Porous, Lightweight, and Semiconducting Chalcogel asHigh Energy Density Electrode for Lithium-ion and Sodium-ion Batteries

Grants and Contracts Details


(a) The planned title of the research application: “Porous, Lightweight, and Semiconducting Chalcogel as High Energy Density Electrode for Lithium-ion and Sodium-ion Batteries” (b) The name and mailing address of the sponsoring institution: Jackson State University, 1400 John R Lynch St, Jackson, MS39217-0002 (c) The name, e-mail address, and telephone number of the PI: Muhammad Saiful Islam e-mail: muhammad.s.islam@jsums.edu Telephone number: 601 979 3485 (d) The topical research area(s): Energy Storage (e) Funding Opportunity Announcement Number: DE-FOA-0002624 (f) DOE Office Sponsoring this FOA: DOE EPSCoR (g) DOE EPSCoR Scientific/Technical Contact: Tim Fitzsimmons (h) Relevant DOE Program Office / Office of Science and research area(s): (i) Materials Chemistry, (ii) EERE/VTO/Battery R&D (i) Relevant DOE Program Office Scientific/Technical Contact: (i) Materials Chemistry: Dr. Michael Sennett (Program Manager) (ii) EERE/VTO/Battery R&D technical contact; Brian Cunningham, Tien Duong, Peter Faguy, and Samm Gillard (j) DOE/national laboratory(s) participating in the proposed research: (i) Oak Ridge National Laboratory, Oak Ridge, TN; (ii) Argonne National Laboratory, Lemont, IL (k) DOE/National laboratory personnel participating in the proposed research: (i) Dr. Ilias Belharouak (ORNL), (ii) Dr. Ruhul Amin (ORNL), and (iii) Dr. Kamila Wiaderek (ANL) (l) The signature and printed name of the Vice President for Research/Chief Technology Officer of the institution submitting the pre-application: Dr. Joseph Whittaker, VP for Research and Economic Development/Associate Provost Tel: 601-979-2008 E-mail: joseph.a.whittaker@jsums.edu Signature: ------------------------------------ 1 Porous, Lightweight, and Semiconducting Chalcogel as High Energy Density Electrode for Lithium-ion and Sodium-ion Batteries 1. INNOVATION AND IMPACT: This proposal describes the development of a novel class of light weight, porous semiconducting chalcogenide-based electrode materials, named chalcogels, that will effectively provide high energy-density anode materials for lithium and sodium-ion batteries (LiSBs and NaSBs). The proposed materials have significant advantages over existing electrode materials in terms of solution processable scalable synthesis and processing, tuning the intrinsic properties, design architecture, storage capability, and cyclic stability. The preliminary data exhibit highly stable capacity of over 600 (LiSBs) and 400 (NaSBs) mAh/g with an average working potential below one voltage against metallic lithium and thus can function as a potential anode (Fig 1). It should be emphasized that these materials can be synthesized at room temperature (RT), which is potentially transformational in its ability to provide amorphous materials with variable compositions that induce to deliver desired materials for high power density. A further advancement from existing electrodes is the design of active and additive materials that can be integrated into during synthesis process and modify to the electrode composition. As a result of the expected impact on both existing and next generation batteries, the proposed research offers an innovative material for grid level energy storage, and directly supports the DOE mission for revolutionary improvements in long duration energy storage from cost-effective earth abundance elements and maintain load and frequency shaving in the gird. 2. PRELIMINARY RESULTS: Chalcogels are nanoaggregated three dimensionally (3D) interlinked meso to microporous, lightweight, and semiconducting chalcogenide-based materials.1 This class of materials can be synthesized using the solution-processable sol-gel synthesis by the condensation of polysulfides or metal sulfides anions at RT and ambient pressure. Recently, we introduced chalcogels, (MoS4)n (n~∞) as MoSx, a novel class of materials as S-equivalent high capacity (~ 600 mAh/g @ 1st discharge cycle) electrode for LiSBs which showed remarkably higher cyclic stability than S electrode.2 This is because of the higher affinity of metal cation toward S that in turn prevents the dissolution of sulfides in the electrolytes.2 This along with the proven efficiencies