Improved cyclic stability of LiNi_0.8Mn_0.1Co_0.1O₂ cathode enabled by a novel CEI forming additive

Abstract

The undesired side reactions at electrode/electrolyte interface as well as the irreversible phase evolution during electrochemical cycling significantly affect the cyclic performances of nickel-rich NMCs electrode materials. Electrolyte optimization is an effective approach to suppress such an adverse side reaction, thereby enhancing the electrochemical properties. Herein, a novel boron-based film forming additive, tris(2,2,2-trifluoroethyl) borate (TTFEB), has been introduced to regulate the interphasial chemistry of LiNi_0.8Mn_0.1Co_0.1O₂ (NMC811) cathode to improve its long-term cyclability and rate properties. The results of multi-model diagnostic study reveal that formation lithium fluoride (LiF)-rich and boron (B) containing cathode electrolyte interphase (CEI) not only stabilizes cathode surface, but also prevents electrolyte decomposition. Moreover, homogenously distributed B containing species serves as a skeleton to form more uniform and denser CEI, reducing the interphasial resistance. Remarkably, the Li/NMC811 cell with the TTFEB additive delivers an exceptional cycling stability with a high-capacity retention of 72.8% after 350 electrochemical cycles at a 1 C current rate, which is significantly higher than that of the cell cycled in the conventional electrolyte (59.7%). These findings provide a feasible pathway for improving the electrochemical performance of Ni-rich NMCs cathode by regulating the interphasial chemistry.

Key words： NMC811; cathode electrolyte interphase; film forming additives; cyclic stability

Acknowledgements

This work was supported by the National Natural Science Foundation of China (Grant No. 22209106).

Competing Interests

The authors declare that they have no competing interests.

Electronic Supplementary Material

Supplementary material is available in the online version of this article at https://doi.org/10.1007/s11708-024-0953-5 and is accessible for authorized users.

References

1 Dunn B, Kamath H, Tarascon J M. Electrical energy storage for the grid: A battery of choices. Science, 2011, 334(6058): 928–935

2 Kim T, Park J, Chang S K. . The current move of lithium ion batteries towards the next phase. Advanced Energy Materials, 2012, 2(7): 860–872

3 Goodenough J B, Park K S. The Li-ion rechargeable battery: A perspective. Journal of the American Chemical Society, 2013, 135(4): 1167–1176

4 Larcher D, Tarascon J M. Towards greener and more sustainable batteries for electrical energy storage. Nature Chemistry, 2015, 7(1): 19–29

5 Lauro S N, Burrow J N, Mullins C B. Restructuring the lithium-ion battery: A perspective on electrode architectures. eScience, 2023, 3(4): 100152

6 Armand M, Tarascon J M. Building better batteries. Nature, 2008, 451(7179): 652–657

7 Qi N, Yan K, Yu Y. . Machine learning and neural network supported state of health simulation and forecasting model for lithium-ion battery. Frontiers in Energy, 2024, 18(2): 223–240

8 Manthiram A. A reflection on lithium-ion battery cathode chemistry. Nature Communications, 2020, 11(1): 1550

9 Kim K, Ma H, Park S. . Electrolyte-additive-driven interfacial engineering for high-capacity electrodes in lithium-ion batteries: Promise and challenges. ACS Energy Letters, 2020, 5(5): 1537–1553

10 Mennel J A, Chidambaram D. A review on the development of electrolytes for lithium-based batteries for low temperature applications. Frontiers in Energy, 2023, 17(1): 43–71

11 Lai Y, Li Z, Zhao W. . An ultrasound-triggered cation chelation and reassembly route to one-dimensional Ni-rich cathode material enabling fast charging and stable cycling of Li-ion batteries. Nano Research, 2020, 13(12): 3347–3357

12 Murdock B E, Toghill K E, Tapia-Ruiz N. A perspective on the sustainability of cathode materials used in lithium-ion batteries. Advanced Energy Materials, 2021, 11(39): 2102028

13 Jeevanantham B, Shobana M K. Enhanced cathode materials for advanced lithium-ion batteries using nickel-rich and lithium/manganese-rich LiNi_xMn_yCo_zO₂. Journal of Energy Storage, 2022, 54: 105353

14 Li C, Liu B, Jiang N. . Elucidating the charge-transfer and Li-ion-migration mechanisms in commercial lithium-ion batteries with advanced electron microscopy. Nano Research Energy, 2022, 1(3): e9120031

15 Ye Z, Qiu L, Yang W. . Nickel-rich layered cathode materials for lithium-ion batteries. Chemistry, 2021, 27(13): 4249–4269

16 Lee S, Su L, Mesnier A. . Cracking vs. surface reactivity in high-nickel cathodes for lithium-ion batteries. Joule, 2023, 7(11): 2430–2444

17 Guo W, Wei W, Zhu H. . In situ surface engineering enables high interface stability and rapid reaction Kinetics for Ni-rich cathodes. eScience, 2023, 3(1): 100082

18 Zeng X, Zhan C, Lu J. . Stabilization of a high-capacity and high-power nickel-based cathode for Li-ion batteries. Chem, 2018, 4(4): 690–704

