The implementation of multifunctional application scenarios for mobile terminal devices has increased the energy density requirements of batteries.Increasing the charging voltage can rapidly increase the specific capa...The implementation of multifunctional application scenarios for mobile terminal devices has increased the energy density requirements of batteries.Increasing the charging voltage can rapidly increase the specific capacity of layered transition metal oxides;however,it also exacerbates the release of lattice oxygen and the contraction of the unit cell.Ternary materials are designed in a secondary particle state to meet the requirements of power battery applications.Therefore,to create ternary materials that can operate under ultrahigh voltages,attention should be given to both surface modification and particle integrity maintenance.By utilizing elemental selenium(Se)with a low melting point,easy sublimation,and multiple variable valence states,deep grain boundary modification was implemented inside the particles.The performance of the cathode material was evaluated through pouch cells,and the improvement mechanism was explored through molecular dynamics simulation calculations.Under the protection of a three-dimensional Se-rich modified layer,LiNi_(1/3)Co_(1/3)Mn_(1/3)O_(2)achieved stable operation at ultrahigh voltages(4.6 V vs.Li/Li^(+));a sacrificial protection mechanism based on the chronic decomposition of the Se-rich layer was proposed to explain the efficacy of Se modification in stabilizing ternary materials.This deep grain boundary modification based on elemental Se provides a new solution for the ultrahigh-voltage operation of transition metal oxides and provides a scientific basis and technical support for solving the interface contact problem of all-solid-state batteries.展开更多
Sulfur and selenium have been paid more and more attention in energy storage systems because of their high theoretical specific gravimetric and volumetric capacities.With the increasing scarcity of lithium resources,s...Sulfur and selenium have been paid more and more attention in energy storage systems because of their high theoretical specific gravimetric and volumetric capacities.With the increasing scarcity of lithium resources,secondary batteries made of sulfur and selenium coupled with other alkali metal/alkaline earth metals(e.g.Na,K,Mg)are expected to play a vital role in future production and human life.Due to the volume expansion,poor conductivity and shuttle effect,the structure design of cathode,as one of the important roles in metal-S/Se batteries,has always been a hot and difficult point.In the review,various host materials of S and Se are clarified and discussed.Typically,carbonaceous materials are the most widely used hosts,while polar materials are becoming more and more popular in metal-S/Se batteries.Through a comprehensive overview,it is hoped that previous research experiences can provide further reference and guidance for the sustainable development of metal-S/Se batteries.展开更多
Sluggish electrode kinetics and polysulfide dissolution severely hinder room-temperature sodium-sulfur batteries(RT Na-S)from achieving high-theoretical capacity and low cost.Metal-based catalysts are often used to ab...Sluggish electrode kinetics and polysulfide dissolution severely hinder room-temperature sodium-sulfur batteries(RT Na-S)from achieving high-theoretical capacity and low cost.Metal-based catalysts are often used to absorb polysulfide intermediates against the shuttle effect in Na-S batteries,but rationalization of an electrode pore structure to improve battery performance is ignored.Herein,a rational micropore/mesopore network structure of macadamia nut shell-derived carbon is constructed as a carbon/sulfur cathode by tuning the ratio of micro to mesopore.展开更多
The structure and characteristic of carbon materials have a direct influence on the electrochemical performance of sulfur-carbon composite electrode materials for lithium-sulfur battery. In this paper, sulfur composit...The structure and characteristic of carbon materials have a direct influence on the electrochemical performance of sulfur-carbon composite electrode materials for lithium-sulfur battery. In this paper, sulfur composite has been synthesized by heating a mixture of elemental sulfur and activated carbon, which is characterized as high specific surface area and microporous structure. The composite, contained 70% sulfur, as cathode in a lithium cell based on organic liquid electrolyte was tested at room temperature. It showed two reduction peaks at 2.05 V and 2.35 V, one oxidation peak at 2.4 V during cyclic voltammogram test. The initial discharge specific capacity was 1180.8 mAh g-1 and the utilization of electrochemically active sulfur was about 70.6% assuming a complete reaction to the product of Li2S. The specific capacity still kept as high as 720.4 mAh g^-1 after 60 cycles retaining 61% of the initial discharge capacity.展开更多
Lithium-ion batteries(LIBs)have become an indispensable part of our daily life,however,the energy and power capability that LIBs can deliver are lagging far behind the ever-increasing demands of portable electronics a...Lithium-ion batteries(LIBs)have become an indispensable part of our daily life,however,the energy and power capability that LIBs can deliver are lagging far behind the ever-increasing demands of portable electronics and electric vehicles.Metal-sulfur batteries as one of the most promising alternatives to LIBs are receiving rapidly growing research interests due to the extremely high energy density and abundant resources of sulfur.In this short review,we will discuss the state-of-art development of high energy density battery technologies based on sulfur cathode in combination with different metal anodes,with focus on sodium,magnesium and aluminum anodes.We leave lithium-sulfur batteries out of discussion since there are already a large number of nicely organized review papers available.The operation mechanism of various anode materials and the variety of electrolytes used in sulfur batteries will be reviewed.Some perspectives on improving the performances and overcoming the remaining issues in sulfur batteries will be discussed.It is expected that this review will draw more attention to sulfur batteries from both the academic and industrial communities.展开更多
Carbon nanotubes （CNTs） are excellent scaffolds for advanced electrode materials, resulting from their intrinsic sp2 carbon hybridization, interconnected electron pathway, large aspect ratio, hierarchical porous str...Carbon nanotubes （CNTs） are excellent scaffolds for advanced electrode materials, resulting from their intrinsic sp2 carbon hybridization, interconnected electron pathway, large aspect ratio, hierarchical porous structures, and low cost at a large-scale production. How to make full utilization of the mass produced CNTs as building blocks for nanocomposite electrodes is not well understood yet. Herein, a composite cathode containing commercial agglomerated multi-walled CNTs and S for Li-S battery was fabricated by a facile melt-diffusion strategy. The hierarchical CNT@S coaxial nanocables exhibited a discharging capacity of 1020 and 740 mAh .g-1 at 0.5 and 2.0 C, respectively. A rapid capacity decay of 0.7% per cycle at the initial 10 cycles and a slow decay rate of 0.14% per cycle for the later 140 cycles were detected. Such hierarchical agglomerated CNT@ S cathodes show advantages in easy fabrication, environmentally benign, low cost, excellent scalability, and good Li ion storage performance, which are extraordinary composites for high performance Li-S battery.展开更多
