Aqueous zinc(Zn)-ion batteries(AZIBs)are one of the most promising large-scale energy storage devices because of the excellent features of zinc metal anodes,including high theoretical capacity(5,855 mAh·cm^(–3)a...Aqueous zinc(Zn)-ion batteries(AZIBs)are one of the most promising large-scale energy storage devices because of the excellent features of zinc metal anodes,including high theoretical capacity(5,855 mAh·cm^(–3)and 820 mAh·g^(−1)),high safety,and natural abundance.Nevertheless,the large-scale applications of AZIBs are mainly limited by the severe interfacial side reactions of zinc metal anodes,which results in low plating/stripping Coulombic efficiency and poor cycling stability.To address this issue,we report an artificial Ta_(2)O_(5)protective layer on zinc foil(Ta_(2)O_(5)@Zn)for suppressing side reactions during Zn deposition/stripping.The results of density functional theory calculation and experiments indicate that Ta_(2)O_(5)@Zn anode can inhibit the side reactions between the electrolyte and zinc anode through the isolation effect.Benefiting from this advantage,the symmetric cells with Ta_(2)O_(5)@Zn anode delivered an ultralong lifespan of 3,000 h with a low overpotential at 0.25 mA·cm^(−2)for 0.05 mAh·cm^(−2).Furthermore,the full cells consisting of Ta_(2)O_(5)@Zn anode and MnO_(2)or NH_(4)V_(4)O_(10)cathode all present outstanding electrochemical performance,indicating its high reliability in practical applications.This strategy brings new opportunities for the future development of rechargeable AZIBs.展开更多
Featured with high power density,improved safety and low-cost,rechargeable aqueous zinc-ion batteries(ZIBs) have been revived as possible candidates for sustainable energy storage systems in recent years.However,the c...Featured with high power density,improved safety and low-cost,rechargeable aqueous zinc-ion batteries(ZIBs) have been revived as possible candidates for sustainable energy storage systems in recent years.However,the challenges inherent in zinc(Zn) anode,namely dendrite formation and interfacial parasitic reactions,have greatly impeded their practical application.Whereas the critical issue of dendrite formation has attracted widespread concern,the parasitic reactions of Zn anodes with mildly acidic electrolytes have received very little attentions.Considering that the low Zn reversibility that stems from interfacial parasitic reactions is the major obstacle to the commercialization of ZIBs,thorough understanding of these side reactions and the development of correlative inhibition strategies are significant.Therefore,in this review,the brief fundamentals of corrosion and hydrogen evolution reactions at Zn surface is presented.In addition,recent advances and research efforts addressing detrimental side reactions are reviewed from the perspective of electrode design,electrode-electrolyte interfacial engineering and electrolyte modification.To facilitate the future researches on this aspect,perspectives and suggestions for relevant investigations are provided lastly.展开更多
Aqueous Zn-ion batteries(AZIBs)have been regarded as promising alternatives to Li-ion batteries due to their advantages,such as low cost,high safety,and environmental friendliness.However,AZIBs face significant challe...Aqueous Zn-ion batteries(AZIBs)have been regarded as promising alternatives to Li-ion batteries due to their advantages,such as low cost,high safety,and environmental friendliness.However,AZIBs face significant challenges in limited stability and lifetime owing to zinc dendrite growth and serious side reactions caused by water molecules in the aqueous electrolyte during cycling.To address these issues,a new eutectic electrolyte based on Zn(ClO_(4))_(2)·6H_(2)O-N-methylacetamide(ZN)is proposed in this work.Compared with aqueous electrolyte,the ZN eutectic electrolyte containing organic N-methylacetamide could regulate the solvated structure of Zn^(2+),effectively suppressing zinc dendrite growth and side reactions.As a result,the Zn//NH4 V4 O10 full cell with the eutectic ZN-1-3 electrolyte demonstrates significantly enhanced cycling stability after 1000 cycles at 1 A g^(-1).Therefore,this study not only presents a new eutectic electrolyte for zinc-ion batteries but also provides a deep understanding of the influence of Zn^(2+)solvation structure on the cycle stability,contributing to the exploration of novel electrolytes for high-performance AZIBs.展开更多
Rechargeable aqueous zinc-based batteries(RZBs)often suffer from poor cycling stability due to the instability of zinc deposition and etching processes.This work achieves dendrite-free zinc deposition with a smaller n...Rechargeable aqueous zinc-based batteries(RZBs)often suffer from poor cycling stability due to the instability of zinc deposition and etching processes.This work achieves dendrite-free zinc deposition with a smaller nucleation radius and rapid completion of the nucleation stage by a"triple regulation strategy"with trace chitosan oligosaccharide(COS)in ZnSO_(4)electrolyte(2 g L^(-1)COS),Theoretical and experimental results indicate that COS,with hydroxyl and amino functional groups,exhibits a high affinity for the(002)_(Zn)and(100)_(Zn)facets.Under the influence of a small amount of COS,the selective exposure of the(101)_(Zn)facet is facilitated.The extensively exposed(101)_(Zn)facet is protected by COS,which inhibits the occurrence of side reactions.Moreover,the presence of trace COS-02 changes the etching mode from three-dimensional(3D)to two-dimensional(2D),ensuring a uniform distribution of Zn^(2+)in the electric field during the deposition process.The unique 3D deposition and 2D etching mechanism induced by the COS additive result in exceptional cycling stability,exceeding 3800 h(1 mA cm^(-2))and 430 h(5 mA cm^(-2))in zinc symmetrical cells.Additionally,COS acts as a"molecular pillar"to stabilize VS_(2),enabling the Zn‖VS_(2)full cell to achieve 1000 stable cycles with 89.6%capacity retention and an average coulombic efficiency of 99.95%.This work reveals a novel multiple regulation mechanism by using trace COS in RZBs,and provides a new approach for the development of long-term stable RZBs with preferential exposure facets.展开更多
Dendrite formation and side reactions,which originate from uncontrolled zinc(Zn)nucleation and growth and high water activity,remain the two critical challenges that hinder the practical implementation of Zn anodes fo...Dendrite formation and side reactions,which originate from uncontrolled zinc(Zn)nucleation and growth and high water activity,remain the two critical challenges that hinder the practical implementation of Zn anodes for rechargeable aqueous batteries.In this work,we propose a cation and anion comodulation strategy to realize highly textured and durable Zn anodes.As a proof of concept,1-ethyl-1-methylpyrrolidinium bromide(MEPBr)is selected as a versatile additive to regulate Zn deposition.Specifically,MEP^(+)cations with preferential adsorption on tips/edges first promote uniform primary Zn nucleation on the substrate,followed by dynamic“edge shielding”of existing deposits to guide highly oriented Zn growth.Meanwhile,the incorporation of Br^(-)anions promotes the enrichment of Zn^(2+)at the electrode-electrolyte interface(EEI),thereby facilitating Zn deposition kinetics.In addition,both the preferentially adsorbed MEP^(+)cations and Br^(-)anions create a water-poor EEI while the two ionic species disrupt the original hydrogen bond network and reduce water within the solvation structure in the bulk electrolyte through ion-water interactions,thus dramatically reducing water-induced side reactions.As a result,the Zn//Zn symmetric battery with the MEPBr-modulated electrolyte exhibits a remarkable lifespan of over 4000 h at 2 m A cm^(-2)and 1 mA h cm^(-2).More excitingly,the newly designed electrolyte enables a Zn//NaV_(3)O_(8)·1.5H_(2)O full battery with a thin Zn anode(50μm)and a high mass-loading cathode(~10 mg cm^(-2))to operate normally for over 300 cycles with remarkable capacity retention,showcasing its great potential for practical applications.展开更多
