TY - JOUR
T1 - Employing the Dynamics of the Electrochemical Interface in Aqueous Zinc-Ion Battery Cathodes
AU - Becknell, Nigel
AU - Lopes, Pietro P.
AU - Hatsukade, Toru
AU - Zhou, Xiuquan
AU - Liu, Yuzi
AU - Fisher, Brandon
AU - Chung, Duck Young
AU - Kanatzidis, Mercouri G.
AU - Markovic, Nenad M.
AU - Tepavcevic, Sanja
AU - Stamenkovic, Vojislav R.
N1 - Funding Information:
Work by P.P.L., N.M.M., and S.T. was supported as part of the Joint Center for Energy Storage Research (JCESR), an Energy Innovation Hub funded by the U.S. Department of Energy, Office of Science, Basic Energy Sciences. Work by N.B. was supported by Laboratory Directed Research and Development (LDRD) funding from Argonne National Laboratory, provided by the Director, Office of Science, of the U.S. Department of Energy under Contract No. DE‐AC02‐06CH11357. Work by V.R.S., T.H., X.Z, D.Y.C., and M.G.K. was supported by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences, Materials Sciences and Engineering Division. Use of the Center for Nanoscale Materials, an Office of Science user facility, was supported by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences, under Contract No. DE‐AC02‐06CH11357. This research used resources of the Advanced Photon Source, a U.S. Department of Energy (DOE) Office of Science User Facility operated for the DOE Office of Science by Argonne National Laboratory under Contract No. DE‐AC02‐06CH11357. The authors thank S. Lee for help in setting up XANES measurements at APS beamline 12‐BM‐B. The authors thank J. F. Mitchell for access to the Panalytical X'Pert Pro.
Publisher Copyright:
© 2021 Wiley-VCH GmbH
PY - 2021/8/26
Y1 - 2021/8/26
N2 - Intrinsically stable materials are desirable for constructing energy storage devices, which aim to demonstrate durability under the harsh electrochemical conditions that are detrimental to their lifespan. However, it is demonstrated here that the intrinsic instability of an electrochemical interface can be converted from an obstacle into an advantage. In aqueous zinc-ion batteries, manganese oxide (MnO2) exhibits considerable dissolution even in electrolyte containing Mn2+ salt. Balancing with redeposition alleviates the harmful impact of dissolution on performance and alters the trajectory of the active phase. Inclusion of Mn2+ salt in the electrolyte induces MnO2 deposition on all conductive surfaces, requiring that distracting side reactions be eliminated to isolate the dynamics of the active phase. Under conditions favoring dissolution, capacity decreases dramatically and a highly crystalline tetragonal ZnMn2O4 phase forms, while redeposition helps maintain capacity and promotes a disordered cubic Zn-rich phase. Ultimately, this work aims to illuminate a path forward to unlock the potential of batteries made with materials that are fundamentally unstable in their operating environment.
AB - Intrinsically stable materials are desirable for constructing energy storage devices, which aim to demonstrate durability under the harsh electrochemical conditions that are detrimental to their lifespan. However, it is demonstrated here that the intrinsic instability of an electrochemical interface can be converted from an obstacle into an advantage. In aqueous zinc-ion batteries, manganese oxide (MnO2) exhibits considerable dissolution even in electrolyte containing Mn2+ salt. Balancing with redeposition alleviates the harmful impact of dissolution on performance and alters the trajectory of the active phase. Inclusion of Mn2+ salt in the electrolyte induces MnO2 deposition on all conductive surfaces, requiring that distracting side reactions be eliminated to isolate the dynamics of the active phase. Under conditions favoring dissolution, capacity decreases dramatically and a highly crystalline tetragonal ZnMn2O4 phase forms, while redeposition helps maintain capacity and promotes a disordered cubic Zn-rich phase. Ultimately, this work aims to illuminate a path forward to unlock the potential of batteries made with materials that are fundamentally unstable in their operating environment.
KW - aqueous zinc-ion batteries
KW - dissolution/redeposition
KW - manganese oxide
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U2 - 10.1002/adfm.202102135
DO - 10.1002/adfm.202102135
M3 - Article
AN - SCOPUS:85108327406
SN - 1616-301X
VL - 31
JO - Advanced Functional Materials
JF - Advanced Functional Materials
IS - 35
M1 - 2102135
ER -