Operando Cross-Sectional Nanoscale Imaging of Na Anode Formation in Zero-Excess Solid-State Batteries: Coupled Phase–Stress Evolution and X-ray Beam Effects
Abstract
Zero-excess solid-state sodium batteries plate Na during charging, which places severe demands on the mechanical stability of the evolving anode and its interfaces. This work resolves the spatiotemporal evolution of phase formation and mechanical stresses across buried interfaces in a Na-Pb model system using a custom-built operando cell for cross-sectional X-ray nanodiffraction with a beam of 150 nm in diameter. The operando phase maps reveal that Na, Pb/NaPb3, and NaPb/Na9Pb4 phases coexist spatially during plating, contradicting the predominantly sequential pathway reported for liquid-electrolyte Na-Pb systems. The temporal evolution of the deviatoric in-plane stress reveals an increasingly compressive state within the solid-state electrolyte, concentrated near the interface and consistent with Na filling residual pores within the ceramic electrolyte, thereby creating local stress concentrations associated with dendritic growth and failure. Unexpectedly, comparison with beam-free reference cells reveals that X-ray exposure measurably suppresses Na plating, evidenced by an altered electrochemical response and substantially reduced Na and alloy formation. Suppressed phase formation at previously unexposed positions further shows that the beam-induced perturbation extends beyond the irradiated region, unlike the predominantly localized effects reported for liquid-electrolyte systems. This non-local response is consistent with radiation-induced charge generation within the ceramic electrolyte and demonstrates that X-ray exposure can directly alter the electrochemical process being probed in solid-state systems under bias.
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BibTeX
@misc{bratlie2026operando,
title = {{Operando Cross-Sectional Nanoscale Imaging of Na Anode Formation in Zero-Excess Solid-State Batteries: Coupled Phase–Stress Evolution and X-ray Beam Effects}},
author = {Henrik Rotvær Bratlie and Verena Reisecker and François Lienard and Juraj Todt and Steven T. Boles and Tobias M. Huber and Manfred Burghammer and Jozef Keckes and Daniel Rettenwander},
howpublished = {ChemRxiv},
year = {2026},
month = sep,
doi = {10.26434/chemrxiv.15008488/v1},
url = {https://chemrxiv.org/doi/full/10.26434/chemrxiv.15008488/v1},
note = {CC BY},
}
RIS
TY - UNPB
TI - Operando Cross-Sectional Nanoscale Imaging of Na Anode Formation in Zero-Excess Solid-State Batteries: Coupled Phase–Stress Evolution and X-ray Beam Effects
AU - Henrik Rotvær Bratlie
AU - Verena Reisecker
AU - François Lienard
AU - Juraj Todt
AU - Steven T. Boles
AU - Tobias M. Huber
AU - Manfred Burghammer
AU - Jozef Keckes
AU - Daniel Rettenwander
PY - 2026
DA - 2026/09/08
PB - ChemRxiv
DO - 10.26434/chemrxiv.15008488/v1
UR - https://chemrxiv.org/doi/full/10.26434/chemrxiv.15008488/v1
AB - Zero-excess solid-state sodium batteries plate Na during charging, which places severe demands on the mechanical stability of the evolving anode and its interfaces. This work resolves the spatiotemporal evolution of phase formation and mechanical stresses across buried interfaces in a Na-Pb model system using a custom-built operando cell for cross-sectional X-ray nanodiffraction with a beam of 150 nm in diameter. The operando phase maps reveal that Na, Pb/NaPb3, and NaPb/Na9Pb4 phases coexist spatially during plating, contradicting the predominantly sequential pathway reported for liquid-electrolyte Na-Pb systems. The temporal evolution of the deviatoric in-plane stress reveals an increasingly compressive state within the solid-state electrolyte, concentrated near the interface and consistent with Na filling residual pores within the ceramic electrolyte, thereby creating local stress concentrations associated with dendritic growth and failure. Unexpectedly, comparison with beam-free reference cells reveals that X-ray exposure measurably suppresses Na plating, evidenced by an altered electrochemical response and substantially reduced Na and alloy formation. Suppressed phase formation at previously unexposed positions further shows that the beam-induced perturbation extends beyond the irradiated region, unlike the predominantly localized effects reported for liquid-electrolyte systems. This non-local response is consistent with radiation-induced charge generation within the ceramic electrolyte and demonstrates that X-ray exposure can directly alter the electrochemical process being probed in solid-state systems under bias.
ER -