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Title: X-ray absorption spectroscopy of lithium insertion and de-insertion in copper birnessite nanoparticle electrodes

Abstract

The combination of ex situ X-ray diffraction (XRD) and X-ray absorption spectroscopy (XAS) measurements on 2D layered copper birnessite cathode materials for lithium ion battery applications provides detailed insight into both bulk-crystalline and localized atomic structural changes resulting from electrochemically driven lithium insertion and de-insertion. Copper birnessite electrodes that had been galvanostatically discharged and charged were measured with XRD to determine the accompanying long-range crystalline structure changes, while Mn and Cu K-edge XAS measurements provided a detailed view of the Mn and Cu oxidation state changes along with variations of the local neighboring atom environments around the Mn and Cu centers. While not detectable with XRD spectra, through XAS measurements it was determined that the copper ions (Cu2+) are reduced to form amorphous nano-sized Cu metal, and can be oxidized back to Cu2+. In this work, the reversible nature of the interconversion provides a rationale to the enhanced discharge capacity of copper birnessite relative to the analogous copper-free birnessite materials. The manganese oxide octahedra comprising the 2D layers in the original copper birnessite crystal structure disperse during lithium insertion, and revert back close to their original orientation after lithium de-insertion. During electrochemical oxidation or reduction the layered birnessite structure doesmore » not collapse, even though significant local disordering around Mn and Cu centers is directly observed.« less

Authors:
 [1];  [2];  [2];  [2];  [3]
  1. Brookhaven National Lab. (BNL), Upton, NY (United States)
  2. Stony Brook Univ., NY (United States)
  3. Brookhaven National Lab. (BNL), Upton, NY (United States); Stony Brook Univ., NY (United States)
Publication Date:
Research Org.:
Energy Frontier Research Centers (EFRC) (United States). Center for Mesoscale Transport Properties (m2M); Brookhaven National Lab. (BNL), Upton, NY (United States). National Synchrotron Light Source II (NSLS-II)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1387361
Grant/Contract Number:  
SC0012673; AC02-98CH10886
Resource Type:
Journal Article: Accepted Manuscript
Journal Name:
Physical Chemistry Chemical Physics. PCCP
Additional Journal Information:
Journal Volume: 18; Journal Issue: 4; Related Information: m2M partners with Stony Brook University (lead); Brookhaven National Laboratory; Columbia University; Georgia Institute of Technology; Oak Ridge National Laboratory; Rensselaer Polytechnic Institute; University of California, Berkeley; University of North Carolina at Chapel Hill; Journal ID: ISSN 1463-9076
Publisher:
Royal Society of Chemistry
Country of Publication:
United States
Language:
English
Subject:
25 ENERGY STORAGE; energy storage (including batteries and capacitors); charge transport; mesostructured materials

Citation Formats

Pelliccione, Christopher J., Li, Yue Ru, Marschilok, Amy C., Takeuchi, Kenneth J., and Takeuchi, Esther S. X-ray absorption spectroscopy of lithium insertion and de-insertion in copper birnessite nanoparticle electrodes. United States: N. p., 2015. Web. doi:10.1039/C5CP05926G.
Pelliccione, Christopher J., Li, Yue Ru, Marschilok, Amy C., Takeuchi, Kenneth J., & Takeuchi, Esther S. X-ray absorption spectroscopy of lithium insertion and de-insertion in copper birnessite nanoparticle electrodes. United States. https://doi.org/10.1039/C5CP05926G
Pelliccione, Christopher J., Li, Yue Ru, Marschilok, Amy C., Takeuchi, Kenneth J., and Takeuchi, Esther S. 2015. "X-ray absorption spectroscopy of lithium insertion and de-insertion in copper birnessite nanoparticle electrodes". United States. https://doi.org/10.1039/C5CP05926G. https://www.osti.gov/servlets/purl/1387361.
@article{osti_1387361,
title = {X-ray absorption spectroscopy of lithium insertion and de-insertion in copper birnessite nanoparticle electrodes},
author = {Pelliccione, Christopher J. and Li, Yue Ru and Marschilok, Amy C. and Takeuchi, Kenneth J. and Takeuchi, Esther S.},
abstractNote = {The combination of ex situ X-ray diffraction (XRD) and X-ray absorption spectroscopy (XAS) measurements on 2D layered copper birnessite cathode materials for lithium ion battery applications provides detailed insight into both bulk-crystalline and localized atomic structural changes resulting from electrochemically driven lithium insertion and de-insertion. Copper birnessite electrodes that had been galvanostatically discharged and charged were measured with XRD to determine the accompanying long-range crystalline structure changes, while Mn and Cu K-edge XAS measurements provided a detailed view of the Mn and Cu oxidation state changes along with variations of the local neighboring atom environments around the Mn and Cu centers. While not detectable with XRD spectra, through XAS measurements it was determined that the copper ions (Cu2+) are reduced to form amorphous nano-sized Cu metal, and can be oxidized back to Cu2+. In this work, the reversible nature of the interconversion provides a rationale to the enhanced discharge capacity of copper birnessite relative to the analogous copper-free birnessite materials. The manganese oxide octahedra comprising the 2D layers in the original copper birnessite crystal structure disperse during lithium insertion, and revert back close to their original orientation after lithium de-insertion. During electrochemical oxidation or reduction the layered birnessite structure does not collapse, even though significant local disordering around Mn and Cu centers is directly observed.},
doi = {10.1039/C5CP05926G},
url = {https://www.osti.gov/biblio/1387361}, journal = {Physical Chemistry Chemical Physics. PCCP},
issn = {1463-9076},
number = 4,
volume = 18,
place = {United States},
year = {Tue Dec 22 00:00:00 EST 2015},
month = {Tue Dec 22 00:00:00 EST 2015}
}

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Cited by: 12 works
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