Cycle stability of solid-state lithium batteries (SSLBs) using a LiCoO2 cathode is improved by atomic layer deposition (ALD) on active material powder with Al2O3. SSLBs with LiCoO2/Li3.15Ge0.15P0.85S4/77.5Li(2)S-22.5P(2)S(5)/Li structure were constructed and tested by charge-discharge cycling at a current density of 45 mu A cm(-2) with a voltage window of 3.3 similar to 4.3 V (vs. Li/Li+). Capacity degradation during cycling is suppressed dramatically by employing Al2O3 ALD-coated LiCoO2 in the composite cathode. Whereas only 70% of capacity retention is achieved for uncoated LiCoO2 after 25 cycles, 90% of capacity retention is observed for LiCoO2 with ALD Al2O3 layers. Electrochemical impedance spectroscopy (EIS) and transmission electron microscopy (TEM) studies show that the presence of ALD Al2O3 layers on the surface of LiCoO2 reduces interfacial resistance development between LiCoO2 and solid state electrolyte (SSE) during cycling. (C) 2012 The Electrochemical Society. [DOI: 10.1149/2.085207jes] All rights reserved.