Abstract
All solid-state batteries (SSBs) are considered the most promising path to enabling higher energy-density portable energy, while concurrently improving safety as compared to current liquid electrolyte solutions. However, the desire for high energy necessitates the choice of high-voltage cathodes, such as nickel-rich layered oxides, where degradation phenomena related to oxygen loss and structural densification at the cathode surface are known to significantly compromise the cycle and thermal stability. In this work, we show, for the first time, that even in an SSB, and when protected by an intact amorphous coating, the LiNi(0.5)Mn(0.3)Co(0.2)O(2) (NMC(532)) surface transforms from a layered structure into a rocksalt-like structure after electrochemical cycling. The transformation of the surface structure of the Li(3)B(11)O(18) (LBO)-coated NMC(532) cathode in a thiophosphate-based solid-state cell is characterized by high-resolution complementary electron microscopy techniques and electron energy loss spectroscopy. Ab initio molecular dynamics corroborate facile transport of O(2-) in the LBO coating and in other typical coating materials. This work identifies that oxygen loss remains a formidable challenge and barrier to long-cycle life high-energy storage, even in SSBs with durable, amorphous cathode coatings, and directs attention to considering oxygen permeability as an important new design criteria for coating materials.