Mo3S13 Chalcogel: A High-Capacity Electrode for Conversion-Based Li-Ion Batteries

Taohedul Islam; Subrata Chandra Roy; Sahar Bayat; Misganaw Adigo Weret; Justin M. Hoffman; Keerthan R. Rao; Conrad Sawicki; Jing Nie; Robiul Alam; Oluwaseun Oketola; Carrie L. Donley; Amar Kumbhar; Renfei Feng; Kamila M. Wiaderek; Chad Risko; Ruhul Amin; Saiful M. Islam

doi:10.1002/cssc.202400084

Mo₃S₁₃ Chalcogel: A High-Capacity Electrode for Conversion-Based Li-Ion Batteries

Taohedul Islam, Subrata Chandra Roy, Sahar Bayat, Misganaw Adigo Weret, Justin M. Hoffman, Keerthan R. Rao, Conrad Sawicki, Jing Nie, Robiul Alam, Oluwaseun Oketola, Carrie L. Donley, Amar Kumbhar, Renfei Feng, Kamila M. Wiaderek, Chad Risko, Ruhul Amin, Saiful M. Islam

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

Abstract

Despite large theoretical energy densities, metal-sulfide electrodes for energy storage systems face several limitations that impact the practical realization. Here, we present the solution-processable, room temperature (RT) synthesis, local structures, and application of a sulfur-rich Mo₃S₁₃ chalcogel as a conversion-based electrode for lithium-sulfide batteries (LiSBs). The structure of the amorphous Mo₃S₁₃ chalcogel is derived through operando Raman spectroscopy, synchrotron X-ray pair distribution function (PDF), X-ray absorption near edge structure (XANES), and extended X-ray absorption fine structure (EXAFS) analysis, along with ab initio molecular dynamics (AIMD) simulations. A key feature of the three-dimensional (3D) network is the connection of Mo₃S₁₃ units through S−S bonds. Li/Mo₃S₁₃ half-cells deliver initial capacity of 1013 mAh g⁻¹ during the first discharge. After the activation cycles, the capacity stabilizes and maintains 312 mAh g⁻¹ at a C/3 rate after 140 cycles, demonstrating sustained performance over subsequent cycling. Such high-capacity and stability are attributed to the high density of (poly)sulfide bonds and the stable Mo−S coordination in Mo₃S₁₃ chalcogel. These findings showcase the potential of Mo₃S₁₃ chalcogels as metal-sulfide electrode materials for LiSBs.

Original language	English
Article number	e202400084
Journal	ChemSusChem
Volume	17
Issue number	11
DOIs	https://doi.org/10.1002/cssc.202400084
State	Published - Jun 10 2024

Bibliographical note

Publisher Copyright:
© 2024 Wiley-VCH GmbH.

Funding

. This work was supported by the US Department of Energy's Building EPSCoR\u2010State/National Laboratory Partnerships DE\u2010FOA\u20100002624. S.\u2005C.\u2005R. acknowledges the NSF Division of Chemistry (NSF\u20102100797). J.\u2005N., R.\u2005A. and O.\u2005O. are thankful to the US Department of Energy's Minority Serving Institution Partnership Program (MSIPP) managed by the Savannah River National Laboratory under SRNS contract (RFP No.\u20050000542525 and 0000458357). Electrochemical tests were performed at Oak Ridge National Laboratory, managed by UT\u2010battelle, LLC for the US Department of Energy. 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\u2010AC02\u201006CH11357. The mail\u2010in program at Beamline 11\u2010ID\u2212B (and/or 17\u2010BM, 11\u2010BM) contributed to the data. X\u2010ray absorption spectroscopy measurements were performed at the VESPERS, Canadian Light Source, which is supported by the Canada Foundation for Innovation (CFI), the Natural Sciences and Engineering Research Council (NSERC), the National Research Council (NRC), the Canadian Institutes of Health Research (CIHR), the Government of Saskatchewan, and the University of Saskatchewan. Any use of trade, firm, or product names is for descriptive purposes only and does not imply endorsement by the U.S. Government. TEM and XPS were data were collected at the Chapel Hill Analytical and Nanofabrication Laboratory, CHANL, a member of the North Carolina Research Triangle Nanotechnology Network, RTNN, which is supported by the National Science Foundation, Grant ECCS\u20102025064, as part of the National Nanotechnology Coordinated Infrastructure, NNCI. A portion of this work was performed using XPS instrumentation supported by the Center for Hybrid Approaches in Solar Energy to Liquid Fuels (CHASE), an Energy Innovation Hub funded by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences under Award Number DE\u2010SC0021173. S.\u2005B., K.\u2005R.\u2005R., and C.\u2005R. acknowledge the University of Kentucky (UK) Information Technology Department and Center for Computational Sciences (CCS) for providing supercomputing resources on the Lipscomb High Performance Computing Cluster

