Investigation into the origin of high stability of δ-MnO2 pseudo-capacitive electrode using operando Raman spectroscopy

Lufeng Yang, Shuang Cheng, Jenghan Wang, Xu Ji, Yu Jiang, Minghai Yao, Peng Wu, Mengkun Wang, Jun Zhou, Meilin Liu

Research output: Contribution to journalArticle

20 Citations (Scopus)

Abstract

Manganese oxides of different structures, especially α-MnO2, have been extensively studied as electrodes for pseudocapacitors. However, the poor stability associated with intercalation of proton has been the main obstacle to their commercial applications. To effectively mitigate this problem, it is necessary to fully understand the energy storage mechanism of the MnO2 phases. In this study, δ phase MnO2 has been synthesized through controllable electroplating on architectural Ga-doped ZnO (GZO) bones, demonstrating a high specific capacitance of 1068 F g−1 and high stability (slight performance drop focus on the first 2000 cycles and then remained relatively constant in the subsequent 13,000 cycles). The charge storage mechanism of the δ-MnO2 coated GZO has been carefully investigated under this extreme reaction condition. Results suggest that the amount of charge stored in the electrode material correlates well with the amount of Na+ inserted into the electrode material from the electrolyte. It is also noted that no spectral features corresponding to H+ insertion were detected during cycling when the sample was probed using in operando Raman spectroscopy. Therefore, for layered δ-MnO2, a charge storage mechanism of Na+ intercalation/deintercalation dominated, accompanied by interlayer spacing expansion/contraction, was proposed. Moreover, theoretical calculations also confirmed that the insertion of Na+ is more energetically favorable than H+ at all sites of the interlayer in δ-MnO2, offering a rational explanation of the proposed mechanism and the observed excellent stability.

Original languageEnglish
Pages (from-to)293-302
Number of pages10
JournalNano Energy
Volume30
DOIs
Publication statusPublished - 2016 Dec 1

Fingerprint

Raman spectroscopy
Intercalation
Electrodes
Manganese oxide
Electroplating
Energy storage
Electrolytes
Protons
Bone
Capacitance
Supercapacitor
manganese oxide

Keywords

  • Charge storage mechanism
  • DFT calculation
  • Pseudo-capacitor
  • in situ Raman spectroscopy
  • δ-MnO

ASJC Scopus subject areas

  • Renewable Energy, Sustainability and the Environment
  • Materials Science(all)
  • Electrical and Electronic Engineering

Cite this

Investigation into the origin of high stability of δ-MnO2 pseudo-capacitive electrode using operando Raman spectroscopy. / Yang, Lufeng; Cheng, Shuang; Wang, Jenghan; Ji, Xu; Jiang, Yu; Yao, Minghai; Wu, Peng; Wang, Mengkun; Zhou, Jun; Liu, Meilin.

In: Nano Energy, Vol. 30, 01.12.2016, p. 293-302.

Research output: Contribution to journalArticle

Yang, Lufeng ; Cheng, Shuang ; Wang, Jenghan ; Ji, Xu ; Jiang, Yu ; Yao, Minghai ; Wu, Peng ; Wang, Mengkun ; Zhou, Jun ; Liu, Meilin. / Investigation into the origin of high stability of δ-MnO2 pseudo-capacitive electrode using operando Raman spectroscopy. In: Nano Energy. 2016 ; Vol. 30. pp. 293-302.
@article{a594479b33214aa696564fe121da856a,
title = "Investigation into the origin of high stability of δ-MnO2 pseudo-capacitive electrode using operando Raman spectroscopy",
abstract = "Manganese oxides of different structures, especially α-MnO2, have been extensively studied as electrodes for pseudocapacitors. However, the poor stability associated with intercalation of proton has been the main obstacle to their commercial applications. To effectively mitigate this problem, it is necessary to fully understand the energy storage mechanism of the MnO2 phases. In this study, δ phase MnO2 has been synthesized through controllable electroplating on architectural Ga-doped ZnO (GZO) bones, demonstrating a high specific capacitance of 1068 F g−1 and high stability (slight performance drop focus on the first 2000 cycles and then remained relatively constant in the subsequent 13,000 cycles). The charge storage mechanism of the δ-MnO2 coated GZO has been carefully investigated under this extreme reaction condition. Results suggest that the amount of charge stored in the electrode material correlates well with the amount of Na+ inserted into the electrode material from the electrolyte. It is also noted that no spectral features corresponding to H+ insertion were detected during cycling when the sample was probed using in operando Raman spectroscopy. Therefore, for layered δ-MnO2, a charge storage mechanism of Na+ intercalation/deintercalation dominated, accompanied by interlayer spacing expansion/contraction, was proposed. Moreover, theoretical calculations also confirmed that the insertion of Na+ is more energetically favorable than H+ at all sites of the interlayer in δ-MnO2, offering a rational explanation of the proposed mechanism and the observed excellent stability.",
keywords = "Charge storage mechanism, DFT calculation, Pseudo-capacitor, in situ Raman spectroscopy, δ-MnO",
author = "Lufeng Yang and Shuang Cheng and Jenghan Wang and Xu Ji and Yu Jiang and Minghai Yao and Peng Wu and Mengkun Wang and Jun Zhou and Meilin Liu",
year = "2016",
month = "12",
day = "1",
doi = "10.1016/j.nanoen.2016.10.018",
language = "English",
volume = "30",
pages = "293--302",
journal = "Nano Energy",
issn = "2211-2855",
publisher = "Elsevier BV",

