Elucidating a dissolution–deposition reaction mechanism by multimodal synchrotron X-ray characterization in aqueous Zn/MnO2 batteries

Varun R. Kankanallu; Xiaoyin Zheng; Denis Leschev; Nicole Zmich; Charles Clark; Cheng-Hung Lin; Hui Zhong; Sanjit Ghose; Andrew M. Kiss; Dmytro Nykypanchuk; Eli Stavitski; Esther S. Takeuchi; Amy C. Marschilok; Kenneth J. Takeuchi; Jianming Bai; Mingyuan Ge; Yu-chen Karen Chen-Wiegart

doi:10.1039/D2EE03731A

Elucidating a dissolution–deposition reaction mechanism by multimodal synchrotron X-ray characterization in aqueous Zn/MnO₂ batteries†

Varun R. Kankanallu,

^a Xiaoyin Zheng,^a Denis Leschev,^b Nicole Zmich,^a Charles Clark,^a Cheng-Hung Lin,

^ab Hui Zhong,^d Sanjit Ghose,^b Andrew M. Kiss,

^b Dmytro Nykypanchuk,^c Eli Stavitski,

^b Esther S. Takeuchi,

^aefg Amy C. Marschilok,

^aefg Kenneth J. Takeuchi,

^aefg Jianming Bai,^b Mingyuan Ge*^b and Yu-chen Karen Chen-Wiegart*^ab

Author affiliations

* Corresponding authors

^a Department of Materials Science and Chemical Engineering, Stony Brook University, Stony Brook, NY, USA
E-mail: Karen.Chen-Wiegart@stonybrook.edu

^b National Synchrotron Light Source II, Brookhaven National Laboratory, Upton, NY, USA
E-mail: mingyuan@bnl.gov

^c Center for Functional Nanomaterials, Brookhaven National Laboratory, Upton, NY, USA

^d Department of Joint Photon Sciences Institute, Stony Brook University, NY, USA

^e Energy and Photon Sciences Directorate, Brookhaven National Laboratory, Upton, NY, USA

^f Department of Chemistry, Stony Brook University, Stony Brook, NY, USA

^g Institute of Energy Sustainability and Equity, Stony Brook University, Stony Brook, NY, USA

Abstract

Aqueous Zn/MnO₂ batteries with their environmental sustainability and competitive cost, are becoming a promising, safe alternative for grid-scale electrochemical energy storage. Presented as a promising design principle to deliver a higher theoretical capacity, this work offers fundamental understanding of the dissolution–deposition mechanism of Zn/β-MnO₂. A multimodal synchrotron characterization approach including three operando X-ray techniques (powder diffraction, absorption spectroscopy, and fluorescence microscopy) is coupled with elementally resolved synchrotron X-ray nano-tomography. Together they provide a direct correlation between structural evolution, reaction chemistry, and 3D morphological changes. Operando synchrotron X-ray diffraction and spectroscopy show a crystalline-to-amorphous phase transition. Quantitative modeling of the operando data by Rietveld refinement for X-ray diffraction and multivariate curve resolution (MCR) for X-ray absorption spectroscopy are used in a complementary fashion to track the structural and chemical transitions of both the long-range (crystalline phases) and short-range (including amorphous phases) ordering upon cycling. Scanning X-ray microscopy and full-field nano-tomography visualizes the morphology of electrodes at different electrochemical states with elemental sensitivity to spatially resolve the formation of the Zn- and Mn-containing phases. Overall, this work critically indicates that for Zn/MnO₂ aqueous batteries, the reaction pathways involving Zn–Mn complex formation upon cycling become independent of the polymorphs of the initial electrode and sheds light on the interplay among structural, chemical, and morphological evolution for electrochemically driven phase transitions.

Energy & Environmental Science

Elucidating a dissolution–deposition reaction mechanism by multimodal synchrotron X-ray characterization in aqueous Zn/MnO₂ batteries†

Abstract

Associated articles

Supplementary files

Article information

Download Citation

Author version available

Permissions

Elucidating a dissolution–deposition reaction mechanism by multimodal synchrotron X-ray characterization in aqueous Zn/MnO₂ batteries

Social activity

Search articles by author

Spotlight

Advertisements

Energy & Environmental Science