Surface Structure Evolution and its Impact on the Electrochemical Performances of Aqueous‐Processed High‐Voltage Spinel LiNi0.5Mn1.5O4 Cathodes in Lithium‐Ion Batteries

• Published in: Advanced functional materials Vol. 32; no. 46
• Main Authors: He, Jiarong, Melinte, Georgian, Darma, Mariyam Susana Dewi, Hua, Weibo, Das, Chittaranjan, Schökel, Alexander, Etter, Martin, Hansen, Anna‐Lena, Mereacre, Liuda, Geckle, Udo, Bergfeldt, Thomas, Sun, Zhipeng, Knapp, Michael, Ehrenberg, Helmut, Maibach, Julia
• Format: Journal Article
• Language: English
• Published: Hoboken Wiley Subscription Services, Inc 10.11.2022
• Subjects: Cathodes; Decay rate; Electric potential; Electrodes; Environmental impact; Evolution; high energy densities; Interface stability; Lithium-ion batteries; Materials science; operando XRDs; pair distribution functions; Phase transitions; Polyacrylic acid; positive electrodes; Spinel; surface reconstruction layers; Surface structure; Voltage
• ISSN: 1616-301X; 1616-3028
• DOI: 10.1002/adfm.202207937

LiNi0.5Mn1.5O4 (LNMO) is a promising cathode in lithium‐ion batteries (LIBs) due to its high operating voltage and open Li+ diffusion framework. However, the instability of the electrode–electrolyte interface and the negative environmental impact of electrode fabrication processes limit its practical application. Therefore, switching electrode processing conditions to aqueous and understanding the accompanying surface structural evolution are imperative. Here, water‐treated, poly(acrylic acid) (PAA)‐treated, and H3PO4‐treated LNMO, labeled as W‐LNMO, A‐LNMO, and H‐LNMO, are studied systematically. W‐LNMO shows a high concentration of Mn3+ induced by Li loss while a conformal PAA layer formed on A‐LNMO reduces this phenomenon. H‐LNMO displays a second MnPO4∙H2O phase. Upon cycling, a fast capacity decay is observed in W‐LNMO while an extra plateau at ≈2.7 V appears in the initial charging, corresponding to a two‐phase transition. A surface reconstruction layer from a spinel to a rock‐salt phase with a reductive Mn2+ segregation is observed in W‐LNMO after 105 cycles. The PAA layer persists on A‐LNMO and alleviates the capacity decay. H‐LNMO delivers a relatively low capacity due to the formation of a MnPO4∙H2O phase. This study provides new insights into manipulating the surface chemistry of LNMO cathodes to enable aqueous, large‐scale processingin LIBs. Surface structural evolution of high‐voltage spinel LNMO cathodes after different aqueous processing and their impact on the electrochemical performances are systematically investigated. It provides new insights into manipulating the surface chemistry of cathode materials toward aqueous fabrication of LNMO electrodes, opening a significant avenue for resolving the current challenges for a wide family of high‐voltage cathode materials (>4.5 V) toward practical applications.