Quantifying Phase Transformations in Alloying Anodes via in-situ Liquid Cell Hard X-ray Spectroscopy and Cryogenic Microscopy
Abstract
Understanding electrochemical phenomena at complex liquid-solid interfaces requires linking real-time structural dynamics with atomic-scale interfacial chemistry. Here, we integrate synchrotron X-ray fluorescence and diffraction with high-resolution cryogenic electron and ion multimodal microscopy to provide a mechanistic understanding of Pt-based alloying anodes across length scales. We directly observe the initial lithiation-driven formation of Li 2 Pt and its evolution to a stable LiPt intermetallic phase during extended cycling via a solid-solution type reaction mechanism. Simultaneously, the solid-electrolyte interphase transitions from an unstable carbonate-rich to a stable LiF-dominated composition, confirmed by cryogenic scanning transmission electron microscopy-electron energy loss spectroscopy. Crucially, cryogenic atom probe tomography reveals spatially distinct compositional regimes within the alloy anode: a lithium-flux-limited, heterogeneous interfacial zone and a diffusion-controlled, homogeneous LiPt alloy bulk. This nanoscale compositional gradient rationalizes the emergent solid-solution reaction mechanism and highlights how kinetic limitations and interface dynamics govern alloy formation and electrochemical stability. Our findings establish a correlative experimental framework that directly links structural dynamics with preserved near-atomic resolution interfacial chemistry, advancing the rational design of durable alloy electrodes for next-generation energy storage.
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BibTeX
@article{mulcahy2026quantifying,
title = {{Quantifying Phase Transformations in Alloying Anodes via in-situ Liquid Cell Hard X-ray Spectroscopy and Cryogenic Microscopy}},
author = {Neil Mulcahy and Syeda Ramin Jannat and Yaqi Li and Tigran Simonian and Mariana Palos and James Douglas and Jessica Walker and Baptiste Gault and Mary Ryan and Michele Shelly Conroy},
journal = {PRX Energy},
year = {2026},
month = aug,
doi = {10.1103/r3tc-hr17},
eprint = {2511.16382},
archivePrefix = {arXiv},
url = {https://hal.science/hal-05762221v1},
note = {CC BY 4.0},
}
RIS
TY - JOUR
TI - Quantifying Phase Transformations in Alloying Anodes via in-situ Liquid Cell Hard X-ray Spectroscopy and Cryogenic Microscopy
AU - Neil Mulcahy
AU - Syeda Ramin Jannat
AU - Yaqi Li
AU - Tigran Simonian
AU - Mariana Palos
AU - James Douglas
AU - Jessica Walker
AU - Baptiste Gault
AU - Mary Ryan
AU - Michele Shelly Conroy
PY - 2026
DA - 2026/08/12
JO - PRX Energy
DO - 10.1103/r3tc-hr17
UR - https://hal.science/hal-05762221v1
AB - Understanding electrochemical phenomena at complex liquid-solid interfaces requires linking real-time structural dynamics with atomic-scale interfacial chemistry. Here, we integrate synchrotron X-ray fluorescence and diffraction with high-resolution cryogenic electron and ion multimodal microscopy to provide a mechanistic understanding of Pt-based alloying anodes across length scales. We directly observe the initial lithiation-driven formation of Li 2 Pt and its evolution to a stable LiPt intermetallic phase during extended cycling via a solid-solution type reaction mechanism. Simultaneously, the solid-electrolyte interphase transitions from an unstable carbonate-rich to a stable LiF-dominated composition, confirmed by cryogenic scanning transmission electron microscopy-electron energy loss spectroscopy. Crucially, cryogenic atom probe tomography reveals spatially distinct compositional regimes within the alloy anode: a lithium-flux-limited, heterogeneous interfacial zone and a diffusion-controlled, homogeneous LiPt alloy bulk. This nanoscale compositional gradient rationalizes the emergent solid-solution reaction mechanism and highlights how kinetic limitations and interface dynamics govern alloy formation and electrochemical stability. Our findings establish a correlative experimental framework that directly links structural dynamics with preserved near-atomic resolution interfacial chemistry, advancing the rational design of durable alloy electrodes for next-generation energy storage.
SN - 2768-5608
ER -