A quantitative reconstruction strategy for the surface structure of LiNi_0.80Co_0.15Al_0.05O₂ cathode material

Abstract

To address the detrimental impact of residual LiOH on the electrochemical performance of LiNi_0.80Co_0.15Al_0.05O₂ (NCA) cathode material, it is imperative to optimize its surface structure. Adding a Li-reactant to react with residual LiOH on the cathode surface not only removes residual LiOH but also forms new surface structure layers. However, this reaction process not only necessitates evaluating the compatibility between the newly formed surface layer and the crystal structure of the NCA cathode material but also requires careful determination of the optimal amount of Li-reactant. Currently, there remains a lack of well-established theoretical guidance for determining the optimal addition amount of lithium reactants. In this study, the quantitative addition of 6,000 ppm Al₂O₃ as a Li-reactant to react with the residual 3,156 ppm LiOH on the NCA surface not only effectively reduces the residual LiOH but also facilitates the formation of a LiAlO₂@NCA heterostructure on the NCA cathode materials. This approach provides a theoretical foundation for the addition of Li-reactant, overcomes the limitations of empirical trial-and-error methods, and achieves quantitative reconstruction of the NCA cathode materials surface structure. Based on an in-depth analysis of the surface structure, first-principles calculations and electrochemical performance tests, the LiAlO₂@NCA heterostructure not only serves as an efficient Li⁺ diffusion channel and reduces the Li⁺ migration energy barrier, but also provides a stable protection of the surface of the cathode material, thereby enhancing its stability and reversibility.

Keywords

Quantitative reconstruction / residual LiOH / Al₂O₃ / heterostructure

References

[1] Lee S,Park G.Doping strategy in developing Ni-rich cathodes for high-performance lithium-ion batteries.ACS Energy Lett2024;9:740-7

[2] Yang J,Ryu H,Sun Y.Ni-rich layered cathodes for lithium-ion batteries: from challenges to the future.Energy Storage Mater2023;63:102969

[3] Xia S,Yao L.Nitrogen-rich two-dimensional π-conjugated porous covalent quinazoline polymer for lithium storage.Energy Storage Mater2022;50:225-33

[4] Xia S,Huang W.Extended π-conjugated N-containing heteroaromatic hexacarboxylate organic anode for high performance rechargeable batteries.J Energy Chem2020;51:303-11

[5] Sagar RUR,Cai Q,Chen YI.A comparative study on morphology dependent performance of neodymium - graphene as an anode material in lithium-ion batteries.J Energy Storage2024;77:109854

[6] Rehman Sagar RU,Fazal MW.An ultralight porous carbon scaffold for anode-free lithium metal batteries.J Mater Chem A2025;13:5081-90

[7] Huang W,Zhao G.Constructing nano spinel phase and Li⁺ conductive network to enhance the electrochemical stability of ultrahigh-Ni cathode.Mater Today2024;79:86-96

[8] Deng Z,Wang L.Challenges of thermal stability of high-energy layered oxide cathode materials for lithium-ion batteries: a review.Mater Today2023;69:236-61

[9] Wu Z,Yuan F.Ni-rich cathode materials for stable high-energy lithium-ion batteries.Nano Energy2024;126:109620

[10] Ryu H,Seo JH.A highly stabilized Ni-rich NCA cathode for high-energy lithium-ion batteries.Mater Today2020;36:73-82

[11] Ryu H,Lee SG.Near-surface reconstruction in Ni-rich layered cathodes for high-performance lithium-ion batteries.Nat Energy2024;9:47-56

[12] Seong WM,Park JW.Controlling residual lithium in high-nickel (> 90 %) lithium layered oxides for cathodes in lithium-ion batteries.Angew Chem Int Ed2020;59:18662-9

[13] Sheng H,Xiao DD.An air-stable high-nickel cathode with reinforced electrochemical performance enabled by convertible amorphous Li₂CO₃ modification.Adv Mater2022;34:e2108947

