Rechargeable lithium-ion batteries(LIBs)afford a profound impact on our modern daily life.However,LIBs are approaching the theoretical energy density,due to the inherent limitations of intercalation chemistry;thus,the...Rechargeable lithium-ion batteries(LIBs)afford a profound impact on our modern daily life.However,LIBs are approaching the theoretical energy density,due to the inherent limitations of intercalation chemistry;thus,they cannot further satisfy the increasing demands of portable electronics,electric vehicles,and grids.Therefore,battery chemistries beyond LIBs are being widely investigated.Next-generation lithium(Li)batteries,which employ Li metal as the anode and intercalation or conversion materials as the cathode,receive the most intensive interest due to their high energy density and excellent potential for commercialization.Moreover,significant progress has been achieved in Li batteries attributed to the increasing fundamental understanding of the materials and reactions,as well as to technological improvement.This review starts by summarizing the electrolytes for next-generation Li batteries.Key challenges and recent progress in lithium-ion,lithium–sulfur,and lithium–oxygen batteries are then reviewed from the perspective of energy and chemical engineering science.Finally,possible directions for further development in Li batteries are presented.Next-generation Li batteries are expected to promote the sustainable development of human civilization.展开更多
Biomass, as the most widely used carbon sources, is the main ingredient in the formation of fossil fuels. Biomass-derived novel carbons(BDNCs) have attracted much attention because of its adjustable physical/chemical ...Biomass, as the most widely used carbon sources, is the main ingredient in the formation of fossil fuels. Biomass-derived novel carbons(BDNCs) have attracted much attention because of its adjustable physical/chemical properties, environmentally friendliness, and considerable economic value. Nature contributes to the biomass with bizarre microstructures with micropores, mesopores or hierarchical pores.Currently, it has been confirmed that biomass has great potential applications in energy storage devices,especially in lithium-sulfur(Li–S) batteries. In this article, the synthesis and function of BDNCs for Li–S batteries are presented, and the electrochemical effects of structural diversity, porosity and surface heteroatom doping of the carbons in Li-S batteries are discussed. In addition, the economic benefits, new trends and challenges are also proposed for further design excellent BDNCs for Li–S batteries.展开更多
Lithium–sulfur batteries exhibit unparalleled merits in theoretical energy density(2600 W h kg^(-1))among next-generation storage systems.However,the sluggish electrochemical kinetics of sulfur reduction reactions,su...Lithium–sulfur batteries exhibit unparalleled merits in theoretical energy density(2600 W h kg^(-1))among next-generation storage systems.However,the sluggish electrochemical kinetics of sulfur reduction reactions,sulfide oxidation reactions in the sulfur cathode,and the lithium dendrite growth resulted from uncontrollable lithium behaviors in lithium anode have inhibited high-rate conversions and uniform deposition to achieve high performances.Thanks to the“adsorption-catalysis”synergetic effects,the reaction kinetics of sulfur reduction reactions/sulfide oxidation reactions composed of the delithiation of Li_(2)S and the interconversions of sulfur species are propelled by lowering the delithiation/diffusion energy barriers,inhibiting polysulfide shuttling.Meanwhile,the anodic plating kinetic behaviors modulated by the catalysts tend to uniformize without dendrite growth.In this review,the various active catalysts in modulating lithium behaviors are summarized,especially for the defect-rich catalysts and single atomic catalysts.The working mechanisms of these highly active catalysts revealed from theoretical simulation to in situ/operando characterizations are also highlighted.Furthermore,the opportunities of future higher performance enhancement to realize practical applications of lithium–sulfur batteries are prospected,shedding light on the future practical development.展开更多
Lithium-sulfur(Li-S)batteries are considered as one of the most promising candidates for next-generation energy storage systems with high energy density and reliable performance.However,the commercial applications of ...Lithium-sulfur(Li-S)batteries are considered as one of the most promising candidates for next-generation energy storage systems with high energy density and reliable performance.However,the commercial applications of lithium-sulfur batteries is hindered by several shortcomings like the poor conductivity of sulfur and its reaction products,and the loss of active materials owing to the diffusion of lithium polysulfides(LiPSs)into the electrolyte.Hence,the effective restraining of the LiPSs and the promotion of the sluggish conversion are highly demanded to fulfill the potential of lithium-sulfur batteries.Here,we summarize the applications of transition-metal sulfides(TMSs)in the cathodes over recent years and demonstrate the unique advantages they possess to realize reliable long-life lithium-sulfur batteries.展开更多
The lithium-sulfur battery is the subject of much recent attention due to the high theoretical energy density,but practical applications are challenged by fast decay owing to polysulfide shuttle and electrode architec...The lithium-sulfur battery is the subject of much recent attention due to the high theoretical energy density,but practical applications are challenged by fast decay owing to polysulfide shuttle and electrode architecture degradation.A comprehensive study of the sulfur host microstructure design and the cell architecture construction based on the MXene phase(Ti3C2Tx nanosheets) is performed,aiming at realize stable cycling performance of Li-S battery with high sulfur areal loading.The interwoven KB@Ti3C2Tx composite formed by self-assembly of MXene and Ktej en black,not only provides superior conductivity and maintains the electrode integrality bearing the volume expansion/shrinkage when used as the sulfur host,but also functions as an interlayer on separator to further retard the polysulfide cross-diffusion that possibly escaped from the cathode.The KB@Ti3C2Tx interlayer is only 0.28 mg cm-2 in areal loading and 3 μm in thickness,which accounts a little contribution to the thick sulfur electrode;thus,the impacts on the energy density is minimal.By coupling the robust KB@Ti3C2Tx cathode and the effective KB@Ti3C2Tx modified separator,a stable Li-S battery with high sulfur areal loading(5.6 mg cm-2) and high areal capacity(6.4 mAh cm-2) at relatively lean electrolyte is achieved.展开更多
