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      Synergistic effect of adsorption and electrocatalysis of CoO/NiO heterostructure nanosheet assembled nanocages for high-performance lithium–sulfur batteries

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          Abstract

          CoO/NiO nanosheet assembled nanocages (CoO/NiO@C-NC) were prepared to improve the electrochemical performance of Li–S batteries. CoO/NiO@C-NC shows a synergistic adsorption–electrocatalysis effect to accelerate the redox of lithium polysulfides.

          Abstract

          The dissolution and sluggish redox kinetics of lithium polysulfides (LiPSs) hinder the practical electrochemical performance of lithium–sulfur (Li–S) batteries. The modification of separators with functional materials plays an important role in improving the electrochemical performance of Li–S batteries. In this work, CoO/NiO heterostructure nanosheet assembled nanocages (CoO/NiO@C-NC) derived from NiCo-LDH with ZIF-67 as the template are synthesized to modify the separator of Li–S batteries. CoO/NiO@C-NC shows strong physical adsorption, chemical interaction, and even superior catalytic activity towards LiPSs due to its high surface area and CoO/NiO heterostructure, thus suppressing the dissolution and accelerating the solid–liquid–solid conversion kinetics of LiPSs. In particular, NiO can promote solid–liquid kinetics, and CoO is more favorable to accelerate the liquid–solid kinetics of LiPSs. With CoO/NiO@C-NC coated on the separator, the electrochemical performance of Li–S batteries is improved significantly due to the synergistic effect of adsorption and electrocatalysis of the CoO/NiO@C-NC. The modified Li–S battery shows a high discharge capacity of 738 mA h g −1 at 3C rate, a low capacity decay rate of 0.075% for 500 cycles at 1C, and an areal capacity of 5.8 mA h cm −2 with a high sulfur loading of 5.87 mg cm −2. This work provides a novel method for the preparation of hollow heterostructure materials for high-performance Li–S batteries.

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          A highly ordered nanostructured carbon-sulphur cathode for lithium-sulphur batteries.

          The Li-S battery has been under intense scrutiny for over two decades, as it offers the possibility of high gravimetric capacities and theoretical energy densities ranging up to a factor of five beyond conventional Li-ion systems. Herein, we report the feasibility to approach such capacities by creating highly ordered interwoven composites. The conductive mesoporous carbon framework precisely constrains sulphur nanofiller growth within its channels and generates essential electrical contact to the insulating sulphur. The structure provides access to Li+ ingress/egress for reactivity with the sulphur, and we speculate that the kinetic inhibition to diffusion within the framework and the sorption properties of the carbon aid in trapping the polysulphides formed during redox. Polymer modification of the carbon surface further provides a chemical gradient that retards diffusion of these large anions out of the electrode, thus facilitating more complete reaction. Reversible capacities up to 1,320 mA h g(-1) are attained. The assembly process is simple and broadly applicable, conceptually providing new opportunities for materials scientists for tailored design that can be extended to many different electrode materials.
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            High-throughput synthesis of zeolitic imidazolate frameworks and application to CO2 capture.

            A high-throughput protocol was developed for the synthesis of zeolitic imidazolate frameworks (ZIFs). Twenty-five different ZIF crystals were synthesized from only 9600 microreactions of either zinc(II)/cobalt(II) and imidazolate/imidazolate-type linkers. All of the ZIF structures have tetrahedral frameworks: 10 of which have two different links (heterolinks), 16 of which are previously unobserved compositions and structures, and 5 of which have topologies as yet unobserved in zeolites. Members of a selection of these ZIFs (termed ZIF-68, ZIF-69, and ZIF-70) have high thermal stability (up to 390 degrees C) and chemical stability in refluxing organic and aqueous media. Their frameworks have high porosity (with surface areas up to 1970 square meters per gram), and they exhibit unusual selectivity for CO2 capture from CO2/CO mixtures and extraordinary capacity for storing CO2: 1 liter of ZIF-69 can hold approximately 83 liters of CO2 at 273 kelvin under ambient pressure.
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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.

                Author and article information

                Contributors
                Journal
                JMCAET
                Journal of Materials Chemistry A
                J. Mater. Chem. A
                Royal Society of Chemistry (RSC)
                2050-7488
                2050-7496
                November 15 2022
                2022
                : 10
                : 44
                : 23811-23822
                Affiliations
                [1 ]School of Environmental Science and Engineering, Huazhong University of Science and Technology, Wuhan, Hubei, 430074, P. R. China
                [2 ]Hubei Provincial Engineering Laboratory of Solid Waste Treatment, Disposal and Recycling, Wuhan, Hubei, 430074, P. R. China
                [3 ]State Key Laboratory of Coal Combustion, Huazhong University of Science and Technology, Wuhan, Hubei, 430074, P. R. China
                Article
                10.1039/D2TA06876A
                f88a58e3-d607-4bca-84db-f48ec65ee881
                © 2022

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

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