Security risks of flammability and explosion represent major problems with the use of conventional lithium rechargeable batteries using a liquid electrolyte.The application of solid-state electrolytes could effectivel...Security risks of flammability and explosion represent major problems with the use of conventional lithium rechargeable batteries using a liquid electrolyte.The application of solid-state electrolytes could effectively help to avoid these safety concerns.However,integrating the solid-state electrolytes into the all-solid-state lithium batteries is still a huge challenge mainly due to the high interfacial resistance present in the entire battery,especially at the interface between the cathode and the solid-state electrolyte pellet and the interfaces inside the cathode.Herein,recent progress made from investigations of cathode/solid-state electrolyte interfacial behaviors including the contact problem,the interlayer diffusion issue,the space-charge layer effect,and electrochemical compatibility is presented according to the classification of oxide-,sulfide-,and polymer-based solid-state electrolytes.We also propose strategies for the construction of ideal next-generation cathode/solid-state electrolyte interfaces with high room-temperature ionic conductivity,stable interfacial contact during long cycling,free formation of the space-charge region,and good compatibility with high-voltage cathodes.展开更多
Li/garnet/LiFePO_(4) solid-state battery was fabricated.The cathode contains LiFePO_(4),Ketjen black,poly(vinylidene fluoride):LiTFSI polymer as active material,electric conductor and Li-ion conducting binder,respecti...Li/garnet/LiFePO_(4) solid-state battery was fabricated.The cathode contains LiFePO_(4),Ketjen black,poly(vinylidene fluoride):LiTFSI polymer as active material,electric conductor and Li-ion conducting binder,respectively.Polyvinylpyrrolidone was added into the cathode to improve cathode/electrolyte interfacial performance.When combined with polyvinylpyrrolidone additive,poly(vinylidene fluoride):polyvinylpyrrol idone:LiTFSI blend forms,and the cathode/electrolyte interfacial resistance reduces from 10.7 kΩto 3.2 kΩ.The Li/garnet/LiFePO_(4) solid-state battery shows 80%capacity retention after 100 cycles at 30℃and 0.05 C.This study offers a general strategy to improve cathode/electrolyte interfacial performance and may enable the practical application of solid-state Li-metal batteries.展开更多
Vanadium pentoxide(V_(2)O_(5))displays the characteristics of high theoretical specific capacity,high operating voltage,and adjustable layered structure,possessing the considerable potential as cathode in magnesium me...Vanadium pentoxide(V_(2)O_(5))displays the characteristics of high theoretical specific capacity,high operating voltage,and adjustable layered structure,possessing the considerable potential as cathode in magnesium metal batteries(MMBs).Nevertheless,the large charge-radius ratio of Mg^(2+)induces the strong interactions of Mg^(2+)with solvent molecules of electrolyte and anionic framework of cathode,resulting in a notable voltage polarization and structural deterioration during cycling process.Herein,an in-situ multi-scale structural engineering is proposed to activate the interlayer-expanded V_(2)O_(5)cathode(pillared by tetrabutylammonium cation)via adding hexadecyltrimethylammonium bromide(CTAB)additive into electrolyte.During cycling,the in-situ incorporation of CTA^(+)not only enhances the electrostatic shielding effect and Mg species migration,but also stabilizes the interlayer spacing.Besides,CTA^(+)is prone to be adsorbed on cathode surface and induces the loss-free pulverization and amorphization of electroactive grains,leading to the pronounced effect of intercalation pseudocapacitance.CTAB additive also enables to scissor the Mg^(2+)solvation sheath and tailor the insertion mode of Mg species,further endowing V_(2)O_(5)cathode with fast reaction kinetics.Based on these merits,the corresponding V2O5‖Mg full cells exhibit the remarkable rate performance with capacities as high as 317.6,274.4,201.1,and 132.7 mAh g^(-1)at the high current densities of 0.1,0.2,0.5,and 1 A g^(-1),respectively.Moreover,after 1000 cycles,the capacity is still preserved to be 90,4 mAh g^(-1)at 1 A g^(-1)with an average coulombic efficiency of~100%.Our strategy of synergetic modulations of cathode host and electrolyte solvation structures provides new guidance for the development of high-rate,large-capacity,and long-life MMBs.展开更多
