Rechargeable Mg batteries(RMBs)have become one of the best subsitutes for lithium-ion batteries due to the high volumetric capacity,abundant resources,and uniform plating behavior of Mg metal anode.However,the safety ...Rechargeable Mg batteries(RMBs)have become one of the best subsitutes for lithium-ion batteries due to the high volumetric capacity,abundant resources,and uniform plating behavior of Mg metal anode.However,the safety hazard induced by the formation of high-modulue Mg dendrites under a high current density(10 mA cm^(-1))was still revealed in recent years.It has forced researchers to re-examine the safety of RMBs.In this review,the intrinsic safety factors of key components in RMBs,such as uneven plating,pitting and flammability of Mg anode,heat release and crystalline water decomposition of cathode,strong corrosion,low oxidition stability and flammability of electrolytes,and soforth,are systematacially summarized.Their origins,formation mechanisms,and possible safety hazards are deeply discussed.To develop high-performance Mg anode,current strategies including designing artificial SEI,three-dimensional substrates,and Mg alloys are summarized.For practical electrolytes,the configurations of boron-centered anions and simple Mg salts and the functionalized solvent with high boiling point and low flammability are suggested to comprehensively design.In addition,the future study should more focus on the investigation on the thermal runaway and decomposition of cathode materials and separa-tors.This review aims to provide fundamental insights into the relationship between electrochemistry and safety,further promoting the sustainable development of RMBs.展开更多
Rechargeable magnesium-metal batteries(RMMBs)are promising next-generation secondary batteries;however,their development is inhibited by the low capacity and short cycle lifespan of cathodes.Although various strategie...Rechargeable magnesium-metal batteries(RMMBs)are promising next-generation secondary batteries;however,their development is inhibited by the low capacity and short cycle lifespan of cathodes.Although various strategies have been devised to enhance the Mg^(2+)migration kinetics and structural stability of cathodes,they fail to improve electronic conductivity,rendering the cathodes incompatible with magnesium-metal anodes.Herein,we propose a dual-defect engineering strategy,namely,the incorporation of Mg^(2+)pre-intercalation defect(P-Mgd)and oxygen defect(Od),to simultaneously improve the Mg^(2+)migration kinetics,structural stability,and electronic conductivity of the cathodes of RMMBs.Using lamellar V_(2)O_(5)·nH_(2)O as a demo cathode material,we prepare a cathode comprising Mg_(0.07)V_(2)O_(5)·1.4H_(2)O nanobelts composited with reduced graphene oxide(MVOH/rGO)with P-Mgd and Od.The Od enlarges interlayer spacing,accelerates Mg^(2+)migration kinetics,and prevents structural collapse,while the P-Mgd stabilizes the lamellar structure and increases electronic conductivity.Consequently,the MVOH/rGO cathode exhibits a high capacity of 197 mAh g^(−1),and the developed Mg foil//MVOH/rGO full cell demonstrates an incredible lifespan of 850 cycles at 0.1 A g^(−1),capable of powering a light-emitting diode.The proposed dual-defect engineering strategy provides new insights into developing high-durability,high-capacity cathodes,advancing the practical application of RMMBs,and other new secondary batteries.展开更多
M-N-C(M=Fe,Co,Ni,etc.) catalyst owns high catalytic activity in the oxygen catalytic reaction which is the most likely to replace the Pt-based catalysts.But it is still a challenge to further increase the active site ...M-N-C(M=Fe,Co,Ni,etc.) catalyst owns high catalytic activity in the oxygen catalytic reaction which is the most likely to replace the Pt-based catalysts.But it is still a challenge to further increase the active site density.This article constructs the high-efficiency FeMn-N/S-C-1000 catalyst to realize ORR/OER bifunctional catalysis by hetero-atom,bimetal(Fe,Mn) doped simultaneously strategy.When evaluated it as bi-functional electro-catalysts,FeMn-N/S-C-1000 exhibits excellent catalytic activity(E_(1/2)=0.924 V,E_(j=10)=1.617 V) in alkaline media,outperforms conventional Pt/C,RuO_(2) and most non-precious-metal catalysts reported recently,Such outstanding performance is owing to N,S co-coordinated with metal to form multi-types of single atom,dual atom active sites to carry out bi-catalysis.Importantly,nitrite poison test provides the proof that the active sites of FeMn-N/S-C are more than that of single-atom catalysts to promote catalytic reactions directly.To better understand the local structure of Fe and Mn active sites,XAS and DFT were employed to reveal that FeMn-N_5/S-C site plays the key role during catalysis.Notably,the FeMn-N/S-C-1000 based low-temperature rechargeable flexible Zn-air also exhibits superior discharge performance and extraordinary durability at-40℃.This work will provide a new idea to design diatomic catalysts applied in low-temperature rechargeable batteries.展开更多
The shuttle effect of lithium polysulfides(LiPSs)and uncontrollable lithium dendrite growth seriously hinder the practical application of lithium-sulfur(Li-S)batteries.To simultaneously address such issues,monodispers...The shuttle effect of lithium polysulfides(LiPSs)and uncontrollable lithium dendrite growth seriously hinder the practical application of lithium-sulfur(Li-S)batteries.To simultaneously address such issues,monodispersed Nb N quantum dots anchored on nitrogen-doped hollow carbon nanorods(NbN@NHCR)are elaborately developed as efficient Li PSs immobilizer and Li stabilizer for high-performance Li-S full batteries.Density functional theory(DFT)calculations and experimental characterizations demonstrate that the sulfiphilic and lithiophilic NbN@NHCR hybrid can not only efficiently immobilize the soluble Li PSs and facilitate diffusion-conversion kinetics for alleviating the shuttling effect,but also homogenize the distribution of Li+ions and regulate uniform Li deposition for suppressing Li-dendrite growth.As a result,the assembled Li-S full batteries(NbN@NHCR-S||Nb N@NHCR-Li)deliver excellent long-term cycling stability with a low decay rate of 0.031%per cycle over 1000 cycles at high rate of 2 C.Even at a high S loading of 5.8 mg cm^(-2)and a low electrolyte/sulfur ratio of 5.2μL mg^(-1),a large areal capacity of 6.2 mA h cm^(-2)can be achieved in Li-S pouch cell at 0.1 C.This study provides a new perspective via designing a dual-functional sulfiphilic and lithiophilic hybrid to address serious issues of the shuttle effect of S cathode and dendrite growth of Li anode.展开更多
As a critical role in battery systems,polymer binders have been shown to efficiently suppress the lithium polysulfide shuttling and accommodate volume changes in recent years.However,preparation processes and safety,a...As a critical role in battery systems,polymer binders have been shown to efficiently suppress the lithium polysulfide shuttling and accommodate volume changes in recent years.However,preparation processes and safety,as the key criterions for Li-S batteries'practical applications,still attract less attention.Herein,an aqueous multifunction binder(named PEI-TIC)is prepared via an easy and fast epoxy-amine ring-opening reaction(10 min),which can not only give the sulfur cathode a stable mechanical property,a strong chemical adsorption and catalytic conversion ability,but also a fire safety improvement.The Li-S batteries based on the PEI-TIC binder display a high discharge capacity(1297.8 mAh g^(-1)),superior rate performance(823.0 mAh g^(-1)at 2 C),and an ultralow capacity decay rate of 0.035%over more than 800 cycles.Even under 7.1 mg cm^(-2)S-loaded,the PEI-TIC electrode can also achieve a high areal capacity of 7.2 mA h g^(-1)and excellent cycling stability,confirming its application potential.Moreover,it is also noted that TG-FTIR test is performed for the first time to explore the flame-retardant mechanism of polymer binders.This work provides an economically and environmentally friendly binder for the practical application and inspires the exploration of the flame-retardant mechanism of all electrode components.展开更多
