TY - JOUR
T1 - Molybdenum polysulfide chalcogels as high-capacity, anion-redox-driven electrode materials for Li-ion batteries
AU - Doan-Nguyen, Vicky V.T.
AU - Subrahmanyam, Kota S.
AU - Butala, Megan M.
AU - Gerbec, Jeffrey A.
AU - Islam, Saiful M.
AU - Kanipe, Katherine N.
AU - Wilson, Catrina E.
AU - Balasubramanian, Mahalingam
AU - Wiaderek, Kamila M.
AU - Borkiewicz, Olaf J.
AU - Chapman, Karena W.
AU - Chupas, Peter J.
AU - Moskovits, Martin
AU - Dunn, Bruce S.
AU - Kanatzidis, Mercouri G.
AU - Seshadri, Ram
N1 - Funding Information:
We gratefully acknowledge the Southern California Electrochemical Energy Storage Alliance (SCEESA), supported by the California NanoSystems Institute (CNSI). Work at Northwestern University was supported by National Science Foundation (NSF) Grant DMR-1410169. The use of shared experimental facilities of the Materials Research Laboratory, a National Science Foundation MRSEC supported by NSF Grant DMR 1121053, is gratefully acknowledged. 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 DE-AC02-06CH11357. X-ray absorption experiments were performed at the APS 20-BM-B beamline under GUP-41555. X-ray scattering experiments were performed at the APS 11-ID-B beamline under GUP-46245. We thank AkzoNobel for providing a free sample of Ketjen Black EC-600JD, Mitsubishi Chemical for providing Sol-Rite, and Coveris for providing carbon-coated Al foil. V.V.T.D.-N. is supported by the University of California President's Postdoctoral Fellowship and the University of California, Santa Barbara CNSI Elings Prize Fellowship. V.V.T.D.-N. thanks Professor Galen D. Stucky, Professor Anton Van der Ven, Dr. Thomas E. Mates, Paige Roberts, Jesse S. Ko, Jonathan S. J. Lau, and Ryan H. DeBlock for helpful discussions.
Publisher Copyright:
© 2016 American Chemical Society.
PY - 2016/11/22
Y1 - 2016/11/22
N2 - Sulfur cathodes in conversion reaction batteries offer high gravimetric capacity but suffer from parasitic polysulfide shuttling. We demonstrate here that transition metal chalcogels of approximate formula MoS3.4 achieve a high gravimetric capacity close to 600 mAh g-1 (close to 1000 mAh g-1 on a sulfur basis) as electrode materials for lithium-ion batteries. Transition metal chalcogels are amorphous and comprise polysulfide chains connected by inorganic linkers. The linkers appear to act as a "glue" in the electrode to prevent polysulfide shuttling. The Mo chalcogels function as electrodes in carbonate- and ether-based electrolytes, which further provides evidence of polysulfide solubility not being a limiting issue. We employ X-ray spectroscopy and operando pair distribution function techniques to elucidate the structural evolution of the electrode. Raman and X-ray photoelectron spectroscopy track the chemical moieties that arise during the anion-redox-driven processes. We find the redox state of Mo remains unchanged across the electrochemical cycling and, correspondingly, the redox is anion-driven.
AB - Sulfur cathodes in conversion reaction batteries offer high gravimetric capacity but suffer from parasitic polysulfide shuttling. We demonstrate here that transition metal chalcogels of approximate formula MoS3.4 achieve a high gravimetric capacity close to 600 mAh g-1 (close to 1000 mAh g-1 on a sulfur basis) as electrode materials for lithium-ion batteries. Transition metal chalcogels are amorphous and comprise polysulfide chains connected by inorganic linkers. The linkers appear to act as a "glue" in the electrode to prevent polysulfide shuttling. The Mo chalcogels function as electrodes in carbonate- and ether-based electrolytes, which further provides evidence of polysulfide solubility not being a limiting issue. We employ X-ray spectroscopy and operando pair distribution function techniques to elucidate the structural evolution of the electrode. Raman and X-ray photoelectron spectroscopy track the chemical moieties that arise during the anion-redox-driven processes. We find the redox state of Mo remains unchanged across the electrochemical cycling and, correspondingly, the redox is anion-driven.
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U2 - 10.1021/acs.chemmater.6b03656
DO - 10.1021/acs.chemmater.6b03656
M3 - Article
AN - SCOPUS:84997610674
VL - 28
SP - 8357
EP - 8365
JO - Chemistry of Materials
JF - Chemistry of Materials
SN - 0897-4756
IS - 22
ER -
