Lithium-sulfur(Li-S)system coupled with thin-film solid electrolyte as a novel high-energy micro-battery has enormous potential for complementing embedded energy harvesters to enable the autonomy of the Internet of Th...Lithium-sulfur(Li-S)system coupled with thin-film solid electrolyte as a novel high-energy micro-battery has enormous potential for complementing embedded energy harvesters to enable the autonomy of the Internet of Things microdevice.However,the volatility in high vacuum and intrinsic sluggish kinetics of S hinder researchers from empirically integrating it into allsolid-state thin-film batteries,leading to inexperience in fabricating all-solid-state thin-film Li-S batteries(TFLSBs).Herein,for the first time,TFLSBs have been successfully constructed by stacking vertical graphene nanosheets-Li2S(VGsLi2S)composite thin-film cathode,lithium-phosphorous-oxynitride(LiPON)thin-film solid electrolyte,and Li metal anode.Fundamentally eliminating Lipolysulfide shuttle effect and maintaining a stable VGs-Li2S/LiPON interface upon prolonged cycles have been well identified by employing the solid-state Li-S system with an“unlimited Li”reservoir,which exhibits excellent longterm cycling stability with a capacity retention of 81%for 3,000 cycles,and an exceptional high temperature tolerance up to 60℃.More impressively,VGs-Li2S-based TFLSBs with evaporated-Li thin-film anode also demonstrate outstanding cycling performance over 500 cycles with a high Coulombic efficiency of 99.71%.Collectively,this study presents a new development strategy for secure and high-performance rechargeable all-solid-state thin-film batteries.展开更多
Owing to their low cost,high energy densities,and superior performance compared with that of Li-ion batteries,Li–S batteries have been recognized as very promising next-generation batteries.However,the commercializat...Owing to their low cost,high energy densities,and superior performance compared with that of Li-ion batteries,Li–S batteries have been recognized as very promising next-generation batteries.However,the commercialization of Li–S batteries has been hindered by the insulation of sulfur,significant volume expansion,shuttling of dissolved lithium polysulfides(Li PSs),and more importantly,sluggish conversion of polysulfide intermediates.To overcome these problems,a state-of-the-art strategy is to use sulfur host materials that feature chemical adsorption and electrocatalytic capabilities for Li PS species.In this review,we comprehensively illustrate the latest progress on the rational design and controllable fabrication of materials with chemical adsorbing and binding capabilities for Li PSs and electrocatalytic activities that allow them to accelerate the conversion of Li PSs for Li–S batteries.Moreover,the current essential challenges encountered when designing these materials are summarized,and possible solutions are proposed.We hope that this review could provide some strategies and theoretical guidance for developing novel chemical anchoring and electrocatalytic materials for high-performance Li–S batteries.展开更多
Use of metallic Li anode raises serious concerns on the safety and operational performance of Li-S batteries due to uncontrolled hazard of Li dendrite formation, which is difficultly eliminated as long as the metallic...Use of metallic Li anode raises serious concerns on the safety and operational performance of Li-S batteries due to uncontrolled hazard of Li dendrite formation, which is difficultly eliminated as long as the metallic Li exists in the cells. Pairing lithium sulfide (Li2S) cathode with currently available metallic Lifree high-capacity anodes offers an alternative solution to this challenge. However, the performance of Li2S cathode is primarily restricted by high activation barrier upon initial charge, low active mass utilization and sluggish redox kinetics. Herein, a MXene-induced multifunctional collaborative interface is proposed to afford superb activity towards redox solid-liquid/liquid-liquid phase transformation, strong chemisorption, high conductivity and fast ionic/charge transport in high Li2S loading cathode. Applying collaborative interface effectively reduces initial voltage barrier of Li2S activation and regulates the kinetic behavior of redox polysulfide conversion. Therefore, stable operation of additive-free Li2S cathode with high areal capacities at high Li2S loading up to 9 mg cm^-2 can be achieved with less sacrifice of high capacity and rate capability in Li-S batteries. Rechargeable metallic Li-free batteries are successfully constructed by pairing this high-performance Li2S cathode with high-capacity metal oxide anodes, which delivers superior energy density to current Li-ion batteries.展开更多