Lithium-sulfur(Li-S) batteries have shown promises for the next-generation, high-energy electrochemical storage, yet are hindered by rapid performance decay due to the polysulfide shuttle in the cathode and safety con...Lithium-sulfur(Li-S) batteries have shown promises for the next-generation, high-energy electrochemical storage, yet are hindered by rapid performance decay due to the polysulfide shuttle in the cathode and safety concerns about potential thermal runaway. To address the above challenges, herein, we show a flame-retardant cathode binder that simultaneously improves the electrochemical stability and safety of batteries. The combination of soft and hard segments in the polymer framework of binders allows high flexibility and mechanical strength for adapting to the drastic volume change during the Li(de)intercalation of the S cathode. The binder contains a large number of polar groups, which show the high affinity to polysulfides so that they help to anchor active S species at the cathode. These polar groups also help to regulate and facilitate the Li-ion transport, promoting the kinetics of polysulfide conversion reaction. The binder contains abundant phosphine oxide groups, which, in the case of battery's thermal runaway, decompose and release PO· radicals to quench the combustion reactions and stop the fire. Consequently, Li-S batteries using the new cathode binder show the improved electrochemical performance, including a low-capacity decay of 0.046% per cycle for 800 cycles at 1 C and favorable rate capabilities of up to 3 C. This work offers new insights on the practical realization of high-energy rechargeable batteries with stable storage electrochemistry and high safety.展开更多
It is especially important to coordinately design the structure and composition of the host in lithium–sulfur batteries(LSBs)for improving its physicochemical adsorption and conversion of lithium polysulfide,which ca...It is especially important to coordinately design the structure and composition of the host in lithium–sulfur batteries(LSBs)for improving its physicochemical adsorption and conversion of lithium polysulfide,which can alleviate the harmful shuttle effect.Herein,a self-supporting multichannel nitrogen-doped carbon fibers membrane embedded with TiO nanoparticles(TiO@NC)was constructed as the electrode for LSBs.The inner channels and the embedded TiO nanoparticles offer spatial confinement and chemical binding for polysulfides,respectively.Moreover,the TiO nanoparticles have abundant oxygen vacancies that promote the conversion of polysulfides.In addition,the nitrogen-doped carbon skeleton can not only serve as highly conductive transportation paths for electrons,but also integrate with the inner channels to sustain the morphology and bear volume expansion during cycling processes.Therefore,the fabricated self-supporting quadruple-channel TiO@NC ultrathin fibers electrode exhibits a high initial specific capacity of 1342.8 mAh g^(-1)at 0.5 C and high-rate capability of 505.8 mAh g^(-1)at 4.0 C.In addition,it maintains 696.0 mAh g^(-1)over 500 cycles with only 0.059%capacity decay per cycle at the high current density of 2.0 C.The multichannel configuration combined with TiO nanoparticles provides a synergetic design strategy for fabricating high-performance electrodes in LSBs.展开更多
Herein,N-Ti3C2@CNT microspheres are successfully synthesized by the simple spray drying method.In the preparation process,HCl-treated melamine(HTM)is selected as the sources of carbon and nitrogen.It not only realizes...Herein,N-Ti3C2@CNT microspheres are successfully synthesized by the simple spray drying method.In the preparation process,HCl-treated melamine(HTM)is selected as the sources of carbon and nitrogen.It not only realizes in situ growth of CNTs on the surface of MXene nanosheets with the catalysis of Ni,but also introduces efficient N-doping in both MXene and CNTs.Within the microsphere,MXene nanosheets interconnect with CNTs to form porous and conductive network.In addition,N-doped MXene and CNTs can provide strong chemical immobilization for polysulfides and effectively entrap them within the porous microspheres.Above-mentioned merits enable N-Ti3C2@CNT microspheres to be ideal sulfur host.When used in lithium–sulfur(Li–S)battery,the N-Ti3C2@CNT microspheres/S cathode delivers initial specific capacity of 927 mAh g−1 at 1 C and retains high capacity of 775 mAh g−1 after 1000 cycles with extremely low fading rate(FR)of 0.016%per cycle.Furthermore,the cathode still shows high cycling stability at high C-rate of 4 C(capacity of 647 mAh g−1 after 650 cycles,FR 0.027%)and high sulfur loading of 3 and 6 mg cm−2 for Li–S batteries.展开更多
Lithium-sulfur batteries(LSBs)are promising alternative energy storage devices to the commercial lithium-ion batteries.However,the LSBs have several limitations including the low electronic conductivity of sulfur(5...Lithium-sulfur batteries(LSBs)are promising alternative energy storage devices to the commercial lithium-ion batteries.However,the LSBs have several limitations including the low electronic conductivity of sulfur(5×10^-30S cm^-1),associated lithium polysulfides(PSs),and their migration from the cathode to the anode.In this study,a separator coated with a Ketjen black(KB)/Nafion composite was used in an LSB with a sulfur loading up to 7.88 mg cm^-2to mitigate the PS migration.A minimum specific capacity(Cs)loss of 0.06%was obtained at 0.2 C-rate at a high sulfur loading of 4.39 mg cm^-2.Furthermore,an initial areal capacity up to 6.70 mAh cm^-2 was obtained at a sulfur loading of 7.88 mg cm^-2.The low Cs loss and high areal capacity associated with the high sulfur loading are attributed to the large surface area of the KB and sulfonate group(SO3^-)of Nafion,respectively,which could physically and chemically trap the PSs.展开更多
Engineering transition metal compounds(TMCs)catalysts with excellent adsorption-catalytic ability has been one of the most effec-tive strategies to accelerate the redox kinetics of sulfur cathodes.Herein,this review f...Engineering transition metal compounds(TMCs)catalysts with excellent adsorption-catalytic ability has been one of the most effec-tive strategies to accelerate the redox kinetics of sulfur cathodes.Herein,this review focuses on engineering TMCs catalysts by cation doping/anion doping/dual doping,bimetallic/bi-anionic TMCs,and TMCs-based heterostructure composites.It is obvious that introducing cations/anions to TMCs or constructing heterostructure can boost adsorption-catalytic capacity by regulating the electronic structure including energy band,d/p-band center,electron filling,and valence state.Moreover,the elec-tronic structure of doped/dual-ionic TMCs are adjusted by inducing ions with different electronegativity,electron filling,and ion radius,resulting in electron redistribution,bonds reconstruction,induced vacancies due to the electronic interaction and changed crystal structure such as lat-tice spacing and lattice distortion.Different from the aforementioned two strategies,heterostructures are constructed by two types of TMCs with different Fermi energy levels,which causes built-in electric field and electrons transfer through the interface,and induces electron redistribution and arranged local atoms to regulate the electronic structure.Additionally,the lacking studies of the three strategies to comprehensively regulate electronic structure for improving catalytic performance are pointed out.It is believed that this review can guide the design of advanced TMCs catalysts for boosting redox of lithium sulfur batteries.展开更多