Aqueous zinc-ion batteries are promising candidates as stationary storage systems for power-grid applications due to their high safety and low cost.The practical implementation of Zn-ion batteries currently still face...Aqueous zinc-ion batteries are promising candidates as stationary storage systems for power-grid applications due to their high safety and low cost.The practical implementation of Zn-ion batteries currently still faces formidable challenges because of Zn dendrite growth,hydrogen evolution,and inadequate environmental adaptability.Herein,to address these challenges,a strategy of regulation of water molecules coordination in electrolyte is proposed via developing a cross-linked hydrophilic hydrogel polymer electrolyte.Within this system,the continuous hydrogen bond among H_(2)O molecules is disrupted and the isolated H_(2)O molecules are strongly bound with a polymeric matrix comprised of polyacrylamide,carboxymethyl cellulose,and ethylene glycol,which can restrain the activity of H_(2)O molecules,thus effectively alleviating Zn dendrite growth and hydrogen evolution and enhancing the anti-freezing ability.With this electrolyte,the Zn||Cu cell presents a high coulombic efficiency of 99.4%over 900 cycles and Zn||Zn symmetric cell exhibits high cycling stability,maintaining plating/stripping for over 1,700 h.Moreover,the assembled Zn||PANI device also demonstrates outstanding electrochemical performance over a wide-temperature range,including a long cycling life over 14,120 cycles at room temperature and an ultralong cycling surpassing 30,000 cycles even at−40℃.This showcases the manipulation of water coordination chemistry for advanced,highly adaptable batteries.展开更多
Due to their high safety and low cost,rechargeable aqueous Zn-ion batteries(RAZIBs)have been receiving increased attention and are expected to be the next generation of energy storage systems.However,metal Zn anodes e...Due to their high safety and low cost,rechargeable aqueous Zn-ion batteries(RAZIBs)have been receiving increased attention and are expected to be the next generation of energy storage systems.However,metal Zn anodes exhibit a limited-service life and inferior reversibility owing to the issues of Zn dendrites and side reactions,which severely hinder the further development of RAZIBs.Researchers have attempted to design high-performance Zn anodes by interfacial engineering,including surface modification and the addition of electrolyte additives,to stabilize Zn anodes.The purpose is to achieve uniform Zn nucleation and flat Zn deposition by regulating the deposition behavior of Zn ions,which effectively improves the cycling stability of the Zn anode.This review comprehensively summarizes the reaction mechanisms of interfacial modification for inhibiting the growth of Zn dendrites and the occurrence of side reactions.In addition,the research progress of interfacial engineering strategies for RAZIBs is summarized and classified.Finally,prospects and suggestions are provided for the design of highly reversible Zn anodes.展开更多
While the rechargeable aqueous zinc-ion batteries(AZIBs)have been recognized as one of the most viable batteries for scale-up application,the instability on Zn anode–electrolyte interface bottleneck the further devel...While the rechargeable aqueous zinc-ion batteries(AZIBs)have been recognized as one of the most viable batteries for scale-up application,the instability on Zn anode–electrolyte interface bottleneck the further development dramatically.Herein,we utilize the amino acid glycine(Gly)as an electrolyte additive to stabilize the Zn anode–electrolyte interface.The unique interfacial chemistry is facilitated by the synergistic“anchor-capture”effect of polar groups in Gly molecule,manifested by simultaneously coupling the amino to anchor on the surface of Zn anode and the carboxyl to capture Zn^(2+)in the local region.As such,this robust anode–electrolyte interface inhibits the disordered migration of Zn^(2+),and effectively suppresses both side reactions and dendrite growth.The reversibility of Zn anode achieves a significant improvement with an average Coulombic efficiency of 99.22%at 1 mA cm^(−2)and 0.5 mAh cm^(−2)over 500 cycles.Even at a high Zn utilization rate(depth of discharge,DODZn)of 68%,a steady cycle life up to 200 h is obtained for ultrathin Zn foils(20μm).The superior rate capability and long-term cycle stability of Zn–MnO_(2)full cells further prove the effectiveness of Gly in stabilizing Zn anode.This work sheds light on additive designing from the specific roles of polar groups for AZIBs.展开更多
Featuring low cost, high abundance, low electrochemical potential, and large specific capacity, zinc(Zn)metal holds great potential as an anode material for next-generation rechargeable aqueous batteries.However, the ...Featuring low cost, high abundance, low electrochemical potential, and large specific capacity, zinc(Zn)metal holds great potential as an anode material for next-generation rechargeable aqueous batteries.However, the poor reversibility resulting from dendrite formation and side reactions poses a major obstacle for its practical application. Electrolyte, which is regarded as the “blood” of batteries, has a direct impact on reaction kinetics, mass transport, and side reactions and thus plays a key role in determining the electrochemical performance of Zn electrodes. Therefore, considerable efforts have been devoted to modulating the electrolytes to improve the performance of Zn electrodes. Although significant progress has been made, achieving stable and highly reversible Zn electrodes remains a critical challenge. This review aims to provide a systematic summary and discussion on electrolyte strategies for highperformance aqueous Zn batteries. The(electro)-chemical behavior and fundamental challenges of Zn electrodes in aqueous electrolytes are first discussed. Electrolyte modulation strategies developed to address these issues are then classified and elaborated according to the underlying mechanisms.Finally, remaining challenges and promising future research directions on aqueous electrolyte engineering are highlighted. This review offers insights into the design of highly efficient electrolytes for new generation of rechargeable Zn batteries.展开更多
Constructing a protective layer on Zn anode surface with high lattice matching to Zn(002)can facilitate preferential growth along the(002)crystal plane and suppress dendritic growth as well as interface side reactions...Constructing a protective layer on Zn anode surface with high lattice matching to Zn(002)can facilitate preferential growth along the(002)crystal plane and suppress dendritic growth as well as interface side reactions.Whereas most of protective layers are complex and costly,making commercial applications challenging.Herein,we introduce a facile method involving the addition of CuCl_(2) electrolyte additives to conventional electrolyte systems,which,through rapid displacement reactions and controlled electrochemical cycling,forms a CuZn_(5) alloy layer with 97.2%lattice matching to the(002)plane(CuZn_(5)@Zn),thus regulating the(002)plane epitaxial deposition.As a result,the symmetric cells with CuZn_(5)@Zn demonstrate an ultra-long cycle life of 3600 h at 1 mA cm^(-2).Under extreme conditions of high current density(20 m A cm^(-2))and high zinc utilization(DOD_(Zn)=50%),stable cycling performance is maintained for 220 and 350 h,respectively.Furthermore,the CuZn_(5)@Zn||NH_(4)V_(4)O_(10)full cell maintains a capacity of 120 m A h g^(-1)even after 10,000 cycles at a high current density of 10 A g^(-1).This work presents a facile and efficient strategy for constructing stable metal anode materials,with implications for the development of next-generation rechargeable batteries.展开更多