[14] Song M,Kim J.Chemical decomposition pathway of residual lithium carbonate of Li-ion battery cathodes.J Power Sources2023;560:232699

[15] Du Y,Meng X.Chemically converting residual lithium to a composite coating layer to enhance the rate capability and stability of single-crystalline Ni-rich cathodes.Nano Energy2022;94:106901

[16] Cao D,Chen Y.Oxidative decomposition mechanisms of lithium carbonate on carbon substrates in lithium battery chemistries.Nat Commun2022;13:4908 PMCID:PMC9392741

[17] Cui Z.Thermal stability and outgassing behaviors of high-nickel cathodes in lithium-ion batteries.Angew Chem Int Ed2023;62:e202307243

[18] Seong WM,Manthiram A.Impact of residual lithium on the adoption of high-nickel layered oxide cathodes for lithium-ion batteries.Chem Mater2020;32:9479-89

[19] Freiberg AT,Solchenbach S.Li₂CO₃ decomposition in Li-ion batteries induced by the electrochemical oxidation of the electrolyte and of electrolyte impurities.Electrochim Acta2020;346:136271

[20] Cui Z,Guo Z,Manthiram A.Formation and detriments of residual alkaline compounds on high-nickel layered oxide cathodes.Adv Mater2024;36:e2402420

[21] Wang C,Guo X.Air-induced degradation and electrochemical regeneration for the performance of layered Ni-rich cathodes.ACS Appl Mater Interfaces2019;11:44036-45

[22] Aktekin B,Müller-Buschbaum K,Janek J.The formation of residual lithium compounds on Ni-rich NCM oxides: their impact on the electrochemical performance of sulfide-based ASSBs.Adv Funct Mater2024;34:2313252

[23] Renfrew SE.Residual lithium carbonate predominantly accounts for first cycle CO₂ and CO outgassing of Li-stoichiometric and Li-rich layered transition-metal oxides.J Am Chem Soc2017;139:17853-60

[24] Xia Y,Wang K.Industrial modification comparison of Ni-Rich cathode materials towards enhanced surface chemical stability against ambient air for advanced lithium-ion batteries.Chem Eng J2022;450:138382

[25] Gao Y,Dai Z.Revealing the relationships between washing/recalcination processes and structure performance of Ni-rich layered cathode materials.ACS Appl Energy Mater2022;5:15069-77

[26] Zhang SS,Wang C.Enhanced electrochemical performance of Ni-rich layered cathode materials by using LiPF₆ as a cathode additive.ChemElectroChem2019;6:1536-41

[27] Kim J,Zhang J,Meng YS.A review on the stability and surface modification of layered transition-metal oxide cathodes.Mater Today2021;46:155-82

[28] Wen Z,Shi H.Improved electrochemical performance of single-crystal nickel-rich cathode by coating with different valence states metal oxides.J Energy Storage2024;98:113037

[29] Wei J,Zhang H,Liu Y.Enhancement in the electrochemical stability at high voltage of high nickel cathode through constructing ultrathin LiCoPO₄ coating.Appl Surf Sci2024;659:159922

[30] Yang H,Zhang XD.Building a self-adaptive protective layer on Ni-rich layered cathodes to enhance the cycle stability of lithium-ion batteries.Adv Mater2022;34:e2204835

[31] Kim S,Ku M,Lee J.Coating robust layers on Ni-rich cathode active materials while suppressing cation mixing for all-solid-state lithium-ion batteries.ACS Nano2024;18:25096-106

[32] Wu F,Chen L.New insights into dry-coating-processed surface engineering enabling structurally and thermally stable high-performance Ni-rich cathode materials for lithium ion batteries.Chem Eng J2023;470:144045

[33] Chu Y,Zou L.Thermodynamically stable dual-modified LiF&FeF₃ layer empowering Ni-rich cathodes with superior cyclabilities.Adv Mater2023;35:e2212308