The practical application of lithium-sulfur batteries is severely hampered by the poor conductivity,polysulfide shuttle effect and sluggish reaction kinetics of sulfur cathodes.Herein,a hierarchi-cally porous three-di...The practical application of lithium-sulfur batteries is severely hampered by the poor conductivity,polysulfide shuttle effect and sluggish reaction kinetics of sulfur cathodes.Herein,a hierarchi-cally porous three-dimension(3D)carbon architecture assembled by cross-linked carbon leaves with implanted atomic Co-N4 has been deli-cately developed as an advanced sulfur host through a SiO_(2)-mediated zeolitic imidazolate framework-L(ZIF-L)strategy.The unique 3D architectures not only provide a highly conductive network for fast electron transfer and buffer the volume change upon lithiation-delithi-ation process but also endow rich interface with full exposure of Co-N4 active sites to boost the lithium polysulfides adsorption and conversion.Owing to the accelerated kinetics and suppressed shuttle effect,the as-prepared sulfur cathode exhibits a superior electrochemical perfor-mance with a high reversible specific capacity of 695 mAh g^(−1) at 5 C and a low capacity fading rate of 0.053%per cycle over 500 cycles at 1 C.This work may provide a promising solution for the design of an advanced sulfur-based cathode toward high-performance Li-S batteries.展开更多
Lithium-sulfur(Li-S) batteries have attracted considerable attention as one of the most appealing energy storage systems.Strenuous efforts have been devoted to tackling the tremendous challenges,mainly pertaining to t...Lithium-sulfur(Li-S) batteries have attracted considerable attention as one of the most appealing energy storage systems.Strenuous efforts have been devoted to tackling the tremendous challenges,mainly pertaining to the severe shuttle effect,sluggish redox kinetics and lithium dendritic growth.Single-atomic mediators as promising candidates exhibit impressive performance in addressing these intractable issues.Related research often utilizes a trial-and-error approach,proposing solutions to fabricate single-atomic materials with diversified features.However,comprehensive review articles especially targeting demand-driven preparation are still in a nascent stage.Inspired by these considerations,this review summarizes the design of single-atomic mediators based on the application case-studies in LiS batteries and other metal-sulfur systems.Emerging preparation routes represented by chemical vapor deposition technology are introduced in a demand-oriented classification.Finally,future research directions are proposed to foster the advancement of single-atomic mediators in Li-S realm.展开更多
多孔碳材料由于具有优异的导电性,高的孔隙率以及可有效地吸附多硫化物等优点被广泛应用于锂硫电池.本文以植酸(PA)和三聚氰胺作为磷源和氮源,通过高温裂解法成功制备了N,P共掺杂的三维多孔碳纳米复合材料(FeNi/FeNiP@NP-C)作为载硫基质...多孔碳材料由于具有优异的导电性,高的孔隙率以及可有效地吸附多硫化物等优点被广泛应用于锂硫电池.本文以植酸(PA)和三聚氰胺作为磷源和氮源,通过高温裂解法成功制备了N,P共掺杂的三维多孔碳纳米复合材料(FeNi/FeNiP@NP-C)作为载硫基质.FeNi/FeNiP@NP-C三维多孔碳骨架具有良好的导电性能,它不仅能够有效地吸附可溶性多硫化物,同时能够促进电子转移从而提高反应动力学.实验结果表明S@FeNi/FeNiP@NP-C正极有较好的电化学性能和循环稳定性,在硫负载量为1.0 mg cm^(-2)以及0.1C的电流密度下,S@FeNi/FeNiP@NPC电极可达到1035.8 mAh g^(-1)的初始放电比容量,在0.1 C电流密度及较高硫负载量(4.3 mg cm^(-2))下循环100圈后仍能保持435.5 mAh g-1的放电比容量.展开更多
A nano sulfur-based composite cathode material featured by uniform core@shell-structured sulfur@polypyrrole nanoparticles sandwiched in three-dimensional graphene sheets conductive network（S@PPy/GS） is fabricated vi...A nano sulfur-based composite cathode material featured by uniform core@shell-structured sulfur@polypyrrole nanoparticles sandwiched in three-dimensional graphene sheets conductive network（S@PPy/GS） is fabricated via a facile solution-based method. The S@PPy nanoparticles are synthesized by in situ chemical oxidative polymerization of pyrrole on the surface of sulfur particles,and then graphene sheets are covered outside the S@PPy nanoparticles,forming a three-dimensional conductive network. When evaluating the electrochemical performance of S@PPy/GS in a lithium–sulfur battery,it delivers large discharge capacity,excellent cycle stability,and good rate capability. The initial discharge capacity is up to 1040 m Ah/g at 0.1 C,the capacity can remain 537.8 m Ah/g at 0.2 C after 200 cycles,even at a higher rate of 1 C,the specific capacity still reaches 566.5 m Ah/g. The good electrochemical performance is attributed to the unique structure of S@PPy/GS,which can not only provide an excellent transport of lithium and electron ions within the electrodes,but also retard the shuttle effect of soluble lithium polysulfides effectively,thus plays a positive role in building better lithium-sulfur batteries.展开更多
Extensive efforts have been devoted to the design of micro-, nano-, and/or molecular structures of sulfur hosts to address the challenges of lithium–sulfur(Li–S) batteries, yet comparatively little research has been...Extensive efforts have been devoted to the design of micro-, nano-, and/or molecular structures of sulfur hosts to address the challenges of lithium–sulfur(Li–S) batteries, yet comparatively little research has been carried out on the binders in Li–S batteries. Herein, we systematically review the polymer composite frameworks that confine the sulfur within the sulfur electrode, taking the roles of sulfur hosts and functions of binders into consideration. In particular, we investigate the binding mechanism between the binder and sulfur host(such as mechanical interlocking and interfacial interactions), the chemical interactions between the polymer binder and sulfur(such as covalent bonding, electrostatic bonding, etc.), as well as the beneficial functions that polymer binders can impart on Li–S cathodes, such as conductive binders, electrolyte intake, adhesion strength etc. This work could provide a more comprehensive strategy in designing sulfur electrodes for long-life, large-capacity and high-rate Li–S battery.展开更多