The practical application of aqueous zinc-ion batteries for large-grid scale systems is still hindered by uncontrolled zinc dendrite and side reactions.Regulating the elec-trical double layer via the electrode/electro...The practical application of aqueous zinc-ion batteries for large-grid scale systems is still hindered by uncontrolled zinc dendrite and side reactions.Regulating the elec-trical double layer via the electrode/electrolyte interface layer is an effective strategy to improve the stability of Zn anodes.Herein,we report an ultrathin zincophilic ZnS layer as a model regu-lator.At a given cycling current,the cell with Zn@ZnS electrode displays a lower potential drop over the Helmholtz layer(stern layer)and a suppressed diffuse layer,indicating the regulated charge distribution and decreased electric double layer repulsion force.Boosted zinc adsorption sites are also expected as proved by the enhanced electric double-layer capacitance.Consequently,the symmetric cell with the ZnS protection layer can stably cycle for around 3,000 h at 1 mA cm^(-2) with a lower overpotential of 25 mV.When coupled with an I2/AC cathode,the cell demonstrates a high rate performance of 160 mAh g^(-1) at 0.1 A g^(-1) and long cycling stability of over 10,000 cycles at 10 A g^(-1).The Zn||MnO_(2) also sustains both high capacity and long cycling stability of 130 mAh g^(-1) after 1,200 cycles at 0.5 A g^(-1).展开更多
Aqueous Zn batteries are promising candidates for grid-scale renewable energy storage.Foil electrodes have been widely investigated and applied as anode materials for aqueous Zn batteries,however,they suffer from limi...Aqueous Zn batteries are promising candidates for grid-scale renewable energy storage.Foil electrodes have been widely investigated and applied as anode materials for aqueous Zn batteries,however,they suffer from limited surface area and severe interfacial issues including metallic dendrites and corrosion side reactions,limiting the depth of discharge(DOD)of the foil electrode materials.Herein,a low-temperature replacement reaction is utilized to in-situ construct a three-dimensional(3D)corrosion-resistant interface for deeply rechargeable Zn foil electrodes.Specifically,the deliberate low-temperature environment controlled the replacement rate between polycrystalline Zn metal and oxalic acid,producing a Zn foil electrode with distinct 3D corrosion-resistant interface(3DCI-Zn),which differed from conventional two-dimensional(2D)protective structure and showed an order of magnitude higher surface area.Consequently,the 3DCI-Zn electrode exhibited dendrite-free and anticorrosion properties,and achieved stable plating/stripping performance for 1000 h at 10 mA cm^(-2)and 10 mAh cm^(-2)with a remarkable DOD of 79%.After pairing with a MnO2cathode with a high areal capacity of 4.2 mAh cm^(-2),the pouch cells delivered 168 Wh L^(-1)and a capacity retention of 89.7%after 100 cycles with a low negative/positive(N/P)ratio of 3:1.展开更多
The potential use of large-size ZnSe quantum dots as blue emitters for display applications has greatly inspired the colloidal synthesis.Herein,we report the negative effects of side reactions of large-size ZnSe quant...The potential use of large-size ZnSe quantum dots as blue emitters for display applications has greatly inspired the colloidal synthesis.Herein,we report the negative effects of side reactions of large-size ZnSe quantum dots.The side reactions between oleic acid and oleylamine generated amidation products and H_(2)O,which led to the hydrolysis of Zn(OA)2 to Zn(OH)2 and the subsequent formation of zinc oxide(ZnO)and zinc bis[diphenylphosphinate](Zn(DPPA)2)precipitates.These side reactions resulted in the formation of a defective surface including a Se-rich surface and oxygen-related defects.Such negative effects can be overcome by adopting an etching strategy using potassium fluoride and myristic acid in combination.By overcoating a ZnS shell,blue emissive ZnSe/ZnS quantum dots with a maximum photoluminescence quantum yield of up to 91%were obtained.We further fabricated ZnSe quantum dots-based blue light-emitting diodes with an emission peak at 456 nm.The device showed a turn-on voltage of 2.7 V with a maximum external quantum efficiency of 4.2%and a maximum luminance of 1223 cd·m^(−2).展开更多
Lithium cobalt oxide(LCO),the first commercialized cathode active material for lithium-ion batteries,is known for high voltage and capacity.However,its application has been limited by relatively low capacity and stabi...Lithium cobalt oxide(LCO),the first commercialized cathode active material for lithium-ion batteries,is known for high voltage and capacity.However,its application has been limited by relatively low capacity and stability at high C-rates.Reducing particle size is considered one of the most straightforward and effective strategies to enhance ion transfer,thus increasing the rate performance.However,side reactions are simultaneously enhanced as the specific surface area increases.Herein,we investigate the impact of LCO particles with varying size distributions and optimize the particle size.To modulate the side reactions associated with particle size reduction,an ultrathin carbon nanotube film(UCNF)is introduced to coat the cathode surface.With this simple process and optimized particle size,the rate performance improves significantly,normal commercial LCO achieves 118 mA·h·g^(−1)at 3.0–4.3 V and 20 C(0.72 mA·h·cm^(−2)),corresponding to power density of 8732 W·kg^(−1).This method is applied to high voltage as well,152 mA·h·g^(−1)at 3.0–4.6 V and 20 C(0.99 mA·h·cm^(−2))was achieved with high-voltage LCO(HVLCO),corresponding to power density of 11,552 W·kg^(−1).The cycling stability is also enhanced,with the capacity retention maintaining more than 96%after 100 cycles at 0.1 C.For the first time,UCNF is demonstrated to suppress the excessive decomposition of the electrolytes and solvents by blocking electron injection/extraction between LCO and electrolyte solution.Our findings provide a simple method for improving LCO rate performance,especially at high C-rates.展开更多
Despite the promising energy storage capabilities of high-capacity silicon-and tin-based alloys,as well as fast-charging hard carbon anodes for lithium-ion batteries(LIBs),their widespread industrial adoption is limit...Despite the promising energy storage capabilities of high-capacity silicon-and tin-based alloys,as well as fast-charging hard carbon anodes for lithium-ion batteries(LIBs),their widespread industrial adoption is limited by low initial Coulombic efficiency(ICE).This primarily arises from active lithium loss during the first cycle,caused by the solid electrolyte interface(SEI)formation on anode surfaces and other irreversible side reactions[1,2].展开更多