Rational design of hybrid carbon host with high electrical conductivity and strong adsorption toward soluble lithium polysulfides is the main challenge for achieving high-performance lithium-sulfur batteries(LSBs).Her...Rational design of hybrid carbon host with high electrical conductivity and strong adsorption toward soluble lithium polysulfides is the main challenge for achieving high-performance lithium-sulfur batteries(LSBs).Herein,novel binder-free Ni@N-doped carbon nanospheres(N-CNSs)films as sulfur host are firstly synthesized via a facile combined hydrothermal-atomic layer deposition method.The cross-linked multilayer N-CNSs films can effectively enhance the electrical conductivity of electrode and provide physical blocking“dams”toward the soluble long-chain polysulfides.Moreover,the doped N heteroatoms and superficial NiO layer on Ni layer can work synergistically to suppress the shuttle of lithium polysulfides by effective chemical interaction/adsorption.In virtue of the unique composite architecture and reinforced dual physical and chemical adsorption to the soluble polysulfides,the obtained Ni@N-CNSs/S electrode is demonstrated with enhanced rate performance(816 mAh g?1 at 2 C)and excellent long cycling life(87%after 200 cycles at 0.1 C),much better than N-CNSs/S electrode and other carbon/S counterparts.Our proposed design strategy offers a promising prospect for construction of advanced sulfur cathodes for applications in LSBs and other energy storage systems.展开更多
Lithium–sulfur(Li–S)batteries have become one of the most promising candidates for next-generation batteries owing to their high specific capacity,low cost,and environment-friendliness.Many efforts have been made to...Lithium–sulfur(Li–S)batteries have become one of the most promising candidates for next-generation batteries owing to their high specific capacity,low cost,and environment-friendliness.Many efforts have been made to mitigate the"shuttle effect"through physical adsorption and chemical bonding.MoS2 has been proposed as a cathode material to provide effective anchoring sites for lithium polysulfides(Li PSs),but is still limited by its layer structure.Herein,we designed novel MoS2 nanorods with inner caves based on our previous work,and performed synchronous encapsulation of sulfur during the synthesis process.The outer MoS2 tubular shells physically inhibit the outward diffusion of polysulfide species while the inner particles chemically anchor the polysulfides to prevent shuttling.As the cathode matrix in Li–S batteries,the electrochemical results deliver a high initial discharge capacity of 1213 mAhg^-1 for sulfur at 0.1 C.After cycling at 1 C for 300 cycles,the cells exhibit a capacity decay of only 0.076%per cycle and high average coulombic efficiency over 95%.The tubular MoS2 structure is an innovative and appealing design,which could be regarded as a prospective substrate for the improved performance of Li–S batteries.展开更多
Binders could play crucial or even decisive roles in the fabrication of low-cost, stable and high-capacity electrodes. This is especially the case for the silicon (Si) anodes and sulfur (S) cathodes that undergo large...Binders could play crucial or even decisive roles in the fabrication of low-cost, stable and high-capacity electrodes. This is especially the case for the silicon (Si) anodes and sulfur (S) cathodes that undergo large volume change and active material loss in lithium-ion batteries during prolonged cycles. Herein, a hydrophilic polymer poly(methyl vinyl ether-alt-maleic acid) (PMVEMA) was explored as a dual-functional aqueous binder for the preparation of high-performance silicon anode and sulfur cathode. Benefiting from the dual functions of PMVEMA, i.e., the excellent dispersion ability and strong binding forces, the as-prepared electrodes exhibit improved capacity, rate capability and long-term cycling performance. In particular, the as-prepared Si electrode delivers a high initial discharge capacity of 1346.5 mAh g^(−1) at a high rate of 8.4 A/g and maintains 834.5 mAh g^(−1) after 300 cycles at 4.2 A/g, while the as-prepared S cathode exhibits enhanced cycling performance with high remaining discharge capacities of 663.4 mAh g^(−1) after 100 cycles at 0.2 C and 487.07 mAh g^(−1) after 300 cycles at 1 C, respectively. These encouraging results suggest that PMVEMA could be a universal binder to facilitate the green manufacture of both anode and cathode for high-capacity energy storage systems.展开更多
All-solid-state lithium-sulfur batteries(ASSLSBs)employing sulfide solid electrolytes are one of the most promising next-generation energy storage systems due to their potential for higher energy density and safety.Ho...All-solid-state lithium-sulfur batteries(ASSLSBs)employing sulfide solid electrolytes are one of the most promising next-generation energy storage systems due to their potential for higher energy density and safety.However,scalable fabrication of sheet-type sulfur cathodes with high sulfur loading and excellent performances remains challenging.In this work,sheet-type freestanding sulfur cathodes with high sulfur loading were fabricated by dry electrode technology.The unique fibrous morphologies of polytetrafluoroethylene(PTFE)binders in dry electrodes not only provides excellent mechanical properties but also uncompromised ionic/electronic conductance.Even employed with thickened dry cathodes with high sulfur loading of 2 mg cm^(-2),ASSLSBs still exhibit outstanding rate performance and cycle stability.Moreover,the all-solid-state lithium-sulfur monolayer pouch cells(9.2 m Ah)were also demonstrated and exhibited excellent safety under a harsh test situation.This work verifies the potential of dry electrode technology in the scalable fabrication of thickened sulfur cathodes and will promote the practical applications of ASSLSBs.展开更多
Lithium sulfur(Li-S)batteries are the promising power sources,but their commercialization is significantly impeded by poor energy-storage functions at high sulfur loading.Here we report that such an issue can be effec...Lithium sulfur(Li-S)batteries are the promising power sources,but their commercialization is significantly impeded by poor energy-storage functions at high sulfur loading.Here we report that such an issue can be effectively addressed by using a mussel-inspired binder comprised of chitosan grafted with catecholic moiety for sulfur cathodes.The resulting sulfur cathodes possess a high loading up to 12.2 mg cm-2 but also exhibit one of the best electrochemical properties among their counterparts.The excellent performances are attributed to the strong adhesion of the binder to sulfur particles,conducting agent,current collector,and polysulfide.The versatile adhesion effectively increases the sulfur loading,depresses the shuttle effect,and alleviates mechanical pulverization during cycling processes.The present investigation offers a new insight into high performance sulfur cathodes through a bio-adhesion viewpoint.展开更多