The lithium-sulfur battery(Li–S)is a promising energy storage system with many advantages over the commercialized lithium-ion battery.It has a high theoretical capacity of 1675 mAh gà1,a high theoretical energy ...The lithium-sulfur battery(Li–S)is a promising energy storage system with many advantages over the commercialized lithium-ion battery.It has a high theoretical capacity of 1675 mAh gà1,a high theoretical energy density(2600 Wh kgà1),and is eco-environmentally friendly.Although only a small amount is used(<10 wt%)in the electrode,binders may affect the discharge capacity and cycling stability of sulfur cathodes in the Li–S battery.In recent years,tremendous efforts have been made to develop functional binders with robust adhesive strength,fast ion/electron transportation,strong anchoring of lithium polysulfide(LiPS),and rapid redox kinetics,to improve capacity,coulombic efficiency,and energy density.This article reviews recent developments in binders for the Li–S battery.After briefly introducing the fundamentals of the Li–S battery,the desireable characteristics of binders are discussed based on the correlation between the functions of the binder molecules and the performance of the battery.Future challenges in developing promising binders and potential solutions are provided in the conclusion.展开更多
The use of carbonized wood in various functional devices is attracting considerable attention due to its low cost,vertical channels,and high electrical conduction.However,the conventional carbonization method requires...The use of carbonized wood in various functional devices is attracting considerable attention due to its low cost,vertical channels,and high electrical conduction.However,the conventional carbonization method requires a long processing time and an inert atmosphere.Here,a microwave-assisted ultrafast carbonization technique was developed that carbonizes natural wood in seconds without the need for an inert atmosphere,and the obtained aligned-porous carbonized wood provided an excellent electrochemical performance as an anode material for lithium-ion batteries.This ultrafast carbonization technique simultaneously produced ZnO nanoparticles during the carbonization process that were uniformly distributed on the alignedporous carbon.The hierarchical structure of carbonized wood functionalized with ZnO nanoparticles was used as a host for achieving high-performance lithium-sulfur batteries:the highly conductive carbonized wood framework with vertical channels provided good electron transport pathways,and the homogeneously dispersed ZnO nanoparticles effectively adsorbed lithium polysulfide and catalyzed its conversion reactions.In summary,a new method was developed to realize the ultrafast carbonization of biomass materials with decorated metal oxide nanoparticles.展开更多
A high sulfur content sulfur–carbon composite was synthesized via in situ generation method in aqueous solution.When the sulfur loading is up to 90%,the electrode still exhibits good cycling performance with a revers...A high sulfur content sulfur–carbon composite was synthesized via in situ generation method in aqueous solution.When the sulfur loading is up to 90%,the electrode still exhibits good cycling performance with a reversible capacity of about 623 mAh·g^(-1)after 100 cycles.To further commercialize the Li–S battery,understanding the capacity degradation mechanism is very essential,especially with a high sulfur loading electrode.To achieve this goal,the electrochemical performance of the high sulfur loading electrode was studied,and the structure change of the electrode after cycling was also examined by ex situ scanning electron microscopy(SEM)and other techniques.The result shows that the Li_(2)S_(2)and Li_(2)S inhomogeneous precipitation contributes to the majority capacity fading of the high sulfur loading Li–S cells.展开更多
As a sulfur-containing cathode material,sulfide polyacrylonitrile(SPAN)is expected to be used for longlife lithium-sulfur battery because there is no shuttle effect occurred in its charge process.However,its specific ...As a sulfur-containing cathode material,sulfide polyacrylonitrile(SPAN)is expected to be used for longlife lithium-sulfur battery because there is no shuttle effect occurred in its charge process.However,its specific capacity and discharge potential need to be further improved to satisfy the urgent demands for high-performance batteries.In this paper,Te0.045S0.955PAN composite was synthesized by co-heating TexS1-x and PAN,and the superior electrochemical performance to that of SPAN was obtained because of doping Te with high conductivity.The as-prepared Te0.045S0.955PAN composite possessed the specific capacity of 675 mAh g^-1 after 100 cycles at the current density of 0.1 A g^-1 with high capacity retention of96.6%compared to the second cycle.Especially,during cycling,Te0.045S0.955PAN showed average discharge voltages of 1.88-1.91 V,which were higher than 1.85-1.88 V for SPAN at the same current density.Thus doping Te provides a new strategy for increasing the energy density of SPAN.展开更多
Lithium-sulfur battery is desirable for the future potential electrochemical energy storage device with advantages of high theoretical energy density,low cost and environmental friendliness.However,some natural hindra...Lithium-sulfur battery is desirable for the future potential electrochemical energy storage device with advantages of high theoretical energy density,low cost and environmental friendliness.However,some natural hindrances,particularly fast capacity degradation resulting from the migration of dissolved polysulfide intermediates,remain to be significant challenges prior to the practical applications.In this work,a composite interlayer of carbon nanofibers(CNFs)which are enriched by Co-based metal organic frameworks(ZIF-67)growth in-situ is exploited.Notably,physical blocking and chemical trapping abilities are obtained synergistically from the ZIF/CNFs interlayer,which enables to restrain the dissolution of polysulfides and alleviate shuttle effect.Moreover,the three-dimensional fiber networks provide an interconnected conductive framework between each ZIF microreactor to promote fast electron transfer during cycling,thus contributing to excellent rate and cycling performance.As a result,Li-S cells with ZIF/CNFs interlayer show a high specific capacity of 1334 mAh g^(-1) at 1 C with an excellent cycling stability over 300 cycles.Besides,this scalable and affordable electrospinning fabrication method provides a promising approach for the design of MOFs-derived carbon materials for high performance Li-S batteries.展开更多
基金the National Key Research and Development Program(2016YFA0202500 and 2016YFA0200102)the National Natural Science Foundation of China(21676160,21776019,and 21825501)the Tsinghua University Initiative Scientific Research Program.
