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      Freestanding 1T MoS2/graphene heterostructures as a highly efficient electrocatalyst for lithium polysulfides in Li–S batteries

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          Abstract

          A novel approach to effectively suppress the “polysulfide shuttle” in Li–S batteries is presented by designing a freestanding, three-dimensional graphene/1T MoS 2 (3DG/TM) heterostructure with highly efficient electrocatalysis properties for lithium polysulfides (LiPSs).

          Abstract

          A novel approach to effectively suppress the “polysulfide shuttle” in Li–S batteries is presented by designing a freestanding, three-dimensional graphene/1T MoS 2 (3DG/TM) heterostructure with highly efficient electrocatalysis properties for lithium polysulfides (LiPSs). The 3DG/TM heterostructure is constructed by few-layered graphene nanosheets sandwiched by hydrophilic, metallic, few-layered 1T MoS 2 nanosheets with abundant active sites. The porous 3D structure and the hydrophilic feature of 1T-MoS 2 are beneficial for electrolyte penetration and Li-ion transfer, and the high conductivities of both graphene and the 1T MoS 2 nanosheets facilitate electron transfer. These merits lead to a high electrocatalytic efficiency for LiPSs due to excellent ion/electron transfer and the presence of sufficient electrocatalytic active sites. Therefore, the cells with 3DG/TM exhibit outstanding electrochemical performance, with a high reversible discharge capacity of 1181 mA h g −1 and a capacity retention of 96.3% after 200 cycles. The electrocatalysis mechanism of LiPSs is further experimentally and theoretically revealed, which provides new insights and opportunities to develop advanced Li–S batteries with highly efficient electrocatalysts for LiPS conversion.

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          Most cited references38

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          Powering Lithium-Sulfur Battery Performance by Propelling Polysulfide Redox at Sulfiphilic Hosts.

          Lithium-sulfur (Li-S) battery system is endowed with tremendous energy density, resulting from the complex sulfur electrochemistry involving multielectron redox reactions and phase transformations. Originated from the slow redox kinetics of polysulfide intermediates, the flood of polysulfides in the batteries during cycling induced low sulfur utilization, severe polarization, low energy efficiency, deteriorated polysulfide shuttle, and short cycling life. Herein, sulfiphilic cobalt disulfide (CoS2) was incorporated into carbon/sulfur cathodes, introducing strong interaction between lithium polysulfides and CoS2 under working conditions. The interfaces between CoS2 and electrolyte served as strong adsorption and activation sites for polar polysulfides and therefore accelerated redox reactions of polysulfides. The high polysulfide reactivity not only guaranteed effective polarization mitigation and promoted energy efficiency by 10% but also promised high discharge capacity and stable cycling performance during 2000 cycles. A slow capacity decay rate of 0.034%/cycle at 2.0 C and a high initial capacity of 1368 mAh g(-1) at 0.5 C were achieved. Since the propelling redox reaction is not limited to Li-S system, we foresee the reported strategy herein can be applied in other high-power devices through the systems with controllable redox reactions.
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            Nanostructured Metal Oxides and Sulfides for Lithium-Sulfur Batteries.

            Lithium-sulfur (Li-S) batteries with high energy density and long cycle life are considered to be one of the most promising next-generation energy-storage systems beyond routine lithium-ion batteries. Various approaches have been proposed to break down technical barriers in Li-S battery systems. The use of nanostructured metal oxides and sulfides for high sulfur utilization and long life span of Li-S batteries is reviewed here. The relationships between the intrinsic properties of metal oxide/sulfide hosts and electrochemical performances of Li-S batteries are discussed. Nanostructured metal oxides/sulfides hosts used in solid sulfur cathodes, separators/interlayers, lithium-metal-anode protection, and lithium polysulfides batteries are discussed respectively. Prospects for the future developments of Li-S batteries with nanostructured metal oxides/sulfides are also discussed.
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              Catalytic oxidation of Li2S on the surface of metal sulfides for Li-S batteries.

              Polysulfide binding and trapping to prevent dissolution into the electrolyte by a variety of materials has been well studied in Li-S batteries. Here we discover that some of those materials can play an important role as an activation catalyst to facilitate oxidation of the discharge product, Li2S, back to the charge product, sulfur. Combining theoretical calculations and experimental design, we select a series of metal sulfides as a model system to identify the key parameters in determining the energy barrier for Li2S oxidation and polysulfide adsorption. We demonstrate that the Li2S decomposition energy barrier is associated with the binding between isolated Li ions and the sulfur in sulfides; this is the main reason that sulfide materials can induce lower overpotential compared with commonly used carbon materials. Fundamental understanding of this reaction process is a crucial step toward rational design and screening of materials to achieve high reversible capacity and long cycle life in Li-S batteries.
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                Author and article information

                Journal
                EESNBY
                Energy & Environmental Science
                Energy Environ. Sci.
                Royal Society of Chemistry (RSC)
                1754-5692
                1754-5706
                January 16 2019
                2019
                : 12
                : 1
                : 344-350
                Affiliations
                [1 ]Materials Science and Engineering Program & Texas Materials Institute
                [2 ]The University of Texas at Austin
                [3 ]Austin
                [4 ]USA
                [5 ]State Key Laboratory of Electronic Thin Films and Integrated Devices
                [6 ]McKetta Department of Chemical Engineering
                [7 ]University of Electronic Science and Technology of China
                [8 ]Chengdu 610054
                [9 ]P. R. China
                Article
                10.1039/C8EE03252A
                68ba4181-f109-41c9-be4c-ecc7772b5b80
                © 2019

                Free to read

                http://rsc.li/journals-terms-of-use#chorus

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