Lithium–sulfur batteries are one of the attractive next-generation energy storage systems owing to theienvironmental friendliness,low cost,and high specific energy densities.However,the low electrical conductivity of...Lithium–sulfur batteries are one of the attractive next-generation energy storage systems owing to theienvironmental friendliness,low cost,and high specific energy densities.However,the low electrical conductivity of sulfur,shuttling of soluble intermediate polysulfides between electrodes,and low capacitretention have hampered their commercial use.To address these issues,we use a halloysitemodulated(H-M)separator in a lithium–sulfur battery to mitigate the shuttling problem.The H-M separator acts as a mutual Coulombic repulsion in lithium-sulfur batteries,thereby selectively permitting Lions and efficiently suppressing the transfer of undesired lithium polysulfides to the Li anode sideMoreover,the use of halloysite switches the surface of the separator from hydrophobic to hydrophilicconsequently improving the electrolyte wettability and adhesion between the separator and cathodeWhen sulfur-multi-walled carbon nanotube(S-MWCNT)composites are used as cathode active materialsa lithium–sulfur battery with an H-M separator exhibits first discharge and charge capacities of 1587 an1527 m Ah g-1,respectively.Moreover,there is a consistent capacity retention up to 100 cyclesAccordingly,our approach demonstrates an economical and easily accessible strategy for commercialization of lithium–sulfur batteries.展开更多
Tremendous effort has been devoted to lithium‐sulfur batteries,where flooded electrolytes have been employed ubiquitously.The use of lean electrolytes albeit indispensable for practical applications often causes low ...Tremendous effort has been devoted to lithium‐sulfur batteries,where flooded electrolytes have been employed ubiquitously.The use of lean electrolytes albeit indispensable for practical applications often causes low capacity and fast capacity fading of the sulfur cathode;thus,the electrolyte/sulfur active mass ratios below 5μL/mg have been rarely reported.Herein,we demonstrate that ZnS coating transforms sulfur cathode materials electrolyte‐philic,which tremendously promotes the performance in lean electrolytes.The ZnS‐coated Li2S@graphene cathode delivers an initial discharge capacity of 944mAh/g at an E/S ratio of 2μL/mg at the active mass loading of 5.0 mg Li2S/cm^2,corresponding to an impressive specific energy of 500Wh/kg based on the mass of cathode,electrolyte,and the assumed minimal mass of lithium metal anode.Density functional theory calculations reveal strong binding between ZnS crystals and electrolyte solvent molecules,explaining the better wetting properties.We also demonstrate the reversible cycling of a hybrid cathode of ZnS‐coated Li2S@graphene mixed with VS2 as an additive at an E/AM(active mass)ratio of 1.1μL/mg,equivalent to the specific energy of 432 Wh/kg on the basis of the mass of electrodes and electrolyte.展开更多