文摘Rechargeable lithium-ion batteries(LIBs)afford a profound impact on our modern daily life.However,LIBs are approaching the theoretical energy density,due to the inherent limitations of intercalation chemistry;thus,they cannot further satisfy the increasing demands of portable electronics,electric vehicles,and grids.Therefore,battery chemistries beyond LIBs are being widely investigated.Next-generation lithium(Li)batteries,which employ Li metal as the anode and intercalation or conversion materials as the cathode,receive the most intensive interest due to their high energy density and excellent potential for commercialization.Moreover,significant progress has been achieved in Li batteries attributed to the increasing fundamental understanding of the materials and reactions,as well as to technological improvement.This review starts by summarizing the electrolytes for next-generation Li batteries.Key challenges and recent progress in lithium-ion,lithium–sulfur,and lithium–oxygen batteries are then reviewed from the perspective of energy and chemical engineering science.Finally,possible directions for further development in Li batteries are presented.Next-generation Li batteries are expected to promote the sustainable development of human civilization.
基金supported by the National Natural Science Foundation of China (U1832136 and 21303038)Think-Tank Union Funds for Energy Storage (Grant No.JZ2016QTXM1097)+3 种基金Open Funds of the State Key Laboratory of Rare Earth Resource Utilization (Grant No. RERU2016004)the Fundamental Research Funds for the Central Universities (JZ2016HGTA0690)Natural Science Foundation of Anhui province (1808085QE140)100 Talents Plan of Anhui
文摘Biomass, as the most widely used carbon sources, is the main ingredient in the formation of fossil fuels. Biomass-derived novel carbons(BDNCs) have attracted much attention because of its adjustable physical/chemical properties, environmentally friendliness, and considerable economic value. Nature contributes to the biomass with bizarre microstructures with micropores, mesopores or hierarchical pores.Currently, it has been confirmed that biomass has great potential applications in energy storage devices,especially in lithium-sulfur(Li–S) batteries. In this article, the synthesis and function of BDNCs for Li–S batteries are presented, and the electrochemical effects of structural diversity, porosity and surface heteroatom doping of the carbons in Li-S batteries are discussed. In addition, the economic benefits, new trends and challenges are also proposed for further design excellent BDNCs for Li–S batteries.
基金fellowship funding supported by the Alexander von Humboldt Foundationfinancial funding support from the Natural Science Foundation of Jiangsu Province(BK.20210636)Natural Science Foundation of China(21773294 and 21972164)。
文摘Lithium–sulfur batteries exhibit unparalleled merits in theoretical energy density(2600 W h kg^(-1))among next-generation storage systems.However,the sluggish electrochemical kinetics of sulfur reduction reactions,sulfide oxidation reactions in the sulfur cathode,and the lithium dendrite growth resulted from uncontrollable lithium behaviors in lithium anode have inhibited high-rate conversions and uniform deposition to achieve high performances.Thanks to the“adsorption-catalysis”synergetic effects,the reaction kinetics of sulfur reduction reactions/sulfide oxidation reactions composed of the delithiation of Li_(2)S and the interconversions of sulfur species are propelled by lowering the delithiation/diffusion energy barriers,inhibiting polysulfide shuttling.Meanwhile,the anodic plating kinetic behaviors modulated by the catalysts tend to uniformize without dendrite growth.In this review,the various active catalysts in modulating lithium behaviors are summarized,especially for the defect-rich catalysts and single atomic catalysts.The working mechanisms of these highly active catalysts revealed from theoretical simulation to in situ/operando characterizations are also highlighted.Furthermore,the opportunities of future higher performance enhancement to realize practical applications of lithium–sulfur batteries are prospected,shedding light on the future practical development.
基金This work was financially supported by the National Natural Science Foundation of China(Grant No.51872012)the National Key R&D Program of China(Grant No.2018YFA900)the Fundamental Research Funds for the Central Universities and the 111 Project(Grant No.B17002).
文摘Lithium-sulfur(Li-S)batteries are considered as one of the most promising candidates for next-generation energy storage systems with high energy density and reliable performance.However,the commercial applications of lithium-sulfur batteries is hindered by several shortcomings like the poor conductivity of sulfur and its reaction products,and the loss of active materials owing to the diffusion of lithium polysulfides(LiPSs)into the electrolyte.Hence,the effective restraining of the LiPSs and the promotion of the sluggish conversion are highly demanded to fulfill the potential of lithium-sulfur batteries.Here,we summarize the applications of transition-metal sulfides(TMSs)in the cathodes over recent years and demonstrate the unique advantages they possess to realize reliable long-life lithium-sulfur batteries.
基金financially supported by National Key Research and Development Program(No.2019YFA0210600)the Major Technological Innovation Project of Hubei Science and Technology Department(No.2019AAA164)+1 种基金the National Natural Science Foundation of China(No.51972107)the Innovative Research Groups of Hunan Province(No.2019JJ10001)。
文摘The lithium-sulfur battery is the subject of much recent attention due to the high theoretical energy density,but practical applications are challenged by fast decay owing to polysulfide shuttle and electrode architecture degradation.A comprehensive study of the sulfur host microstructure design and the cell architecture construction based on the MXene phase(Ti3C2Tx nanosheets) is performed,aiming at realize stable cycling performance of Li-S battery with high sulfur areal loading.The interwoven KB@Ti3C2Tx composite formed by self-assembly of MXene and Ktej en black,not only provides superior conductivity and maintains the electrode integrality bearing the volume expansion/shrinkage when used as the sulfur host,but also functions as an interlayer on separator to further retard the polysulfide cross-diffusion that possibly escaped from the cathode.The KB@Ti3C2Tx interlayer is only 0.28 mg cm-2 in areal loading and 3 μm in thickness,which accounts a little contribution to the thick sulfur electrode;thus,the impacts on the energy density is minimal.By coupling the robust KB@Ti3C2Tx cathode and the effective KB@Ti3C2Tx modified separator,a stable Li-S battery with high sulfur areal loading(5.6 mg cm-2) and high areal capacity(6.4 mAh cm-2) at relatively lean electrolyte is achieved.
