TY - JOUR
T1 - Zerovalent copper intercalated Birnessite as a cathode for lithium ion batteries
T2 - Extending cycle life
AU - Li, Yue Ru
AU - Poyraz, Altug S.
AU - Hu, Xiaobing
AU - Cuiffo, Michael
AU - Clayton, Clive R.
AU - Wu, Lijun
AU - Zhu, Yimei
AU - Takeuchi, Esther S.
AU - Marschilok, Amy C.
AU - Takeuchi, Kenneth J.
N1 - Funding Information:
The materials synthesis and electrochemistry was supported as part of the Center for Mesoscale Transport Properties, an Energy Frontier Research Center supported by the U. S. Department of Energy, Office of Science, Basic Energy Sciences, under award #DE-SC0012673. XPS studies were supported by the Stony Brook University-Brookhaven National Laboratory Seed grant Program. EELS studies were supported by the U. S. Department of Energy, Office of Basic Energy Science, Division of Materials Science and Engineering, under Contract No. DE-SC0012704. The authors thank Chung-Chueh (Simon) Chang of the Materials Instrumentation Center at the Advanced Energy Research and Technology Center for assistance with TEM and SAED.
Publisher Copyright:
© 2017 The Electrochemical Society.
PY - 2017
Y1 - 2017
N2 - 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.
AB - 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.
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U2 - 10.1149/2.1431709jes
DO - 10.1149/2.1431709jes
M3 - Article
AN - SCOPUS:85042353797
SN - 0013-4651
VL - 164
SP - A2151-A2158
JO - Journal of the Electrochemical Society
JF - Journal of the Electrochemical Society
IS - 9
ER -