Lithium–sulfur batteries have been attracting considerable research attention due to their high energy densities and low costs. However, one of their main challenges is the undesired shuttling of polysulfides, causin...Lithium–sulfur batteries have been attracting considerable research attention due to their high energy densities and low costs. However, one of their main challenges is the undesired shuttling of polysulfides, causing rapid capacity degradation. Herein, we report the first example of sulfiphilic VSe2 ultrafine nanocrystals immobilized on nitrogen-doped graphene to modify the battery separator for alleviating the shuttling problem. VSe2 nanocrystals provide numerous active sites for chemisorption of polysulfides as well as benefit the nucleation and growth of Li2S. Furthermore, the kinetic reactions are accelerated which is confirmed by higher exchange current density and higher lithium ion diffusion coefficient. And the first-principles calculations further show that the exposed sulfiphilic planes of VSe2 boost the redox of Li2S. When used as separators within the lithium sulfur batteries, the cell indicates greatly enhanced electrochemical performances with excellent long cycling stability and exceptional rate capability up to 8 C. Moreover, it delivers a higher areal capacity of 4.04 mAh·cm^−2 as well as superior cycling stability with sulfur areal loading up to 6.1 mg·cm^−2. The present strategy can encourage us in engineering novel multifunctional separators for energy-storage devices.展开更多
以湿法制备的硫溶胶和氧化石墨烯为前驱体,采用水热法还原不同酸碱体系的氧化石墨烯,制备石墨烯-硫复合材料。通过XRD和场发射扫描电子显微镜（FESEM）等对产物进行分析。石墨烯以薄膜状包覆在硫颗粒表面。恒流充放电、交流阻抗和循环...以湿法制备的硫溶胶和氧化石墨烯为前驱体,采用水热法还原不同酸碱体系的氧化石墨烯,制备石墨烯-硫复合材料。通过XRD和场发射扫描电子显微镜（FESEM）等对产物进行分析。石墨烯以薄膜状包覆在硫颗粒表面。恒流充放电、交流阻抗和循环伏安测试结果表明：180℃、酸性条件下水热12 h制备的复合材料电化学性能较好,以0.2 m A/cm2的电流密度在1.5-3.0 V充放电,首次放电比容量为803.72 m Ah/g,循环20次衰减至592.40 m Ah/g,容量保持率为73.71%。展开更多
分别以气相生长碳纤维（VGCF）、多壁碳纳米管（MWCNT）和活性炭（AC）作为单质硫载体,通过高温热处理制备锂硫电池用S/C正极材料。采用SEM、XRD、热重分析（TG）、循环伏安、电化学阻抗谱（EIS）和恒流充放电等方法,分析复合材料的结...分别以气相生长碳纤维（VGCF）、多壁碳纳米管（MWCNT）和活性炭（AC）作为单质硫载体,通过高温热处理制备锂硫电池用S/C正极材料。采用SEM、XRD、热重分析（TG）、循环伏安、电化学阻抗谱（EIS）和恒流充放电等方法,分析复合材料的结构及电化学性能。碳材料形态对锂硫电池的放电比容量和循环性能有重要影响,S/VGCF复合材料的电化学性能较好。以0.1 C的电流在1.5-3.0 V充放电,首次和第100次循环的放电比容量分别为1 204.87 m Ah/g、547.62 m Ah/g。展开更多
锂硫(Li-S)电池具有比锂离子电池更高的能量密度,是近10年来的研究热点,但目前锂硫电池的循环性能和倍率性能远远不能满足人们的需求。在本研究中,二(2,2,2-三氟乙基)碳酸酯(DTFEC)作为一种电解液添加剂应用到锂硫电池中,以提高电池的...锂硫(Li-S)电池具有比锂离子电池更高的能量密度,是近10年来的研究热点,但目前锂硫电池的循环性能和倍率性能远远不能满足人们的需求。在本研究中,二(2,2,2-三氟乙基)碳酸酯(DTFEC)作为一种电解液添加剂应用到锂硫电池中,以提高电池的电化学性能,并对DTFEC的添加量进行了筛选和优化。结果表明,DTFEC的添加量对电池性能有很大的影响,当添加体积分数为5%时,复合硫正极材料(S@p PAN)表现出最佳的循环稳定性和倍率性能。室温条件下进行充放电测试,在1C的充放电电流下,锂硫电池在循环200圈后容量保持率比常规电解液约高20%;在7C的大倍率充放电电流下,依然可以得到1246.3 m A·h/g的可逆比容量。以上结果表明,DTFEC可以有效提高锂硫电池的电化学性能,是一种适合用于锂硫电池电解液体系的添加剂。展开更多
基金supported by National Natural Science Foundation of China(No.U22A20118)Fujian Science&Technology Innovation Laboratory for Optoelectronic Information of China(No.2021ZR146,2021ZZ122)Award Program for Fujian Minjiang Scholar Professorship。
文摘Lithium-sulfur(Li-S)system coupled with thin-film solid electrolyte as a novel high-energy micro-battery has enormous potential for complementing embedded energy harvesters to enable the autonomy of the Internet of Things microdevice.However,the volatility in high vacuum and intrinsic sluggish kinetics of S hinder researchers from empirically integrating it into allsolid-state thin-film batteries,leading to inexperience in fabricating all-solid-state thin-film Li-S batteries(TFLSBs).Herein,for the first time,TFLSBs have been successfully constructed by stacking vertical graphene nanosheets-Li2S(VGsLi2S)composite thin-film cathode,lithium-phosphorous-oxynitride(LiPON)thin-film solid electrolyte,and Li metal anode.Fundamentally eliminating Lipolysulfide shuttle effect and maintaining a stable VGs-Li2S/LiPON interface upon prolonged cycles have been well identified by employing the solid-state Li-S system with an“unlimited Li”reservoir,which exhibits excellent longterm cycling stability with a capacity retention of 81%for 3,000 cycles,and an exceptional high temperature tolerance up to 60℃.More impressively,VGs-Li2S-based TFLSBs with evaporated-Li thin-film anode also demonstrate outstanding cycling performance over 500 cycles with a high Coulombic efficiency of 99.71%.Collectively,this study presents a new development strategy for secure and high-performance rechargeable all-solid-state thin-film batteries.
基金supported by the National Natural Science Foundation of China(No.51403094)Program of Liaoning Education Department of China(No.LJ2017FBL002)Australian Research Council through the Discovery Early Career Researcher Award(DECRA,No.DE170100871)Program.