Precision engineering of catalytic sites to guide more favorable pathways for Li_(2)O_(2) nucleation and decom-position represents an enticing kinetic strategy for mitigating overpotential,enhancing discharge capac-it...Precision engineering of catalytic sites to guide more favorable pathways for Li_(2)O_(2) nucleation and decom-position represents an enticing kinetic strategy for mitigating overpotential,enhancing discharge capac-ity,and improving recycling stability of Li-O_(2) batteries.In this work,we employ metal-organic frameworks(MOFs)derivation and ion substitution strategies to construct atomically dispersed Mn-N_(4) moieties on hierarchical porous nitrogen-doped carbon(Mn SAs-NC)with the aim of reducing the over-potential and improving the cycling stability of Li-O_(2) batteries.The porous structure provides more chan-nels for mass transfer and exposes more highly active sites for electrocatalytic reactions,thus promoting the formation and decomposition of Li_(2)O_(2).The Li-O_(2) batteries with Mn SAs-NC cathode achieve lower overpotential,higher specific capacity(14290 mA h g^(-1) at 100 mAg^(-1)),and superior cycle stability(>100 cycles at 200 mA g^(-1))compared with the Mn NPs-NC and NC.Density functional theory(DFT)cal-culations reveal that the construction of Mn-N_(4) moiety tunes the charge distribution of the pyridinic N-rich vacancy and balances the affinity of the intermediates(LiO_(2) and Li_(2)O_(2)).The initial nucleation of Li_(2)O_(2) on Mn SAs-NC favors the O_(2)-→LiO_(2)→Li_(2)O_(2) surface-adsorption pathway,which mitigates the overpoten-tials of the oxygen reduction(ORR)and oxygen evolution reaction(OER).As a result,Mn SAs-NC with Mn-N_(4) moiety effectively facilitates the Li_(2)O_(2) nucleation and enables its reversible decomposition.This work establishes a methodology for constructing carbon-based electrocatalysts with high activity and selectivity for Li-O_(2)batteries.展开更多
Use of metallic Li anode raises serious concerns on the safety and operational performance of Li-S batteries due to uncontrolled hazard of Li dendrite formation, which is difficultly eliminated as long as the metallic...Use of metallic Li anode raises serious concerns on the safety and operational performance of Li-S batteries due to uncontrolled hazard of Li dendrite formation, which is difficultly eliminated as long as the metallic Li exists in the cells. Pairing lithium sulfide (Li2S) cathode with currently available metallic Lifree high-capacity anodes offers an alternative solution to this challenge. However, the performance of Li2S cathode is primarily restricted by high activation barrier upon initial charge, low active mass utilization and sluggish redox kinetics. Herein, a MXene-induced multifunctional collaborative interface is proposed to afford superb activity towards redox solid-liquid/liquid-liquid phase transformation, strong chemisorption, high conductivity and fast ionic/charge transport in high Li2S loading cathode. Applying collaborative interface effectively reduces initial voltage barrier of Li2S activation and regulates the kinetic behavior of redox polysulfide conversion. Therefore, stable operation of additive-free Li2S cathode with high areal capacities at high Li2S loading up to 9 mg cm^-2 can be achieved with less sacrifice of high capacity and rate capability in Li-S batteries. Rechargeable metallic Li-free batteries are successfully constructed by pairing this high-performance Li2S cathode with high-capacity metal oxide anodes, which delivers superior energy density to current Li-ion batteries.展开更多
Three-dimensional(3D)printing,an additive manufacturing technique,is widely employed for the fabrication of various electrochemical energy storage devices(EESDs),such as batteries and supercapacitors,ranging from nano...Three-dimensional(3D)printing,an additive manufacturing technique,is widely employed for the fabrication of various electrochemical energy storage devices(EESDs),such as batteries and supercapacitors,ranging from nanoscale to macroscale.This technique offers excellent manufacturing flexibility,geometric designability,cost-effectiveness,and eco-friendliness.Recent studies have focused on the utilization of 3D-printed critical materials for EESDs,which have demonstrated remarkable electrochemical performances,including high energy densities and rate capabilities,attributed to improved ion/electron transport abilities and fast kinetics.However,there is a lack of comprehensive reviews summarizing and discussing the recent advancements in the structural design and application of 3D-printed critical materials for EESDs,particularly rechargeable batteries.In this review,we primarily concentrate on the current progress in 3D printing(3DP)critical materials for emerging batteries.We commence by outlining the key characteristics of major 3DP methods employed for fabricating EESDs,encompassing design principles,materials selection,and optimization strategies.Subsequently,we summarize the recent advancements in 3D-printed critical materials(anode,cathode,electrolyte,separator,and current collector)for secondary batteries,including conventional Li-ion(LIBs),Na-ion(SIBs),K-ion(KIBs)batteries,as well as Li/Na/K/Zn metal batteries,Zn-air batteries,and Ni–Fe batteries.Within these sections,we discuss the 3DP precursor,design principles of 3D structures,and working mechanisms of the electrodes.Finally,we address the major challenges and potential applications in the development of 3D-printed critical materials for rechargeable batteries.展开更多
An emerging practice in the realm of Li-S batteries lies in the employment of single-atom catalysts(SACs)as effective mediators to promote polysulfide conversion,but monometallic SACs affording isolated geometric disp...An emerging practice in the realm of Li-S batteries lies in the employment of single-atom catalysts(SACs)as effective mediators to promote polysulfide conversion,but monometallic SACs affording isolated geometric dispersion and sole electronic configuration limit the catalytic benefits and curtail the cell performance.Here,we propose a class of dual-atom catalytic moieties comprising hetero-or homo-atomic pairs anchored on N-doped graphene(NG)to unlock the liquid–solid redox puzzle of sulfur,readily realizing Li-S full cell under high-rate-charging conditions.As for Fe-Ni-NG,in-depth experimental and theoretical analysis reveal that the hetero-atomic orbital coupling leads to altered energy levels,unique electronic structures,and varied Fe oxidation states in comparison with homo-atomic structures(FeFe-NG or Ni-Ni-NG).This would weaken the bonding energy of polysulfide intermediates and thus enable facile electrochemical kinetics to gain rapid liquid-solid Li_(2)S_(4)?Li_(2)S conversion.Encouragingly,a Li-S battery based on the S@Fe-Ni-NG cathode demonstrates unprecedented fast-charging capability,documenting impressive rate performance(542.7 mA h g^(-1)at 10.0 C)and favorable cyclic stability(a capacity decay of 0.016%per cycle over 3000 cycles at 10.0 C).This finding offers insights to the rational design and application of dual-atom mediators for Li-S batteries.展开更多
Efficient bifunctional catalysts for oxygen reduction reaction(ORR)and oxygen evolution reaction(OER)are vital for rechargeable Zn-air batteries(ZABs).Herein,an oxygen-respirable sponge-like Co@C–O–Cs catalyst with ...Efficient bifunctional catalysts for oxygen reduction reaction(ORR)and oxygen evolution reaction(OER)are vital for rechargeable Zn-air batteries(ZABs).Herein,an oxygen-respirable sponge-like Co@C–O–Cs catalyst with oxygen-rich active sites was designed and constructed for both ORR and OER by a facile carbon dot-assisted strategy.The aerophilic triphase interface of Co@C–O–Cs cathode efficiently boosts oxygen diffusion and transfer.The theoretical calculations and experimental studies revealed that the Co–C–COC active sites can redistribute the local charge density and lower the reaction energy barrier.The Co@C–O–Cs catalyst displays superior bifunctional catalytic activities with a half-wave potential of 0.82 V for ORR and an ultralow overpotential of 294 mV at 10 mA cm^(−2) for OER.Moreover,it can drive the liquid ZABs with high peak power density(106.4 mW cm^(−2)),specific capacity(720.7 mAh g^(−1)),outstanding long-term cycle stability(over 750 cycles at 10 mA cm^(−2)),and exhibits excellent feasibility in flexible all-solid-state ZABs.These findings provide new insights into the rational design of efficient bifunctional oxygen catalysts in rechargeable metal-air batteries.展开更多
