Deconvoluting Effects of Lithium Morphology and SEI Stability through Interface Engineering
Authors: Shuchi Sanzeeda Baig , Oyakhire Solomon , Cui Yi , Bent Stacey F. 
Published: August 2024

The widespread use of renewable energy resources and electrification is mandatory for transitioning into a fossil-fuel-free world. Currently, Li-ion battery (LIB) is the universal mode of electrochemical energy storage, but it is reaching the theoretical limit, creating the urgency of more efficient batteries for next-generation applications. Li-metal batteries (LMBs) are considered a key technology to overcome the current energy density limitations of LIBs. In the most energy-dense LMB configuration, the anode-free LMB, Li is directly plated on and stripped from the Cu current collector (CC), subjecting it to the most stringent cycling conditions and making performance regulation crucial. Therefore, engineering the Cu-electrolyte interface is both fundamentally and practically significant.

The two most crucial performance modulators in LMBs are electrodeposited Li morphology and solid electrolyte interphase (SEI). The literature has shown that low surface area morphology and anion-derived SEIs are usually beneficial for improved performance. However, it is difficult to deconvolute the individual impact of low surface area morphology and anionic SEI species on performance as they coexist and are correlated. One reported approach to understand the decoupled effects of morphology and SEI is ultrafast electrodeposition of lithium outpacing SEI formation (>100 mA cm-2). Our work establishes a new approach applicable at regular plating and stripping conditions (1 mA cm-2) that uses interface engineering with atomic layer deposited (ALD) thin films to deconvolve Li morphology and SEI stability effects. First, we modify the Cu CC surface using two different thin films with distinct characteristics: resistive, acidic HfO2; and conductive, acidic ZnO.

Leveraging ALD, we precisely control the thickness of the nanofilms and establish that increasing the film resistance results in improved performance due to resistance-derived Li morphology. Our approach of decoupling the impact of SEI species from morphology is to preform the SEI before cycling using a simple potential hold step for both these acidic films with opposite electrical properties at different thicknesses. We find that with increasing film thickness, generally, the preformed SEI has more anionic species due to the surface acidity of the thin films. Despite being anion-rich, the preformed SEI does not improve performance, which we attribute to its evolution into an organic-rich SEI during plating. Moreover, the impact of the preformed SEI is statistically insignificant during long-term cycling, whereas the role of resistance becomes more apparent. The effects are demonstrated through interface characterization and performance measurements in three different electrolytes, with at least a twofold increase in cycle life and improved capacity retention achieved in practical anode-free pouch cells. Our results thus indicate that morphological control is more effective for improved battery cyclability due to the inherent challenges with preformed SEI preservation, and as a result the resistance of the thin films is more important than surface acidity for CC modification.