}

TY - JOUR

T1 - Investigation into the origin of high stability of δ-MnO2 pseudo-capacitive electrode using operando Raman spectroscopy

AU - Yang, Lufeng

AU - Cheng, Shuang

AU - Wang, Jenghan

AU - Ji, Xu

AU - Jiang, Yu

AU - Yao, Minghai

AU - Wu, Peng

AU - Wang, Mengkun

AU - Zhou, Jun

AU - Liu, Meilin

PY - 2016/12/1

Y1 - 2016/12/1

N2 - Manganese oxides of different structures, especially α-MnO2, have been extensively studied as electrodes for pseudocapacitors. However, the poor stability associated with intercalation of proton has been the main obstacle to their commercial applications. To effectively mitigate this problem, it is necessary to fully understand the energy storage mechanism of the MnO2 phases. In this study, δ phase MnO2 has been synthesized through controllable electroplating on architectural Ga-doped ZnO (GZO) bones, demonstrating a high specific capacitance of 1068 F g−1 and high stability (slight performance drop focus on the first 2000 cycles and then remained relatively constant in the subsequent 13,000 cycles). The charge storage mechanism of the δ-MnO2 coated GZO has been carefully investigated under this extreme reaction condition. Results suggest that the amount of charge stored in the electrode material correlates well with the amount of Na+ inserted into the electrode material from the electrolyte. It is also noted that no spectral features corresponding to H+ insertion were detected during cycling when the sample was probed using in operando Raman spectroscopy. Therefore, for layered δ-MnO2, a charge storage mechanism of Na+ intercalation/deintercalation dominated, accompanied by interlayer spacing expansion/contraction, was proposed. Moreover, theoretical calculations also confirmed that the insertion of Na+ is more energetically favorable than H+ at all sites of the interlayer in δ-MnO2, offering a rational explanation of the proposed mechanism and the observed excellent stability.

AB - Manganese oxides of different structures, especially α-MnO2, have been extensively studied as electrodes for pseudocapacitors. However, the poor stability associated with intercalation of proton has been the main obstacle to their commercial applications. To effectively mitigate this problem, it is necessary to fully understand the energy storage mechanism of the MnO2 phases. In this study, δ phase MnO2 has been synthesized through controllable electroplating on architectural Ga-doped ZnO (GZO) bones, demonstrating a high specific capacitance of 1068 F g−1 and high stability (slight performance drop focus on the first 2000 cycles and then remained relatively constant in the subsequent 13,000 cycles). The charge storage mechanism of the δ-MnO2 coated GZO has been carefully investigated under this extreme reaction condition. Results suggest that the amount of charge stored in the electrode material correlates well with the amount of Na+ inserted into the electrode material from the electrolyte. It is also noted that no spectral features corresponding to H+ insertion were detected during cycling when the sample was probed using in operando Raman spectroscopy. Therefore, for layered δ-MnO2, a charge storage mechanism of Na+ intercalation/deintercalation dominated, accompanied by interlayer spacing expansion/contraction, was proposed. Moreover, theoretical calculations also confirmed that the insertion of Na+ is more energetically favorable than H+ at all sites of the interlayer in δ-MnO2, offering a rational explanation of the proposed mechanism and the observed excellent stability.

KW - Charge storage mechanism

KW - DFT calculation

KW - Pseudo-capacitor

KW - in situ Raman spectroscopy

KW - δ-MnO

UR - http://www.scopus.com/inward/record.url?scp=84992223504&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=84992223504&partnerID=8YFLogxK

U2 - 10.1016/j.nanoen.2016.10.018

DO - 10.1016/j.nanoen.2016.10.018

M3 - Article

AN - SCOPUS:84992223504

VL - 30

SP - 293

EP - 302

JO - Nano Energy

JF - Nano Energy

SN - 2211-2855

ER -