The commercial viability of lithium-sulfur batteries is still challenged by the notorious lithium polysulfides(Li PSs)shuttle effect on the sulfur cathode and uncontrollable Li dendrites growth on the Li anode.Herein,...The commercial viability of lithium-sulfur batteries is still challenged by the notorious lithium polysulfides(Li PSs)shuttle effect on the sulfur cathode and uncontrollable Li dendrites growth on the Li anode.Herein,a bi-service host with Co-Fe binary-metal selenide quantum dots embedded in three-dimensional inverse opal structured nitrogen-doped carbon skeleton(3DIO FCSe-QDs@NC)is elaborately designed for both sulfur cathode and Li metal anode.The highly dispersed FCSe-QDs with superb adsorptive-catalytic properties can effectively immobilize the soluble Li PSs and improve diffusion-conversion kinetics to mitigate the polysulfide-shutting behaviors.Simultaneously,the 3D-ordered porous networks integrated with abundant lithophilic sites can accomplish uniform Li deposition and homogeneous Li-ion flux for suppressing the growth of dendrites.Taking advantage of these merits,the assembled Li-S full batteries with 3DIO FCSe-QDs@NC host exhibit excellent rate performance and stable cycling ability(a low decay rate of 0.014%over 2,000 cycles at 2C).Remarkably,a promising areal capacity of 8.41 mAh cm^(-2)can be achieved at the sulfur loading up to 8.50 mg cm^(-2)with an ultra-low electrolyte/sulfur ratio of 4.1μL mg^(-1).This work paves the bi-serve host design from systematic experimental and theoretical analysis,which provides a viable avenue to solve the challenges of both sulfur and Li electrodes for practical Li-S full batteries.展开更多
Sulfur-rich polymers have gained a great deal of attention as the next-generation active materials in lithium-sulfur(Li-S)batteries due to their low cost,environmental compatibility,naturally sulfur uniform dispersion...Sulfur-rich polymers have gained a great deal of attention as the next-generation active materials in lithium-sulfur(Li-S)batteries due to their low cost,environmental compatibility,naturally sulfur uniform dispersion,and distinctive structure covalently bonding with sulfur atoms.However,the poor electrical conductivity and undesirable additional shuttle effect still hinder the commercial application of sulfur-rich polymers.Herein,we report a flexible semi-immobilization strategy to prepare allylterminated hyperbranched poly(ethyleneimine)-functionalized reduced graphene oxide(A-PEI-EGO)as sulfur-rich copolymer backbone.The semi-immobilization strategy can effectively reconcile the demand for polymer skeleton and conductive substrates through forming quaternary ammonium groups and reducing oxygen-containing functional groups,resulting in enhanced skeleton adsorption capacity and substrate electronic conductivity,respectively.Furthermore,the stable covalent bonding connection based on polymer molecules(A-PEI)not only completely prevents the additional shuttle effect of lithiation organic molecules and even sulfur-rich oligomers,but provides more inverse vulcanization active sites.As a result,the as-prepared A-PEI-EGO-S cathodes display an initial discharge capacity of1338 m A h g^(-1)at a rate of 0.1 C and an outstanding cycling stability of 0.046%capacity decay per cycle over 600 cycles.Even under 6.2 mg cm^(-2)S-loaded and sparing electrolyte of 6μL mg^(-1),the A-PEI-EGO-S cathode can also achieve a superior cycling performance of 98%capacity retention after 60 cycles,confirming its application potential.展开更多
Zinc–bromine rechargeable batteries(ZBRBs)are one of the most powerful candidates for next-generation energy storage due to their potentially lower material cost,deep discharge capability,non-flammable electrolytes,r...Zinc–bromine rechargeable batteries(ZBRBs)are one of the most powerful candidates for next-generation energy storage due to their potentially lower material cost,deep discharge capability,non-flammable electrolytes,relatively long lifetime and good reversibility.However,many opportunities remain to improve the efficiency and stability of these batteries for long-life operation.Here,we discuss the device configurations,working mechanisms and performance evaluation of ZBRBs.Both non-flow(static)and flow-type cells are highlighted in detail in this review.The fundamental electrochemical aspects,including the key challenges and promising solutions,are discussed,with particular attention paid to zinc and bromine half-cells,as their performance plays a critical role in determining the electrochemical performance of the battery system.The following sections examine the key performance metrics of ZBRBs and assessment methods using various ex situ and in situ/operando techniques.The review concludes with insights into future developments and prospects for high-performance ZBRBs.展开更多
Lithium sulfur batteries are regarded as a promising candidate for high-energy-density energy storage devices.However,the lithium metal anode in lithium-sulfur batteries encounters the problem of lithium dendrites and...Lithium sulfur batteries are regarded as a promising candidate for high-energy-density energy storage devices.However,the lithium metal anode in lithium-sulfur batteries encounters the problem of lithium dendrites and lithium metal consumption caused by polysulfide corrosion.Herein we design a dualfunction PMMA/PPC/LiNO3composite as an artificial solid electrolyte interphase(PMCN-SEI)to protect Li metal anode.This SEI offers multiple sites of C=O for polysulfide anchoring to constrain corrosion of Li metal anode.The lithiated polymer group and Li3N in PMCN-SEI can homogenize lithium-ion deposition behavior to achieve a dendrite-free anode.As a result,the PMCN-SEI protected Li metal anode enables the Li||Li symmetric batteries to maintain over 300 cycles(1300 h)at a capacity of 5 m Ah cm^(-2),corresponding to a cumulative capacity of 3.25 Ah cm^(-2).Moreover,Li-S batteries assembled with 20μm of Li metal anode(N/P=1.67)still deliver an initial capacity of 1166 m A h g-1at 0.5C.Hence,introducing polycarbonate polymer/inorganic composite SEI on Li provides a new solution for achieving the high energy density of Li-S batteries.展开更多
Cu-based cathodes in aqueous batteries become very attractive in view of high theoretical capacity,moderate operation voltage and rich reserves of raw materials.However,their applications are obstructed by serious sid...Cu-based cathodes in aqueous batteries become very attractive in view of high theoretical capacity,moderate operation voltage and rich reserves of raw materials.However,their applications are obstructed by serious side reactions.The side reaction mainly arises from the spontaneous formation of Cu_(2)O,which occupies the electrode surface and lowers the reaction reversibility.Here,Na_(2)EDTA is introduced to address these issues.Both experimental results and theoretical calculations indicate that the Na_(2)EDTA reshapes the solvation structure of Cu^(2+)and modifies the electrode/electrolyte interface.Therefore,the redox potential of Cu^(2+)/Cu_(2)O is reduced and the surface of Cu is protected from H2O,thereby inhibiting the formation of Cu_(2)O.Meanwhile,the change in the solvation structure reduces the electrostatic repulsion between Cu^(2+)and the cathode,leading to high local concentration and benefiting uniform deposition.The results shed light on the applications of rechargeable Cu-based batteries.展开更多