基金financially supported by the National Key R&D Program of China(2019YFA0705703)Natural Science Foundation of Hubei Province(2021CFB082)+4 种基金Scientific Research Foundation of Wuhan Institute of Technology(K2021042)the Open Key Fund Project of State Key Laboratory of Advanced Technology for Materials Synthesis and Processing(Wuhan University of Technology,2022-KF-10)National Natural Science Foundation of China(22275142,U22B6011)China Postdoctoral Science Foundation(2021M703268)the Junior Fellow Program of Beijing National Laboratory for Molecular Sciences(2021BMS20062)。
文摘Lithium-sulfur(Li-S) batteries have shown promises for the next-generation, high-energy electrochemical storage, yet are hindered by rapid performance decay due to the polysulfide shuttle in the cathode and safety concerns about potential thermal runaway. To address the above challenges, herein, we show a flame-retardant cathode binder that simultaneously improves the electrochemical stability and safety of batteries. The combination of soft and hard segments in the polymer framework of binders allows high flexibility and mechanical strength for adapting to the drastic volume change during the Li(de)intercalation of the S cathode. The binder contains a large number of polar groups, which show the high affinity to polysulfides so that they help to anchor active S species at the cathode. These polar groups also help to regulate and facilitate the Li-ion transport, promoting the kinetics of polysulfide conversion reaction. The binder contains abundant phosphine oxide groups, which, in the case of battery's thermal runaway, decompose and release PO· radicals to quench the combustion reactions and stop the fire. Consequently, Li-S batteries using the new cathode binder show the improved electrochemical performance, including a low-capacity decay of 0.046% per cycle for 800 cycles at 1 C and favorable rate capabilities of up to 3 C. This work offers new insights on the practical realization of high-energy rechargeable batteries with stable storage electrochemistry and high safety.
基金supported by the National Natural Science Foundation of China(NSFC)(Grant Nos.22175007,21975007,52172080,22105012,22005012,22105059)the National Natural Science Foundation for Outstanding Youth Foundation,the Fundamental Research Funds for the Central Universities(YWF-22-K-101)+2 种基金the National Program for Support of Topnotch Young Professionals,the 111 project(Grant No.B14009)the Youth Top-notch Talent Foundation of Hebei Provincial Universities(BJK2022023)the Interdisciplinary Research Project for Young Teachers of USTB(Fundamental Research Funds for the Central Universities)(FRF-IDRY-21-015).
文摘It is especially important to coordinately design the structure and composition of the host in lithium–sulfur batteries(LSBs)for improving its physicochemical adsorption and conversion of lithium polysulfide,which can alleviate the harmful shuttle effect.Herein,a self-supporting multichannel nitrogen-doped carbon fibers membrane embedded with TiO nanoparticles(TiO@NC)was constructed as the electrode for LSBs.The inner channels and the embedded TiO nanoparticles offer spatial confinement and chemical binding for polysulfides,respectively.Moreover,the TiO nanoparticles have abundant oxygen vacancies that promote the conversion of polysulfides.In addition,the nitrogen-doped carbon skeleton can not only serve as highly conductive transportation paths for electrons,but also integrate with the inner channels to sustain the morphology and bear volume expansion during cycling processes.Therefore,the fabricated self-supporting quadruple-channel TiO@NC ultrathin fibers electrode exhibits a high initial specific capacity of 1342.8 mAh g^(-1)at 0.5 C and high-rate capability of 505.8 mAh g^(-1)at 4.0 C.In addition,it maintains 696.0 mAh g^(-1)over 500 cycles with only 0.059%capacity decay per cycle at the high current density of 2.0 C.The multichannel configuration combined with TiO nanoparticles provides a synergetic design strategy for fabricating high-performance electrodes in LSBs.
文摘Herein,N-Ti3C2@CNT microspheres are successfully synthesized by the simple spray drying method.In the preparation process,HCl-treated melamine(HTM)is selected as the sources of carbon and nitrogen.It not only realizes in situ growth of CNTs on the surface of MXene nanosheets with the catalysis of Ni,but also introduces efficient N-doping in both MXene and CNTs.Within the microsphere,MXene nanosheets interconnect with CNTs to form porous and conductive network.In addition,N-doped MXene and CNTs can provide strong chemical immobilization for polysulfides and effectively entrap them within the porous microspheres.Above-mentioned merits enable N-Ti3C2@CNT microspheres to be ideal sulfur host.When used in lithium–sulfur(Li–S)battery,the N-Ti3C2@CNT microspheres/S cathode delivers initial specific capacity of 927 mAh g−1 at 1 C and retains high capacity of 775 mAh g−1 after 1000 cycles with extremely low fading rate(FR)of 0.016%per cycle.Furthermore,the cathode still shows high cycling stability at high C-rate of 4 C(capacity of 647 mAh g−1 after 650 cycles,FR 0.027%)and high sulfur loading of 3 and 6 mg cm−2 for Li–S batteries.
基金the Australian Government and University of Queensland for the research training program scholarship and research facilities used in this study.
文摘Lithium-sulfur batteries(LSBs)are promising alternative energy storage devices to the commercial lithium-ion batteries.However,the LSBs have several limitations including the low electronic conductivity of sulfur(5×10^-30S cm^-1),associated lithium polysulfides(PSs),and their migration from the cathode to the anode.In this study,a separator coated with a Ketjen black(KB)/Nafion composite was used in an LSB with a sulfur loading up to 7.88 mg cm^-2to mitigate the PS migration.A minimum specific capacity(Cs)loss of 0.06%was obtained at 0.2 C-rate at a high sulfur loading of 4.39 mg cm^-2.Furthermore,an initial areal capacity up to 6.70 mAh cm^-2 was obtained at a sulfur loading of 7.88 mg cm^-2.The low Cs loss and high areal capacity associated with the high sulfur loading are attributed to the large surface area of the KB and sulfonate group(SO3^-)of Nafion,respectively,which could physically and chemically trap the PSs.
基金The authors acknowledge funding from National Natural Science Foundation of China(52302307)Shaanxi Province(2023-ZDLGY-24,2023-JC-QN-0473)+2 种基金project funded by China Postdoctoral Science Foundation(2023MD734210)the Open Foundation of State Key Laboratory for Advanced Metals and Materials(2022-Z01)Shaanxi Provincial Department of Education industrialization project(21JC018).
