Rechargeable sodium ion batteries with high energy density are a promising technology to address the demand for grid storage. Cathode materials with oxygen redox activity exhibit higher energy density than expected from Na-ion removal and charge compensation solely by transition metal redox. One strategy to enable oxygen redox in materials is to alter the oxygen environment through transition metal layer ordering. In this work, we report the investigation of oxygen redox activity induced by transition metal ordering in P2-type Na0.8Li0.12Ni0.22Mn0.66O2 cathode synthesized by carbonate co-precipitation. Irreversible oxygen activity was observed and correlated with Ni migration that resulted in the loss of transition metal ordering in the structure. Calculated density of states shows that after Ni migration, the number of unoccupied states of O above Fermi level decreases, inhibiting the reduction of oxygen during sodiation. This paper provides insights on how Ni migration has a detrimental effect on transition metal ordering and reversibility of oxygen redox at high voltage.

All solid-state batteries (ASSBs) have the potential to deliver higher energy densities, wider operating temperature range, and improved safety compared with today's liquid-electrolyte-based batteries. However, of the various solid-state electrolyte (SSE) classes - polymers, sulfides, or oxides - none alone can deliver the combined properties of ionic conductivity, mechanical, and chemical stability needed to address scalability and commercialization challenges. While promising strategies to overcome these include the use of polymer/oxide or sulfide composites, there is still a lack of fundamental understanding between different SSE-polymer-solvent systems and its selection criteria. Here, we isolate various SSE-polymer-solvent systems and study their molecular level interactions by combining various characterization tools. With these findings, we introduce a suitable Li7P3S11SSE-SEBS polymer-xylene solvent combination that significantly reduces SSE thickness (∼50 μm). The SSE-polymer composite displays high room temperature conductivity (0.7 mS cm-1) and good stability with lithium metal by plating and stripping over 2000 h at 1.1 mAh cm-2. This study suggests the importance of understanding fundamental SSE-polymer-solvent interactions and provides a design strategy for scalable production of ASSBs.

Enabling long cyclability of high-voltage oxide cathodes is a persistent challenge for all-solid-state batteries, largely because of their poor interfacial stabilities against sulfide solid electrolytes. While protective oxide coating layers such as LiNbO₃ (LNO) have been proposed, its precise working mechanisms are still not fully understood. Existing literature attributes reductions in interfacial impedance growth to the coating's ability to prevent interfacial reactions. However, its true nature is more complex, with cathode interfacial reactions and electrolyte electrochemical decomposition occurring simultaneously, making it difficult to decouple each effect. Herein, we utilized various advanced characterization tools and first-principles calculations to probe the interfacial phenomenon between solid electrolyte Li₆PS₅Cl (LPSCl) and high-voltage cathode LiNi_0.85Co_0.1Al_0.05O₂ (NCA). We segregated the effects of spontaneous reaction between LPSCl and NCA at the interface and quantified the intrinsic electrochemical decomposition of LPSCl during cell cycling. Both experimental and computational results demonstrated improved thermodynamic stability between NCA and LPSCl after incorporation of the LNO coating. Additionally, we revealed the in situ passivation effect of LPSCl electrochemical decomposition. When combined, both these phenomena occurring at the first charge cycle result in a stabilized interface, enabling long cyclability of all-solid-state batteries.