Dynamic Electrode-Electrolyte Intermixing in Solid-State Sodium Nano-Batteries.

Nanostructured solid-state batteries (SSBs) are poised to meet the demands of next-generation energy storage technologies by realizing performance competitive to their liquid-based counterparts while simultaneously offering improved safety and expanded form factors. Atomic layer deposition (ALD) is among the tools essential to fabricate nanostructured devices with challenging aspect ratios. Here, we report the fabrication and electrochemical testing of the first nanoscale sodium all-solid-state battery (SSB) using ALD to deposit both the V 2 O 5 cathode and NaPON solid electrolyte followed by evaporation of a thin-film Na metal anode. NaPON exhibits remarkable stability against evaporated Na metal, showing no electrolyte breakdown or significant interphase formation in the voltage range of 0.05-6.0 V vs Na/Na + . Electrochemical analysis of the SSB suggests intermixing of the NaPON/V 2 O 5 layers during fabrication, which we investigate in three ways: in situ spectroscopic ellipsometry, time-resolved X-ray photoelectron spectroscopy (XPS) depth profiling, and cross-sectional cryo-scanning transmission electron microscopy (cryo-STEM) coupled with electron energy loss spectroscopy (EELS). We characterize the interfacial reaction during the ALD NaPON deposition on V 2 O 5 to be twofold: (1) reduction of V 2 O 5 to VO 2 and (2) Na + insertion into VO 2 to form Na x VO 2 . Despite the intermixing of NaPON-V 2 O 5 , we demonstrate that NaPON-coated V 2 O 5 electrodes display enhanced electrochemical cycling stability in liquid-electrolyte coin cells through the formation of a stable electrolyte interphase. In all-SSBs, the Na metal evaporation process is found to intensify the intermixing reaction, resulting in the irreversible formation of mixed interphases between discrete battery layers. Despite this graded composition, the SSB can operate for over 100 charge-discharge cycles at room temperature and represents the first demonstration of a functional thin-film solid-state sodium-ion battery.