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Labyrinth maze-like long travel-reduction of sulfur and polysulfides in micropores of a spherical honeycomb carbon to greatly confine shuttle effects in lithium-sulfur batteries

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Materials Reports(Energy) 2022年第4期2卷 54-61页

作者： Yanyan Chang Jie Chen Zhuo Zou Juan Li Chao Wu Yali Jiang Yue Chen Qingxin Zeng Xiaoshui Wu Wei Sun Chang Ming Li Institute of Materials Science and Devices School of Material Science and EngineeringSuzhou University of Science and TechnologySuzhou215011PR China Institute of Clean Energy and Advanced Materials School of Materials and EnergySouthwest UniversityChongqing400715PR China Jiuhuan Xinyue New Energy Technology Co.LTD Qingdao266071PR China College of Chemistry and Chemical Engineering Hainan Normal UniversityHaikou571158PR China

Polysulfide absorption in a micropore-rich structure has been reported to be capable of efficiently confining the shuttle effect for high-performance lithium-sulfur(Li–S)batteries.Here,a labyrinth maze-like spherical honeycomb-like carbon with micropore-rich structure was synthesized,which is employed as a template host material of sulfur to study the shuttle effects.The results strongly confirm that a diffusion controlled process rather than an absorption resulted surface-controlled process occurs in an even micropore-rich cathode but still greatly inhibits the shuttle effect.Thus,the battery achieves a high initial discharge specific capacity of 1120 mAh g1 at 0.25 C and super cycling stability for 1635 cycles with only 0.035%capacity decay per cycle with 100%Coulombic efficiency.We would like to propose a new mechanism for shuttle effect inhibition in micropores.In terms of the diffusion control process in microporous paths of a labyrinth maze structure,polysulfides experience a long travel to realize continuous reductions of sulfur and polysulfides until formation of the final solid product.This efficiently prevents the polysulfides escaping to electrolyte.The labyrinth maze-like honeycomb structure also offers fast electron transfer and enhanced mass transport as well as robust mechanical strength retaining intact structure for long cycle life.This work sheds lights on new fundamental insights behind the shuttle effects with universal significance while demonstrating prominent merits of a robust labyrinth maze-like structure in high performance cathode for high-performance Li–S batteries.

关键词： Lithium-sulfur batteries Labyrinth maze-like spherical honeycomb-like carbon Diffusion-controlled process shuttle effects High performance

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Phosphorus modulated porous CeO_(2)nanocrystallines for accelerated polysulfide catalysis in advanced Li-S batteries

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Journal of Materials Science & Technology 2022年第36期131卷 212-220页

作者： Xuefeng Tao Zhao Yang Menghao Cheng Rui Yan Fan Chen Sujiao Cao Shuang Li Tian Ma Chong Cheng Wei Yang College of Polymer Science and Engineering State Key Laboratory of Polymer Materials EngineeringSichuan UniversityChengdu 610065China State Key Laboratory of Advanced Processing and Recycling of Non-ferrous Metals Lanzhou University of TechnologyLanzhou 730050China Department of Ultrasound National Clinical Research Center for GeriatricsWest China HospitalSichuan UniversityChengdu 610041China

The insulating nature of sulfur species,sluggish reaction kinetics,and uncontrolled dissolution of lithium polysulfide(LiPS)intermediates during the complex and multiphase sulfur redox process,have severely inhibited the applications of Li-S batteries.In this study,we report a rational strategy to accelerate the polysulfide catalysis via constructing phosphorus modulated porous CeO_(2)(P-CeO_(2))for advanced Li-S batteries.The morphology and surface analysis demonstrate that the P-CeO_(2)consists of abundant Pmodulated porous CeO_(2)nanocrystallines.The battery performance reveals that the introduction of P will lead to an improved initial capacity of 1027 mA hg^(-1)than that of bare CeO_(2)(895.7 mA hg^(-1))at 0.2 C.In addition,the P-CeO_(2)cathode can maintain a low capacity decay ratio of 0.10%per cycle after 500 cycles at 1.0 C.The coin battery tests suggest that the P-CeO_(2)cathode presents faster oxidation-reduction kinetics of LiPS and quick diffusion of Li^+ions.Meanwhile,the studies of redox processes and chemical interactions of LiPS have demonstrated the P-CeO_(2)cathode displays stronger adsorption of Li_(2)S_(6),higher redox peak current,and earlier precipitation of Li_(2)S than the bare CeO_(2).This study demonstrates for the first time that the P-modulation of metal oxide surface can simultaneously promote the catalytic reaction kinetics and chemical interaction of LiPS.We anticipate that this P-modulation method can be extended to many other nanostructured metal catalytic sites for developing affordable advanced Li-S batteries.