文摘Engineering transition metal compounds(TMCs)catalysts with excellent adsorption-catalytic ability has been one of the most effec-tive strategies to accelerate the redox kinetics of sulfur cathodes.Herein,this review focuses on engineering TMCs catalysts by cation doping/anion doping/dual doping,bimetallic/bi-anionic TMCs,and TMCs-based heterostructure composites.It is obvious that introducing cations/anions to TMCs or constructing heterostructure can boost adsorption-catalytic capacity by regulating the electronic structure including energy band,d/p-band center,electron filling,and valence state.Moreover,the elec-tronic structure of doped/dual-ionic TMCs are adjusted by inducing ions with different electronegativity,electron filling,and ion radius,resulting in electron redistribution,bonds reconstruction,induced vacancies due to the electronic interaction and changed crystal structure such as lat-tice spacing and lattice distortion.Different from the aforementioned two strategies,heterostructures are constructed by two types of TMCs with different Fermi energy levels,which causes built-in electric field and electrons transfer through the interface,and induces electron redistribution and arranged local atoms to regulate the electronic structure.Additionally,the lacking studies of the three strategies to comprehensively regulate electronic structure for improving catalytic performance are pointed out.It is believed that this review can guide the design of advanced TMCs catalysts for boosting redox of lithium sulfur batteries.
基金financially supported by the National Natural Science Foundation of China(Grant Nos.51871060,52071084 and 51831009)Recruit Program of Global Youth Experts and Fudan’s Undergraduate Research Opportunities Program(FDUROP)。
文摘The practical application of lithium-sulfur batteries is severely hampered by the poor conductivity,polysulfide shuttle effect and sluggish reaction kinetics of sulfur cathodes.Herein,a hierarchi-cally porous three-dimension(3D)carbon architecture assembled by cross-linked carbon leaves with implanted atomic Co-N4 has been deli-cately developed as an advanced sulfur host through a SiO_(2)-mediated zeolitic imidazolate framework-L(ZIF-L)strategy.The unique 3D architectures not only provide a highly conductive network for fast electron transfer and buffer the volume change upon lithiation-delithi-ation process but also endow rich interface with full exposure of Co-N4 active sites to boost the lithium polysulfides adsorption and conversion.Owing to the accelerated kinetics and suppressed shuttle effect,the as-prepared sulfur cathode exhibits a superior electrochemical perfor-mance with a high reversible specific capacity of 695 mAh g^(−1) at 5 C and a low capacity fading rate of 0.053%per cycle over 500 cycles at 1 C.This work may provide a promising solution for the design of an advanced sulfur-based cathode toward high-performance Li-S batteries.
基金supported by the National Natural Science Foundation of China(22179089)the Postgraduate Research&Practice Innovation Program of Jiangsu Province(KYCX23_3245)support from Suzhou Key Laboratory for Advanced Carbon Materials and Wearable Energy Technologies,Suzhou,China。
文摘Lithium-sulfur(Li-S) batteries have attracted considerable attention as one of the most appealing energy storage systems.Strenuous efforts have been devoted to tackling the tremendous challenges,mainly pertaining to the severe shuttle effect,sluggish redox kinetics and lithium dendritic growth.Single-atomic mediators as promising candidates exhibit impressive performance in addressing these intractable issues.Related research often utilizes a trial-and-error approach,proposing solutions to fabricate single-atomic materials with diversified features.However,comprehensive review articles especially targeting demand-driven preparation are still in a nascent stage.Inspired by these considerations,this review summarizes the design of single-atomic mediators based on the application case-studies in LiS batteries and other metal-sulfur systems.Emerging preparation routes represented by chemical vapor deposition technology are introduced in a demand-oriented classification.Finally,future research directions are proposed to foster the advancement of single-atomic mediators in Li-S realm.
文摘多孔碳材料由于具有优异的导电性,高的孔隙率以及可有效地吸附多硫化物等优点被广泛应用于锂硫电池.本文以植酸(PA)和三聚氰胺作为磷源和氮源,通过高温裂解法成功制备了N,P共掺杂的三维多孔碳纳米复合材料(FeNi/FeNiP@NP-C)作为载硫基质.FeNi/FeNiP@NP-C三维多孔碳骨架具有良好的导电性能,它不仅能够有效地吸附可溶性多硫化物,同时能够促进电子转移从而提高反应动力学.实验结果表明S@FeNi/FeNiP@NP-C正极有较好的电化学性能和循环稳定性,在硫负载量为1.0 mg cm^(-2)以及0.1C的电流密度下,S@FeNi/FeNiP@NPC电极可达到1035.8 mAh g^(-1)的初始放电比容量,在0.1 C电流密度及较高硫负载量(4.3 mg cm^(-2))下循环100圈后仍能保持435.5 mAh g-1的放电比容量.
文摘A nano sulfur-based composite cathode material featured by uniform core@shell-structured sulfur@polypyrrole nanoparticles sandwiched in three-dimensional graphene sheets conductive network（S@PPy/GS） is fabricated via a facile solution-based method. The S@PPy nanoparticles are synthesized by in situ chemical oxidative polymerization of pyrrole on the surface of sulfur particles,and then graphene sheets are covered outside the S@PPy nanoparticles,forming a three-dimensional conductive network. When evaluating the electrochemical performance of S@PPy/GS in a lithium–sulfur battery,it delivers large discharge capacity,excellent cycle stability,and good rate capability. The initial discharge capacity is up to 1040 m Ah/g at 0.1 C,the capacity can remain 537.8 m Ah/g at 0.2 C after 200 cycles,even at a higher rate of 1 C,the specific capacity still reaches 566.5 m Ah/g. The good electrochemical performance is attributed to the unique structure of S@PPy/GS,which can not only provide an excellent transport of lithium and electron ions within the electrodes,but also retard the shuttle effect of soluble lithium polysulfides effectively,thus plays a positive role in building better lithium-sulfur batteries.
基金supported by the Australian Research Council Future FellowshipDiscovery Projects and Griffith University Ph.D. Scholarships
文摘Extensive efforts have been devoted to the design of micro-, nano-, and/or molecular structures of sulfur hosts to address the challenges of lithium–sulfur(Li–S) batteries, yet comparatively little research has been carried out on the binders in Li–S batteries. Herein, we systematically review the polymer composite frameworks that confine the sulfur within the sulfur electrode, taking the roles of sulfur hosts and functions of binders into consideration. In particular, we investigate the binding mechanism between the binder and sulfur host(such as mechanical interlocking and interfacial interactions), the chemical interactions between the polymer binder and sulfur(such as covalent bonding, electrostatic bonding, etc.), as well as the beneficial functions that polymer binders can impart on Li–S cathodes, such as conductive binders, electrolyte intake, adhesion strength etc. This work could provide a more comprehensive strategy in designing sulfur electrodes for long-life, large-capacity and high-rate Li–S battery.