Aqueous rechargeable Zn-ion batteries are regarded as a promising alternative to lithium-ion batteries owing to their high energy density,low cost,and high safety.However,their commercialization is severely restricted...Aqueous rechargeable Zn-ion batteries are regarded as a promising alternative to lithium-ion batteries owing to their high energy density,low cost,and high safety.However,their commercialization is severely restricted by the Zn dendrite formation and side reactions.Herein,we propose that these issues can be minimized by modifying the interfacial properties through introducing electrochemically inert Al_(2)O_(3)nanocoatings on Zn meal anodes(Al_(2)O_(3)@Zn).The Al_(2)O_(3)nanocoatings can effectively suppress both the dendrite growth and side reactions.As a result,the Al_(2)O_(3)@Zn symmetric cells show excellent electrochemical performance with a long lifespan of more than 4,000 h at 1 mA·cm^(−2)and 1 mAh·cm^(−2).Meanwhile,the assembled Al_(2)O_(3)@Zn//V_(2)O_(5)full cells can deliver a high capacity(236.2 mAh·g^(−1))and long lifespan with a capacity retention of 76.11%after 1,000 cycles at 4 A·g^(−1).展开更多
Development of catholytes with long-cycle lifespan,high interfacial stability,and fast electrochemical kinetics is crucial for the comprehensive deployment of high-energy density lithium metal batteries(LMBs)with cost...Development of catholytes with long-cycle lifespan,high interfacial stability,and fast electrochemical kinetics is crucial for the comprehensive deployment of high-energy density lithium metal batteries(LMBs)with cost-efficiency.In this study,a lithiated 2-mercaptopyridine(2-MP-Li)organosulfide was synthesized and used as the soluble catholyte for the first time.Under the routine working mode,the LMB using this 2-MP-Li catholyte possessed high capacity retention of 55.4%with a Coulombic efficiency(CE)of near 100%after 2,000 cycles.When a cell system was fully filled with 2-MP-Li catholyte,it yielded a double capacity with 15%improvement in the capacity retention,corresponding to 0.0182%capacity decay per cycle,as well as excellent rate performance even at 6 mA·cm^(−2).These superior achievements resulted from the enhanced interfacial stability of Li anode induced by the salt-type 2-MP-Li molecule and the avoiding of using neutral catholyte as the initial active material,thereby mitigating the side reactions originating from the polysulfide shuttle effect.Furthermore,density functional theory(DFT)calculation and kinetics investigations proved the pseudocapacitive characteristic and faster ion diffusion coefficient with this design.Besides,the fabricated energy storage device showed excellent performance but with low economic cost and easy processing.Such a LMB with an alterable amount of capacity has a high potential to be applied in flow-cell type batteries for large-scale grid energy storage in the future.展开更多
The research and development of advanced nanocoatings for high-capacity cathode materials is currently a hot topic in the field of solid-state batteries(SSBs).Protective surface coatings prevent direct contact between...The research and development of advanced nanocoatings for high-capacity cathode materials is currently a hot topic in the field of solid-state batteries(SSBs).Protective surface coatings prevent direct contact between the cathode material and solid electrolyte,thereby inhibiting detrimental interfacial decomposition reactions.This is particularly important when using lithium thiophosphate superionic solid electrolytes,as these materials exhibit a narrow electrochemical stability window,and therefore,are prone to degradation during battery operation.Herein we show that the cycling performance of LiNbO_(3)-coated Ni-rich LiNi_(x)Co_(y)Mn_(z)O_(2)cathode materials is strongly dependent on the sample history and(coating)synthesis conditions.We demonstrate that post-treatment in a pure oxygen atmosphere at 350℃results in the formation of a surface layer with a unique microstructure,consisting of LiNbO_(3)nanoparticles distributed in a carbonate matrix.If tested at 45℃and C/5 rate in pellet-stack SSB full cells with Li_(4)Ti_(5)O_(12)and Li_(6)PS_(5)Cl as anode material and solid electrolyte,respectively,around 80%of the initial specific discharge capacity is retained after 200 cycles(~160 mAh·g^(−1),~1.7 mAh·cm^(−2)).Our results highlight the importance of tailoring the coating chemistry to the electrode material(s)for practical SSB applications.展开更多
As the world enters into the era of electrifying transportation for cleaner energy,lithium-ion battery(LIB)-powered electric vehicles have drawn great attention in recent years.However,the fast-charging capability of ...As the world enters into the era of electrifying transportation for cleaner energy,lithium-ion battery(LIB)-powered electric vehicles have drawn great attention in recent years.However,the fast-charging capability of LIBs has long been regarded as the technological obstacle to the wider adoption of battery electric vehicles(BEVs)in the market.A substantial challenge associated with fast charging is the formation of Li plating on the graphite anode as it is the major contributor of side reactions during cell operations.In this review,the fundamentals of Li plating and corresponding influencing factors(including state of charge[SOC],charging current density,temperature,and N/P ratio)for the Li-ion intercalation process are first elucidated under fast-charging conditions.Furthermore,conventional strategies to suppress Li plating by enhancing ion transport kinetics between interface and electrode through anode engineering and electrolyte design are also summarized and analyzed.Then,innovative strategies for achieving ultrahigh SOC of anodes by regulating Li plating morphology on host materials to construct hybrid anode storage are discussed in detail.Two types of strategies are compared in terms of cell performance,process simplicity,and safety concerns.Last,we highlight some research orientations and perspectives pertaining to the development of hybrid anode storage,providing effective approaches to address Li plating issues for fast-charging LIBs.展开更多
基金the National Key Research and Development Program of China(No.2020YFB1713500)Open Fund of State Key Laboratory of Advanced Refractories(No.SKLAR202210)+1 种基金the Student Research Training Plan of Henan University of Science and Technology(Nos.2021026 and 2021035)the Undergraduate Innovation and Entrepreneurship Training Program of Henan Province(No.S202110464005).
文摘Aqueous zinc(Zn)-ion batteries(AZIBs)are one of the most promising large-scale energy storage devices because of the excellent features of zinc metal anodes,including high theoretical capacity(5,855 mAh·cm^(–3)and 820 mAh·g^(−1)),high safety,and natural abundance.Nevertheless,the large-scale applications of AZIBs are mainly limited by the severe interfacial side reactions of zinc metal anodes,which results in low plating/stripping Coulombic efficiency and poor cycling stability.To address this issue,we report an artificial Ta_(2)O_(5)protective layer on zinc foil(Ta_(2)O_(5)@Zn)for suppressing side reactions during Zn deposition/stripping.The results of density functional theory calculation and experiments indicate that Ta_(2)O_(5)@Zn anode can inhibit the side reactions between the electrolyte and zinc anode through the isolation effect.Benefiting from this advantage,the symmetric cells with Ta_(2)O_(5)@Zn anode delivered an ultralong lifespan of 3,000 h with a low overpotential at 0.25 mA·cm^(−2)for 0.05 mAh·cm^(−2).Furthermore,the full cells consisting of Ta_(2)O_(5)@Zn anode and MnO_(2)or NH_(4)V_(4)O_(10)cathode all present outstanding electrochemical performance,indicating its high reliability in practical applications.This strategy brings new opportunities for the future development of rechargeable AZIBs.
