Molybdenum polysulfide chalcogels as high-capacity, anion-redox-driven electrode materials for Li-ion batteries

Vicky V.T. Doan-Nguyen; Kota S. Subrahmanyam; Megan M. Butala; Jeffrey A. Gerbec; Saiful M. Islam; Katherine N. Kanipe; Catrina E. Wilson; Mahalingam Balasubramanian; Kamila M. Wiaderek; Olaf J. Borkiewicz; Karena W. Chapman; Peter J. Chupas; Martin Moskovits; Bruce S. Dunn; Mercouri G. Kanatzidis; Ram Seshadri

doi:10.1021/acs.chemmater.6b03656

Molybdenum polysulfide chalcogels as high-capacity, anion-redox-driven electrode materials for Li-ion batteries

Vicky V.T. Doan-Nguyen^*, Kota S. Subrahmanyam, Megan M. Butala, Jeffrey A. Gerbec, Saiful M. Islam, Katherine N. Kanipe, Catrina E. Wilson, Mahalingam Balasubramanian, Kamila M. Wiaderek, Olaf J. Borkiewicz, Karena W. Chapman, Peter J. Chupas, Martin Moskovits, Bruce S. Dunn, Mercouri G. Kanatzidis, Ram Seshadri

^*Corresponding author for this work

Chemistry

Research output: Contribution to journal › Article › peer-review

38 Scopus citations

Abstract

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 MoS_3.4 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.

Original language	English (US)
Pages (from-to)	8357-8365
Number of pages	9
Journal	Chemistry of Materials
Volume	28
Issue number	22
DOIs	https://doi.org/10.1021/acs.chemmater.6b03656
State	Published - Nov 22 2016

ASJC Scopus subject areas

Chemistry(all)
Chemical Engineering(all)
Materials Chemistry

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Doan-Nguyen, V. V. T., Subrahmanyam, K. S., Butala, M. M., Gerbec, J. A., Islam, S. M., Kanipe, K. N., Wilson, C. E., Balasubramanian, M., Wiaderek, K. M., Borkiewicz, O. J., Chapman, K. W., Chupas, P. J., Moskovits, M., Dunn, B. S., Kanatzidis, M. G., & Seshadri, R. (2016). Molybdenum polysulfide chalcogels as high-capacity, anion-redox-driven electrode materials for Li-ion batteries. Chemistry of Materials, 28(22), 8357-8365. https://doi.org/10.1021/acs.chemmater.6b03656

Doan-Nguyen, Vicky V.T. ; Subrahmanyam, Kota S. ; Butala, Megan M. ; Gerbec, Jeffrey A. ; Islam, Saiful M. ; Kanipe, Katherine N. ; Wilson, Catrina E. ; Balasubramanian, Mahalingam ; Wiaderek, Kamila M. ; Borkiewicz, Olaf J. ; Chapman, Karena W. ; Chupas, Peter J. ; Moskovits, Martin ; Dunn, Bruce S. ; Kanatzidis, Mercouri G. ; Seshadri, Ram. / Molybdenum polysulfide chalcogels as high-capacity, anion-redox-driven electrode materials for Li-ion batteries. In: Chemistry of Materials. 2016 ; Vol. 28, No. 22. pp. 8357-8365.

@article{a83195f2f5264c5ca428f9a57eb19598,

title = "Molybdenum polysulfide chalcogels as high-capacity, anion-redox-driven electrode materials for Li-ion batteries",

abstract = "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.",

author = "Doan-Nguyen, {Vicky V.T.} and Subrahmanyam, {Kota S.} and Butala, {Megan M.} and Gerbec, {Jeffrey A.} and Islam, {Saiful M.} and Kanipe, {Katherine N.} and Wilson, {Catrina E.} and Mahalingam Balasubramanian and Wiaderek, {Kamila M.} and Borkiewicz, {Olaf J.} and Chapman, {Karena W.} and Chupas, {Peter J.} and Martin Moskovits and Dunn, {Bruce S.} and Kanatzidis, {Mercouri G.} and Ram Seshadri",

note = "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.",

year = "2016",

month = nov,

day = "22",

doi = "10.1021/acs.chemmater.6b03656",

language = "English (US)",

volume = "28",

pages = "8357--8365",

journal = "Chemistry of Materials",

issn = "0897-4756",

publisher = "American Chemical Society",

number = "22",

}

Doan-Nguyen, VVT, Subrahmanyam, KS, Butala, MM, Gerbec, JA, Islam, SM, Kanipe, KN, Wilson, CE, Balasubramanian, M, Wiaderek, KM, Borkiewicz, OJ, Chapman, KW, Chupas, PJ, Moskovits, M, Dunn, BS, Kanatzidis, MG & Seshadri, R 2016, 'Molybdenum polysulfide chalcogels as high-capacity, anion-redox-driven electrode materials for Li-ion batteries', Chemistry of Materials, vol. 28, no. 22, pp. 8357-8365. https://doi.org/10.1021/acs.chemmater.6b03656

Molybdenum polysulfide chalcogels as high-capacity, anion-redox-driven electrode materials for Li-ion batteries. / Doan-Nguyen, Vicky V.T.; Subrahmanyam, Kota S.; Butala, Megan M.; Gerbec, Jeffrey A.; Islam, Saiful M.; Kanipe, Katherine N.; Wilson, Catrina E.; Balasubramanian, Mahalingam; Wiaderek, Kamila M.; Borkiewicz, Olaf J.; Chapman, Karena W.; Chupas, Peter J.; Moskovits, Martin; Dunn, Bruce S.; Kanatzidis, Mercouri G.; Seshadri, Ram.

In: Chemistry of Materials, Vol. 28, No. 22, 22.11.2016, p. 8357-8365.

Research output: Contribution to journal › Article › peer-review

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.

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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DO - 10.1021/acs.chemmater.6b03656

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JO - Chemistry of Materials

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