Funders	Funder number
Cummings Foundation
University of Saskatchewan
Canada Foundation for Innovation
U.S. Department of Energy EPSCoR
National Research Council
Natural Sciences and Engineering Research Council of Canada
Office of Science Programs
Canadian Institutes of Health Research
Government of Saskatchewan
MSIPP
DOE Basic Energy Sciences	DE‐SC0021173
DOE Basic Energy Sciences
Department of Chemistry and Division of Medicinal Chemistry and Pharmaceutics	NSF‐2100797
Department of Chemistry and Division of Medicinal Chemistry and Pharmaceutics
National Science Foundation Arctic Social Science Program	ECCS‐2025064
National Science Foundation Arctic Social Science Program
Argonne National Laboratory	DE‐AC02‐06CH11357
Argonne National Laboratory
Savannah River National Laboratory	0000458357, 0000542525
Savannah River National Laboratory

Keywords

MoS chalcogels
aerogels
conversion-based batteries
lithium-sulfide batteries

ASJC Scopus subject areas

Environmental Chemistry
General Chemical Engineering
General Materials Science
General Energy

Access to Document

10.1002/cssc.202400084

Cite this

Islam, T., Chandra Roy, S., Bayat, S., Adigo Weret, M., Hoffman, J. M., Rao, K. R., Sawicki, C., Nie, J., Alam, R., Oketola, O., Donley, C. L., Kumbhar, A., Feng, R., Wiaderek, K. M., Risko, C., Amin, R., & Islam, S. M. (2024). Mo₃S₁₃ Chalcogel: A High-Capacity Electrode for Conversion-Based Li-Ion Batteries. ChemSusChem, 17(11), Article e202400084. https://doi.org/10.1002/cssc.202400084

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abstract = "Despite large theoretical energy densities, metal-sulfide electrodes for energy storage systems face several limitations that impact the practical realization. Here, we present the solution-processable, room temperature (RT) synthesis, local structures, and application of a sulfur-rich Mo3S13 chalcogel as a conversion-based electrode for lithium-sulfide batteries (LiSBs). The structure of the amorphous Mo3S13 chalcogel is derived through operando Raman spectroscopy, synchrotron X-ray pair distribution function (PDF), X-ray absorption near edge structure (XANES), and extended X-ray absorption fine structure (EXAFS) analysis, along with ab initio molecular dynamics (AIMD) simulations. A key feature of the three-dimensional (3D) network is the connection of Mo3S13 units through S−S bonds. Li/Mo3S13 half-cells deliver initial capacity of 1013 mAh g−1 during the first discharge. After the activation cycles, the capacity stabilizes and maintains 312 mAh g−1 at a C/3 rate after 140 cycles, demonstrating sustained performance over subsequent cycling. Such high-capacity and stability are attributed to the high density of (poly)sulfide bonds and the stable Mo−S coordination in Mo3S13 chalcogel. These findings showcase the potential of Mo3S13 chalcogels as metal-sulfide electrode materials for LiSBs.",

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AU - Islam, Taohedul

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AU - Adigo Weret, Misganaw

AU - Hoffman, Justin M.

AU - Rao, Keerthan R.

AU - Sawicki, Conrad

AU - Nie, Jing

AU - Alam, Robiul

AU - Oketola, Oluwaseun

AU - Donley, Carrie L.

AU - Kumbhar, Amar

AU - Feng, Renfei

AU - Wiaderek, Kamila M.

AU - Risko, Chad

AU - Amin, Ruhul

AU - Islam, Saiful M.

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AB - Despite large theoretical energy densities, metal-sulfide electrodes for energy storage systems face several limitations that impact the practical realization. Here, we present the solution-processable, room temperature (RT) synthesis, local structures, and application of a sulfur-rich Mo3S13 chalcogel as a conversion-based electrode for lithium-sulfide batteries (LiSBs). The structure of the amorphous Mo3S13 chalcogel is derived through operando Raman spectroscopy, synchrotron X-ray pair distribution function (PDF), X-ray absorption near edge structure (XANES), and extended X-ray absorption fine structure (EXAFS) analysis, along with ab initio molecular dynamics (AIMD) simulations. A key feature of the three-dimensional (3D) network is the connection of Mo3S13 units through S−S bonds. Li/Mo3S13 half-cells deliver initial capacity of 1013 mAh g−1 during the first discharge. After the activation cycles, the capacity stabilizes and maintains 312 mAh g−1 at a C/3 rate after 140 cycles, demonstrating sustained performance over subsequent cycling. Such high-capacity and stability are attributed to the high density of (poly)sulfide bonds and the stable Mo−S coordination in Mo3S13 chalcogel. These findings showcase the potential of Mo3S13 chalcogels as metal-sulfide electrode materials for LiSBs.

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