, 1240–1245 (2017). https://doi.org/10.1021/acsenergylett.7b00263
  14. X. Hu, W. Yang, Z. Jiang, Z. Huang, Y. Wang et al., Improving diffusion kinetics and phase stability of LiCoO2 via surface modification at elevated voltage. Electrochim. Acta 380, 138227 (2021). https://doi.org/10.1016/j.electacta.2021.138227
  15. S. Mao, Z. Shen, W. Zhang, Q. Wu, Z. Wang et al., Outside-In nanostructure fabricated on LiCoO2 surface for high-voltage lithium-ion batteries. Adv. Sci. 9, e2104841 (2022). https://doi.org/10.1002/advs.202104841
  16. J.-H. Shim, K.-S. Lee, A. Missyul, J. Lee, B. Linn et al., Characterization of spinel LixCo2O4-coated LiCoO2 prepared with post-thermal treatment as a cathode material for lithium ion batteries. Chem. Mater. 27, 3273–3279 (2015). https://doi.org/10.1021/acs.chemmater.5b00159
  17. H. Ren, J. Hu, H. Ji, Y. Huang, W. Zhao et al., Densification of cathode/electrolyte interphase to enhance reversibility of LiCoO2 at 4.65 V. Adv. Mater. 36, e2408875 (2024). https://doi.org/10.1002/adma.202408875
  18. Y.-S. Hong, X. Huang, C. Wei, J. Wang, J.-N. Zhang et al., Hierarchical defect engineering for LiCoO2 through low-solubility trace element doping. Chem 6, 2759–2769 (2020). https://doi.org/10.1016/j.chempr.2020.07.017
  19. Y. Huang, Y. Zhu, H. Fu, M. Ou, C. Hu et al., Mg-pillared LiCoO2: towards stable cycling at 4.6 V. Angew. Chem. Int. Ed. 60, 4682–4688 (2021). https://doi.org/10.1002/anie.202014226
  20. J. Xiang, Y. Wei, Y. Zhong, Y. Yang, H. Cheng et al., Building practical high-voltage cathode materials for lithium-ion batteries. Adv. Mater. 34, 2200912 (2022). https://doi.org/10.1002/adma.202200912
  21. J.-N. Zhang, Q. Li, C. Ouyang, X. Yu, M. Ge et al., Trace doping of multiple elements enables stable battery cycling of LiCoO2 at 4.6 V. Nat. Energy 4, 594–603 (2019). https://doi.org/10.1038/s41560-019-0409-z
  22. X.-M. Fan, Z. Zhang, G.-Q. Mao, Y.-J. Tong, K.-B. Lin et al., Reducing structural degradation of high-voltage single-crystal Ni-rich cathode through in situ doping strategy. Rare Met. 42, 2993–3003 (2023). https://doi.org/10.1007/s12598-023-02288-y
  23. S. Kalluri, M. Yoon, M. Jo, S. Park, S. Myeong et al., Surface engineering strategies of layered LiCoO2 cathode material to realize high-energy and high-voltage Li-ion cells. Adv. Energy Mater. 7, 1601507 (2017). https://doi.org/10.1002/aenm.201601507
  24. L. Chen, X. Shen, H. Chen, T. Wen, R. Rao et al., High-stable nonflammable electrolyte regulated by coordination-number rule for all-climate and safer lithium-ion batteries. Energy Storage Mater. 55, 836–846 (2023). https://doi.org/10.1016/j.ensm.2022.12.044
  25. L. Chen, J. Wang, M. Chen, Z. Pan, Y. Ding et al., “Dragging effect” induced fast desolvation kinetics and −50 °C workable high-safe lithium batteries. Energy Storage Mater. 65, 103098 (2024). https://doi.org/10.1016/j.ensm.2023.103098
  26. X. Fan, L. Chen, O. Borodin, X. Ji, J. Chen et al., Non-flammable electrolyte enables Li-metal batteries with aggressive cathode chemistries. Nat. Nanotechnol. 13, 715–722 (2018). https://doi.org/10.1038/s41565-018-0183-2
  27. B. Tong, Z. Song, H. Wan, W. Feng, M. Armand et al., Sulfur-containing compounds as electrolyte additives for lithium-ion batteries. InfoMat 3, 1364–1392 (2021). https://doi.org/10.1002/inf2.12235
  28. E. Spencer Williams, J. Panko, D.J. Paustenbach, The European union’s REACH regulation: a review of its history and requirements. Crit. Rev. Toxicol. 39, 553–575 (2009). https://doi.org/10.1080/10408440903036056
  29. S. Chen, G. Zheng, X. Yao, J. Xiao, W. Zhao et al., Constructing matching cathode-anode interphases with improved chemo-mechanical stability for high-energy batteries. ACS Nano 18, 6600–6611 (2024). https://doi.org/10.1021/acsnano.3c12823
  30. Y. Huang, Y. Ji, G. Zheng, H. Cao, H. Xue et al., Tailored interphases construction for enhanced Si Anode and Ni-rich cathode performance in lithium-ion batteries. CCS Chem. 7, 429–439 (2025). https://doi.org/10.31635/ccschem.024.202404120
  31. L. Chen, M. Chen, Q. Meng, J. Zhang, G. Feng et al., Reconstructing Helmholtz plane enables robust F-rich interface for long-life and high-safe sodium-ion batteries. Angew. Chem. Int. Ed. 63, e202407717 (2024). https://doi.org/10.1002/anie.202407717