基金financially supported by the National Key R&D Program of China (grant no. 2018YFB0905400)the National Natural Science Foundation of China (grant nos. 22075331, 51702376, 21905057)+2 种基金the Fundamental Research Funds for the Central Universities (19lgzd02)the Guangdong Pearl River Talents Plan (2019QN01L117)the National Thousand Youth Talents Project of the Chinese Government.
文摘Featured with high power density,improved safety and low-cost,rechargeable aqueous zinc-ion batteries(ZIBs) have been revived as possible candidates for sustainable energy storage systems in recent years.However,the challenges inherent in zinc(Zn) anode,namely dendrite formation and interfacial parasitic reactions,have greatly impeded their practical application.Whereas the critical issue of dendrite formation has attracted widespread concern,the parasitic reactions of Zn anodes with mildly acidic electrolytes have received very little attentions.Considering that the low Zn reversibility that stems from interfacial parasitic reactions is the major obstacle to the commercialization of ZIBs,thorough understanding of these side reactions and the development of correlative inhibition strategies are significant.Therefore,in this review,the brief fundamentals of corrosion and hydrogen evolution reactions at Zn surface is presented.In addition,recent advances and research efforts addressing detrimental side reactions are reviewed from the perspective of electrode design,electrode-electrolyte interfacial engineering and electrolyte modification.To facilitate the future researches on this aspect,perspectives and suggestions for relevant investigations are provided lastly.
基金supported by the Natural Science Foundation of Henan Province(No.242300420021)the Major Science and Technology Projects of Henan Province(No.221100230200)+4 种基金the Open Fund of State Key Laboratory of Advanced Refractories(No.SKLAR202210)the Key Science and Technology Program of Henan Province(No.232102241020)the Undergraduate Innovation and Entrepreneurship Training Program of Henan Province(No.S202310464012)the Ph.D.Research Startup Foundation of Henan University of Science and Technology(No.400613480015)the Postdoctoral Research Startup Foundation of Henan University of Science and Technology(No.400613554001).
文摘Aqueous Zn-ion batteries(AZIBs)have been regarded as promising alternatives to Li-ion batteries due to their advantages,such as low cost,high safety,and environmental friendliness.However,AZIBs face significant challenges in limited stability and lifetime owing to zinc dendrite growth and serious side reactions caused by water molecules in the aqueous electrolyte during cycling.To address these issues,a new eutectic electrolyte based on Zn(ClO_(4))_(2)·6H_(2)O-N-methylacetamide(ZN)is proposed in this work.Compared with aqueous electrolyte,the ZN eutectic electrolyte containing organic N-methylacetamide could regulate the solvated structure of Zn^(2+),effectively suppressing zinc dendrite growth and side reactions.As a result,the Zn//NH4 V4 O10 full cell with the eutectic ZN-1-3 electrolyte demonstrates significantly enhanced cycling stability after 1000 cycles at 1 A g^(-1).Therefore,this study not only presents a new eutectic electrolyte for zinc-ion batteries but also provides a deep understanding of the influence of Zn^(2+)solvation structure on the cycle stability,contributing to the exploration of novel electrolytes for high-performance AZIBs.
基金supported by the National Natural Science Foundation of China(52161145503)。
文摘Rechargeable aqueous zinc-based batteries(RZBs)often suffer from poor cycling stability due to the instability of zinc deposition and etching processes.This work achieves dendrite-free zinc deposition with a smaller nucleation radius and rapid completion of the nucleation stage by a"triple regulation strategy"with trace chitosan oligosaccharide(COS)in ZnSO_(4)electrolyte(2 g L^(-1)COS),Theoretical and experimental results indicate that COS,with hydroxyl and amino functional groups,exhibits a high affinity for the(002)_(Zn)and(100)_(Zn)facets.Under the influence of a small amount of COS,the selective exposure of the(101)_(Zn)facet is facilitated.The extensively exposed(101)_(Zn)facet is protected by COS,which inhibits the occurrence of side reactions.Moreover,the presence of trace COS-02 changes the etching mode from three-dimensional(3D)to two-dimensional(2D),ensuring a uniform distribution of Zn^(2+)in the electric field during the deposition process.The unique 3D deposition and 2D etching mechanism induced by the COS additive result in exceptional cycling stability,exceeding 3800 h(1 mA cm^(-2))and 430 h(5 mA cm^(-2))in zinc symmetrical cells.Additionally,COS acts as a"molecular pillar"to stabilize VS_(2),enabling the Zn‖VS_(2)full cell to achieve 1000 stable cycles with 89.6%capacity retention and an average coulombic efficiency of 99.95%.This work reveals a novel multiple regulation mechanism by using trace COS in RZBs,and provides a new approach for the development of long-term stable RZBs with preferential exposure facets.
基金supported by the Research Grants Council of the Hong Kong Special Administrative Region,China(16205721)the PolyU Start-up Fund(1-BDC4)。
文摘Dendrite formation and side reactions,which originate from uncontrolled zinc(Zn)nucleation and growth and high water activity,remain the two critical challenges that hinder the practical implementation of Zn anodes for rechargeable aqueous batteries.In this work,we propose a cation and anion comodulation strategy to realize highly textured and durable Zn anodes.As a proof of concept,1-ethyl-1-methylpyrrolidinium bromide(MEPBr)is selected as a versatile additive to regulate Zn deposition.Specifically,MEP^(+)cations with preferential adsorption on tips/edges first promote uniform primary Zn nucleation on the substrate,followed by dynamic“edge shielding”of existing deposits to guide highly oriented Zn growth.Meanwhile,the incorporation of Br^(-)anions promotes the enrichment of Zn^(2+)at the electrode-electrolyte interface(EEI),thereby facilitating Zn deposition kinetics.In addition,both the preferentially adsorbed MEP^(+)cations and Br^(-)anions create a water-poor EEI while the two ionic species disrupt the original hydrogen bond network and reduce water within the solvation structure in the bulk electrolyte through ion-water interactions,thus dramatically reducing water-induced side reactions.As a result,the Zn//Zn symmetric battery with the MEPBr-modulated electrolyte exhibits a remarkable lifespan of over 4000 h at 2 m A cm^(-2)and 1 mA h cm^(-2).More excitingly,the newly designed electrolyte enables a Zn//NaV_(3)O_(8)·1.5H_(2)O full battery with a thin Zn anode(50μm)and a high mass-loading cathode(~10 mg cm^(-2))to operate normally for over 300 cycles with remarkable capacity retention,showcasing its great potential for practical applications.