19 Liu L, Zhao Y, Shan L. . Improved electrochemical performance of Co-free Ni-rich cathode material for lithium-ion battery through multi-element composite modification. Electrochimica Acta, 2024, 477: 143804

20 Hou P, Gong M, Tian Y. . A new high-valence cation pillar within the Li layer of compositionally optimized Ni-rich LiNi_0.9Co_0.1O₂ with improved structural stability for Li-ion battery. Journal of Colloid and Interface Science, 2024, 653: 129–136

21 Qi N, Yan K, Yu Y. . Machine learning and neural network supported state of health simulation and forecasting model for lithium-ion battery. Frontiers in Energy, 2024, 18(2): 223–240

22 Dong J, Wu F, Zhao J. . Multifunctional self-reconstructive cathode/electrolyte interphase layer for cobalt-free Li-rich layered oxide cathode. Energy Storage Materials, 2023, 60: 102798

23 Wu K, Wu X, Lin Z. . Identifying the calendar aging boundary and high temperature capacity fading mechanism of Li ion battery with Ni-rich cathode. Journal of Power Sources, 2024, 589: 233736

24 Wu F, Dong J, Chen L. . High-voltage and high-safety nickel-rich layered cathode enabled by a self-reconstructive cathode/electrolyte interphase layer. Energy Storage Materials, 2021, 41: 495–504

25 Duan Y, Chen S P, Zhang L. . Review on oxygen release mechanism and modification strategy of nickel-rich NCM cathode materials for lithium-ion batteries: Recent advances and future directions. Energy & Fuels, 2024, 38(7): 5607–5631

26 Zhao H, Yu X, Li J. . Film-forming electrolyte additives for rechargeable lithium-ion batteries: Progress and outlook. Journal of Materials Chemistry. A, Materials for Energy and Sustainability, 2019, 7(15): 8700–8722

27 Manthiram A, Knight J C, Myung S. . Nickel-rich and lithium-rich layered oxide cathodes: Progress and perspectives. Advanced Energy Materials, 2016, 6(1): 1501010

28 Li H, Liu A, Zhang N. . An unavoidable challenge for Ni-rich positive electrode materials for lithium-ion batteries. Chemistry of Materials, 2019, 31(18): 7574–7583

29 Wood D L III, Wood M, Li J. . Perspectives on the relationship between materials chemistry and roll-to-roll electrode manufacturing for high-energy lithium-ion batteries. Energy Storage Materials, 2020, 29: 254–265

30 Dreyer S L, Kretschmer K R, Tripković Đ. . Multi-element surface coating of layered Ni-rich oxide cathode materials and their long-term cycling performance in lithium-ion batteries. Advanced Materials Interfaces, 2022, 9(8): 2101100

31 Ran Q, Zhao H, Shu X. . Enhancing the electrochemical performance of Ni-rich layered oxide cathodes by combination of the gradient doping and dual-conductive layers coating. ACS Applied Energy Materials, 2019, 2(5): 3120–3130

32 Kim H, Jang J, Byun D. . Selective TiO₂ nanolayer coating by polydopamine modification for highly stable Ni-rich layered oxides. ChemSusChem, 2019, 12(24): 5253–5264

33 Wang H, Li X, Li F. . Formation and modification of cathode electrolyte interphase: A mini review. Electrochemistry Communications, 2021, 122: 106870

34 Li Q, Wang Y, Wang X. . Investigations on the fundamental process of cathode electrolyte interphase formation and evolution of high-voltage cathodes. ACS Applied Materials & Interfaces, 2020, 12(2): 2319–2326

35 Kühn S P, Edström K, Winter M. . Face to face at the cathode electrolyte interphase: From interface features to interphase formation and dynamics. Advanced Materials Interfaces, 2022, 9(8): 2102078

36 Gao H, Maglia F, Lamp P. . Mechanistic study of electrolyte additives to stabilize high-voltage cathode–electrolyte interface in lithium-ion batteries. ACS Applied Materials & Interfaces, 2017, 9(51): 44542–44549

37 Liu Y, Hong L, Jiang R. . Multifunctional electrolyte additive stabilizes electrode–electrolyte interface layers for high-voltage lithium metal batteries. ACS Applied Materials & Interfaces, 2021, 13(48): 57430–57441

38 Li G, Feng Y, Zhu J. . Achieving a highly stable electrode/electrolyte interface for a nickel-rich cathode via an additive-containing gel polymer electrolyte. ACS Applied Materials & Interfaces, 2022, 14(32): 36656–36667

39 Wang Y, Yang X, Meng Y. . Fluorine chemistry in rechargeable batteries: Challenges, progress, and perspectives. Chemical Reviews, 2024, 124(6): 3494–3589

40 Zhang Z, Qin C, Cheng X. . Electron energy levels determining cathode electrolyte interphase formation. Electron, 2023, 1(2): e9

41 Gao T, Tian P, Xu Q. . Coating effect of various-phase alumina nanoparticles on NCM811 cathode for enhancing electrochemical performance of lithium-ion batteries. ACS Applied Energy Materials, 2024, 7(9): 3904–3915

42 Wu Y, Guo J, Qin F. . Harmless pre-lithiation via advantageous surface reconstruction in sacrificial cathode additives for lithium-ion batteries. Journal of Colloid and Interface Science, 2024, 658: 976–985