  32. H. Wang, X. Li, F. Li, X. Liu, S. Yang et al., Formation and modification of cathode electrolyte interphase: a mini review. Electrochem. Commun. 122, 106870 (2021). https://doi.org/10.1016/j.elecom.2020.106870
  33. M. Ma, R. Huang, M. Ling, Y.-S. Hu, H. Pan, Towards stable electrode–electrolyte interphases: regulating solvation structures in electrolytes for rechargeable batteries. Interdiscip. Mater. 2, 833–854 (2023). https://doi.org/10.1002/idm2.12131
  34. M. Wang, L. Yin, M. Zheng, X. Liu, C. Yang et al., Temperature-responsive solvation enabled by dipole-dipole interactions towards wide-temperature sodium-ion batteries. Nat. Commun. 15, 8866 (2024). https://doi.org/10.1038/s41467-024-53259-5
  35. X. Bai, X. Zhao, Y. Zhang, C. Ling, Y. Zhou et al., Dynamic stability of copper single-atom catalysts under working conditions. J. Am. Chem. Soc. 144, 17140–17148 (2022). https://doi.org/10.1021/jacs.2c07178
  36. X. Zhao, Y. Liu, Unveiling the active structure of single nickel atom catalysis: critical roles of charge capacity and hydrogen bonding. J. Am. Chem. Soc. 142, 5773–5777 (2020). https://doi.org/10.1021/jacs.9b13872
  37. H. Huang, Z. Li, S. Gu, J. Bian, Y. Li et al., Dextran sulfate lithium as versatile binder to stabilize high-voltage LiCoO2 to 4.6 V. Adv. Energy Mater. 11, 2101864 (2021). https://doi.org/10.1002/aenm.202101864
  38. F. Zhang, N. Qin, Y. Li, H. Guo, Q. Gan et al., Phytate lithium as a multifunctional additive stabilizes LiCoO2 to 4.6 V. Energy Environ. Sci. 16, 4345–4355 (2023). https://doi.org/10.1039/D3EE01209C
  39. M. Cai, Y. Dong, M. Xie, W. Dong, C. Dong et al., Stalling oxygen evolution in high-voltage cathodes by lanthurization. Nat. Energy 8, 159–168 (2023). https://doi.org/10.1038/s41560-022-01179-3
  40. J. Cheng, W. Lin, J. Hou, Y. Liao, Y. Huang, Uniform Al doping in LiCoO2 for 4.55 V lithium-ion pouch cells. ACS Appl. Mater. Interfaces 16, 7243–7251 (2024). https://doi.org/10.1021/acsami.3c17471
  41. W. Huang, Q. Zhao, M. Zhang, S. Xu, H. Xue et al., Surface design with cation and anion dual gradient stabilizes high-voltage LiCoO2. Adv. Energy Mater. 12, 2200813 (2022). https://doi.org/10.1002/aenm.202200813
  42. X. Lin, F. Zeng, J. Lin, W. Zhang, X. Zhou et al., B-/ Si-containing electrolyte additive efficiently establish a stable interface for high-voltage LiCoO2 cathode and its synergistic effect on LiCoO2/graphite pouch cells. J. Colloid Interface Sci. 642, 292–303 (2023). https://doi.org/10.1016/j.jcis.2023.03.156
  43. L. Luo, K. Chen, R. Cao, H. Chen, M. Xia et al., Ethyl fluoroacetate with weak Li+ interaction and high oxidation resistant induced low-temperature and high-voltage graphite// LiCoO2 batteries. Energy Storage Mater. 70, 103438 (2024). https://doi.org/10.1016/j.ensm.2024.103438
  44. G.K. Mishra, M. Gautam, K. Bhawana, J. Ghosh, S. Mitra, High energy density lithium-ion pouch cell with modified high voltage lithium cobalt oxide cathode and graphite anode: Prototype stabilization, electrochemical and thermal study. J. Power Sources 580, 233395 (2023). https://doi.org/10.1016/j.jpowsour.2023.233395
  45. C. Tang, Y. Chen, Z. Zhang, W. Li, J. Jian et al., Stable cycling of practical high-voltage LiCoO2 pouch cell via electrolyte modification. Nano Res. 16, 3864–3871 (2023). https://doi.org/10.1007/s12274-022-4955-5
  46. C. Yang, X. Zhou, R. Sun, W. Hu, M. Wang et al., A safe electrolyte enriched with flame-retardant solvents for high-voltage LiCoO2|| Graphite pouch cells. ACS Energy Lett. 9, 5364–5372 (2024). https://doi.org/10.1021/acsenergylett.4c02466
  47. J. Zhang, P.-F. Wang, P. Bai, H. Wan, S. Liu et al., Interfacial design for a 4.6 V high-voltage single-crystalline LiCoO2 cathode. Adv. Mater. 34, e2108353 (2022). https://doi.org/10.1002/adma.202108353
  48. T. Zhou, J. Wang, L. Lv, R. Li, L. Chen et al., Anion–π interaction and solvent dehydrogenation control enable high-voltage lithium-ion batteries. Energy Environ. Sci. 17, 9185–9194 (2024). https://doi.org/10.1039/d4ee03027c
  49. Z. Zhuang, J. Wang, K. Jia, G. Ji, J. Ma et al., Ultrahigh-voltage LiCoO2 at 4.7 V by interface stabilization and band structure modification. Adv. Mater. 35, e2212059 (2023). https://doi.org/10.1002/adma.202212059
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