基金the financial support from Guangdong Basic and Applied Basic Research Foundation(Grant No.2025A1515012077)National Natural Science Foundation of China(No.52401296)+3 种基金the financial support by Guangdong Provincial Pearl River Talents Program(Grant No.2023CX10L019)Bureau of Science and Technology of Jiangmen Municipality(Grant No.2320002001062)And this work is also partly supported by Guangdong S&T Programme(No.2022B1212040001)Guangdong-Hong Kong-Macao joint Laboratory(No.2023B1212120003).
文摘Aqueous zinc-ion batteries are promising candidates as stationary storage systems for power-grid applications due to their high safety and low cost.The practical implementation of Zn-ion batteries currently still faces formidable challenges because of Zn dendrite growth,hydrogen evolution,and inadequate environmental adaptability.Herein,to address these challenges,a strategy of regulation of water molecules coordination in electrolyte is proposed via developing a cross-linked hydrophilic hydrogel polymer electrolyte.Within this system,the continuous hydrogen bond among H_(2)O molecules is disrupted and the isolated H_(2)O molecules are strongly bound with a polymeric matrix comprised of polyacrylamide,carboxymethyl cellulose,and ethylene glycol,which can restrain the activity of H_(2)O molecules,thus effectively alleviating Zn dendrite growth and hydrogen evolution and enhancing the anti-freezing ability.With this electrolyte,the Zn||Cu cell presents a high coulombic efficiency of 99.4%over 900 cycles and Zn||Zn symmetric cell exhibits high cycling stability,maintaining plating/stripping for over 1,700 h.Moreover,the assembled Zn||PANI device also demonstrates outstanding electrochemical performance over a wide-temperature range,including a long cycling life over 14,120 cycles at room temperature and an ultralong cycling surpassing 30,000 cycles even at−40℃.This showcases the manipulation of water coordination chemistry for advanced,highly adaptable batteries.
基金financially supported by the National Natural Science Foundation of China(Nos.51872090,51772097,51972346)the Hebei Natural Science Fund for Distinguished Young Scholar(No.E2019209433)+3 种基金the Natural Science Foundation of Hebei Province(No.E2020209151)the Hunan Natural Science Fund for Distinguished Young Scholar(2021JJ10064)the Program of Youth Talent Support for Hunan Province(2020RC3011)the Innovation-Driven Project of Central South University(No.2020CX024).
文摘Due to their high safety and low cost,rechargeable aqueous Zn-ion batteries(RAZIBs)have been receiving increased attention and are expected to be the next generation of energy storage systems.However,metal Zn anodes exhibit a limited-service life and inferior reversibility owing to the issues of Zn dendrites and side reactions,which severely hinder the further development of RAZIBs.Researchers have attempted to design high-performance Zn anodes by interfacial engineering,including surface modification and the addition of electrolyte additives,to stabilize Zn anodes.The purpose is to achieve uniform Zn nucleation and flat Zn deposition by regulating the deposition behavior of Zn ions,which effectively improves the cycling stability of the Zn anode.This review comprehensively summarizes the reaction mechanisms of interfacial modification for inhibiting the growth of Zn dendrites and the occurrence of side reactions.In addition,the research progress of interfacial engineering strategies for RAZIBs is summarized and classified.Finally,prospects and suggestions are provided for the design of highly reversible Zn anodes.
基金supported by National Key R&D Program(2022YFB2502000)Zhejiang Provincial Natural Science Foundation of China(LZ23B030003)+1 种基金the Fundamental Research Funds for the Central Universities(2021FZZX001-09)the National Natural Science Foundation of China(52175551).
文摘While the rechargeable aqueous zinc-ion batteries(AZIBs)have been recognized as one of the most viable batteries for scale-up application,the instability on Zn anode–electrolyte interface bottleneck the further development dramatically.Herein,we utilize the amino acid glycine(Gly)as an electrolyte additive to stabilize the Zn anode–electrolyte interface.The unique interfacial chemistry is facilitated by the synergistic“anchor-capture”effect of polar groups in Gly molecule,manifested by simultaneously coupling the amino to anchor on the surface of Zn anode and the carboxyl to capture Zn^(2+)in the local region.As such,this robust anode–electrolyte interface inhibits the disordered migration of Zn^(2+),and effectively suppresses both side reactions and dendrite growth.The reversibility of Zn anode achieves a significant improvement with an average Coulombic efficiency of 99.22%at 1 mA cm^(−2)and 0.5 mAh cm^(−2)over 500 cycles.Even at a high Zn utilization rate(depth of discharge,DODZn)of 68%,a steady cycle life up to 200 h is obtained for ultrathin Zn foils(20μm).The superior rate capability and long-term cycle stability of Zn–MnO_(2)full cells further prove the effectiveness of Gly in stabilizing Zn anode.This work sheds light on additive designing from the specific roles of polar groups for AZIBs.
文摘Featuring low cost, high abundance, low electrochemical potential, and large specific capacity, zinc(Zn)metal holds great potential as an anode material for next-generation rechargeable aqueous batteries.However, the poor reversibility resulting from dendrite formation and side reactions poses a major obstacle for its practical application. Electrolyte, which is regarded as the “blood” of batteries, has a direct impact on reaction kinetics, mass transport, and side reactions and thus plays a key role in determining the electrochemical performance of Zn electrodes. Therefore, considerable efforts have been devoted to modulating the electrolytes to improve the performance of Zn electrodes. Although significant progress has been made, achieving stable and highly reversible Zn electrodes remains a critical challenge. This review aims to provide a systematic summary and discussion on electrolyte strategies for highperformance aqueous Zn batteries. The(electro)-chemical behavior and fundamental challenges of Zn electrodes in aqueous electrolytes are first discussed. Electrolyte modulation strategies developed to address these issues are then classified and elaborated according to the underlying mechanisms.Finally, remaining challenges and promising future research directions on aqueous electrolyte engineering are highlighted. This review offers insights into the design of highly efficient electrolytes for new generation of rechargeable Zn batteries.
基金financially supported by the National Key R&D Program of China(2022YFB3807700)the National Natural Science Foundation of China(Grant no.52125405 and U22A20108)+4 种基金the support from the Hubei Provincial Natural Science Foundation of China(Grant No.2023AFB155)the opening project of State Key Laboratory of Metastable Materials Science and Technology(Yanshan University)(opening project number:202401,202404)the Thailand Science Research and Innovation Fund Chulalongkorn University(INDF67620003)the National Science,Research and Innovation Fund(NSRF)via the Program Management Unit for Human Resources&Institutional Development,Research and Innovation(Grant no.B05F640153)the National Research Council of Thailand(NRCT)and Chulalongkorn University(N42A660383)。
文摘Constructing a protective layer on Zn anode surface with high lattice matching to Zn(002)can facilitate preferential growth along the(002)crystal plane and suppress dendritic growth as well as interface side reactions.Whereas most of protective layers are complex and costly,making commercial applications challenging.Herein,we introduce a facile method involving the addition of CuCl_(2) electrolyte additives to conventional electrolyte systems,which,through rapid displacement reactions and controlled electrochemical cycling,forms a CuZn_(5) alloy layer with 97.2%lattice matching to the(002)plane(CuZn_(5)@Zn),thus regulating the(002)plane epitaxial deposition.As a result,the symmetric cells with CuZn_(5)@Zn demonstrate an ultra-long cycle life of 3600 h at 1 mA cm^(-2).Under extreme conditions of high current density(20 m A cm^(-2))and high zinc utilization(DOD_(Zn)=50%),stable cycling performance is maintained for 220 and 350 h,respectively.Furthermore,the CuZn_(5)@Zn||NH_(4)V_(4)O_(10)full cell maintains a capacity of 120 m A h g^(-1)even after 10,000 cycles at a high current density of 10 A g^(-1).This work presents a facile and efficient strategy for constructing stable metal anode materials,with implications for the development of next-generation rechargeable batteries.