of carbonaceous materials as anode materials for LiSBs and NaSBs, we have designed and developed a novel class of carbonaceous – metal sulfide gels that we named “carbochalcogels”. The novel metal-sulfide, hence, MoSx and graphene oxide (GO) carbochalcogel, MoSx-GO synergistically delivers an excellent specific capacity and cyclic efficiencies, over 600 mAh/g after 60th cycle for LiSBs and 300 mA/g after 100 cycles for NaSBs, Figure 1. Electrochemical performances of the unoptimized MoSx- GO composites as the sulfur-equivalent material for LiSBs and as shown in the Fig. 1. NaSBs; (A) Galvanostatic charge and discharge curves at 50 mA/g, and (B) Cycling stability of a 1.2 mgactive/cm2 loading of electrode. This outstanding finding introduces the MoSx-GO as a solution processable, scalable, and RT synthesized novel class of high capacity, highly cyclic stable anode for LiSBs and NaSBs. These results further demand the study of the basic science of the charge/discharge properties, chemical compositions optimization, understanding of the local structures, and exploring new materials toward the goal of achieving high energy-density anode materials that has the potential to replace the low energy density hard 2 carbon, especially against the earth abundance and cheaper Na+ for its widespread applications in NaSBs batteries. PROPOSED RESEARCH: This proposed research will integrate rational design, synthesis, and the functionalization of chalcogels to develop high energy density, cycling stable, and low-cost electrodes materials, as well as atomistic understanding of the properties of the novel electrode materials. To achieve these goals, the proposed research will be focused on: (a) Development of novel chalcogels electrodes: Motivated by effectiveness of MoSx gels for LiSBs and NaSBs (discussed in the preliminary results), we will expand the chemistry of the binary Mo-S chalcogels- based electrodes with variable compositions and local structures. To achieve this goal, we will introduce the new [(MoS(S4)2]n, [(Mo2(S6)2]n, and [Mo3S(S2)6]n (n=∞) chalcogels. Among these, we have already synthesized [Mo3S(S2)6]n (n=∞) and other will be synthesized using the oxidative coupling or metathesis synthesis at RT and pressure, that we have already established for similar systems. The new [MoS(S4)2]n, [(Mo2(S6)2]n, and [Mo3S(S2)6]n (n=∞) gels will provide a diverse Mo:S ratio, distinct local structures, and diverse length of polysulfide ions in the solid state matrix of the Mo-S gels that will ultimately impact on the charge-discharge capacity and cyclic stability. This investigation will provide detailed understanding of the chemical compositions driven local structural evolution as well as its relationship with electrochemical energy storage phenomena. Moreover, we will incorporate 3d transition of Mn+ (Mn+ ~ Fe2+, Mn2+, Ni2+, Co2+, Zn2+), into the structural matrices of the each Mo-S binary gels of (MoS4)n, [(Mo2(S6)2]n, and (MoS(S4)2]n to synthesize the compositions of MzMoSx, where z < 0.5. We hypothesize that the incorporation of such diverse Mn+ cations in the Mo-S gels with different degrees of Lewis acidity, chemical hardness, polarizability, and their synergistic interactions of the Mo ions of the MoSx, and (poly)sulfides chain will develop a critical role that can tune the working potentials of the novel anode materials. Thus, this investigation will provide a better understanding the ternary metal-sulfides chalcogel electrodes for electrochemical energy storage. Consequently, this study will have the potential to accelerate the development of high energy density, cyclic stable and efficient anode material. (b) Development of the stable nanocomposites electrodes: Sulfur-based electrodes exhibit numerous drawbacks, such as cyclic instability, polysulfide dissolution and shuttling, dendrites formation, large volume change, poor electrical and ionic conductivity. Recent studies show that carbonaceous materials functionalized sulfur electrodes can substantially mitigate the above problems.3 Moreover, as discussed in the preliminary results, our study shows that both the specific capacity and the cyclic stability can be greatly increased for the graphene oxides and MoSx composite gels. With this understanding, we hypothesize that chalcogel-carbonaceous composites will deliver