In order to analyze the interfacial reaction between cathode and electrolyte, thin-film model electrode with LiCoO2 cathode and Li2S-P2S5 solid electrolyte was deposited on mirror-polished platinum substrate by pulsed laser deposition (PLD). A Li3PO4 interlayer was also deposited between cathode and solid electrolyte by PLD. Electrochemical measurements were performed by using liquid electrolyte (1M LiClO4 in propylene carbonate) and lithium metal anode. Cyclic voltammetry measurement (CV) was carried out from 3.2 V to 4.4 V at 0.1 mV/s. EIS measurement was performed at 3.9 V, 4.0 V, 4.1 V, 4.2 V, 4.3 V and 4.4 V with a 30 mV amplitude. The frequency range of EIS was limited from 10-2 to 106 Hz. Depth-resolved XAS measurements were conducted using the BL37XU beamline, SPring-8, Japan, with a two-dimensional pixel array detector, PILATUS (Dectris, Switzerland).
The first cycle of CV curves of the film without Li3PO4 interlayer shows a current peak around 3.2 V, which is considered to come from the reaction between cathode and electrolyte. EIS measurements show that the interfacial resistance of the films with Li3PO4 interlayer does not increase compared with the film without Li3PO4 interlayer. In order to discuss the interfacial structure, depth resolved X-ray near edge structure at Co K-edge is analyzed. The energy shift around the interface in the film with Li3PO4 interlayer is smaller than that of sample without Li3PO4 interlayer. These results indicate that valence changes of cobalt ions near cathode/solid electrolyte interface are suppressed by using Li3PO4 interlayer. The introducing of Li3PO4 interlayer reduces the inter-diffusion between cathode and solid electrolyte.
 K. Takada, N. Ohta, L. Zhang, K. Fukuda, I. Sakaguchi, R. Ma, M. Osada, T. Sasaki., Solid State Ionics, 179 (2008) 1333.
 A. Sakuda, A. Hayashi, M. Tatsumisago., Chem Mater, 22 (2010) 949.
 K. Kishida, N. Wada, H. Adachi, K. Tanaka, H. Inui, C. Yada, Y. Iriyama, Z. Ogumi., Acta Materialia, 55 (2007) 4713.
This research was financially supported by the Japan Science and Technology Agency (JST), Advanced Low Carbon Technology Research and Development Program (ALCA), Specially Promoted Research for Innovative Next Generation Batteries (SPRING) Project.