[34] Xia S,Shen X.Rearrangement on surface structures by boride to enhanced cycle stability for LiNi_0.80Co_0.15Al_0.05O₂ cathode in lithium ion batteries.J Energy Chem2020;45:110-8

[35] Negi RS,Pan R.A dry-processed Al₂O₃/LiAlO₂ coating for stabilizing the cathode/electrolyte interface in high-Ni NCM-based all-solid-state batteries.Adv Mater Inter2022;9:2101428

[36] Park HG,Park K.A synergistic effect of Na⁺ and Al³⁺ dual doping on electrochemical performance and structural stability of LiNi_0.88Co_0.08Mn_0.04O₂ cathodes for Li-ion batteries.ACS Appl Mater Interfaces2022;14:5168-76

[37] Yang Z,Yang H.Promoting air stability of Co-Li₂O cathode additive via LiAlO₂ coating for lithium-ion batteries.J Electroanal Chem2025;983:119042

[38] Liang C,Lv C.Surface oxygen-locked LiNi_0.6Mn_0.4O₂: towards stable cycling at 4.7 V.Energy Storage Mater2025;75:104087

[39] Sun Y,Chen X,Xiang F.Enhancing the stabilities and electrochemical performances of LiNi_0.5Co_0.2Mn_0.3O₂ cathode material by simultaneous LiAlO₂ coating and Al doping.Electrochim Acta2021;376:138038

[40] Guo X,Dai S,Liu D.The intricate roles of Al₂O₃ on the structure and electrochemical performances of LiNi_0.5Co_0.2Mn_0.3O₂ cathodematerials.J Alloys Compd2024;984:173931

[41] Lv Y,Zhang J.Antimony doping enabled radially aligned microstructurein LiNi_0.91Co_0.06Al_0.03O₂ cathode for high-voltage and low-temperature lithium battery.Adv Funct Mater2024;34:2312284

[42] Zhou Y,Wang Y.Relieving stress concentration through anion-cation codoping toward highly stable nickel-rich cathode.ACS Nano2023;17:20621-33

[43] Li L,Zhang Q.A hydrolysis-hydrothermal route for the synthesis of ultrathin LiAlO₂-inlaid LiNi_0.5Co_0.2Mn_0.3O₂ as a high-performance cathode material for lithium ion batteries.J Mater Chem A2015;3:894-904

[44] Bichon M,Dupré N.Study of immersion of LiNi_0.5Mn_0.3Co_0.2O₂ material in water for aqueous processing of positive electrode for Li-ion batteries.ACS Appl Mater Interfaces2019;11:18331-41

[45] Wood KN.XPS on Li-battery-related compounds: analysis of inorganic SEI phases and a methodology for charge correction.ACS Appl Energy Mater2018;1:4493-504

[46] Wu F,Chen L.High-voltage and high-safety nickel-rich layered cathode enabled by a self-reconstructive cathode/electrolyte interphase layer.Energy Storage Mater2021;41:495-504

[47] Wu F,Kuenzel M.Elucidating the effect of iron doping on the electrochemical performance of cobalt-free lithium-rich layered cathode materials.Adv Energy Mater2019;9:1902445

[48] Chen Z,Bresser D.MnPO₄-coated Li(Ni_0.4Co_0.2Mn_0.4)O₂ for Lithium(-ion) batteries with outstanding cycling stability and enhanced lithiation kinetics.Adv Energy Mater2018;8:1801573

[49] Jung C,Eum D.New insight into microstructure engineering of Ni-rich layered oxide cathode for high performance lithium ion batteries.Adv Funct Mater2021;31:2010095

[50] Sun Y,Huang W.One-step calcination synthesis of bulk-doped surface-modified Ni-rich cathodes with superlattice for long-cycling Li-ion batteries.Angew Chem Int Ed2023;62:e202300962

[51] Lv Y,Lu S.Engineering of cobalt-free Ni-rich cathode material by dual-element modification to enable 4.5 V-class high-energy-density lithium-ion batteries.Chem Eng J2023;455:140652