electrodes materials with superior specific capacity and cyclic stability. Reasonably, we plan to engineer the binary Mo-S {(MoS4)n, [(Mo2(S6)2]n (MoS(S4)2]} and the ternary MzMoSx chalcogels with carbonaceous materials to develop chalcogels?carbonaceous composite electrodes. More specifically, we will utilize the MoSx, and MzMoSx chalcogels to develop composite materials with (i) graphene oxides, (ii) microporous carbon, and (iii) carbon nanotube, and will investigate synthesis-composition, synthesis-morphology, and synthesis-local structures; and will determine their electrochemical properties for charge-discharge energy storage for LiSBs and NaSBs. Moreover, the promising composite electrode materials will be studied by in-situ and ex-situ synchrotron radiation including pair distribution functions (PDF), X-ray near edge absorption spectroscopy (XANES), and extended X-ray absorption fine structure studies (EXAFS), and ORNL’s in-situ X-powder diffraction (XRD), and X-ray Photoelectron Spectroscopy (XPS) facilities. (c) Mechanistic understanding of the MoSx and MzMoSx electrodes: We will integrate comprehensive experimental and computational studies of the binary Mo-S {(MoS4)n, [(Mo2(S6)2]n and (MoS(S4)2]} and the ternary MxMoSn chalcogel electrodes to understand the charge-discharge mechanisms, the origin of capacity loss especially at the few charge/discharge cycles, and subsequent slow capacity fading. We will investigate local structural changes during the electrochemical process and the roles of pore density, surface area, particles sizes, microstructures, annealing (below the decomposition temperature), chemical hardness, and polarizability of the metal (Mn+) ions at different stage of charged-discharge cycles. In particular, we 3 will investigate these chalcogels and their composite electrodes by operando study using the DOE’s PDF, XANES, EXAFS, XPS, and XRD facilities at ANL and ORNL. We will also conduct ex-situ high resolution transmission electron microscopy (HRTEM), scanning electron microscopy (SEM), and XPS of disassembles electrodes at different c-rates and charge/discharge cycles. Our theoretical investigations will make use of both quantum-chemical methods and molecular dynamics simulations to explore the local structure of the chalcogel electrodes, interactions of the Na+/Li+ ions with polysulfides species, the role of pore sizes and density, the paths and activation energies for the diffusion of this ions, electrochemical lithi- /sodi-ation or delithi-/deso-diation mechanisms, and the origin of capacity loss at the different charge- discharge stage at various c-rates. Overall, such broad range of experimental and computational studies will provide a detailed understanding of the electrochemical properties of the materials which will assist to the design and development of novel chalcogels based high energy density and highly stable electrodes. 3. Team organization and capacity: The Principal Investigator, Dr. M. Saiful Islam, is an Assistant Professor of Chemistry at Jackson State University (JSU) and is an expert on the design, development, and functionalization crystalline and amorphous solids as well as chalcogenide-based aerogels. He will synthesize and functionalize the electrode materials and will characterize them by XRD, SEM, TEM, IR/Raman, and solid-state UV/Vis optical reflectance. The PI will also study the basic charge-discharge capacity and tuning the properties of the electrodes at his research lab in Jackson State University (JSU). The ORNL team will be led by Dr. Ruhul Amin, who is an expert in battery fabrication and characterizations, materials development, interfacial kinetics, and transport properties of electrode and electrolytes materials, evaluation, and monitoring of battery degradation by electrochemical, microscopic, and spectroscopic techniques. During the summer months, Dr. Amin will host and supervise a JSU graduate student at his lab at ORNL to conduct advanced research especially the in-situ experiments. Dr. Kamila Wiaderek is a chemist who runs the Electrochemistry Facility at the Advanced Photon Source, ANL will assist and monitor the operando electrochemical charge-discharge experiment by PDF, XANES, and EXAFS using the user facilities at ANL’s advanced photon sources. Dr. Chad Risko is an Associate Professor of