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Title: Biphase Cobalt-Manganese Oxide with High Capacity and Rate Performance for Aqueous Sodium-Ion Electrochemical Energy Storage

Abstract

Manganese-based metal oxide electrode materials are of great importance in electrochemical energy storage for their favorable redox behavior, low cost and environmental-friendliness. However, their storage capacity and cycle life in aqueous Na-ion electrolytes is not satisfactory. In this paper, we report the development of a bi-phase cobalt-manganese oxide (Co-Mn-O) nanostructured electrode material, comprised of a layered MnO2.H2O birnessite phase and a (Co0.83Mn0.13Va0.04)tetra(Co0.38Mn1.62)octaO3.72 (Va: vacancy; tetra: tetrahedral sites; octa: octahedral sites) spinel phase, verified by neutron total scattering and pair distribution function analyses. The bi-phase Co-Mn-O material demonstrates an excellent storage capacity towards Na-ions in an aqueous electrolyte (121 mA h g-1 at a scan rate of 1 mV s-1 in the half-cell and 81 mA h g-1 at a current density of 2 A g-1 after 5000 cycles in full-cells), as well as high rate performance (57 mA h g-1 a rate of 360 C). Electro-kinetic analysis and in situ X-ray diffraction measurements further confirm that the synergistic interaction between the spinel and layered phases, as well as the vacancy of the tetrahedral sites of spinel phase, contribute to the improved capacity and rate performance of the Co-Mn-O material by facilitating both diffusion-limited redox and capacitive charge storage processes.

Authors:
 [1];  [1];  [2];  [3];  [4]; ORCiD logo [1]
  1. Univ. of New Hampshire, Durham, NH (United States). Dept. of Chemical Engineering
  2. Argonne National Lab. (ANL), Argonne, IL (United States). Advanced Photon Source (APS). X-ray Science Division
  3. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Chemical and Engineering Materials Division and Spallation Neutron Source (SNS) outstation Juelich Centre for Neutron Science (JCNS), Forschungszentrum Juelich GmbH
  4. Brookhaven National Lab. (BNL), Upton, NY (United States). Center for Functional Nanomaterials (CFN)
Publication Date:
Research Org.:
Brookhaven National Laboratory (BNL), Upton, NY (United States); Argonne National Laboratory (ANL), Argonne, IL (United States). Advanced Photon Source (APS); Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States); Xiaowei Teng/University of New Hampshire
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES); Univ. of New Hampshire, Durham, NH (United States); USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22). Materials Sciences & Engineering Division
OSTI Identifier:
1430860
Alternate Identifier(s):
OSTI ID: 1410130; OSTI ID: 1430704; OSTI ID: 1594488
Report Number(s):
BNL-203384-2018-JAAM
Journal ID: ISSN 1616-301X
Grant/Contract Number:  
SC0012704; AC05‐00OR22725; SC0010286; AC02-06CH11357
Resource Type:
Accepted Manuscript
Journal Name:
Advanced Functional Materials
Additional Journal Information:
Journal Volume: 28; Journal Issue: 3; Journal ID: ISSN 1616-301X
Publisher:
Wiley
Country of Publication:
United States
Language:
English
Subject:
25 ENERGY STORAGE; 77 NANOSCIENCE AND NANOTECHNOLOGY; 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; 36 MATERIALS SCIENCE; bi-phase cobalt-manganese oxide; aqueous Na-ion storage; capacitive and diffusion-limited redox capacities; in situ X-ray diffraction; pair distribution function

Citation Formats

Shan, Xiaoqiang, Charles, Daniel S., Xu, Wenqian, Feygenson, Mikhail, Su, Dong, and Teng, Xiaowei. Biphase Cobalt-Manganese Oxide with High Capacity and Rate Performance for Aqueous Sodium-Ion Electrochemical Energy Storage. United States: N. p., 2017. Web. doi:10.1002/adfm.201703266.
Shan, Xiaoqiang, Charles, Daniel S., Xu, Wenqian, Feygenson, Mikhail, Su, Dong, & Teng, Xiaowei. Biphase Cobalt-Manganese Oxide with High Capacity and Rate Performance for Aqueous Sodium-Ion Electrochemical Energy Storage. United States. https://doi.org/10.1002/adfm.201703266
Shan, Xiaoqiang, Charles, Daniel S., Xu, Wenqian, Feygenson, Mikhail, Su, Dong, and Teng, Xiaowei. Wed . "Biphase Cobalt-Manganese Oxide with High Capacity and Rate Performance for Aqueous Sodium-Ion Electrochemical Energy Storage". United States. https://doi.org/10.1002/adfm.201703266. https://www.osti.gov/servlets/purl/1430860.
@article{osti_1430860,
title = {Biphase Cobalt-Manganese Oxide with High Capacity and Rate Performance for Aqueous Sodium-Ion Electrochemical Energy Storage},
author = {Shan, Xiaoqiang and Charles, Daniel S. and Xu, Wenqian and Feygenson, Mikhail and Su, Dong and Teng, Xiaowei},
abstractNote = {Manganese-based metal oxide electrode materials are of great importance in electrochemical energy storage for their favorable redox behavior, low cost and environmental-friendliness. However, their storage capacity and cycle life in aqueous Na-ion electrolytes is not satisfactory. In this paper, we report the development of a bi-phase cobalt-manganese oxide (Co-Mn-O) nanostructured electrode material, comprised of a layered MnO2.H2O birnessite phase and a (Co0.83Mn0.13Va0.04)tetra(Co0.38Mn1.62)octaO3.72 (Va: vacancy; tetra: tetrahedral sites; octa: octahedral sites) spinel phase, verified by neutron total scattering and pair distribution function analyses. The bi-phase Co-Mn-O material demonstrates an excellent storage capacity towards Na-ions in an aqueous electrolyte (121 mA h g-1 at a scan rate of 1 mV s-1 in the half-cell and 81 mA h g-1 at a current density of 2 A g-1 after 5000 cycles in full-cells), as well as high rate performance (57 mA h g-1 a rate of 360 C). Electro-kinetic analysis and in situ X-ray diffraction measurements further confirm that the synergistic interaction between the spinel and layered phases, as well as the vacancy of the tetrahedral sites of spinel phase, contribute to the improved capacity and rate performance of the Co-Mn-O material by facilitating both diffusion-limited redox and capacitive charge storage processes.},
doi = {10.1002/adfm.201703266},
journal = {Advanced Functional Materials},
number = 3,
volume = 28,
place = {United States},
year = {Wed Nov 22 00:00:00 EST 2017},
month = {Wed Nov 22 00:00:00 EST 2017}
}

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