Probing the Charge Storage Mechanism of a Pseudocapacitive MnO2 Electrode Using in Operando Raman Spectroscopy

Chen, Dongchang; Ding, Dong; Li, Xiaxi; Waller, Gordon Henry; Xiong, Xunhui; El-Sayed, Mostafa A.; Liu, Meilin

doi:10.1021/acs.chemmater.5b03118

Title: Probing the Charge Storage Mechanism of a Pseudocapacitive MnO₂ Electrode Using in Operando Raman Spectroscopy

Journal Article · Thu Sep 24 00:00:00 EDT 2015 · Chemistry of Materials

DOI:https://doi.org/10.1021/acs.chemmater.5b03118· OSTI ID:1370164

Chen, Dongchang ^[1]; Ding, Dong ^[1]; Li, Xiaxi ^[1]; Waller, Gordon Henry ^[1]; Xiong, Xunhui ^[1]; El-Sayed, Mostafa A. ^[1]; Liu, Meilin ^[1]

Georgia Inst. of Technology, Atlanta, GA (United States)

Although manganese oxide (MnO₂) has been extensively studied as an electrode material for pseudocapacitors, a clear understanding of its charge storage mechanism is still lacking. Here we report our findings in probing the structural changes of a thin-film model MnO₂ electrode during cycling using in operando Raman spectroscopy. The spectral features (e.g., band position, intensity, and width) are correlated quantitatively with the size (Li⁺, Na⁺, and K⁺) of cations in different electrolytes and with the degree of discharge to gain better understanding of the cation-incorporation mechanism into the interlayers of pseudocapacitive MnO₂. Also, theoretical calculations of phonon energy associated with the models of interlayer cation-incorporated MnO₂ agree with the experimental observations of cation-size effect on the positions of Raman bands. Additionally, the cation-size effects on spectral features at different potentials of MnO₂ electrode are correlated quantitatively with the amount of charge stored in the MnO₂ electrode. The understanding of the structural changes associated with charge storage gained from Raman spectroscopy provides valuable insights into the cation-size effects on the electrochemical performances of the MnO₂ electrode.

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Research Organization:: Energy Frontier Research Centers (EFRC) (United States). Heterogeneous Functional Materials Center (HeteroFoaM)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: SC0001061

OSTI ID:: 1370164

Journal Information:: Chemistry of Materials, Vol. 27, Issue 19; Related Information: HeteroFoaM partners with University of South Carolina (lead); University of California, Santa Barbara; University of Connecticut; Georgia Institute of Technology; Princeton University; Rochester Institute of Technology; Savannah River National Laboratory; University of South Carolina; University of Utah; ISSN 0897-4756

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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Cited by: 173 works

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Exchange bias effect in hybrid improper ferroelectricity Ca _2.94 Na _0.06 Mn ₂ O ₇ Li, Songyang; Wang, Shouyu; Lu, Yangong AIP Advances, Vol. 8, Issue 1 https://doi.org/10.1063/1.5003877	journal	January 2018
In Situ Growth of a Feather-like MnO ₂ Nanostructure on Carbon Paper for High-Performance Rechargeable Sodium-Ion Batteries Li, Huan; Liu, Anmin; Zhao, Shuai ChemElectroChem, Vol. 5, Issue 21 https://doi.org/10.1002/celc.201800830	journal	August 2018
Site-specific surface tailoring for metal ion selectivity via under-coordinated structure engineering Yu, Li; Zhang, Gong; Liu, Chunlei Nanoscale Horizons, Vol. 3, Issue 6 https://doi.org/10.1039/c8nh00094h	journal	January 2018
Efficient Capacitive Deionization Using Thin Film Sodium Manganese Oxide Wallas, Jasmine M.; Young, Matthias J.; Sun, Huaxing Journal of The Electrochemical Society, Vol. 165, Issue 10 https://doi.org/10.1149/2.0751810jes	journal	January 2018
Carbon fibre paper coated by a layered manganese oxide: a nano-structured electrocatalyst for water-oxidation with high activity over a very wide pH range Melder, Jens; Mebs, Stefan; Heizmann, Philipp A. Freie Universität Berlin https://doi.org/10.17169/refubium-27049	text	January 2019

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Title: Probing the Charge Storage Mechanism of a Pseudocapacitive MnO₂ Electrode Using in Operando Raman Spectroscopy