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Title: Effect of Electrode/Electrolyte Coupling on Birnessite (δ-MnO2) Mechanical Response and Degradation

Journal Article · · ACS Applied Materials and Interfaces

Understanding the deformation of energy storage electrodes at a local scale and its correlation to electrochemical performance is crucial for designing effective electrode architectures. In this work, the effect of electrolyte cation and electrode morphology on birnessite (δ-MnO2) deformation during charge storage in aqueous electrolytes was investigated using a mechanical cyclic voltammetry approach via operando atomic force microscopy (AFM) and molecular dynamics (MD) simulation. In both K2SO4 and Li2SO4 electrolytes, the δ-MnO2 host electrode underwent expansion during cation intercalation, but with different potential dependencies. When intercalating Li+, the δ-MnO2 electrode presents a nonlinear correlation between electrode deformation and electrode height, which is morphologically dependent. Further, these results suggest that the stronger cation–birnessite interaction is the reason for higher local stress heterogeneity when cycling in Li2SO4 electrolyte, which might be the origin of the pronounced electrode degradation in this electrolyte.

Research Organization:
Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States). Center for Nanophase Materials Sciences (CNMS); Energy Frontier Research Centers (EFRC) (United States). Fluid Interface Reactions, Structures and Transport Center (FIRST)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES); National Science Foundation (NSF)
Grant/Contract Number:
AC05-00OR22725; 571800; ECCS-1542015
OSTI ID:
1975382
Journal Information:
ACS Applied Materials and Interfaces, Vol. 15, Issue 21; ISSN 1944-8244
Publisher:
American Chemical Society (ACS)Copyright Statement
Country of Publication:
United States
Language:
English

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