With the emergence and development of wearable devices,the novel ene rgy storage systems with flexible feature and high energy density are urgently needed.As we all know,for next generation high energystorage systems,...With the emergence and development of wearable devices,the novel ene rgy storage systems with flexible feature and high energy density are urgently needed.As we all know,for next generation high energystorage systems,lithium-sulfur(Li-S) batteries with a high theoretical capacity are regarded as one of the most promising candidates.In addition,the flexible Li-S batteries have received more and more attention.The determined factor in the flexible Li-S batteries is how to design the foldable electrodes including both anode and cathode.As for the flexible sulfur cathode,it could be obtained by integrating the electroactive sulfur with a flexible substrate,generally.In recent years,the flexible cathode of Li-S batteries have made considerable progress,however there are also many huge challenges needing to overcome,such as low content of sulfur,fast decrease of capacity and short cycle life.In this paper,the current develop status of flexible cathodes of Li-S batteries have been summarized,and the future trend also be pointed out.展开更多
In situ chemical oxidation polymerization of pyrrole on the surface of sulfur particles was carried out to synthesize a sulfur/polypyrrole （SIPPy） nanocomposite with core-shell structure. The composite was character...In situ chemical oxidation polymerization of pyrrole on the surface of sulfur particles was carried out to synthesize a sulfur/polypyrrole （SIPPy） nanocomposite with core-shell structure. The composite was characterized by elemental analysis, X-ray diffraction, scanning/transmission electron microscopy, and electrochemical measurements. XRD and FTIR results showed that sulfur well dispersed in the core-shell structure and PPy structure was successfully obtained via in situ oxidative polymerization of pyrrole on the surface of sulfur particles. TEM observation revealed that PPy was formed and fixed to the surface of sulfur nanoparticle after polymerization, developing a well-defined core-shell structure and the thickness of PPy coating layer was in the range of 20-30 nm. In the composite, PPy worked as a conducting matrix as well as a coating agent, which confined the active materials within the electrode. Consequently, the as prepared SIPPy composite cathode exhibited good cycling and rate performances for rechargeable lithium/sulfur batteries. The resulting cell containing SIPPy composite cathode yields a discharge capacity of 1039 mAh·g^-1 at the initial cycle and retains 59% of this value over 50 cycles at 0.1 C rate. At 1 C rate, the SIPPy composite showed good cycle stability, and the discharge capacity was 475 mAh·g^-1 after 50 cycles.展开更多
Sulfur element possesses an ultrahigh theoretical specific capacity,while the utilization of sulfur in the whole cathode is lower obviously owing to the sluggish kinetics of sulfur and discharged products,limiting the...Sulfur element possesses an ultrahigh theoretical specific capacity,while the utilization of sulfur in the whole cathode is lower obviously owing to the sluggish kinetics of sulfur and discharged products,limiting the enhancement on energy density of lithium-sulfur batteries.Herein,for the first time,Fe_(0.24)Co_(0.26)Ni_(0.10)Cu_(0.15)Mn_(0.25)high-entropy alloy is introduced as the core catalytic host to activate the electrochemical performance of the sulfur cathode for lithium-sulfur batteries.It is manifested that Fe_(0.24)Co_(0.26)Ni_(0.10)Cu_(0.15)Mn_(0.25)high-entropy alloy nanocrystallites distributed on nitrogen-doped carbon exhibit high electrocatalytic activity toward the conversion of solid sulfur to solid discharged products across soluble intermediate lithium polysulfides.In particular,benefiting from the accelerated kinetics by high-entropy alloy nanocrystallites and synergistic adsorption by nitrogen-doped carbon,the cathode exhibits high reversible capacity of 1079.5 mAh g_(-cathode)^(-1)(high utilization of 89.4%)with the whole cathode as active material,instead of sulfur element.Moreover,under both lean electrolyte(3μmg^(-1))and ultrahigh sulfur loading(27.0 mg cm^(-2))condition,the high discharge capacity of 868.2 mAh g_(-cathode)^(-1)can be still achieved for the sulfur cathode.This strategy opens up a new path to explore catalytic host materials for enhancing the utilization of sulfur in the whole cathode for lithium-sulfur batteries.展开更多
Lithium−sulfur batteries are one of the most competitive high-energy batteries due to their high theoretical energy density of _(2)600 W·h·kg^(−1).However,their commercialization is limited by poor cycle sta...Lithium−sulfur batteries are one of the most competitive high-energy batteries due to their high theoretical energy density of _(2)600 W·h·kg^(−1).However,their commercialization is limited by poor cycle stability mainly due to the low intrinsic electrical conductivity of sulfur and its discharged products(Li_(2)S_(2)/Li_(2)S),the sluggish reaction kinetics of sulfur cathode,and the“shuttle effect”of soluble intermediate lithi-um polysulfides in ether-based electrolyte.To address these challenges,catalytic hosts have recently been introduced in sulfur cathodes to en-hance the conversion of soluble polysulfides to the final solid products and thus prevent the dissolution and loss of active-sulfur material.In this review,we summarize the recent progress on the use of metal phosphides and borides of different dimensions as the catalytic host of sulfur cathodes and demonstrate the catalytic conversion mechanism of sulfur cathodes with the help of metal phosphides and borides for high-en-ergy and long-life lithium-sulfur batteries.Finally,future outlooks are proposed on developing advanced catalytic host materials to improve battery performance.展开更多
Binders are of vital importance in stabilizing the cathodes to enhance the cycling stability of lithiumsulfur(Li-S) batteries. However, conventional binders are typically confronted with the drawback of inability for ...Binders are of vital importance in stabilizing the cathodes to enhance the cycling stability of lithiumsulfur(Li-S) batteries. However, conventional binders are typically confronted with the drawback of inability for adsorbing lithium polysulfide(Li PS), thus resulting in severe active material losing and rapid capacity fading. Herein, a novel water-soluble hyperbranched poly(amidoamine)(HPAA) binder with controllable hyperbranched molecular structure and abundant amino end groups for Li-S battery is designed and fabricated, which can improve efficient adsorption for Li PS and stability of the sulfur cathodes. Besides, the strong intermolecular hydrogen bonds in HPAA binder can contribute to the structural stability of S cathode and integration of the conductive paths. Therefore, the Li-S battery with this functional binder exhibits excellent cycle performance with a capacity retention of 91% after 200 cycles at 0.1 C.Even at a high sulfur loading of 5.3 mg cm-2, a specific capacity of 601 mA h g-1 can also be achieved.Density functional theory(DFT) calculation further demonstrates that the enhanced electrochemical stability derives from the high binding energy between amino groups and LiP S and the wide electrochemical window(6.87 e V) of HPAA molecule. Based on the above all, this functional polymer will lighten a new species of binders for eco-friendly sulfur cathodes and significantly promote the practical applications of high-performance Li-S batteries.展开更多
