High-energy All-solid-state Lithium Batteries Enabled by Co-free LiNiO Cathodes with Robust Outside-in Structures

A critical current challenge in the development of all-solid-state lithium batteries (ASSLBs) is reducing the cost of fabrication without compromising the performance. Here we report a sulfide ASSLB based on a high-energy, Co-free LiNiO cathode with a robust outside-in structure. This promising cathode is enabled by the high-pressure O synthesis and subsequent atomic layer deposition of a unique ultrathin LiAlZnO protective layer comprising a LiAlZnO surface coating region and an Al and Zn near-surface doping region. This high-quality artificial interphase enhances the structural stability and interfacial dynamics of the cathode as it mitigates the contact loss and continuous side reactions at the cathode/solid electrolyte interface. As a result, our ASSLBs exhibit a high areal capacity (4.65 mAh cm), a high specific cathode capacity (203 mAh g), superior cycling stability (92% capacity retention after 200 cycles) and a good rate capability (93 mAh g at 2C). This work also offers mechanistic insights into how to break through the limitation of using expensive cathodes (for example, Co-based) and coatings (for example, Nb-, Ta-, La- or Zr-based) while still achieving a high-energy ASSLB performance.