The next-generation energy storage systems such as fuel cells,metal-air batteries,and alkali metal(Li,Na)-chalcogen(S,Se)batteries have received increasing attention owing to their high energy density and low cost.How...The next-generation energy storage systems such as fuel cells,metal-air batteries,and alkali metal(Li,Na)-chalcogen(S,Se)batteries have received increasing attention owing to their high energy density and low cost.However,one of the main obstacles of these systems is the poor reaction kinetics in the involved chemical reactions.Therefore,it is essential to incorporate suitable and efficient catalysts into the cell.These years,single-atom catalysts(SACs)are emerging as a frontier in catalysis due to their maximum atom efficiency and unique reaction selectivity.For SACs fabrication,metal-organic frameworks(MOFs)have been confirmed as promising templates or precursors due to their high metal loadings,structural adjustability,porosity,and tailorable catalytic site.In this review,we summarize effective strategies for fabricating SACs by MOFs with corresponding advanced characterization techniques and illustrate the key role of MOFs-based SACs in these batteries by explaining their reaction mechanisms and challenges.Finally,current applications,prospects,and opportunities for MOFs-based SACs in energy storage systems are discussed.展开更多
Rational design and exploration of low-cost and robust bifunctional oxygen electrocatalysts are vitally important for developing high-performance zinc-air batteries(ZABs).Herein,we reported a facile yet cost-efficient...Rational design and exploration of low-cost and robust bifunctional oxygen electrocatalysts are vitally important for developing high-performance zinc-air batteries(ZABs).Herein,we reported a facile yet cost-efficient approach to construct a bifunctional oxygen reduction reaction(ORR)/oxygen evolution reaction(OER)electrocatalyst composed of N-doped porous carbon nanosheet flowers decorated with Fe Co nanoparticles(Fe Co/N-CF).Rational design of this catalyst is achieved by designing Schiff-base polymer with unique molecular structure via hydrogen bonding of cyanuramide and terephthalaldehyde polycondensate in the presence of metal cations.It exhibits excellent activity and stability for electrocatalysis of ORR/OER,enabling ZAB with a high peak power density of 172 m W cm^(-2)and a large specific capacity of 811 m A h g^(-1)Znat large current.The rechargeable ZAB demonstrates excellent durability for 1000 h with slight voltage decay,far outperforming a couple of precious Pt/Ir-based catalysts.Density functional theory(DFT)calculations reveal that high activity of bimetallic Fe Co stems from enhanced O_(2)and OH-adsorption and accelerated O_(2)dissociation by OAO bond activation.展开更多
Rechargeable magnesium batteries(RMBs)are considered the promising candidates for post lithium-ion batteries due to the abundant storage,high capacity,and dendrite-rare characteristic of Mg anode.However,the lack of p...Rechargeable magnesium batteries(RMBs)are considered the promising candidates for post lithium-ion batteries due to the abundant storage,high capacity,and dendrite-rare characteristic of Mg anode.However,the lack of practical electrolytes impedes the development and application of RMBs.Here,through a one-step reaction of LiCl congenital-containing Knochel–Hauser base TMPL(2,2,6,6-tetrame thylpiperidinylmagnesium chloride lithium chloride complex)with Lewis acid AlCl_(3),we successfully synthesized an efficient amino-magnesium halide TMPLA electrolyte.Raman and mass spectroscopy identified that the electrolyte comprises the typical di-nuclear copolymer[Mg_(2)Cl_(3)·6THF]+cation group and[(TMP)2AlCl_(2)]-anion group,further supported by the results of density functional theory calculations(DFT)and the Molecular dynamics(MD)simulations.The TMPLA electrolyte exhibits promising electrochemical performance,including available anodic stability(>2.65 V vs.SS),high ionic conductivity(6.05mS cm^(-1)),and low overpotential(<0.1 V)as well as appropriate Coulombic efficiency(97.3%)for Mg plating/stripping.Both the insertion Mo6S8cathode and conversion Cu S cathode delivered a desirable electrochemical performance with high capacity and good cycling stability based on the TMPLA electrolyte.In particular,when compatible with low cost and easily synthesized Cu S,the Cu S||Mg cell displayed an extremely high discharge capacity of 458.8 mAh g^(-1)for the first cycle and stabilized at 170.2 mAh g^(-1)with high Coulombic efficiency(99.1%)after 50 cycles at 0.05 C.Our work proposes an efficient electrolyte with impressive compatibility with Mg anode and insertion/conversion cathode for practical RMBs and provides a more profound knowledge of the Lewis acid–base reaction mechanisms.展开更多
Rechargeable aluminum batteries(RABs)are attractive cadidates for next-generation energy storage and conversion,due to the low cost and high safety of Al resources,and high capacity of metal Al based on the three-elec...Rechargeable aluminum batteries(RABs)are attractive cadidates for next-generation energy storage and conversion,due to the low cost and high safety of Al resources,and high capacity of metal Al based on the three-electrons reaction mechanism.However,the development of RABs is greatly limited,because of the lack of advanced cathode materials,and their complicated and unclear reaction mechanisms.Exploring the novel nanostructured transition metal and carbon composites is an effective route for obtaining ideal cathode materials.In this work,we synthesize porous CoSnO_(3)/C nanocubes with oxygen vacancies for utilizing as cathodes in RABs for the first time.The intrinsic structure stability of the mixed metal cations and carbon coating can improve the cycling performance of cathodes by regulating the internal strains of the electrodes during volume expansion.The nanocubes with porous structures contribute to fast mass transportation which improves the rate capability.In addition to this,abundant oxygen vacancies promote the adsorption affinity of cathodes,which improves storage capacity.As a result,the CoSnO_(3)/C cathodes display an excellent reversible capacity of 292.1 mAh g^(-1) at 0.1 A g^(-1),a good rate performance with 109 mAh g^(-1) that is maintained even at 1 A g^(-1) and the provided stable cycling behavior for 500 cycles.Besides,a mechanism of intercalation of Al^(3+)within CoSnO_(3)/C cathode is proposed for the electrochemical process.Overall,this work provides a step toward the development of advanced cathode materials for RABs by engineering novel nanostructured mixed transition-metal oxides with carbon composite and proposes novel insights into chemistry for RABs.展开更多
Lithium–sulfur(Li–S)batteries are supposed to be one of the most potential next-generation batteries owing to their high theoretical capacity and low cost.Nevertheless,the shuttle effect of firm multi-step two-elect...Lithium–sulfur(Li–S)batteries are supposed to be one of the most potential next-generation batteries owing to their high theoretical capacity and low cost.Nevertheless,the shuttle effect of firm multi-step two-electron reaction between sulfur and lithium in liquid electrolyte makes the capacity much smaller than the theoretical value.Many methods were proposed for inhibiting the shuttle effect of polysulfide,improving corresponding redox kinetics and enhancing the integral performance of Li–S batteries.Here,we will comprehensively and systematically summarize the strategies for inhibiting the shuttle effect from all components of Li–S batteries.First,the electrochemical principles/mechanism and origin of the shuttle effect are described in detail.Moreover,the efficient strategies,including boosting the sulfur conversion rate of sulfur,confining sulfur or lithium polysulfides(LPS)within cathode host,confining LPS in the shield layer,and preventing LPS from contacting the anode,will be discussed to suppress the shuttle effect.Then,recent advances in inhibition of shuttle effect in cathode,electrolyte,separator,and anode with the aforementioned strategies have been summarized to direct the further design of efficient materials for Li–S batteries.Finally,we present prospects for inhibition of the LPS shuttle and potential development directions in Li–S batteries.展开更多
基金supported by the National Key R&D Program of China(No.2023YFB3809500)the National Natural Science Foundation of China(No.U23A20555,52202211)+1 种基金the Ninth Young Elite Scientists Sponsorship Program by CAST(2023QNRC001)the Chongqing Technology Innovation and Application Development Project(No.CSTB2022TIAD-KPX0028).
