Several active areas of research in novel energy storage technologies, including three-dimensional solid state batteries and passivation coatings for reactive battery electrode components, require conformal solid state electrolytes. We describe an atomic layer deposition (ALD) process for a member of the lithium phosphorus oxynitride (LiPON) family, which is employed as a thin film lithium-conducting solid electrolyte. The reaction between lithium tert-butoxide (LiOtBu) and diethyl phosphoramidate (DEPA) produces conformal, ionically conductive thin films with a stoichiometry close to Li2PO2N between 250 and 300∘C. The P/N ratio of the films is always 1, indicative of a particular polymorph of LiPON which closely resembles a polyphosphazene. Films grown at 300∘C have an ionic conductivity of 6.51(±0.36)×10−7 S/cm at 35∘C, and are functionally electrochemically stable in the window from 0 to 5.3V vs. Li/Li+. We demonstrate the viability of the ALD-grown electrolyte by integrating it into full solid state batteries, including thin film devices using LiCoO2 as the cathode and Si as the anode operating at up to 1 mA/cm2. The high quality of the ALD growth process allows pinhole-free deposition even on rough crystalline surfaces, and we demonstrate the fabrication and operation of thin film batteries with the thinnest (<100nm) solid state electrolytes yet reported. Finally, we show an additional application of the moderate-temperature ALD process by demonstrating a flexible solid state battery fabricated on a polymer substrate.
@article{arxiv.1702.04009,
title = {Nanoscale Solid State Batteries Enabled By Thermal Atomic Layer Deposition of a Lithium Polyphosphazene Solid State Electrolyte},
author = {Alexander J. Pearse and Thomas E. Schmitt and Elliot J. Fuller and Farid El-Gabaly and Chuan-Fu Lin and Konstantinos Gerasopoulos and Alexander C. Kozen and A. Alec Talin and Gary Rubloff and Keith E. Gregorcyzck},
journal= {arXiv preprint arXiv:1702.04009},
year = {2017}
}