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

Journal Article · · Journal of the Electrochemical Society
DOI:https://doi.org/10.1149/2.1431709jes· OSTI ID:1425040
 [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)
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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.

Research Organization:
Brookhaven National Lab. (BNL), Upton, NY (United States); Energy Frontier Research Centers (EFRC) (United States). Center for Mesoscale Transport Properties (m2M)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
Grant/Contract Number:
SC0012704
OSTI ID:
1425040
Report Number(s):
BNL-114876-2017-JAAM
Journal Information:
Journal of the Electrochemical Society, Vol. 164, Issue 9; ISSN 0013-4651
Publisher:
The Electrochemical SocietyCopyright Statement
Country of Publication:
United States
Language:
English
Citation Metrics:
Cited by: 7 works
Citation information provided by
Web of Science

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Cited By (2)

Chemical intercalation of heavy metal, semimetal, and semiconductor atoms into 2D layered chalcogenides journal July 2018
An Operando Study of the Initial Discharge of Bi and Bi/Cu Modified MnO 2 journal January 2018

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