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

被引:237
作者
Chen, Dongchang [1 ,2 ]
Ding, Dong [1 ]
Li, Xiaxi [1 ]
Waller, Gordon Henry [1 ]
Xiong, Xunhui [1 ]
El-Sayed, Mostafa A. [2 ]
Liu, Meilin [1 ]
机构
[1] Georgia Inst Technol, Ctr Innovat Fuel Cell & Battery Technol, Sch Mat Sci & Engn, 771 Ferst Dr, Atlanta, GA 30332 USA
[2] Georgia Inst Technol, Laser Dynam Lab, Sch Chem & Biochem, Atlanta, GA 30332 USA
基金
美国国家科学基金会;
关键词
LAYERED-MANGANESE OXIDES; ELECTRICAL ENERGY-STORAGE; LITHIUM-ION BATTERIES; IN-SITU; HIGH-PERFORMANCE; ELECTROCHEMICAL CAPACITORS; AQUEOUS-ELECTROLYTES; LATTICE-VIBRATIONS; ANODIC DEPOSITION; CARBON NANOTUBES;
D O I
10.1021/acs.chemmater.5b03118
中图分类号
O64 [物理化学(理论化学)、化学物理学];
学科分类号
070304 ; 081704 ;
摘要
While 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. Furthermore, 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.
引用
收藏
页码:6608 / 6619
页数:12
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