Investigations into the superionic glass phase of Li${}_4$PS${}_4$I for improving the stability of high-loading all-solid-state batteries

In recent years, investigations into improving the performance of bulk-type solid-state batteries (SSBs) have attracted much attention. This is due, in part, to the fact that they offer an opportunity to outperform the present Li-ion battery technology in terms of energy density. Ni-rich Li${}_{1+x}$(Ni${}_{1-y-z}$Co${}_y$Mn${}_z$)${}_{1-x}$O${}_2$ (NCM) and lithium-thiophosphate-based solid electrolytes appear to be a promising material combination for application at the cathode side. Here, we report about exploratory investigations into the 1.5Li${}_2$S/0.5P${}_2$S${}_5$/LiI phase system and demonstrate that a glassy solid electrolyte has more than an order of magnitude higher room-temperature ionic conductivity than the crystalline counterpart, tetragonal Li${}_4$PS${}_4$I with the P4/nmm space group (∼1.3 versus ∼0.2 mS cm${}^{-1}$). In addition, preliminary results show that usage of the glassy 1.5Li${}_2$S–0.5P${}_2$S${}_5$–LiI in pellet stack SSB cells with an NCM622 (60% Ni content) cathode and a Li${}_4$Ti${}_5$O${}_{12}$ anode leads to enhanced capacity retention when compared to the frequently employed argyrodite Li${}_6$PS${}_5$Cl solid electrolyte. ... mehrThis indicates that, apart from interfacial instabilities, the stiffness (modulus) of the solid electrolyte and associated mechanical effects may also impact significantly the long-term performance. Moreover, SSB cells with the glassy 1.5Li${}_2$S–0.5P${}_2$S${}_5$–LiI and high-loading cathode (∼22 mg${}_{NCM622}$ cm${}^{-2}$) manufactured using a slurry-casting process are found to cycle stably for 200 cycles at C/5 rate and 45 °C, with areal capacities in excess of 3 mA h cm${}^{-2}$.