文摘Rechargeable Mg batteries(RMBs)have become one of the best subsitutes for lithium-ion batteries due to the high volumetric capacity,abundant resources,and uniform plating behavior of Mg metal anode.However,the safety hazard induced by the formation of high-modulue Mg dendrites under a high current density(10 mA cm^(-1))was still revealed in recent years.It has forced researchers to re-examine the safety of RMBs.In this review,the intrinsic safety factors of key components in RMBs,such as uneven plating,pitting and flammability of Mg anode,heat release and crystalline water decomposition of cathode,strong corrosion,low oxidition stability and flammability of electrolytes,and soforth,are systematacially summarized.Their origins,formation mechanisms,and possible safety hazards are deeply discussed.To develop high-performance Mg anode,current strategies including designing artificial SEI,three-dimensional substrates,and Mg alloys are summarized.For practical electrolytes,the configurations of boron-centered anions and simple Mg salts and the functionalized solvent with high boiling point and low flammability are suggested to comprehensively design.In addition,the future study should more focus on the investigation on the thermal runaway and decomposition of cathode materials and separa-tors.This review aims to provide fundamental insights into the relationship between electrochemistry and safety,further promoting the sustainable development of RMBs.
基金supported by the National Natural Science Foundation of China(52222407).
文摘Rechargeable magnesium-metal batteries(RMMBs)are promising next-generation secondary batteries;however,their development is inhibited by the low capacity and short cycle lifespan of cathodes.Although various strategies have been devised to enhance the Mg^(2+)migration kinetics and structural stability of cathodes,they fail to improve electronic conductivity,rendering the cathodes incompatible with magnesium-metal anodes.Herein,we propose a dual-defect engineering strategy,namely,the incorporation of Mg^(2+)pre-intercalation defect(P-Mgd)and oxygen defect(Od),to simultaneously improve the Mg^(2+)migration kinetics,structural stability,and electronic conductivity of the cathodes of RMMBs.Using lamellar V_(2)O_(5)·nH_(2)O as a demo cathode material,we prepare a cathode comprising Mg_(0.07)V_(2)O_(5)·1.4H_(2)O nanobelts composited with reduced graphene oxide(MVOH/rGO)with P-Mgd and Od.The Od enlarges interlayer spacing,accelerates Mg^(2+)migration kinetics,and prevents structural collapse,while the P-Mgd stabilizes the lamellar structure and increases electronic conductivity.Consequently,the MVOH/rGO cathode exhibits a high capacity of 197 mAh g^(−1),and the developed Mg foil//MVOH/rGO full cell demonstrates an incredible lifespan of 850 cycles at 0.1 A g^(−1),capable of powering a light-emitting diode.The proposed dual-defect engineering strategy provides new insights into developing high-durability,high-capacity cathodes,advancing the practical application of RMMBs,and other new secondary batteries.
基金supported by the National Natural Science Foundation of China(21603171)the Basic Research Foundation of Xi’an Jiaotong University(xjh012020027)。
文摘M-N-C(M=Fe,Co,Ni,etc.) catalyst owns high catalytic activity in the oxygen catalytic reaction which is the most likely to replace the Pt-based catalysts.But it is still a challenge to further increase the active site density.This article constructs the high-efficiency FeMn-N/S-C-1000 catalyst to realize ORR/OER bifunctional catalysis by hetero-atom,bimetal(Fe,Mn) doped simultaneously strategy.When evaluated it as bi-functional electro-catalysts,FeMn-N/S-C-1000 exhibits excellent catalytic activity(E_(1/2)=0.924 V,E_(j=10)=1.617 V) in alkaline media,outperforms conventional Pt/C,RuO_(2) and most non-precious-metal catalysts reported recently,Such outstanding performance is owing to N,S co-coordinated with metal to form multi-types of single atom,dual atom active sites to carry out bi-catalysis.Importantly,nitrite poison test provides the proof that the active sites of FeMn-N/S-C are more than that of single-atom catalysts to promote catalytic reactions directly.To better understand the local structure of Fe and Mn active sites,XAS and DFT were employed to reveal that FeMn-N_5/S-C site plays the key role during catalysis.Notably,the FeMn-N/S-C-1000 based low-temperature rechargeable flexible Zn-air also exhibits superior discharge performance and extraordinary durability at-40℃.This work will provide a new idea to design diatomic catalysts applied in low-temperature rechargeable batteries.
基金supported by the open research fund of Songshan Lake Materials Laboratory (2022SLABFN26)the National Natural Science Foundation of China (21773024)+1 种基金the Sichuan Science and Technology program (2020YJ0324,2020YJ0262)the Reformation and Development Funds for Local Region Universities from China Government in 2020 (ZCKJ 2020-11)。
文摘The shuttle effect of lithium polysulfides(LiPSs)and uncontrollable lithium dendrite growth seriously hinder the practical application of lithium-sulfur(Li-S)batteries.To simultaneously address such issues,monodispersed Nb N quantum dots anchored on nitrogen-doped hollow carbon nanorods(NbN@NHCR)are elaborately developed as efficient Li PSs immobilizer and Li stabilizer for high-performance Li-S full batteries.Density functional theory(DFT)calculations and experimental characterizations demonstrate that the sulfiphilic and lithiophilic NbN@NHCR hybrid can not only efficiently immobilize the soluble Li PSs and facilitate diffusion-conversion kinetics for alleviating the shuttling effect,but also homogenize the distribution of Li+ions and regulate uniform Li deposition for suppressing Li-dendrite growth.As a result,the assembled Li-S full batteries(NbN@NHCR-S||Nb N@NHCR-Li)deliver excellent long-term cycling stability with a low decay rate of 0.031%per cycle over 1000 cycles at high rate of 2 C.Even at a high S loading of 5.8 mg cm^(-2)and a low electrolyte/sulfur ratio of 5.2μL mg^(-1),a large areal capacity of 6.2 mA h cm^(-2)can be achieved in Li-S pouch cell at 0.1 C.This study provides a new perspective via designing a dual-functional sulfiphilic and lithiophilic hybrid to address serious issues of the shuttle effect of S cathode and dendrite growth of Li anode.
基金the support from National Outstanding Youth Science Fund Project of National Natural Science Foundation of China(52222314)CNPC Innovation Fund(2021DQ02-1001)+2 种基金Liao Ning Revitalization Talents Program(XLYC1907144)Xinghai Talent Cultivation Plan(X20200303)Fundamental Research Funds for the Central Universities(DUT22JC02,DUT22LAB605)
文摘As a critical role in battery systems,polymer binders have been shown to efficiently suppress the lithium polysulfide shuttling and accommodate volume changes in recent years.However,preparation processes and safety,as the key criterions for Li-S batteries'practical applications,still attract less attention.Herein,an aqueous multifunction binder(named PEI-TIC)is prepared via an easy and fast epoxy-amine ring-opening reaction(10 min),which can not only give the sulfur cathode a stable mechanical property,a strong chemical adsorption and catalytic conversion ability,but also a fire safety improvement.The Li-S batteries based on the PEI-TIC binder display a high discharge capacity(1297.8 mAh g^(-1)),superior rate performance(823.0 mAh g^(-1)at 2 C),and an ultralow capacity decay rate of 0.035%over more than 800 cycles.Even under 7.1 mg cm^(-2)S-loaded,the PEI-TIC electrode can also achieve a high areal capacity of 7.2 mA h g^(-1)and excellent cycling stability,confirming its application potential.Moreover,it is also noted that TG-FTIR test is performed for the first time to explore the flame-retardant mechanism of polymer binders.This work provides an economically and environmentally friendly binder for the practical application and inspires the exploration of the flame-retardant mechanism of all electrode components.