The defect chemistry is successfully modulated on free-standing and binder-free carbon cathodes for highly efficient Li-S redox reactions.Such rationally regulated defect engineering realizes the synchronization of io...The defect chemistry is successfully modulated on free-standing and binder-free carbon cathodes for highly efficient Li-S redox reactions.Such rationally regulated defect engineering realizes the synchronization of ion/electron-conductive and defect-rich networks on the threedimension carbon cathode,leading to its tunable activity for both relieving the shuttle phenomenon and accelerating the sulfur redox reaction kinetics.As expected,the defective carbon cathode harvests a high rate capacity of 1217.8 mAh g^(-1)at 0.2 C and a superior capacity retention of61.7%at 2 C after 500 cycles.Even under the sulfur mass loading of 11.1 mg cm^(-2),the defective cathode still holds a remarkable areal capacity of 8.5 mAh cm^(-2).展开更多
Small molecules with adjustable sulfur atoms in the confined structure were acted as precursor for the synthesis of polymer cathodes for lithium-organosulfur batteries.Among them,poly(diallyl tetrasulfide)(PDATtS)deli...Small molecules with adjustable sulfur atoms in the confined structure were acted as precursor for the synthesis of polymer cathodes for lithium-organosulfur batteries.Among them,poly(diallyl tetrasulfide)(PDATtS)delivered a high capacity of 700 mAh g^(-1),stable capacity retention of 85%after 300 cycles,high areal capacity~4 m Ah cm^(-2) for electrode with up to 10.3 mg cm^(-2) loading.New insight into the reaction mechanism of PDATtS electrode that radicals arisen from the homolytic cleavage of S-S bond in PDATtS reacted with Li+to generate thiolates(RSLi)and insoluble lithium sulfides(Li_(2)S)or lithium disulfide(Li_(2)S_(2))was clearly verified by in-situ UV/Vis spectroscopy,nuclear magnetic resonance(NMR)studies and density-functional theory(DFT)calculations.Therefore,based on the unique reaction mechanism,problems of rapid capacity fading due to the formation of soluble polysulfide intermediates and their serious shuttle effect in conventional lithium-sulfur(Li-S)batteries was totally avoided,realizing the dendrite-free lithium sulfur batteries.This study sets new trends for avenues of further research to advance Li-S battery technologies.展开更多
Lithium–sulfur(Li-S)batteries are regarded as one of the most promising energy storage devices because of their low cost,high energy density,and environmental friendliness.However,Li-S batteries suffer from sluggish ...Lithium–sulfur(Li-S)batteries are regarded as one of the most promising energy storage devices because of their low cost,high energy density,and environmental friendliness.However,Li-S batteries suffer from sluggish reaction kinetics and serious“shuttle effect”of lithium polysulfides(LiPSs),which causes rapid decay of battery capacity and prevent their practical application.To address these problems,introducing single-atom catalysts(SACs)is an effective method to improve the electrochemical performance of Li-S batteries,due to their high catalytic efficiency and definite active sites for LiPSs.In this paper,we summarized the latest developments in enhancing the electrochemical performance of cathode for Li-S batteries through introducing different SACs.Furthermore,we briefly introduced the catalytic mechanism of SACs and discussed the strategies of synthesizing SACs,including the spatial confinement strategy and the coordination design strategy.Finally,the challenges and prospects in this field are proposed.We believe that this review would help to design and fabricate high-performance Li-S batteries via introducing SACs and boost their practical application.展开更多
Rechargeable Mg batteries potentially display lower cost and competitive energy density compared with their Li-ion counterparts.However,the practical implementation of high area-capacity cathodes still remains a formi...Rechargeable Mg batteries potentially display lower cost and competitive energy density compared with their Li-ion counterparts.However,the practical implementation of high area-capacity cathodes still remains a formidably challenging task.This work presents the sulfur/copper integrated cathodes fabricated by the conventional blade-coating process and slurry-dipping method.The sulfur/copper foil integrated cathodes deliver a high area-capacity of 2.6 mAh cm^(-2)after 40 cycles,while the sulfur/copperfoam integrated cathode exhibits an ultrahigh area-capacity of 35.4 mAh cm^(-2),corresponding to 743.1 Wh L^(-1)at the electrode level(1.5 times higher than the LiCoO_(2)-graphite system).The in-situ formed copper sulfide intermediates with sufficient cation defects can act as functional intermediates to regulate the sulfur electrochemistry during the first discharge process.The subsequent cycles are operated by the reversible displacement reaction between Mg-ions and copper sulfide active substances.In particular,the copper ions prefer to extrude along the[001]direction in copper sulfides lattice and simultaneously the rock-salt MgS crystals are generated.Besides,the nonuniform surface topography of the cycled Mgmetal anode,caused by the spatial inhomogeneity in current distribution,is demonstrated to lead to the battery performance degradation for high area-capacity Mg batteries.展开更多
基金supported by the National Natural Science Foundation of China (52302259)the China Postdoctoral Science Foundation (CPSF) under Grant Number 2023M741479+4 种基金the Postdoctoral Fellowship Program of CPSF under Grant Number GZB20240280the Jiangxi Provincial Natural Science Foundation (20224ACB218006)the financial support from High-level Talent Research Special Funds of Jiangxi University of Science and Technology (Grant No. 205200100670)the Jiangxi Provincial Key Laboratory of Power Energy Storage Batteries and Materials (2024SSY10011)the Major Scientific and Technological Research R&D Special Project of Jiangxi Province(20244AFI92002)
文摘The implementation of multifunctional application scenarios for mobile terminal devices has increased the energy density requirements of batteries.Increasing the charging voltage can rapidly increase the specific capacity of layered transition metal oxides;however,it also exacerbates the release of lattice oxygen and the contraction of the unit cell.Ternary materials are designed in a secondary particle state to meet the requirements of power battery applications.Therefore,to create ternary materials that can operate under ultrahigh voltages,attention should be given to both surface modification and particle integrity maintenance.By utilizing elemental selenium(Se)with a low melting point,easy sublimation,and multiple variable valence states,deep grain boundary modification was implemented inside the particles.The performance of the cathode material was evaluated through pouch cells,and the improvement mechanism was explored through molecular dynamics simulation calculations.Under the protection of a three-dimensional Se-rich modified layer,LiNi_(1/3)Co_(1/3)Mn_(1/3)O_(2)achieved stable operation at ultrahigh voltages(4.6 V vs.Li/Li^(+));a sacrificial protection mechanism based on the chronic decomposition of the Se-rich layer was proposed to explain the efficacy of Se modification in stabilizing ternary materials.This deep grain boundary modification based on elemental Se provides a new solution for the ultrahigh-voltage operation of transition metal oxides and provides a scientific basis and technical support for solving the interface contact problem of all-solid-state batteries.