High-nickel cathode LiNi_(0.8)Co_(0.1)Mn_(0.1)O_(2)(NCM811)could enable lithium-ion batteries(LIBs)with high energy density.However,excessive decomposition of the electrolyte would happen in the high operating voltage...High-nickel cathode LiNi_(0.8)Co_(0.1)Mn_(0.1)O_(2)(NCM811)could enable lithium-ion batteries(LIBs)with high energy density.However,excessive decomposition of the electrolyte would happen in the high operating voltage range.In addition,the utilization of flammable organic solvents would increase safety risks in the high temperature environment.Herein,an electrolyte consisting of flame-retardant solvents with lower highest occupied molecular orbital(HOMO)level and LiDFOB salt is proposed to address above two issues.As a result,a thin and robust cathode-electrolyte interface containing rich LiF and Li-B-O compounds is formed on the cathode to effectively suppress electrolyte decomposition in the high operating voltage.The NCM811||Li cell paired with this designed electrolyte possesses a capacity retention of 72%after 300 cycles at 55℃.This work provides insights into developing electrolyte for stable high-nickel cathode operated in the high temperature.展开更多
High-voltage dual-ion batteries(DIBs)face significant challenges,including graphite cathode degradation,cathode-electrolyte interphase(CEI)instability,and the thermodynamic instability of conventional carbonate-based ...High-voltage dual-ion batteries(DIBs)face significant challenges,including graphite cathode degradation,cathode-electrolyte interphase(CEI)instability,and the thermodynamic instability of conventional carbonate-based electrolytes,particularly at extreme temperatures.In this study,we develop a stable electrolyte incorporating lithium difluorophosphate(LiDFP)as an additive to enhance the electrochemical performance of DIBs over a wide temperature range.LiDFP preferentially decomposes to form a rapid anion-transporting,mechanically robust CEI layer on graphite,which provides better protection by suppressing graphite's volume expansion,preventing electrolyte oxidative decomposition,and enhancing reaction kinetics.As a result,Li||graphite half cells using LiDFP electrolyte exhibit outstanding rate performance(90.8% capacity retention at 30 C)and excellent cycle stability(82.2% capacity retention after 5000 cycles)at room temperature.Moreover,graphite||graphite full cells with LiDFP electrolyte demonstrate stable discharge capacity across a temperature range of-20 to 40℃,expanding the potential applications of LiDFP.This work establishes a novel strategy for optimizing the interphase through electrolyte design,paving the way for all-climate DIBs with improved performance and stability.展开更多
All-solid-state batteries(ASSBs)assembled with sulfide solid electrolytes(SSEs)and nickel(Ni)-rich oxide cathode materials are expected to achieve high energy density and safety,representing potential candidates for t...All-solid-state batteries(ASSBs)assembled with sulfide solid electrolytes(SSEs)and nickel(Ni)-rich oxide cathode materials are expected to achieve high energy density and safety,representing potential candidates for the next-generation energy storage systems.However,interfacial issues between SSEs and Nirich oxide cathode materials,attributed to space charge layer,interfacial side reactions,and mechanical contact failure,significantly restrict the performances of ASSBs.The interface degradation is closely related to the components of the composite cathode and the process of electrode fabrication.Focusing on the influencing factors of interface compatibility between SSEs and Ni-rich oxide cathode,this article systematically discusses how cathode active materials(CAMs),electrolytes,conductive additives,binders,and electrode fabrication impact the interface compatibility.In addition,the strategies for the compatibility modification are reviewed.Furthermore,the challenges and prospects of intensive research on the degradation and modification of the SSE/Ni-rich cathode material interface are discussed.This review is intended to inspire the development of high-energy-density and high-safety all-solid-state batteries.展开更多