基金supported by the National Natural Science Foundation of China (21878340)supported in part by the High-Performance Computing Center of Central South University
文摘Precision engineering of catalytic sites to guide more favorable pathways for Li_(2)O_(2) nucleation and decom-position represents an enticing kinetic strategy for mitigating overpotential,enhancing discharge capac-ity,and improving recycling stability of Li-O_(2) batteries.In this work,we employ metal-organic frameworks(MOFs)derivation and ion substitution strategies to construct atomically dispersed Mn-N_(4) moieties on hierarchical porous nitrogen-doped carbon(Mn SAs-NC)with the aim of reducing the over-potential and improving the cycling stability of Li-O_(2) batteries.The porous structure provides more chan-nels for mass transfer and exposes more highly active sites for electrocatalytic reactions,thus promoting the formation and decomposition of Li_(2)O_(2).The Li-O_(2) batteries with Mn SAs-NC cathode achieve lower overpotential,higher specific capacity(14290 mA h g^(-1) at 100 mAg^(-1)),and superior cycle stability(>100 cycles at 200 mA g^(-1))compared with the Mn NPs-NC and NC.Density functional theory(DFT)cal-culations reveal that the construction of Mn-N_(4) moiety tunes the charge distribution of the pyridinic N-rich vacancy and balances the affinity of the intermediates(LiO_(2) and Li_(2)O_(2)).The initial nucleation of Li_(2)O_(2) on Mn SAs-NC favors the O_(2)-→LiO_(2)→Li_(2)O_(2) surface-adsorption pathway,which mitigates the overpoten-tials of the oxygen reduction(ORR)and oxygen evolution reaction(OER).As a result,Mn SAs-NC with Mn-N_(4) moiety effectively facilitates the Li_(2)O_(2) nucleation and enables its reversible decomposition.This work establishes a methodology for constructing carbon-based electrocatalysts with high activity and selectivity for Li-O_(2)batteries.
基金supported by the National Natural Science Foundation of China (NSFC, No. 51522203, 51772040)Fok Ying Tung Education Foundation (No. 151047)+2 种基金the Recruitment Program of Global Youth ExpertsXinghai Scholarship of Dalian University of Technologythe Fundamental Research Funds for the Central Universities (No. DUT18LAB19)
文摘Use of metallic Li anode raises serious concerns on the safety and operational performance of Li-S batteries due to uncontrolled hazard of Li dendrite formation, which is difficultly eliminated as long as the metallic Li exists in the cells. Pairing lithium sulfide (Li2S) cathode with currently available metallic Lifree high-capacity anodes offers an alternative solution to this challenge. However, the performance of Li2S cathode is primarily restricted by high activation barrier upon initial charge, low active mass utilization and sluggish redox kinetics. Herein, a MXene-induced multifunctional collaborative interface is proposed to afford superb activity towards redox solid-liquid/liquid-liquid phase transformation, strong chemisorption, high conductivity and fast ionic/charge transport in high Li2S loading cathode. Applying collaborative interface effectively reduces initial voltage barrier of Li2S activation and regulates the kinetic behavior of redox polysulfide conversion. Therefore, stable operation of additive-free Li2S cathode with high areal capacities at high Li2S loading up to 9 mg cm^-2 can be achieved with less sacrifice of high capacity and rate capability in Li-S batteries. Rechargeable metallic Li-free batteries are successfully constructed by pairing this high-performance Li2S cathode with high-capacity metal oxide anodes, which delivers superior energy density to current Li-ion batteries.
基金supported by Stable Support Plan Program for Higher Education Institutions(20220815094504001)Shenzhen Key Laboratory of Advanced Energy Storage(No.ZDSYS20220401141000001).
文摘Three-dimensional(3D)printing,an additive manufacturing technique,is widely employed for the fabrication of various electrochemical energy storage devices(EESDs),such as batteries and supercapacitors,ranging from nanoscale to macroscale.This technique offers excellent manufacturing flexibility,geometric designability,cost-effectiveness,and eco-friendliness.Recent studies have focused on the utilization of 3D-printed critical materials for EESDs,which have demonstrated remarkable electrochemical performances,including high energy densities and rate capabilities,attributed to improved ion/electron transport abilities and fast kinetics.However,there is a lack of comprehensive reviews summarizing and discussing the recent advancements in the structural design and application of 3D-printed critical materials for EESDs,particularly rechargeable batteries.In this review,we primarily concentrate on the current progress in 3D printing(3DP)critical materials for emerging batteries.We commence by outlining the key characteristics of major 3DP methods employed for fabricating EESDs,encompassing design principles,materials selection,and optimization strategies.Subsequently,we summarize the recent advancements in 3D-printed critical materials(anode,cathode,electrolyte,separator,and current collector)for secondary batteries,including conventional Li-ion(LIBs),Na-ion(SIBs),K-ion(KIBs)batteries,as well as Li/Na/K/Zn metal batteries,Zn-air batteries,and Ni–Fe batteries.Within these sections,we discuss the 3DP precursor,design principles of 3D structures,and working mechanisms of the electrodes.Finally,we address the major challenges and potential applications in the development of 3D-printed critical materials for rechargeable 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An emerging practice in the realm of Li-S batteries lies in the employment of single-atom catalysts(SACs)as effective mediators to promote polysulfide conversion,but monometallic SACs affording isolated geometric dispersion and sole electronic configuration limit the catalytic benefits and curtail the cell performance.Here,we propose a class of dual-atom catalytic moieties comprising hetero-or homo-atomic pairs anchored on N-doped graphene(NG)to unlock the liquid–solid redox puzzle of sulfur,readily realizing Li-S full cell under high-rate-charging conditions.As for Fe-Ni-NG,in-depth experimental and theoretical analysis reveal that the hetero-atomic orbital coupling leads to altered energy levels,unique electronic structures,and varied Fe oxidation states in comparison with homo-atomic structures(FeFe-NG or Ni-Ni-NG).This would weaken the bonding energy of polysulfide intermediates and thus enable facile electrochemical kinetics to gain rapid liquid-solid Li_(2)S_(4)?Li_(2)S conversion.Encouragingly,a Li-S battery based on the S@Fe-Ni-NG cathode demonstrates unprecedented fast-charging capability,documenting impressive rate performance(542.7 mA h g^(-1)at 10.0 C)and favorable cyclic stability(a capacity decay of 0.016%per cycle over 3000 cycles at 10.0 C).This finding offers insights to the rational design and application of dual-atom mediators for Li-S batteries.
基金supported by the National Key Research and Development Program of China(No.2019YFC1907801)National Natural Science Foundation of China(No.52174286)+1 种基金the Science and Technology Innovation Program of Hunan Province(2021RC3014)Innovation-Driven Project of Central South University(No.2020CX007)。
文摘Efficient bifunctional catalysts for oxygen reduction reaction(ORR)and oxygen evolution reaction(OER)are vital for rechargeable Zn-air batteries(ZABs).Herein,an oxygen-respirable sponge-like Co@C–O–Cs catalyst with oxygen-rich active sites was designed and constructed for both ORR and OER by a facile carbon dot-assisted strategy.The aerophilic triphase interface of Co@C–O–Cs cathode efficiently boosts oxygen diffusion and transfer.The theoretical calculations and experimental studies revealed that the Co–C–COC active sites can redistribute the local charge density and lower the reaction energy barrier.The Co@C–O–Cs catalyst displays superior bifunctional catalytic activities with a half-wave potential of 0.82 V for ORR and an ultralow overpotential of 294 mV at 10 mA cm^(−2) for OER.Moreover,it can drive the liquid ZABs with high peak power density(106.4 mW cm^(−2)),specific capacity(720.7 mAh g^(−1)),outstanding long-term cycle stability(over 750 cycles at 10 mA cm^(−2)),and exhibits excellent feasibility in flexible all-solid-state ZABs.These findings provide new insights into the rational design of efficient bifunctional oxygen catalysts in rechargeable metal-air batteries.