关键词： Metal oxides P-modulated porous CeO_(2) Polysulfide catalytic materials shuttle effects Lithium-sulfur batteries

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A molecular sieve-containing protective separator to suppress the shuttle effect of redox mediators in lithium-oxygen batteries

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Nano Research 2023年第7期16卷 9453-9460页

作者： Xinbin Wu Huiping Wu Shundong Guan Ying Liang Kaihua Wen Huanchun Wang Xuanjun Wang Ce-Wen Nan Liangliang Li State Key Laboratory of New Ceramics and Fine Processing School of Materials Science and EngineeringTsinghua UniversityBeijing 100084China High-Tech Institute of Xi’an Xi’an 710025China

Lithium-oxygen(Li-O_(2))batteries have a great potential in energy storage and conversion due to their ultra-high theoretical specific energy,but their applications are hindered by sluggish redox reaction kinetics in the charge/discharge processes.Redox mediators(RMs),as soluble catalysts,are widely used to facilitate the electrochemical processes in the Li-O_(2)batteries.A drawback of RMs is the shuttle effect due to their solubility and mobility,which leads to the corrosion of a Li metal anode and the degradation of the electrochemical performance of the batteries.Herein,we synthesize a polymer-based composite protective separator containing molecular sieves.The nanopores with a diameter of 4Åin the zeolite powder(4A zeolite)are able to physically block the migration of 2,2,6,6-tetramethylpiperidinyloxy(TEMPO)molecules with a larger size;therefore,the shuttle effect of TEMPO is restrained.With the assistance of the zeolite molecular sieves,the cycle life of the Li-O_(2)batteries is significantly extended from~20 to 170 cycles at a current density of 250 mA·g^(-1)and a limited capacity of 500 mAh·g^(-1).Our work provides a highly effective approach to suppress the shuttle effects of RMs and boost the electrochemical performance of Li-O_(2)batteries.

关键词： lithium-oxygen batteries redox mediators shuttle effects protective separators zeolite molecular sieves

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Cobalt coordination modified double-schiff-base with low solubility as a long-cycle life anode for sodium-ion batteries

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Progress in Natural Science:Materials International 2022年第4期32卷 510-516页

作者： Mengyuan Yue Huinan Guo Zhaoxia Yuan Weiqin Li Yafei Liu Kai Chen Yusang Guo Yijing Wang Key Laboratory of Advanced Energy Materials Chemistry (Ministry of Education) Renewable Energy Conversion and Storage Center College of Chemistry Nankai University

Sodium-ion batteries（SIBs） have been recently considered as an intriguing candidate for next-generation battery systems with their advantages in large-scale energy storage applications. However, the design of electrode materials of SIBs still suffers from severe volume expansion and low capacity caused by the larger ion radius, high redox potential and heavy atom weight of Na. Organic electrode materials with structural flexibility have attracted great attention recently for their potential in alleviating volume expansion. However, most organic electrode materials suffer from dissolution in electrolytes and consequent capacity fading during the long-term cycling process. In this work, a method coordinating with Co2+was applied to solve the shuttle effect of H4salphdc(N, N'-phenylene-bis-（salicylideneimine） dicarboxylic acid). By virtue of the Co2+coordination, the Co（H2salphdc）electrode delivered a desirable discharge capacity of 123 m Ah g-1after 1500 cycles at the current density of 200m A g-1, while the H4salphdc electrode exhibited severe capacity fading. Such excellent electrochemical performance can be credited to the Co2+coordination repressing the electrode dissolution and improving the structure stability.

关键词： Double-Schiff-base Sodium-ion battery shuttle effects

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