Nickel(Ni)-rich layered oxides have drawn great attention as cathode for lithium batteries due to their high capacity,high working voltage and competitive cost.Unfortunately,the operation of Ni-rich cathodes suffers f...Nickel(Ni)-rich layered oxides have drawn great attention as cathode for lithium batteries due to their high capacity,high working voltage and competitive cost.Unfortunately,the operation of Ni-rich cathodes suffers from the notorious structural degradation and interfacial side reactions with electrolytes and thus incurs premature failure,especially at high charge cut-off voltages(≥4.4 V).For this,various structural and interphase regulation strategies(such as coating modification,element doping,and electrolyte engineering)are developed to enhance the cycling survivability of Ni-rich cathodes.Among them,electrolyte engineering by changing solvation structure and introducing additives has been considered an efficient method for constructing robust cathode-electrolyte interphases(CEI),inhibiting the formation of harmful species(such as HF and H_(2)O)or restraining the dissolution of transition metal ions.However,there is still an absence of systematic guidelines for selecting and designing competitive electrolyte systems for Ni-rich layered cathodes.In this review,we comprehensively summarize the recent research progress on electrolyte engineering for Ni-rich layered cathodes according to their working mechanisms.Moreover,we propose future perspectives of improving the electrolyte performance,which will provide new insights for designing novel electrolytes toward high-performance Ni-rich layered cathodes.展开更多
Lithium-rich manganese-based oxides(LRMOs;xLi_(2)MnO_(3)(1−x)LiMO_(2);M=transition metal,0<x<1)with excellent specific capacity(>300 mAh/g)and high operating voltage(≥4.8V)are the preferred cathode materials...Lithium-rich manganese-based oxides(LRMOs;xLi_(2)MnO_(3)(1−x)LiMO_(2);M=transition metal,0<x<1)with excellent specific capacity(>300 mAh/g)and high operating voltage(≥4.8V)are the preferred cathode materials for high-specific-energy lithium metal batteries(LMBs)[1].However,LRMOs face a series of serious problems such as irreversible lattice oxygen loss,transition metal(TM)migration,phase transfer,and interfacial side reactions at high voltages,resulting in rapid decay of capacity and voltage[2,3].In situ generating well-functional CEI through electrolyte engineering can effectively address these challenges[4].展开更多
As a potential candidate for high-energy lithium-ion batteries (LIBs),nickel-rich cathodes encounter significant challenges due to structural instability arising from interphases.In this work,tris(ethenyl)-tris(etheny...As a potential candidate for high-energy lithium-ion batteries (LIBs),nickel-rich cathodes encounter significant challenges due to structural instability arising from interphases.In this work,tris(ethenyl)-tris(ethenyl)silyloxysilane (HVDS) with Si–O bonds and unsaturated bonds is introduced as additive designing functional electrolyte to enhance the long-cycle stability of LiNi_(0.8)Co_(0.1)Mn_(0.1)O_(2)(NCM811)/graphite LIBs at elevated temperature.The preferential oxidization and component of HVDS facilitate the generation of an extremely robust and ultra-thin cathode electrolyte interphase (CEI) comprising a chemically bonded silane polymer.This interphase effectively suppresses side-reactions of electrolyte,mitigates HF erosion,and reduces irreversible phase transitions.Benefiting from the above merits,the batteries’capacity retention shows a remarkable increase from 20% to 92% after nearly 1550 cycles conducted at room temperature.And under elevated temperature conditions (45℃),the capacity retention remains 80%after 670 cycles,in comparison to a drop to 80%after only 250 cycles with the blank electrolyte.These findings highlight HVDS’s potential to functionalize the electrolyte,marking a breakthrough in improving the longevity and reliability of NCM811/graphite LIBs under challenging conditions.展开更多