基金financially supported by the Natural Sciences and Engineering Research Council of Canada (NSERC),through the Discovery Grant Program (RGPIN-2018-06725)the Discovery Accelerator Supplement Grant program (RGPAS-2018-522651)+2 种基金the New Frontiers in Research Fund-Exploration program (NFRFE-2019-00488)supported by funding from the Canada First Research Excellence Fund as part of the University of Alberta’s Future Energy Systems research initiative (FES-T06-Q03)supported by the Chinese Scholarship Council (CSC)(Grant No. 202006450027).
文摘The practical application of aqueous zinc-ion batteries for large-grid scale systems is still hindered by uncontrolled zinc dendrite and side reactions.Regulating the elec-trical double layer via the electrode/electrolyte interface layer is an effective strategy to improve the stability of Zn anodes.Herein,we report an ultrathin zincophilic ZnS layer as a model regu-lator.At a given cycling current,the cell with Zn@ZnS electrode displays a lower potential drop over the Helmholtz layer(stern layer)and a suppressed diffuse layer,indicating the regulated charge distribution and decreased electric double layer repulsion force.Boosted zinc adsorption sites are also expected as proved by the enhanced electric double-layer capacitance.Consequently,the symmetric cell with the ZnS protection layer can stably cycle for around 3,000 h at 1 mA cm^(-2) with a lower overpotential of 25 mV.When coupled with an I2/AC cathode,the cell demonstrates a high rate performance of 160 mAh g^(-1) at 0.1 A g^(-1) and long cycling stability of over 10,000 cycles at 10 A g^(-1).The Zn||MnO_(2) also sustains both high capacity and long cycling stability of 130 mAh g^(-1) after 1,200 cycles at 0.5 A g^(-1).
基金financially supported by the National Natural Science Foundation of China (No.22205068,22109144)the“CUG Scholar”Scientific Research Funds at China University of Geosciences (Wuhan) (Project No.2022118)the Fundamental Research Funds for the Central Universities,China University of Geosciences (Wuhan) (No.162301202673)。
文摘Aqueous Zn batteries are promising candidates for grid-scale renewable energy storage.Foil electrodes have been widely investigated and applied as anode materials for aqueous Zn batteries,however,they suffer from limited surface area and severe interfacial issues including metallic dendrites and corrosion side reactions,limiting the depth of discharge(DOD)of the foil electrode materials.Herein,a low-temperature replacement reaction is utilized to in-situ construct a three-dimensional(3D)corrosion-resistant interface for deeply rechargeable Zn foil electrodes.Specifically,the deliberate low-temperature environment controlled the replacement rate between polycrystalline Zn metal and oxalic acid,producing a Zn foil electrode with distinct 3D corrosion-resistant interface(3DCI-Zn),which differed from conventional two-dimensional(2D)protective structure and showed an order of magnitude higher surface area.Consequently,the 3DCI-Zn electrode exhibited dendrite-free and anticorrosion properties,and achieved stable plating/stripping performance for 1000 h at 10 mA cm^(-2)and 10 mAh cm^(-2)with a remarkable DOD of 79%.After pairing with a MnO2cathode with a high areal capacity of 4.2 mAh cm^(-2),the pouch cells delivered 168 Wh L^(-1)and a capacity retention of 89.7%after 100 cycles with a low negative/positive(N/P)ratio of 3:1.
基金supported by the National Natural Science Foundation of China(No.U23A20683)the Beijing Natural Science Foundation(No.Z210018).
文摘The potential use of large-size ZnSe quantum dots as blue emitters for display applications has greatly inspired the colloidal synthesis.Herein,we report the negative effects of side reactions of large-size ZnSe quantum dots.The side reactions between oleic acid and oleylamine generated amidation products and H_(2)O,which led to the hydrolysis of Zn(OA)2 to Zn(OH)2 and the subsequent formation of zinc oxide(ZnO)and zinc bis[diphenylphosphinate](Zn(DPPA)2)precipitates.These side reactions resulted in the formation of a defective surface including a Se-rich surface and oxygen-related defects.Such negative effects can be overcome by adopting an etching strategy using potassium fluoride and myristic acid in combination.By overcoating a ZnS shell,blue emissive ZnSe/ZnS quantum dots with a maximum photoluminescence quantum yield of up to 91%were obtained.We further fabricated ZnSe quantum dots-based blue light-emitting diodes with an emission peak at 456 nm.The device showed a turn-on voltage of 2.7 V with a maximum external quantum efficiency of 4.2%and a maximum luminance of 1223 cd·m^(−2).
基金supported by the National Key R&D Program of China(Nos.2018YFA0208402 and 2020YFA0714700)the National Natural Science Foundation of China(Nos.11634014 and 51372269)the“Strategic Priority Research Program”of the Chinese Academy of Sciences(No.XDA09040202).
文摘Lithium cobalt oxide(LCO),the first commercialized cathode active material for lithium-ion batteries,is known for high voltage and capacity.However,its application has been limited by relatively low capacity and stability at high C-rates.Reducing particle size is considered one of the most straightforward and effective strategies to enhance ion transfer,thus increasing the rate performance.However,side reactions are simultaneously enhanced as the specific surface area increases.Herein,we investigate the impact of LCO particles with varying size distributions and optimize the particle size.To modulate the side reactions associated with particle size reduction,an ultrathin carbon nanotube film(UCNF)is introduced to coat the cathode surface.With this simple process and optimized particle size,the rate performance improves significantly,normal commercial LCO achieves 118 mA·h·g^(−1)at 3.0–4.3 V and 20 C(0.72 mA·h·cm^(−2)),corresponding to power density of 8732 W·kg^(−1).This method is applied to high voltage as well,152 mA·h·g^(−1)at 3.0–4.6 V and 20 C(0.99 mA·h·cm^(−2))was achieved with high-voltage LCO(HVLCO),corresponding to power density of 11,552 W·kg^(−1).The cycling stability is also enhanced,with the capacity retention maintaining more than 96%after 100 cycles at 0.1 C.For the first time,UCNF is demonstrated to suppress the excessive decomposition of the electrolytes and solvents by blocking electron injection/extraction between LCO and electrolyte solution.Our findings provide a simple method for improving LCO rate performance,especially at high C-rates.
