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Title: Zerovalent Copper Intercalated Birnessite as a Cathode for Lithium Ion Batteries: Extending Cycle Life

Birnessite type layered manganese dioxides (δ-MnO 2) have attracted considerable attention in recent years as 2D intercalation cathodes for rechargeable Li +, Na +, and Mg 2+ batteries due to fast ion diffusion through their negatively charged δ-MnO 2 sheets separated by interlayer cations and a stable Mn 3+/4+ redox couple. Here we report the preparation and electrochemistry of zero and divalent copper co-intercalated birnessite type manganese dioxide (Cu 0 0.03Cu 2+ 0.21Na 0.12MnO 2·0.9H 2O). The copper intercalated birnessite materials were fully characterized utilizing powder X-ray diffraction (XRD), inductively coupled plasma optical emission spectroscopy (ICP-OES), transmission electron microscopy (TEM). The mixed valent nature of intercalated Cu 0 and Cu 2+ was confirmed by X-ray photoelectron spectroscopy (XPS) and electron energy loss spectroscopy (EELS). Electrochemical evaluation results show that zero valent copper intercalated birnessite exhibits higher discharge capability, improved cyclability, and lower impedance compared to the Cu 2+ only intercalated (Cu 0.26MnO 2·1.0H 2O) and Cu free Na birnessite (Na 0.40MnO 2·1.0H 2O) materials. Remarkably, zero valent copper birnessite shows almost no fade after 10 cycles at 0.1 mV/s. Electrochemical impedance spectroscopy results suggest that charge transfer resistivity of Cu 0 modified samples was much lower than that of Cumore » 2+ and Cu free birnessite, indicating that the presence of a small amount of Cu 0 improves the conductivity of birnessite and results in better electrochemical cyclability, rate capability, and lower impedance.« less
Authors:
 [1] ;  [2] ;  [2] ;  [1] ;  [1] ;  [2] ;  [2] ;  [3] ;  [1] ;  [1]
  1. Stony Brook Univ., NY (United States)
  2. Brookhaven National Lab. (BNL), Upton, NY (United States)
  3. Brookhaven National Lab. (BNL), Upton, NY (United States); Stony Brook Univ., NY (United States)
Publication Date:
Report Number(s):
BNL-114876-2017-JAAM
Journal ID: ISSN 0013-4651
Grant/Contract Number:
SC0012704
Type:
Accepted Manuscript
Journal Name:
Journal of the Electrochemical Society
Additional Journal Information:
Journal Volume: 164; Journal Issue: 9; Journal ID: ISSN 0013-4651
Publisher:
The Electrochemical Society
Research Org:
Brookhaven National Laboratory (BNL), Upton, NY (United States); Energy Frontier Research Centers (EFRC) (United States). Center for Mesoscale Transport Properties (m2M)
Sponsoring Org:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
Country of Publication:
United States
Language:
English
Subject:
75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND SUPERFLUIDITY
OSTI Identifier:
1425040

Li, Yue Ru, Poyraz, Altug S., Hu, Xiaobing, Cuiffo, Michael, Clayton, Clive R., Wu, Lijun, Zhu, Yimei, Takeuchi, Esther S., Marschilok, Amy C., and Takeuchi, Kenneth J.. Zerovalent Copper Intercalated Birnessite as a Cathode for Lithium Ion Batteries: Extending Cycle Life. United States: N. p., Web. doi:10.1149/2.1431709jes.
Li, Yue Ru, Poyraz, Altug S., Hu, Xiaobing, Cuiffo, Michael, Clayton, Clive R., Wu, Lijun, Zhu, Yimei, Takeuchi, Esther S., Marschilok, Amy C., & Takeuchi, Kenneth J.. Zerovalent Copper Intercalated Birnessite as a Cathode for Lithium Ion Batteries: Extending Cycle Life. United States. doi:10.1149/2.1431709jes.
Li, Yue Ru, Poyraz, Altug S., Hu, Xiaobing, Cuiffo, Michael, Clayton, Clive R., Wu, Lijun, Zhu, Yimei, Takeuchi, Esther S., Marschilok, Amy C., and Takeuchi, Kenneth J.. 2017. "Zerovalent Copper Intercalated Birnessite as a Cathode for Lithium Ion Batteries: Extending Cycle Life". United States. doi:10.1149/2.1431709jes. https://www.osti.gov/servlets/purl/1425040.
@article{osti_1425040,
title = {Zerovalent Copper Intercalated Birnessite as a Cathode for Lithium Ion Batteries: Extending Cycle Life},
author = {Li, Yue Ru and Poyraz, Altug S. and Hu, Xiaobing and Cuiffo, Michael and Clayton, Clive R. and Wu, Lijun and Zhu, Yimei and Takeuchi, Esther S. and Marschilok, Amy C. and Takeuchi, Kenneth J.},
abstractNote = {Birnessite type layered manganese dioxides (δ-MnO2) have attracted considerable attention in recent years as 2D intercalation cathodes for rechargeable Li+, Na+, and Mg2+ batteries due to fast ion diffusion through their negatively charged δ-MnO2 sheets separated by interlayer cations and a stable Mn3+/4+ redox couple. Here we report the preparation and electrochemistry of zero and divalent copper co-intercalated birnessite type manganese dioxide (Cu00.03Cu2+0.21Na0.12MnO2·0.9H2O). The copper intercalated birnessite materials were fully characterized utilizing powder X-ray diffraction (XRD), inductively coupled plasma optical emission spectroscopy (ICP-OES), transmission electron microscopy (TEM). The mixed valent nature of intercalated Cu0 and Cu2+ was confirmed by X-ray photoelectron spectroscopy (XPS) and electron energy loss spectroscopy (EELS). Electrochemical evaluation results show that zero valent copper intercalated birnessite exhibits higher discharge capability, improved cyclability, and lower impedance compared to the Cu2+ only intercalated (Cu0.26MnO2·1.0H2O) and Cu free Na birnessite (Na0.40MnO2·1.0H2O) materials. Remarkably, zero valent copper birnessite shows almost no fade after 10 cycles at 0.1 mV/s. Electrochemical impedance spectroscopy results suggest that charge transfer resistivity of Cu0 modified samples was much lower than that of Cu2+ and Cu free birnessite, indicating that the presence of a small amount of Cu0 improves the conductivity of birnessite and results in better electrochemical cyclability, rate capability, and lower impedance.},
doi = {10.1149/2.1431709jes},
journal = {Journal of the Electrochemical Society},
number = 9,
volume = 164,
place = {United States},
year = {2017},
month = {1}
}