基金support from National Natural Science Foundation of China(No.21772188,No.22179109)Chongqing Natural Science Foundation(cstc2021ycjh-bgzxm0164,cstc2020jcyj-zdxmX0010)。
文摘Sulfur and selenium have been paid more and more attention in energy storage systems because of their high theoretical specific gravimetric and volumetric capacities.With the increasing scarcity of lithium resources,secondary batteries made of sulfur and selenium coupled with other alkali metal/alkaline earth metals(e.g.Na,K,Mg)are expected to play a vital role in future production and human life.Due to the volume expansion,poor conductivity and shuttle effect,the structure design of cathode,as one of the important roles in metal-S/Se batteries,has always been a hot and difficult point.In the review,various host materials of S and Se are clarified and discussed.Typically,carbonaceous materials are the most widely used hosts,while polar materials are becoming more and more popular in metal-S/Se batteries.Through a comprehensive overview,it is hoped that previous research experiences can provide further reference and guidance for the sustainable development of metal-S/Se batteries.
基金financial support from the Institute for Materials Science&Devices,School of Materials Science and Engineering,Suzhou University of Science and Technology,Suzhou,China。
文摘Sluggish electrode kinetics and polysulfide dissolution severely hinder room-temperature sodium-sulfur batteries(RT Na-S)from achieving high-theoretical capacity and low cost.Metal-based catalysts are often used to absorb polysulfide intermediates against the shuttle effect in Na-S batteries,but rationalization of an electrode pore structure to improve battery performance is ignored.Herein,a rational micropore/mesopore network structure of macadamia nut shell-derived carbon is constructed as a carbon/sulfur cathode by tuning the ratio of micro to mesopore.
基金supported by the National Key Program for Basic Research of China(No. 2009CB220100)the National 863 Program(No.2007AA03Z226)
文摘The structure and characteristic of carbon materials have a direct influence on the electrochemical performance of sulfur-carbon composite electrode materials for lithium-sulfur battery. In this paper, sulfur composite has been synthesized by heating a mixture of elemental sulfur and activated carbon, which is characterized as high specific surface area and microporous structure. The composite, contained 70% sulfur, as cathode in a lithium cell based on organic liquid electrolyte was tested at room temperature. It showed two reduction peaks at 2.05 V and 2.35 V, one oxidation peak at 2.4 V during cyclic voltammogram test. The initial discharge specific capacity was 1180.8 mAh g-1 and the utilization of electrochemically active sulfur was about 70.6% assuming a complete reaction to the product of Li2S. The specific capacity still kept as high as 720.4 mAh g^-1 after 60 cycles retaining 61% of the initial discharge capacity.
基金supported by the National Natural Science Foundation of China (No. 21671096, and No. 21603094)the Natural Science Foundation of Shenzhen (No. JCYJ20170412153139454 and, No. JCYJ20170817110251498)the Guangdong Special Support for the Science and Technology Leading Young Scientist (No. 2016TQ03C919)
文摘Lithium-ion batteries(LIBs)have become an indispensable part of our daily life,however,the energy and power capability that LIBs can deliver are lagging far behind the ever-increasing demands of portable electronics and electric vehicles.Metal-sulfur batteries as one of the most promising alternatives to LIBs are receiving rapidly growing research interests due to the extremely high energy density and abundant resources of sulfur.In this short review,we will discuss the state-of-art development of high energy density battery technologies based on sulfur cathode in combination with different metal anodes,with focus on sodium,magnesium and aluminum anodes.We leave lithium-sulfur batteries out of discussion since there are already a large number of nicely organized review papers available.The operation mechanism of various anode materials and the variety of electrolytes used in sulfur batteries will be reviewed.Some perspectives on improving the performances and overcoming the remaining issues in sulfur batteries will be discussed.It is expected that this review will draw more attention to sulfur batteries from both the academic and industrial communities.
基金supported by National Basic Research Program of China (973 Program, 2011CB932602)Research Fund for the Doctoral Program of Higher Education of China (20120002120047)China Postdoctoral Science Foundation (2012M520293)
文摘Carbon nanotubes （CNTs） are excellent scaffolds for advanced electrode materials, resulting from their intrinsic sp2 carbon hybridization, interconnected electron pathway, large aspect ratio, hierarchical porous structures, and low cost at a large-scale production. How to make full utilization of the mass produced CNTs as building blocks for nanocomposite electrodes is not well understood yet. Herein, a composite cathode containing commercial agglomerated multi-walled CNTs and S for Li-S battery was fabricated by a facile melt-diffusion strategy. The hierarchical CNT@S coaxial nanocables exhibited a discharging capacity of 1020 and 740 mAh .g-1 at 0.5 and 2.0 C, respectively. A rapid capacity decay of 0.7% per cycle at the initial 10 cycles and a slow decay rate of 0.14% per cycle for the later 140 cycles were detected. Such hierarchical agglomerated CNT@ S cathodes show advantages in easy fabrication, environmentally benign, low cost, excellent scalability, and good Li ion storage performance, which are extraordinary composites for high performance Li-S battery.
基金supported by National Natural Science Foundation of China(Nos.51772272 and 51728204)Fundamental Research Funds for the Central Universities(No.2018QNA4011)+3 种基金Science and Technology Program of Guangdong Province of China(No.2016A010104020)Pearl River S&T Nova Program of Guangzhou(No.201610010116)Qianjiang Talents Plan D(QJD1602029)Startup Foundation for Hundred-Talent Program of Zhejiang University.
