Three-Dimensional Solid-State Lithium-Ion Batteries Fabricated Via Conformal Vapor-Phase Chemistry

Abstract

Thin film solid state lithium-based batteries (TSSBs) are increasingly attractive for their intrinsic safety due to the use of a nonflammable solid electrolyte, cycling stability, and ability to be easily patterned in small form factors. However, existing methods for fabricating TSSBs are limited to planar geometries, which severely limits areal energy density when the electrodes are kept sufficiently thin to achieve high areal power. In order to circumvent this limitation, we report the first successful fabrication of fully conformal, 3D full cell TSSBs formed in micromachined silicon substrates with aspect ratios up to ~10 using atomic layer deposition (ALD) at low processing temperatures (at or below 250C) to deposit all active battery components. The cells utilize a prelithiated LiV$_2$O$_5$ cathode, a very thin (40 - 100 nm) LiPON-like lithium polyphosphazene (Li$_2$PO$_2$N) solid electrolyte, and a SnN$_x$ conversion anode, along with Ru and TiN current collectors. Planar all-ALD solid state cells deliver 37 {\mu}Ah/cm$^2${\mu}m normalized to the cathode thickness with only 0.02% per-cycle capacity loss for hundreds of cycles. Fabrication of full cells in 3D substrates increases the areal discharge capacity by up to a factor of 9.3x while simultaneously improving the rate performance, which corresponds well to trends identified by finite element simulations of the cathode film. This work shows that the exceptional conformality of ALD, combined with conventional semiconductor fabrication methods, provides an avenue for the successful realization of long-sought 3D TSSBs which provide power performance scaling in regimes inaccessible to planar form factor devices.