  Using a new class of (BH4)- substituted argyrodite Li6PS5Z0.83(BH4)0.17, (Z =
Cl, I) solid electrolyte, Li-metal solid-state batteries operating at room
temperature have been developed. The cells were made by combining the modified
argyrodite with an In-Li anode and two types of cathode: an oxide, LixMO2 (M =
1/3Ni, 1/3Mn, 1/3Co; so called NMC) and a titanium disulfide, TiS2. The
performance of the cells was evaluated through galvanostatic cycling and
Alternating Current AC electrochemical impedance measurements. Reversible
capacities were observed for both cathodes for at least tens of cycles.
However, the high-voltage oxide cathode cell shows lower reversible capacity
and larger fading upon cycling than the sulfide one. The AC impedance
measurements revealed an increasing interfacial resistance at the cathode side
for the oxide cathode inducing the capacity fading. This resistance was
attributed to the intrinsic poor conductivity of NMC and interfacial reactions
between the oxide material and the argyrodite electrolyte. On the contrary, the
low interfacial resistance of the TiS2 cell during cycling evidences a better
chemical compatibility between this active material and substituted
argyrodites, allowing full cycling of the cathode material, 240 mAhg-1, for at
least 35 cycles with a coulombic efficiency above 97%.