文摘Rational design of hybrid carbon host with high electrical conductivity and strong adsorption toward soluble lithium polysulfides is the main challenge for achieving high-performance lithium-sulfur batteries(LSBs).Herein,novel binder-free Ni@N-doped carbon nanospheres(N-CNSs)films as sulfur host are firstly synthesized via a facile combined hydrothermal-atomic layer deposition method.The cross-linked multilayer N-CNSs films can effectively enhance the electrical conductivity of electrode and provide physical blocking“dams”toward the soluble long-chain polysulfides.Moreover,the doped N heteroatoms and superficial NiO layer on Ni layer can work synergistically to suppress the shuttle of lithium polysulfides by effective chemical interaction/adsorption.In virtue of the unique composite architecture and reinforced dual physical and chemical adsorption to the soluble polysulfides,the obtained Ni@N-CNSs/S electrode is demonstrated with enhanced rate performance(816 mAh g?1 at 2 C)and excellent long cycling life(87%after 200 cycles at 0.1 C),much better than N-CNSs/S electrode and other carbon/S counterparts.Our proposed design strategy offers a promising prospect for construction of advanced sulfur cathodes for applications in LSBs and other energy storage systems.
基金supported by the National Natural Science Foundation of China(No.21771143)Natural Science Foundation of Shaanxi Province(grant no.2017ZDJC-30,2018JQ2027)+4 种基金Key Research Project of Shaanxi Province(2018ZDCXLGY-08-06)Natural Science Foundation of Jiangsu Province(grant no.BK20170413)Fundamental Research Funds for the Central Universities(grant no.xjj2017084)Foshan Science and Technology Bureau Project(No.2017AG100443)supported by the Cyrus Tang Foundation through the Tang Scholar Program。
文摘Lithium–sulfur(Li–S)batteries have become one of the most promising candidates for next-generation batteries owing to their high specific capacity,low cost,and environment-friendliness.Many efforts have been made to mitigate the"shuttle effect"through physical adsorption and chemical bonding.MoS2 has been proposed as a cathode material to provide effective anchoring sites for lithium polysulfides(Li PSs),but is still limited by its layer structure.Herein,we designed novel MoS2 nanorods with inner caves based on our previous work,and performed synchronous encapsulation of sulfur during the synthesis process.The outer MoS2 tubular shells physically inhibit the outward diffusion of polysulfide species while the inner particles chemically anchor the polysulfides to prevent shuttling.As the cathode matrix in Li–S batteries,the electrochemical results deliver a high initial discharge capacity of 1213 mAhg^-1 for sulfur at 0.1 C.After cycling at 1 C for 300 cycles,the cells exhibit a capacity decay of only 0.076%per cycle and high average coulombic efficiency over 95%.The tubular MoS2 structure is an innovative and appealing design,which could be regarded as a prospective substrate for the improved performance of Li–S batteries.
基金This work was financially supported by the Australian Research Council(ARC)Discovery Projects(DP210103266 and DPI 701048343)the Griffith University Ph.D.Scholarships.
文摘Binders could play crucial or even decisive roles in the fabrication of low-cost, stable and high-capacity electrodes. This is especially the case for the silicon (Si) anodes and sulfur (S) cathodes that undergo large volume change and active material loss in lithium-ion batteries during prolonged cycles. Herein, a hydrophilic polymer poly(methyl vinyl ether-alt-maleic acid) (PMVEMA) was explored as a dual-functional aqueous binder for the preparation of high-performance silicon anode and sulfur cathode. Benefiting from the dual functions of PMVEMA, i.e., the excellent dispersion ability and strong binding forces, the as-prepared electrodes exhibit improved capacity, rate capability and long-term cycling performance. In particular, the as-prepared Si electrode delivers a high initial discharge capacity of 1346.5 mAh g^(−1) at a high rate of 8.4 A/g and maintains 834.5 mAh g^(−1) after 300 cycles at 4.2 A/g, while the as-prepared S cathode exhibits enhanced cycling performance with high remaining discharge capacities of 663.4 mAh g^(−1) after 100 cycles at 0.2 C and 487.07 mAh g^(−1) after 300 cycles at 1 C, respectively. These encouraging results suggest that PMVEMA could be a universal binder to facilitate the green manufacture of both anode and cathode for high-capacity energy storage systems.
基金supported by the National Key Research and Development Program of China(2021YFB2500300)the National Natural Science Foundation of China(22075029,22108151,22109084)the China Postdoctoral Science Foundation(2021TQ0164)。
文摘All-solid-state lithium-sulfur batteries(ASSLSBs)employing sulfide solid electrolytes are one of the most promising next-generation energy storage systems due to their potential for higher energy density and safety.However,scalable fabrication of sheet-type sulfur cathodes with high sulfur loading and excellent performances remains challenging.In this work,sheet-type freestanding sulfur cathodes with high sulfur loading were fabricated by dry electrode technology.The unique fibrous morphologies of polytetrafluoroethylene(PTFE)binders in dry electrodes not only provides excellent mechanical properties but also uncompromised ionic/electronic conductance.Even employed with thickened dry cathodes with high sulfur loading of 2 mg cm^(-2),ASSLSBs still exhibit outstanding rate performance and cycle stability.Moreover,the all-solid-state lithium-sulfur monolayer pouch cells(9.2 m Ah)were also demonstrated and exhibited excellent safety under a harsh test situation.This work verifies the potential of dry electrode technology in the scalable fabrication of thickened sulfur cathodes and will promote the practical applications of ASSLSBs.
基金supported by the National Natural Science Foundation of China(51473041)the Foundation for Innovative Research Groups of the National Natural Science Foundation of China(51521003)+2 种基金China Postdoctoral Science Foundation(no.2017M621262)Fundamental Research Funds for the Central Universities(No.HIT.NSRIF.201831)Postdoctoral Foundation of Hei long Jiang Province(LBH-Z17065)。
文摘Lithium sulfur(Li-S)batteries are the promising power sources,but their commercialization is significantly impeded by poor energy-storage functions at high sulfur loading.Here we report that such an issue can be effectively addressed by using a mussel-inspired binder comprised of chitosan grafted with catecholic moiety for sulfur cathodes.The resulting sulfur cathodes possess a high loading up to 12.2 mg cm-2 but also exhibit one of the best electrochemical properties among their counterparts.The excellent performances are attributed to the strong adhesion of the binder to sulfur particles,conducting agent,current collector,and polysulfide.The versatile adhesion effectively increases the sulfur loading,depresses the shuttle effect,and alleviates mechanical pulverization during cycling processes.The present investigation offers a new insight into high performance sulfur cathodes through a bio-adhesion viewpoint.
