Degradation and SEI Evolution in Alloy Anodes Revealed by Correlative Liquid-Cell Electrochemistry and Cryogenic Microscopy

TL;DR

This study combines advanced cryogenic microscopy and electrochemical techniques to visualize and understand the dynamic evolution of solid electrolyte interphase and lithium alloying in alloy anodes, revealing degradation mechanisms.

Contribution

It introduces a correlative operando characterization workflow that captures interfacial processes in alloy anodes with high spatial and chemical resolution.

Findings

Heterogeneous SEI formation observed at the solid-liquid interface.

Lithium carbonate-rich inner SEI layers identified.

Retention of elemental lithium along grain boundaries and lithium loss mechanisms.

Abstract

Understanding solid liquid interfaces at high spatial and chemical resolution is crucial for advancing electrochemical energy storage technologies, yet this remains a persistent challenge due to the lack of characterisation techniques that can capture dynamic processes and preserve fragile interfacial chemistries. In lithium ion batteries, interfacial phenomena such as lithium alloying, solid electrolyte interphase formation, and electrode degradation play a decisive role in capacity retention and failure mechanisms but are difficult to observe in their native state due to high mobility, reactivity, and low atomic number of lithium. Here, we use a recently introduced correlative operando characterisation approach that integrates electrochemical liquid cell transmission electron microscopy with cryogenic atom probe tomography to resolve the evolution of a platinum alloy anode at the solid liquid interface during electrochemical cycling. This correlative, cryo enabled workflow reveals spatially heterogeneous SEI formation, the presence of lithium carbonate rich inner SEI layers, and the retention of elemental lithium within the platinum electrode, most likely trapped along grain boundaries. Additionally, we observe the formation of mossy lithium structures and irreversible lithium loss through dead lithium accumulation. Our results provide direct mechanistic insight into lithium alloying and degradation pathways in alloy based anodes and establish a generalised platform for probing dynamic electrochemical interfaces with complementary structural and chemical sensitivity. The methodology is broadly applicable to next generation electrode materials and electrochemical devices where interfacial dynamics dictate performance and stability.