基金supported by the National Natural Science Foundation of China(Grant No.52072118,51772089 and 21872046)the Youth 1000 Talent Program of China+4 种基金the Outstanding Youth Scientist Foundation of Hunan Province(Grant No.2018JJ1009)the Natural Science Foundation of Hunan Province(Grant No.2020JJ4174)the Provincial Science and Technology Innovation Platform and Talent Plan-Changsha,Zhuzhou and Xiangtan High-level Talents Accumulation Project(Grant No.2017XK2023)the Research and Development Plan of Key Areas in Hunan Province(Grant No.2019GK2235)the Key Research and Development Program of Ningxia(2020BDE03007)。
文摘The lithium-sulfur battery(Li–S)is a promising energy storage system with many advantages over the commercialized lithium-ion battery.It has a high theoretical capacity of 1675 mAh gà1,a high theoretical energy density(2600 Wh kgà1),and is eco-environmentally friendly.Although only a small amount is used(<10 wt%)in the electrode,binders may affect the discharge capacity and cycling stability of sulfur cathodes in the Li–S battery.In recent years,tremendous efforts have been made to develop functional binders with robust adhesive strength,fast ion/electron transportation,strong anchoring of lithium polysulfide(LiPS),and rapid redox kinetics,to improve capacity,coulombic efficiency,and energy density.This article reviews recent developments in binders for the Li–S battery.After briefly introducing the fundamentals of the Li–S battery,the desireable characteristics of binders are discussed based on the correlation between the functions of the binder molecules and the performance of the battery.Future challenges in developing promising binders and potential solutions are provided in the conclusion.
基金supported by the National Natural Science Foundation of China (No.52222311)the Shanghai RisingStar Program (20QA1406600)+2 种基金ChEM,SPST of Shanghai Tech University (#EM02161943)Shanghai Science and Technology Plan (21DZ2260400)Double First-Class Initiative Fund of Shanghai Tech University for supporting
文摘The use of carbonized wood in various functional devices is attracting considerable attention due to its low cost,vertical channels,and high electrical conduction.However,the conventional carbonization method requires a long processing time and an inert atmosphere.Here,a microwave-assisted ultrafast carbonization technique was developed that carbonizes natural wood in seconds without the need for an inert atmosphere,and the obtained aligned-porous carbonized wood provided an excellent electrochemical performance as an anode material for lithium-ion batteries.This ultrafast carbonization technique simultaneously produced ZnO nanoparticles during the carbonization process that were uniformly distributed on the alignedporous carbon.The hierarchical structure of carbonized wood functionalized with ZnO nanoparticles was used as a host for achieving high-performance lithium-sulfur batteries:the highly conductive carbonized wood framework with vertical channels provided good electron transport pathways,and the homogeneously dispersed ZnO nanoparticles effectively adsorbed lithium polysulfide and catalyzed its conversion reactions.In summary,a new method was developed to realize the ultrafast carbonization of biomass materials with decorated metal oxide nanoparticles.
基金financially supported by the Beijing Municipal Science and Technology Project (No.Z171100000917021)。
文摘A high sulfur content sulfur–carbon composite was synthesized via in situ generation method in aqueous solution.When the sulfur loading is up to 90%,the electrode still exhibits good cycling performance with a reversible capacity of about 623 mAh·g^(-1)after 100 cycles.To further commercialize the Li–S battery,understanding the capacity degradation mechanism is very essential,especially with a high sulfur loading electrode.To achieve this goal,the electrochemical performance of the high sulfur loading electrode was studied,and the structure change of the electrode after cycling was also examined by ex situ scanning electron microscopy(SEM)and other techniques.The result shows that the Li_(2)S_(2)and Li_(2)S inhomogeneous precipitation contributes to the majority capacity fading of the high sulfur loading Li–S cells.
基金financially supported by the National Key Research and Development program of China(no.2016YFB0100200)Beijing Municipal Science and Technology Project(no.Z181100004518001)
文摘As a sulfur-containing cathode material,sulfide polyacrylonitrile(SPAN)is expected to be used for longlife lithium-sulfur battery because there is no shuttle effect occurred in its charge process.However,its specific capacity and discharge potential need to be further improved to satisfy the urgent demands for high-performance batteries.In this paper,Te0.045S0.955PAN composite was synthesized by co-heating TexS1-x and PAN,and the superior electrochemical performance to that of SPAN was obtained because of doping Te with high conductivity.The as-prepared Te0.045S0.955PAN composite possessed the specific capacity of 675 mAh g^-1 after 100 cycles at the current density of 0.1 A g^-1 with high capacity retention of96.6%compared to the second cycle.Especially,during cycling,Te0.045S0.955PAN showed average discharge voltages of 1.88-1.91 V,which were higher than 1.85-1.88 V for SPAN at the same current density.Thus doping Te provides a new strategy for increasing the energy density of SPAN.
基金financially supported by the National Natural Science Foundation of China(51971080)the Natural Science Foundation of Guangdong Province,China(2018A030313182)+1 种基金Shenzhen Bureau of Science,Technology and Innovation Commission(JCYJ20170811154527927)the Opening Project of State Key Laboratory of Advanced Chemical Power Sources。
文摘Lithium-sulfur battery is desirable for the future potential electrochemical energy storage device with advantages of high theoretical energy density,low cost and environmental friendliness.However,some natural hindrances,particularly fast capacity degradation resulting from the migration of dissolved polysulfide intermediates,remain to be significant challenges prior to the practical applications.In this work,a composite interlayer of carbon nanofibers(CNFs)which are enriched by Co-based metal organic frameworks(ZIF-67)growth in-situ is exploited.Notably,physical blocking and chemical trapping abilities are obtained synergistically from the ZIF/CNFs interlayer,which enables to restrain the dissolution of polysulfides and alleviate shuttle effect.Moreover,the three-dimensional fiber networks provide an interconnected conductive framework between each ZIF microreactor to promote fast electron transfer during cycling,thus contributing to excellent rate and cycling performance.As a result,Li-S cells with ZIF/CNFs interlayer show a high specific capacity of 1334 mAh g^(-1) at 1 C with an excellent cycling stability over 300 cycles.Besides,this scalable and affordable electrospinning fabrication method provides a promising approach for the design of MOFs-derived carbon materials for high performance Li-S batteries.
