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

Wan Yu Tsai; Shelby B. Pillai; Karthik Ganeshan; Saeed Saeed; Yawei Gao; Adri C.T. van Duin; Veronica Augustyn; Nina Balke

doi:10.1021/acsami.3c02055

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

Wan Yu Tsai, Shelby B. Pillai, Karthik Ganeshan, Saeed Saeed, Yawei Gao, Adri C.T. van Duin, Veronica Augustyn, Nina Balke

Research output: Contribution to journal › Article › peer-review

3 Scopus citations

Abstract

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. 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.

Original language	English
Pages (from-to)	26120-26127
Number of pages	8
Journal	ACS Applied Materials and Interfaces
Volume	15
Issue number	21
DOIs	https://doi.org/10.1021/acsami.3c02055
State	Published - May 31 2023
Externally published	Yes

Funding

Operando AFM measurements and materials synthesis were supported by the Fluid Interface Reactions, Structures and Transport (FIRST) Center, an Energy Frontier Research Center (EFRC) funded by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences (W.-Y.T., N.B., V.A.). S.B. acknowledges support from the National Science Foundation Graduate Research Fellowship Program under Grant No. 571800. The experiments and sample preparation in this work were performed and supported at the Center for Nanophase Materials Sciences in Oak Ridge National Lab, which is a DOE Office of Science user facility. This work was performed in part at the Analytical Instrumentation Facility (AIF) at North Carolina State University, which is supported by the State of North Carolina and the National Science Foundation (award number ECCS-1542015). The AIF is a member of the North Carolina Research Triangle Nanotechnology Network (RTNN), a site in the National Nanotechnology Coordinated Infrastructure (NNCI). This work was performed in part at the NCSU Nanofabrication Facility (NNF), a member of the North Carolina Research Triangle Nanotechnology Network (RTNN), which is supported by the National Science Foundation (Grant ECCS-1542015) as part of the National Nanotechnology Coordinated Infrastructure (NNCI).

Funders	Funder number
National Science Foundation	571800
U.S. Department of Energy
Office of Science
Basic Energy Sciences
North Carolina State University	ECCS-1542015
Energy Frontier Research Centers

Keywords

Electro-chemo-mechanical coupling
Electrode microstructure
Mechanical cyclic voltammetry
Operando AFM
Pseudocapacitors

Access to Document

10.1021/acsami.3c02055

Cite this

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title = "Effect of Electrode/Electrolyte Coupling on Birnessite (δ-MnO2) Mechanical Response and Degradation",

abstract = "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. 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.",

keywords = "Electro-chemo-mechanical coupling, Electrode microstructure, Mechanical cyclic voltammetry, Operando AFM, Pseudocapacitors",

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AU - Saeed, Saeed

AU - Gao, Yawei

AU - van Duin, Adri C.T.

AU - Augustyn, Veronica

AU - Balke, Nina

PY - 2023/5/31

Y1 - 2023/5/31

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