基金This work was financially supported by the National Natural Science Foundation of China(No.51771076)the Innovative Research Groups of the National Natural Science Foundation of China(No.NSFC51621001)+2 种基金the“1000 plan”from Chinese Governmentthe Guangdong“Pearl River Talents Plan”(No.2017GC010218)the Guangzhou Science and Technology Plan Projects(No.201804010104)。
文摘With the emergence and development of wearable devices,the novel ene rgy storage systems with flexible feature and high energy density are urgently needed.As we all know,for next generation high energystorage systems,lithium-sulfur(Li-S) batteries with a high theoretical capacity are regarded as one of the most promising candidates.In addition,the flexible Li-S batteries have received more and more attention.The determined factor in the flexible Li-S batteries is how to design the foldable electrodes including both anode and cathode.As for the flexible sulfur cathode,it could be obtained by integrating the electroactive sulfur with a flexible substrate,generally.In recent years,the flexible cathode of Li-S batteries have made considerable progress,however there are also many huge challenges needing to overcome,such as low content of sulfur,fast decrease of capacity and short cycle life.In this paper,the current develop status of flexible cathodes of Li-S batteries have been summarized,and the future trend also be pointed out.
基金supported by the Natural Science Foundation of Shaanxi Province,China(2013JM2009)
文摘In situ chemical oxidation polymerization of pyrrole on the surface of sulfur particles was carried out to synthesize a sulfur/polypyrrole （SIPPy） nanocomposite with core-shell structure. The composite was characterized by elemental analysis, X-ray diffraction, scanning/transmission electron microscopy, and electrochemical measurements. XRD and FTIR results showed that sulfur well dispersed in the core-shell structure and PPy structure was successfully obtained via in situ oxidative polymerization of pyrrole on the surface of sulfur particles. TEM observation revealed that PPy was formed and fixed to the surface of sulfur nanoparticle after polymerization, developing a well-defined core-shell structure and the thickness of PPy coating layer was in the range of 20-30 nm. In the composite, PPy worked as a conducting matrix as well as a coating agent, which confined the active materials within the electrode. Consequently, the as prepared SIPPy composite cathode exhibited good cycling and rate performances for rechargeable lithium/sulfur batteries. The resulting cell containing SIPPy composite cathode yields a discharge capacity of 1039 mAh·g^-1 at the initial cycle and retains 59% of this value over 50 cycles at 0.1 C rate. At 1 C rate, the SIPPy composite showed good cycle stability, and the discharge capacity was 475 mAh·g^-1 after 50 cycles.
基金Financial support from National Natural Science Foundation of China(21935006)is gratefully acknowledged。
文摘Sulfur element possesses an ultrahigh theoretical specific capacity,while the utilization of sulfur in the whole cathode is lower obviously owing to the sluggish kinetics of sulfur and discharged products,limiting the enhancement on energy density of lithium-sulfur batteries.Herein,for the first time,Fe_(0.24)Co_(0.26)Ni_(0.10)Cu_(0.15)Mn_(0.25)high-entropy alloy is introduced as the core catalytic host to activate the electrochemical performance of the sulfur cathode for lithium-sulfur batteries.It is manifested that Fe_(0.24)Co_(0.26)Ni_(0.10)Cu_(0.15)Mn_(0.25)high-entropy alloy nanocrystallites distributed on nitrogen-doped carbon exhibit high electrocatalytic activity toward the conversion of solid sulfur to solid discharged products across soluble intermediate lithium polysulfides.In particular,benefiting from the accelerated kinetics by high-entropy alloy nanocrystallites and synergistic adsorption by nitrogen-doped carbon,the cathode exhibits high reversible capacity of 1079.5 mAh g_(-cathode)^(-1)(high utilization of 89.4%)with the whole cathode as active material,instead of sulfur element.Moreover,under both lean electrolyte(3μmg^(-1))and ultrahigh sulfur loading(27.0 mg cm^(-2))condition,the high discharge capacity of 868.2 mAh g_(-cathode)^(-1)can be still achieved for the sulfur cathode.This strategy opens up a new path to explore catalytic host materials for enhancing the utilization of sulfur in the whole cathode for lithium-sulfur batteries.
基金financially supported by the National Natural Science Foundation of China (Nos. 51725401, 51904030, and 21935006)
文摘Lithium−sulfur batteries are one of the most competitive high-energy batteries due to their high theoretical energy density of _(2)600 W·h·kg^(−1).However,their commercialization is limited by poor cycle stability mainly due to the low intrinsic electrical conductivity of sulfur and its discharged products(Li_(2)S_(2)/Li_(2)S),the sluggish reaction kinetics of sulfur cathode,and the“shuttle effect”of soluble intermediate lithi-um polysulfides in ether-based electrolyte.To address these challenges,catalytic hosts have recently been introduced in sulfur cathodes to en-hance the conversion of soluble polysulfides to the final solid products and thus prevent the dissolution and loss of active-sulfur material.In this review,we summarize the recent progress on the use of metal phosphides and borides of different dimensions as the catalytic host of sulfur cathodes and demonstrate the catalytic conversion mechanism of sulfur cathodes with the help of metal phosphides and borides for high-en-ergy and long-life lithium-sulfur batteries.Finally,future outlooks are proposed on developing advanced catalytic host materials to improve battery performance.