Chemistry at the University of Kentucky (UK), with expertise in computational materials chemistry as it relates to materials of interest for advanced and electrochemical energy storage. He will work in close conjunction with the synthesis and characterization team to enable in silico-driven guidance and interpretation of experimental data. 4. ANTICIPATED PROJECT RESULTS AND BROADER IMPACT: The innovation of this proposal is to produce a solution-processable, high energy density and cyclic stable chalcogels based electrode materials for electrochemical energy storage. The porous and semiconductive nature of this class of lightweight materials can address the bottleneck issues of sulfur electrodes such as large volume expansion, insulation, polysulfide shuttling and dendrites. Further, the effectiveness of MoSx-GO both for Na and Li-ion batteries and its stability in the organic electrolytes and water could be indicative that this class of materials may have the potential use for sea water batteries. Moreover, these materials can be employed in electrocatalysis (e.g. CO2 reduction, H2 production), DOE’s legacy tank waste, and toxic heavy metals remediation. This project will also facilitate the establishment of a battery research lab in JSU, and train under-represented minority students on rechargeable battery technology and will contribute to the growth of sate Mississippi as well as the country. 5. ESTIMATED TOTAL PROJECT COST: The PI proposes a budget of $750,000 for three years for this collaborative research with JSU, UK, ANL and ORNL, where ANL and ORNL claim no funding for this collaboration. At JSU, the PI requests a grant of total $525,000 for three years that will support one graduate ($28,000/y) and two undergraduate students($1×56,00/y), one postdoctoral research associate (RA) ($42,000/y), PI’s one month’s summer salary and release times ($2×14,822/y), $8000/y travel, and $6000 for lab supplies. In addition, JSU applies 37% fringes benefit for PI’s and RA’s salary, and 51% IDC for PI’s and RA’s salary, travel and supplies costs. At, UK, the Co-PI requests a funds of $225K for three years to one graduate student’s stipend, tuition, materials, and travel. REFERENCES: (1) Bag, et al. Science 2007, 317, 5837; (2) Doan-Nguyen, et al. Chem. Mater. 2016, 28, 8357; (3) Wang, et. al. Energy Environ. Sci. 2020, 13, 3848. 4 Appendix Table 1: Team Members Team members Ruhul Institute name Amin Muhammad Oak Ridge National Laboratory Islam Chad Jackson State University Risko Kamila University of Kentucky Wiaderek Argonne National Laboratory Table 2: Persons with Potential Conflict of Interest. Personnel Robert Institute Nature of Mercouri Relationship Glaum Dien University of Bonn advisor Kanatzidis Northwestern University Advisor Li Taylor-Pashow Savannah River National Collaborator Laboratory Kathryn Bruce Savannah River National Collaborator Vinayak, Laboratory Wessels Matthew Northwestern University Co-author Dravid Michael Northwestern University Co-author Grayson Chris Northwestern University Co-author Bedzyk Mark Northwestern University Co-author Wolverton Christos Northwestern University Co-author Hersam Chung Northwestern University Co-author Malliakas Robert Northwestern University Co-author Duck Young Fengxiang Argonne national laboratory Co-author Chang Zikri Northwestern University Co-author Han Micheal Jackson State University Co-author Arslan Shulan US Geological Survey Co-author Wasieleswski Jan Northwestern University Co-author Ma Beijing Normal University Co-author Allen David Army Research laboratory, Adelphi Co-author MD Baker Nanda Army Research laboratory, Adelphi Co-author Belharouak MD Jagjit Muralitharan Oak Ridge National Laboratory Co-author Ilias Essehli Oak Ridge National Laboratory Co-author Nitin Wood Oak Ridge National Laboratory Co-author Rachid Shakoor Oak Ridge National Laboratory Co-author David Dixit Sky Nano Co-author Abdur Abuoimrane Qatar University Co-author Marm Zagib Oak Ridge National Laboratory Co-author Ali Ahmet QEERI-HBKU Co-author Karim Alicia Hydro Quebec Co-author Celik Jing Jackson State University advisee Blanton Jackson State University advisee Nie Jackson State University advisee 5
Effective start/end date9/1/228/31/25


  • Jackson State University: $154,929.00


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