基金financial support from the National Natural Science Foundation of China(Grant Nos.51871188 and 51931006)the Fundamental Research Funds for the Central Universities of China(Xiamen University:Nos.20720200068,20720190007 and 20720220074)+2 种基金Guangdong Basic and Applied Basic Research Foundation(No.2021A1515010139)Science and Technology Projects of Innovation Laboratory for Sciences and Technologies of Energy Materials of Fujian Province(HRTP-[2022]-22)the“Double-First Class”Foundation of Materials Intelligent Manufacturing Discipline of Xiamen University。
文摘The commercial viability of lithium-sulfur batteries is still challenged by the notorious lithium polysulfides(Li PSs)shuttle effect on the sulfur cathode and uncontrollable Li dendrites growth on the Li anode.Herein,a bi-service host with Co-Fe binary-metal selenide quantum dots embedded in three-dimensional inverse opal structured nitrogen-doped carbon skeleton(3DIO FCSe-QDs@NC)is elaborately designed for both sulfur cathode and Li metal anode.The highly dispersed FCSe-QDs with superb adsorptive-catalytic properties can effectively immobilize the soluble Li PSs and improve diffusion-conversion kinetics to mitigate the polysulfide-shutting behaviors.Simultaneously,the 3D-ordered porous networks integrated with abundant lithophilic sites can accomplish uniform Li deposition and homogeneous Li-ion flux for suppressing the growth of dendrites.Taking advantage of these merits,the assembled Li-S full batteries with 3DIO FCSe-QDs@NC host exhibit excellent rate performance and stable cycling ability(a low decay rate of 0.014%over 2,000 cycles at 2C).Remarkably,a promising areal capacity of 8.41 mAh cm^(-2)can be achieved at the sulfur loading up to 8.50 mg cm^(-2)with an ultra-low electrolyte/sulfur ratio of 4.1μL mg^(-1).This work paves the bi-serve host design from systematic experimental and theoretical analysis,which provides a viable avenue to solve the challenges of both sulfur and Li electrodes for practical Li-S full batteries.
基金the support from National Outstanding Youth Science Fund (52222314)the CNPC Innovation Found (2021DQ02-1001)+2 种基金the Liao Ning Revitalization Talents Program (XLYC1907144)the Xinghai Talent Cultivation Plan (X20200303)the Fundamental Research Funds for the Central Universities (DUT22JC02,DUT22LAB605)。
文摘Sulfur-rich polymers have gained a great deal of attention as the next-generation active materials in lithium-sulfur(Li-S)batteries due to their low cost,environmental compatibility,naturally sulfur uniform dispersion,and distinctive structure covalently bonding with sulfur atoms.However,the poor electrical conductivity and undesirable additional shuttle effect still hinder the commercial application of sulfur-rich polymers.Herein,we report a flexible semi-immobilization strategy to prepare allylterminated hyperbranched poly(ethyleneimine)-functionalized reduced graphene oxide(A-PEI-EGO)as sulfur-rich copolymer backbone.The semi-immobilization strategy can effectively reconcile the demand for polymer skeleton and conductive substrates through forming quaternary ammonium groups and reducing oxygen-containing functional groups,resulting in enhanced skeleton adsorption capacity and substrate electronic conductivity,respectively.Furthermore,the stable covalent bonding connection based on polymer molecules(A-PEI)not only completely prevents the additional shuttle effect of lithiation organic molecules and even sulfur-rich oligomers,but provides more inverse vulcanization active sites.As a result,the as-prepared A-PEI-EGO-S cathodes display an initial discharge capacity of1338 m A h g^(-1)at a rate of 0.1 C and an outstanding cycling stability of 0.046%capacity decay per cycle over 600 cycles.Even under 6.2 mg cm^(-2)S-loaded and sparing electrolyte of 6μL mg^(-1),the A-PEI-EGO-S cathode can also achieve a superior cycling performance of 98%capacity retention after 60 cycles,confirming its application potential.
基金flnancial support from Australian Research Council through its Discovery,Future Fellowship ProgramsImam Mohammad Ibn Saud Islamic University (IMSIU) in Riyadh,Saudi Arabia,for flnancial support of this work.
文摘Zinc–bromine rechargeable batteries(ZBRBs)are one of the most powerful candidates for next-generation energy storage due to their potentially lower material cost,deep discharge capability,non-flammable electrolytes,relatively long lifetime and good reversibility.However,many opportunities remain to improve the efficiency and stability of these batteries for long-life operation.Here,we discuss the device configurations,working mechanisms and performance evaluation of ZBRBs.Both non-flow(static)and flow-type cells are highlighted in detail in this review.The fundamental electrochemical aspects,including the key challenges and promising solutions,are discussed,with particular attention paid to zinc and bromine half-cells,as their performance plays a critical role in determining the electrochemical performance of the battery system.The following sections examine the key performance metrics of ZBRBs and assessment methods using various ex situ and in situ/operando techniques.The review concludes with insights into future developments and prospects for high-performance ZBRBs.
基金supported by the Jilin Province Science and Technology Department Program(YDZJ202201ZYTS304)the Science and Technology Project of Jilin Provincial Education Department(JJKH20220428KJ)+3 种基金the Jilin Province Science and Technology Department Program(YDZJ202101ZYTS047)the National Natural Science Foundation of China(21905110,21905041,22279045,22102020)the Special foundation of Jilin Province Industrial Technology Research and Development(2019C042)the Fundamental Research Funds for the Central Universities(2412020FZ008)。
文摘Lithium sulfur batteries are regarded as a promising candidate for high-energy-density energy storage devices.However,the lithium metal anode in lithium-sulfur batteries encounters the problem of lithium dendrites and lithium metal consumption caused by polysulfide corrosion.Herein we design a dualfunction PMMA/PPC/LiNO3composite as an artificial solid electrolyte interphase(PMCN-SEI)to protect Li metal anode.This SEI offers multiple sites of C=O for polysulfide anchoring to constrain corrosion of Li metal anode.The lithiated polymer group and Li3N in PMCN-SEI can homogenize lithium-ion deposition behavior to achieve a dendrite-free anode.As a result,the PMCN-SEI protected Li metal anode enables the Li||Li symmetric batteries to maintain over 300 cycles(1300 h)at a capacity of 5 m Ah cm^(-2),corresponding to a cumulative capacity of 3.25 Ah cm^(-2).Moreover,Li-S batteries assembled with 20μm of Li metal anode(N/P=1.67)still deliver an initial capacity of 1166 m A h g-1at 0.5C.Hence,introducing polycarbonate polymer/inorganic composite SEI on Li provides a new solution for achieving the high energy density of Li-S batteries.
基金financial support from the Natural Science Foundation of Shandong Province(ZR2021ZD05)the Outstanding Talents in Shandong University。
文摘Cu-based cathodes in aqueous batteries become very attractive in view of high theoretical capacity,moderate operation voltage and rich reserves of raw materials.However,their applications are obstructed by serious side reactions.The side reaction mainly arises from the spontaneous formation of Cu_(2)O,which occupies the electrode surface and lowers the reaction reversibility.Here,Na_(2)EDTA is introduced to address these issues.Both experimental results and theoretical calculations indicate that the Na_(2)EDTA reshapes the solvation structure of Cu^(2+)and modifies the electrode/electrolyte interface.Therefore,the redox potential of Cu^(2+)/Cu_(2)O is reduced and the surface of Cu is protected from H2O,thereby inhibiting the formation of Cu_(2)O.Meanwhile,the change in the solvation structure reduces the electrostatic repulsion between Cu^(2+)and the cathode,leading to high local concentration and benefiting uniform deposition.The results shed light on the applications of rechargeable Cu-based batteries.