基金supported by the National Key R&D Program of China(2022YFA1504100)the National Natural Science Foundation of China(22125903,22439003,and 22409192)+2 种基金Liaoning Revitalization Talents Program—Leading Talents(XLYC2402032)the Science and Technology Major Project of Liaoning Province(2024JH1/11700012),DICP(DICP I202324,DICP I202471)the State Key Laboratory of Catalysis(2024SKL-A-001).
文摘Despite the promising energy storage capabilities of high-capacity silicon-and tin-based alloys,as well as fast-charging hard carbon anodes for lithium-ion batteries(LIBs),their widespread industrial adoption is limited by low initial Coulombic efficiency(ICE).This primarily arises from active lithium loss during the first cycle,caused by the solid electrolyte interface(SEI)formation on anode surfaces and other irreversible side reactions[1,2].
基金the National Natural Science Foundation of China(Nos.51601163,22001081,and 22075236)the National Key Research and Development Program of China(No.2017YFE0198100)+1 种基金the Natural Science Foundation of Fujian Province(No.2021J011211)Xiamen Municipal Bureau of Science and Technology(No.3502Z20206070),and Xiamen University.
文摘Aqueous rechargeable Zn-ion batteries are regarded as a promising alternative to lithium-ion batteries owing to their high energy density,low cost,and high safety.However,their commercialization is severely restricted by the Zn dendrite formation and side reactions.Herein,we propose that these issues can be minimized by modifying the interfacial properties through introducing electrochemically inert Al_(2)O_(3)nanocoatings on Zn meal anodes(Al_(2)O_(3)@Zn).The Al_(2)O_(3)nanocoatings can effectively suppress both the dendrite growth and side reactions.As a result,the Al_(2)O_(3)@Zn symmetric cells show excellent electrochemical performance with a long lifespan of more than 4,000 h at 1 mA·cm^(−2)and 1 mAh·cm^(−2).Meanwhile,the assembled Al_(2)O_(3)@Zn//V_(2)O_(5)full cells can deliver a high capacity(236.2 mAh·g^(−1))and long lifespan with a capacity retention of 76.11%after 1,000 cycles at 4 A·g^(−1).
基金supported by the National Natural Science Foundation of China(22222902,52027801,51871113,and 52111530236)the National Key R&D Program of China(2022YFA1203902 and 2022YFA1200093)the Natural Science Foundation of Jiangsu Province(BK20200047)。
基金supported by the ZiQoo Chemical Co.,Ltd.All authors greatly acknowledge Associate Professor Akihiro Yoshida at Hirosaki University,Japan,to help measuring 1H NMR spectrum.Z.K.X.greatly acknowledges the Key Scientific Research Project of Universities in Henan Province(No.22A150023)Zhengzhou University Young Teacher Special Fund(No.226-33212552).
文摘Development of catholytes with long-cycle lifespan,high interfacial stability,and fast electrochemical kinetics is crucial for the comprehensive deployment of high-energy density lithium metal batteries(LMBs)with cost-efficiency.In this study,a lithiated 2-mercaptopyridine(2-MP-Li)organosulfide was synthesized and used as the soluble catholyte for the first time.Under the routine working mode,the LMB using this 2-MP-Li catholyte possessed high capacity retention of 55.4%with a Coulombic efficiency(CE)of near 100%after 2,000 cycles.When a cell system was fully filled with 2-MP-Li catholyte,it yielded a double capacity with 15%improvement in the capacity retention,corresponding to 0.0182%capacity decay per cycle,as well as excellent rate performance even at 6 mA·cm^(−2).These superior achievements resulted from the enhanced interfacial stability of Li anode induced by the salt-type 2-MP-Li molecule and the avoiding of using neutral catholyte as the initial active material,thereby mitigating the side reactions originating from the polysulfide shuttle effect.Furthermore,density functional theory(DFT)calculation and kinetics investigations proved the pseudocapacitive characteristic and faster ion diffusion coefficient with this design.Besides,the fabricated energy storage device showed excellent performance but with low economic cost and easy processing.Such a LMB with an alterable amount of capacity has a high potential to be applied in flow-cell type batteries for large-scale grid energy storage in the future.
文摘The research and development of advanced nanocoatings for high-capacity cathode materials is currently a hot topic in the field of solid-state batteries(SSBs).Protective surface coatings prevent direct contact between the cathode material and solid electrolyte,thereby inhibiting detrimental interfacial decomposition reactions.This is particularly important when using lithium thiophosphate superionic solid electrolytes,as these materials exhibit a narrow electrochemical stability window,and therefore,are prone to degradation during battery operation.Herein we show that the cycling performance of LiNbO_(3)-coated Ni-rich LiNi_(x)Co_(y)Mn_(z)O_(2)cathode materials is strongly dependent on the sample history and(coating)synthesis conditions.We demonstrate that post-treatment in a pure oxygen atmosphere at 350℃results in the formation of a surface layer with a unique microstructure,consisting of LiNbO_(3)nanoparticles distributed in a carbonate matrix.If tested at 45℃and C/5 rate in pellet-stack SSB full cells with Li_(4)Ti_(5)O_(12)and Li_(6)PS_(5)Cl as anode material and solid electrolyte,respectively,around 80%of the initial specific discharge capacity is retained after 200 cycles(~160 mAh·g^(−1),~1.7 mAh·cm^(−2)).Our results highlight the importance of tailoring the coating chemistry to the electrode material(s)for practical SSB applications.
基金financially supported by the National Key R&D Program of China(2021YFB2400300)Fundamental Research Funds for the Central Universities(22X010201631 and 23X010301599)“Xiaomi Young Scholar”Funding Project,and CATL Future Energy Research Institute(22H010102023).
文摘As the world enters into the era of electrifying transportation for cleaner energy,lithium-ion battery(LIB)-powered electric vehicles have drawn great attention in recent years.However,the fast-charging capability of LIBs has long been regarded as the technological obstacle to the wider adoption of battery electric vehicles(BEVs)in the market.A substantial challenge associated with fast charging is the formation of Li plating on the graphite anode as it is the major contributor of side reactions during cell operations.In this review,the fundamentals of Li plating and corresponding influencing factors(including state of charge[SOC],charging current density,temperature,and N/P ratio)for the Li-ion intercalation process are first elucidated under fast-charging conditions.Furthermore,conventional strategies to suppress Li plating by enhancing ion transport kinetics between interface and electrode through anode engineering and electrolyte design are also summarized and analyzed.Then,innovative strategies for achieving ultrahigh SOC of anodes by regulating Li plating morphology on host materials to construct hybrid anode storage are discussed in detail.Two types of strategies are compared in terms of cell performance,process simplicity,and safety concerns.Last,we highlight some research orientations and perspectives pertaining to the development of hybrid anode storage,providing effective approaches to address Li plating issues for fast-charging LIBs.