基金the Startup Research Fund of Dongguan University of Technology(KCYKYQD2017015)Leading Talents of Innovation and Entrepreneurship of the Dongguan City D2017(16)the Australian Research Council(ARC)through the ARC Discovery project(DP160104340)。
文摘Binders are of vital importance in stabilizing the cathodes to enhance the cycling stability of lithiumsulfur(Li-S) batteries. However, conventional binders are typically confronted with the drawback of inability for adsorbing lithium polysulfide(Li PS), thus resulting in severe active material losing and rapid capacity fading. Herein, a novel water-soluble hyperbranched poly(amidoamine)(HPAA) binder with controllable hyperbranched molecular structure and abundant amino end groups for Li-S battery is designed and fabricated, which can improve efficient adsorption for Li PS and stability of the sulfur cathodes. Besides, the strong intermolecular hydrogen bonds in HPAA binder can contribute to the structural stability of S cathode and integration of the conductive paths. Therefore, the Li-S battery with this functional binder exhibits excellent cycle performance with a capacity retention of 91% after 200 cycles at 0.1 C.Even at a high sulfur loading of 5.3 mg cm-2, a specific capacity of 601 mA h g-1 can also be achieved.Density functional theory(DFT) calculation further demonstrates that the enhanced electrochemical stability derives from the high binding energy between amino groups and LiP S and the wide electrochemical window(6.87 e V) of HPAA molecule. Based on the above all, this functional polymer will lighten a new species of binders for eco-friendly sulfur cathodes and significantly promote the practical applications of high-performance Li-S batteries.
基金supported by the National Natural Science Foundation of China(52172239)Project of State Key Laboratory of Environment-Friendly Energy Materials+2 种基金Southwest University of Science and Technology(Grant Nos.21fksy24 and 18ZD320304)Chongqing Talents:Exceptional Young Talents Project(Grant No.CQYC201905041)Natural Science Foundation of Chongqing China(Grant No.cstc2021jcyj-jqX0031)。
文摘The defect chemistry is successfully modulated on free-standing and binder-free carbon cathodes for highly efficient Li-S redox reactions.Such rationally regulated defect engineering realizes the synchronization of ion/electron-conductive and defect-rich networks on the threedimension carbon cathode,leading to its tunable activity for both relieving the shuttle phenomenon and accelerating the sulfur redox reaction kinetics.As expected,the defective carbon cathode harvests a high rate capacity of 1217.8 mAh g^(-1)at 0.2 C and a superior capacity retention of61.7%at 2 C after 500 cycles.Even under the sulfur mass loading of 11.1 mg cm^(-2),the defective cathode still holds a remarkable areal capacity of 8.5 mAh cm^(-2).
基金support from the National Natural Science Foundations of China(grants 51622208,21703149,and 51872193)the Priority Academic Program Development of Jiangsu Higher Education Institutions(PAPD)。
文摘Small molecules with adjustable sulfur atoms in the confined structure were acted as precursor for the synthesis of polymer cathodes for lithium-organosulfur batteries.Among them,poly(diallyl tetrasulfide)(PDATtS)delivered a high capacity of 700 mAh g^(-1),stable capacity retention of 85%after 300 cycles,high areal capacity~4 m Ah cm^(-2) for electrode with up to 10.3 mg cm^(-2) loading.New insight into the reaction mechanism of PDATtS electrode that radicals arisen from the homolytic cleavage of S-S bond in PDATtS reacted with Li+to generate thiolates(RSLi)and insoluble lithium sulfides(Li_(2)S)or lithium disulfide(Li_(2)S_(2))was clearly verified by in-situ UV/Vis spectroscopy,nuclear magnetic resonance(NMR)studies and density-functional theory(DFT)calculations.Therefore,based on the unique reaction mechanism,problems of rapid capacity fading due to the formation of soluble polysulfide intermediates and their serious shuttle effect in conventional lithium-sulfur(Li-S)batteries was totally avoided,realizing the dendrite-free lithium sulfur batteries.This study sets new trends for avenues of further research to advance Li-S battery technologies.
基金supported by the National Key Research and Development Program of China(No.2020YFB1713500)the Student Research Training Plan of Henan University of Science and Technology(No.2020026)the National Undergraduate Innovation and Entrepreneurship Training Program(Nos.202010464031,202110464005)。
文摘Lithium–sulfur(Li-S)batteries are regarded as one of the most promising energy storage devices because of their low cost,high energy density,and environmental friendliness.However,Li-S batteries suffer from sluggish reaction kinetics and serious“shuttle effect”of lithium polysulfides(LiPSs),which causes rapid decay of battery capacity and prevent their practical application.To address these problems,introducing single-atom catalysts(SACs)is an effective method to improve the electrochemical performance of Li-S batteries,due to their high catalytic efficiency and definite active sites for LiPSs.In this paper,we summarized the latest developments in enhancing the electrochemical performance of cathode for Li-S batteries through introducing different SACs.Furthermore,we briefly introduced the catalytic mechanism of SACs and discussed the strategies of synthesizing SACs,including the spatial confinement strategy and the coordination design strategy.Finally,the challenges and prospects in this field are proposed.We believe that this review would help to design and fabricate high-performance Li-S batteries via introducing SACs and boost their practical application.
基金supported by the National Natural Science Foundation of China(21805157,51972187)the Project funded by China Postdoctoral Science Foundation(2021M701817)+2 种基金the Natural Science Foundation of Shandong Provincial(ZR2021QE166)the National Natural Science Foundation for Distinguished Young Scholars of China(51625204)the Major Basic Research Program of Natural Science Foundation of Shandong Province(ZR2020ZD09)。
文摘Rechargeable Mg batteries potentially display lower cost and competitive energy density compared with their Li-ion counterparts.However,the practical implementation of high area-capacity cathodes still remains a formidably challenging task.This work presents the sulfur/copper integrated cathodes fabricated by the conventional blade-coating process and slurry-dipping method.The sulfur/copper foil integrated cathodes deliver a high area-capacity of 2.6 mAh cm^(-2)after 40 cycles,while the sulfur/copperfoam integrated cathode exhibits an ultrahigh area-capacity of 35.4 mAh cm^(-2),corresponding to 743.1 Wh L^(-1)at the electrode level(1.5 times higher than the LiCoO_(2)-graphite system).The in-situ formed copper sulfide intermediates with sufficient cation defects can act as functional intermediates to regulate the sulfur electrochemistry during the first discharge process.The subsequent cycles are operated by the reversible displacement reaction between Mg-ions and copper sulfide active substances.In particular,the copper ions prefer to extrude along the[001]direction in copper sulfides lattice and simultaneously the rock-salt MgS crystals are generated.Besides,the nonuniform surface topography of the cycled Mgmetal anode,caused by the spatial inhomogeneity in current distribution,is demonstrated to lead to the battery performance degradation for high area-capacity Mg batteries.