基金Financial support was provided by the Guangdong College Students’Innovative Project(202110580014)the Guangdong “Climbing”Program for Research Items(pdjh2021b0544)。
文摘The next-generation energy storage systems such as fuel cells,metal-air batteries,and alkali metal(Li,Na)-chalcogen(S,Se)batteries have received increasing attention owing to their high energy density and low cost.However,one of the main obstacles of these systems is the poor reaction kinetics in the involved chemical reactions.Therefore,it is essential to incorporate suitable and efficient catalysts into the cell.These years,single-atom catalysts(SACs)are emerging as a frontier in catalysis due to their maximum atom efficiency and unique reaction selectivity.For SACs fabrication,metal-organic frameworks(MOFs)have been confirmed as promising templates or precursors due to their high metal loadings,structural adjustability,porosity,and tailorable catalytic site.In this review,we summarize effective strategies for fabricating SACs by MOFs with corresponding advanced characterization techniques and illustrate the key role of MOFs-based SACs in these batteries by explaining their reaction mechanisms and challenges.Finally,current applications,prospects,and opportunities for MOFs-based SACs in energy storage systems are discussed.
基金supported by the National Science Foundation of China(21805235)the Opening Foundation of Creative Platform of the Key Laboratory of the Education Department of Hunan Province(20K131)the Construct Program of the Key Discipline in Hunan Province。
文摘Rational design and exploration of low-cost and robust bifunctional oxygen electrocatalysts are vitally important for developing high-performance zinc-air batteries(ZABs).Herein,we reported a facile yet cost-efficient approach to construct a bifunctional oxygen reduction reaction(ORR)/oxygen evolution reaction(OER)electrocatalyst composed of N-doped porous carbon nanosheet flowers decorated with Fe Co nanoparticles(Fe Co/N-CF).Rational design of this catalyst is achieved by designing Schiff-base polymer with unique molecular structure via hydrogen bonding of cyanuramide and terephthalaldehyde polycondensate in the presence of metal cations.It exhibits excellent activity and stability for electrocatalysis of ORR/OER,enabling ZAB with a high peak power density of 172 m W cm^(-2)and a large specific capacity of 811 m A h g^(-1)Znat large current.The rechargeable ZAB demonstrates excellent durability for 1000 h with slight voltage decay,far outperforming a couple of precious Pt/Ir-based catalysts.Density functional theory(DFT)calculations reveal that high activity of bimetallic Fe Co stems from enhanced O_(2)and OH-adsorption and accelerated O_(2)dissociation by OAO bond activation.
基金financial support from the National Natural Science Foundation of China(Nos.21975159,2157316)the Shanghai Aerospace Science and Technology Innovation Fund(No.SAST2018-117)the Oceanic Interdisciplinary Program of Shanghai Jiao Tong University(No.WH410260401/006)。
文摘Rechargeable magnesium batteries(RMBs)are considered the promising candidates for post lithium-ion batteries due to the abundant storage,high capacity,and dendrite-rare characteristic of Mg anode.However,the lack of practical electrolytes impedes the development and application of RMBs.Here,through a one-step reaction of LiCl congenital-containing Knochel–Hauser base TMPL(2,2,6,6-tetrame thylpiperidinylmagnesium chloride lithium chloride complex)with Lewis acid AlCl_(3),we successfully synthesized an efficient amino-magnesium halide TMPLA electrolyte.Raman and mass spectroscopy identified that the electrolyte comprises the typical di-nuclear copolymer[Mg_(2)Cl_(3)·6THF]+cation group and[(TMP)2AlCl_(2)]-anion group,further supported by the results of density functional theory calculations(DFT)and the Molecular dynamics(MD)simulations.The TMPLA electrolyte exhibits promising electrochemical performance,including available anodic stability(>2.65 V vs.SS),high ionic conductivity(6.05mS cm^(-1)),and low overpotential(<0.1 V)as well as appropriate Coulombic efficiency(97.3%)for Mg plating/stripping.Both the insertion Mo6S8cathode and conversion Cu S cathode delivered a desirable electrochemical performance with high capacity and good cycling stability based on the TMPLA electrolyte.In particular,when compatible with low cost and easily synthesized Cu S,the Cu S||Mg cell displayed an extremely high discharge capacity of 458.8 mAh g^(-1)for the first cycle and stabilized at 170.2 mAh g^(-1)with high Coulombic efficiency(99.1%)after 50 cycles at 0.05 C.Our work proposes an efficient electrolyte with impressive compatibility with Mg anode and insertion/conversion cathode for practical RMBs and provides a more profound knowledge of the Lewis acid–base reaction mechanisms.
基金supported by the National Natural Science Foundation of China (Grant No.22075028).
文摘Rechargeable aluminum batteries(RABs)are attractive cadidates for next-generation energy storage and conversion,due to the low cost and high safety of Al resources,and high capacity of metal Al based on the three-electrons reaction mechanism.However,the development of RABs is greatly limited,because of the lack of advanced cathode materials,and their complicated and unclear reaction mechanisms.Exploring the novel nanostructured transition metal and carbon composites is an effective route for obtaining ideal cathode materials.In this work,we synthesize porous CoSnO_(3)/C nanocubes with oxygen vacancies for utilizing as cathodes in RABs for the first time.The intrinsic structure stability of the mixed metal cations and carbon coating can improve the cycling performance of cathodes by regulating the internal strains of the electrodes during volume expansion.The nanocubes with porous structures contribute to fast mass transportation which improves the rate capability.In addition to this,abundant oxygen vacancies promote the adsorption affinity of cathodes,which improves storage capacity.As a result,the CoSnO_(3)/C cathodes display an excellent reversible capacity of 292.1 mAh g^(-1) at 0.1 A g^(-1),a good rate performance with 109 mAh g^(-1) that is maintained even at 1 A g^(-1) and the provided stable cycling behavior for 500 cycles.Besides,a mechanism of intercalation of Al^(3+)within CoSnO_(3)/C cathode is proposed for the electrochemical process.Overall,this work provides a step toward the development of advanced cathode materials for RABs by engineering novel nanostructured mixed transition-metal oxides with carbon composite and proposes novel insights into chemistry for RABs.
基金support from the “Joint International Laboratory on Environmental and Energy Frontier Materials”“Innovation Research Team of High-Level Local Universities in Shanghai”support from the National Natural Science Foundation of China (22209103)
文摘Lithium–sulfur(Li–S)batteries are supposed to be one of the most potential next-generation batteries owing to their high theoretical capacity and low cost.Nevertheless,the shuttle effect of firm multi-step two-electron reaction between sulfur and lithium in liquid electrolyte makes the capacity much smaller than the theoretical value.Many methods were proposed for inhibiting the shuttle effect of polysulfide,improving corresponding redox kinetics and enhancing the integral performance of Li–S batteries.Here,we will comprehensively and systematically summarize the strategies for inhibiting the shuttle effect from all components of Li–S batteries.First,the electrochemical principles/mechanism and origin of the shuttle effect are described in detail.Moreover,the efficient strategies,including boosting the sulfur conversion rate of sulfur,confining sulfur or lithium polysulfides(LPS)within cathode host,confining LPS in the shield layer,and preventing LPS from contacting the anode,will be discussed to suppress the shuttle effect.Then,recent advances in inhibition of shuttle effect in cathode,electrolyte,separator,and anode with the aforementioned strategies have been summarized to direct the further design of efficient materials for Li–S batteries.Finally,we present prospects for inhibition of the LPS shuttle and potential development directions in Li–S batteries.