文摘Owing to their low cost,high energy densities,and superior performance compared with that of Li-ion batteries,Li–S batteries have been recognized as very promising next-generation batteries.However,the commercialization of Li–S batteries has been hindered by the insulation of sulfur,significant volume expansion,shuttling of dissolved lithium polysulfides(Li PSs),and more importantly,sluggish conversion of polysulfide intermediates.To overcome these problems,a state-of-the-art strategy is to use sulfur host materials that feature chemical adsorption and electrocatalytic capabilities for Li PS species.In this review,we comprehensively illustrate the latest progress on the rational design and controllable fabrication of materials with chemical adsorbing and binding capabilities for Li PSs and electrocatalytic activities that allow them to accelerate the conversion of Li PSs for Li–S batteries.Moreover,the current essential challenges encountered when designing these materials are summarized,and possible solutions are proposed.We hope that this review could provide some strategies and theoretical guidance for developing novel chemical anchoring and electrocatalytic materials for high-performance Li–S batteries.
基金supported by the National Natural Science Foundation of China (NSFC, No. 51522203, 51772040)Fok Ying Tung Education Foundation (No. 151047)+2 种基金the Recruitment Program of Global Youth ExpertsXinghai Scholarship of Dalian University of Technologythe Fundamental Research Funds for the Central Universities (No. DUT18LAB19)
文摘Use of metallic Li anode raises serious concerns on the safety and operational performance of Li-S batteries due to uncontrolled hazard of Li dendrite formation, which is difficultly eliminated as long as the metallic Li exists in the cells. Pairing lithium sulfide (Li2S) cathode with currently available metallic Lifree high-capacity anodes offers an alternative solution to this challenge. However, the performance of Li2S cathode is primarily restricted by high activation barrier upon initial charge, low active mass utilization and sluggish redox kinetics. Herein, a MXene-induced multifunctional collaborative interface is proposed to afford superb activity towards redox solid-liquid/liquid-liquid phase transformation, strong chemisorption, high conductivity and fast ionic/charge transport in high Li2S loading cathode. Applying collaborative interface effectively reduces initial voltage barrier of Li2S activation and regulates the kinetic behavior of redox polysulfide conversion. Therefore, stable operation of additive-free Li2S cathode with high areal capacities at high Li2S loading up to 9 mg cm^-2 can be achieved with less sacrifice of high capacity and rate capability in Li-S batteries. Rechargeable metallic Li-free batteries are successfully constructed by pairing this high-performance Li2S cathode with high-capacity metal oxide anodes, which delivers superior energy density to current Li-ion batteries.
基金supported by the National Research Foundation of Korea(NRF)grant funded by the Korean government(MSIP)(No.2018R1C1B6004689)the Basic Science Research Program through the National Research Foundation of Korea(NRF)funded by the Ministry of Education(No.2020R1I1A306182111)the Electronics and Telecommunications Research Institute(ETRI)grant funded by the Korean government(21ZB1200,Development of ICT Materials,Components and Equipment Technologies)。
文摘Lithium–sulfur batteries are one of the attractive next-generation energy storage systems owing to theienvironmental friendliness,low cost,and high specific energy densities.However,the low electrical conductivity of sulfur,shuttling of soluble intermediate polysulfides between electrodes,and low capacitretention have hampered their commercial use.To address these issues,we use a halloysitemodulated(H-M)separator in a lithium–sulfur battery to mitigate the shuttling problem.The H-M separator acts as a mutual Coulombic repulsion in lithium-sulfur batteries,thereby selectively permitting Lions and efficiently suppressing the transfer of undesired lithium polysulfides to the Li anode sideMoreover,the use of halloysite switches the surface of the separator from hydrophobic to hydrophilicconsequently improving the electrolyte wettability and adhesion between the separator and cathodeWhen sulfur-multi-walled carbon nanotube(S-MWCNT)composites are used as cathode active materialsa lithium–sulfur battery with an H-M separator exhibits first discharge and charge capacities of 1587 an1527 m Ah g-1,respectively.Moreover,there is a consistent capacity retention up to 100 cyclesAccordingly,our approach demonstrates an economical and easily accessible strategy for commercialization of lithium–sulfur batteries.
基金Office of Energy Efficiency and Renewable Energy,Grant/Award Number:DE‐FOA‐0001629U.S.Department of Energy,Grant/Award Number:DE‐AC02‐06CH11357。
文摘Tremendous effort has been devoted to lithium‐sulfur batteries,where flooded electrolytes have been employed ubiquitously.The use of lean electrolytes albeit indispensable for practical applications often causes low capacity and fast capacity fading of the sulfur cathode;thus,the electrolyte/sulfur active mass ratios below 5μL/mg have been rarely reported.Herein,we demonstrate that ZnS coating transforms sulfur cathode materials electrolyte‐philic,which tremendously promotes the performance in lean electrolytes.The ZnS‐coated Li2S@graphene cathode delivers an initial discharge capacity of 944mAh/g at an E/S ratio of 2μL/mg at the active mass loading of 5.0 mg Li2S/cm^2,corresponding to an impressive specific energy of 500Wh/kg based on the mass of cathode,electrolyte,and the assumed minimal mass of lithium metal anode.Density functional theory calculations reveal strong binding between ZnS crystals and electrolyte solvent molecules,explaining the better wetting properties.We also demonstrate the reversible cycling of a hybrid cathode of ZnS‐coated Li2S@graphene mixed with VS2 as an additive at an E/AM(active mass)ratio of 1.1μL/mg,equivalent to the specific energy of 432 Wh/kg on the basis of the mass of electrodes and electrolyte.
基金The authors acknowledge the financial supports provided by the National Natural Science Foundation of China(Nos.21871164,21803036,and U1764258)the Taishan Scholar Project Foundation of Shandong Province(Nos.ts20190908 and ts201511004)the National Science Foundation of Shandong Province(No.ZR2019MB024).The theoretical calculations in this work were performed on the HPC Cloud Platform of Shandong University.We also thank Anhui Kemi Machinery Technology Co,Ltd for providing Teflon-lined stainless steel autoclave.
文摘Lithium–sulfur batteries have been attracting considerable research attention due to their high energy densities and low costs. However, one of their main challenges is the undesired shuttling of polysulfides, causing rapid capacity degradation. Herein, we report the first example of sulfiphilic VSe2 ultrafine nanocrystals immobilized on nitrogen-doped graphene to modify the battery separator for alleviating the shuttling problem. VSe2 nanocrystals provide numerous active sites for chemisorption of polysulfides as well as benefit the nucleation and growth of Li2S. Furthermore, the kinetic reactions are accelerated which is confirmed by higher exchange current density and higher lithium ion diffusion coefficient. And the first-principles calculations further show that the exposed sulfiphilic planes of VSe2 boost the redox of Li2S. When used as separators within the lithium sulfur batteries, the cell indicates greatly enhanced electrochemical performances with excellent long cycling stability and exceptional rate capability up to 8 C. Moreover, it delivers a higher areal capacity of 4.04 mAh·cm^−2 as well as superior cycling stability with sulfur areal loading up to 6.1 mg·cm^−2. The present strategy can encourage us in engineering novel multifunctional separators for energy-storage devices.
文摘以湿法制备的硫溶胶和氧化石墨烯为前驱体,采用水热法还原不同酸碱体系的氧化石墨烯,制备石墨烯-硫复合材料。通过XRD和场发射扫描电子显微镜（FESEM）等对产物进行分析。石墨烯以薄膜状包覆在硫颗粒表面。恒流充放电、交流阻抗和循环伏安测试结果表明：180℃、酸性条件下水热12 h制备的复合材料电化学性能较好,以0.2 m A/cm2的电流密度在1.5-3.0 V充放电,首次放电比容量为803.72 m Ah/g,循环20次衰减至592.40 m Ah/g,容量保持率为73.71%。
文摘分别以气相生长碳纤维（VGCF）、多壁碳纳米管（MWCNT）和活性炭（AC）作为单质硫载体,通过高温热处理制备锂硫电池用S/C正极材料。采用SEM、XRD、热重分析（TG）、循环伏安、电化学阻抗谱（EIS）和恒流充放电等方法,分析复合材料的结构及电化学性能。碳材料形态对锂硫电池的放电比容量和循环性能有重要影响,S/VGCF复合材料的电化学性能较好。以0.1 C的电流在1.5-3.0 V充放电,首次和第100次循环的放电比容量分别为1 204.87 m Ah/g、547.62 m Ah/g。
文摘锂硫(Li-S)电池具有比锂离子电池更高的能量密度,是近10年来的研究热点,但目前锂硫电池的循环性能和倍率性能远远不能满足人们的需求。在本研究中,二(2,2,2-三氟乙基)碳酸酯(DTFEC)作为一种电解液添加剂应用到锂硫电池中,以提高电池的电化学性能,并对DTFEC的添加量进行了筛选和优化。结果表明,DTFEC的添加量对电池性能有很大的影响,当添加体积分数为5%时,复合硫正极材料(S@p PAN)表现出最佳的循环稳定性和倍率性能。室温条件下进行充放电测试,在1C的充放电电流下,锂硫电池在循环200圈后容量保持率比常规电解液约高20%;在7C的大倍率充放电电流下,依然可以得到1246.3 m A·h/g的可逆比容量。以上结果表明,DTFEC可以有效提高锂硫电池的电化学性能,是一种适合用于锂硫电池电解液体系的添加剂。