Iron-based Prussian white(PW)materials have attracted considerable attention as promising cathodes for potassium-ion batteries(PIBs)due to their high capacity,easy preparation,and economic merits.However,the intrinsic...Iron-based Prussian white(PW)materials have attracted considerable attention as promising cathodes for potassium-ion batteries(PIBs)due to their high capacity,easy preparation,and economic merits.However,the intrinsic iron dissolution and uncontrollable cathode-electrolyte interface(CEI)formation in conventional organic electrolytes severely hinder their long-term cycling stability.Herein,we employ succinonitrile(SN),a bifunctional electrolyte additive,to suppress the iron dissolution and promote thin,uniform,and stable CEI formation of the PW cathode,thus improving its structural stability.Benefited from the coordination between the cyano groups in SN and iron atoms,this molecule can preferentially adsorb on the surface of PW to mitigate iron dissolution.SN also facilitates the decomposition of anions in potassium salt rather than organic solvents in electrolyte due to the attractive reaction between SN and anions.Consequently,the PW cathode with SN additive provides better electrochemical reversibility,showing capacity retention of 93.6%after 3000 cycles at 5C.In comparison,without SN,the capacity retention is only 87.4%after 1000 cycles under the same conditions.Moreover,the full cells of PW matched with commercial graphite(Gr)achieve stable cycling for 3500 cycles at a high rate of 20C,with an exceptional capacity decay of only 0.005%per cycle,surpassing the majority of recently reported results in literature.展开更多
Halide solid-state electrolytes(SSEs)have become a new research focus for all-solid-state batteries because of their significant safety advantages,high ionic conductivity,high-voltage stability,and good ductility.None...Halide solid-state electrolytes(SSEs)have become a new research focus for all-solid-state batteries because of their significant safety advantages,high ionic conductivity,high-voltage stability,and good ductility.Nonetheless,stability issues are a key barrier to their practical application.In past reports,the analysis of halide electrolyte stability and its enhancement methods lacked relevance,which limited the design and optimization of halide solid electrolytes.This review focus on stability issues from a chemical,electrochemical,and interfacial point of view,with particular emphasis on the interaction of halide SSEs with anode and cathode interfaces.By focusing on innovative strategies to address the stability issue,this paper aims to further deepen the understanding and development of halide all-solid-state batteries by proposing to focus research efforts on improving their stability in order to address their inherent challenges and match higher voltage cathodes,paving the way for their wider application in the next generation of energy storage technologies.展开更多
This study demonstrates the successful fabrication of solid-state bilayers using LiFePO_(4)(LFP)cathodes and Li_(1.3)Al_(0.3)Ti_(1.7)(PO_(4))_(3)(LATP)-based Composite Solid Electrolytes(CSEs)via Cold Sintering Proces...This study demonstrates the successful fabrication of solid-state bilayers using LiFePO_(4)(LFP)cathodes and Li_(1.3)Al_(0.3)Ti_(1.7)(PO_(4))_(3)(LATP)-based Composite Solid Electrolytes(CSEs)via Cold Sintering Process(CSP).By optimizing the sintering pressure,it is achieved an intimate contact between the cathode and the solid electrolyte,leading to an enhanced electrochemical performance.Bilayers cold sintered at 300 MPa and a low-sintering temperature of 150℃exhibit high ionic conductivities(0.5 mS cm^(-1))and stable specific capacities at room temperature(160.1 mAh g^(-1)LFP at C/10 and 75.8 mAh g^(-1)_(LFP)at 1 C).Moreover,an operando electrochemical impedance spectroscopy(EIS)technique is employed to identify limiting factors of the bilayer kinetics and to anticipate the overall electrochemical behavior.Results suggest that capacity fading can occur in samples prepared with high sintering pressures due to a volume reduction in the LFP crystalline cell.This work demonstrates the potential of CSP to produce straightforward high-performance bilayers and introduces a valuable non-destructive instrument for understanding and avoiding degradation in solid-state lithium-based batteries.展开更多
Batteries power numerous technolo-gies,yet higher energy density de-mands push lithium cobalt oxide(Li-CoO_(2)referred as LCO)cathodes to higher voltages,triggering unwanted chemical reactions.In this work,we in-vesti...Batteries power numerous technolo-gies,yet higher energy density de-mands push lithium cobalt oxide(Li-CoO_(2)referred as LCO)cathodes to higher voltages,triggering unwanted chemical reactions.In this work,we in-vestigate how carbonate-based elec-trolytes degrade on deeply delithiated LCO surfaces via extensive reactive molecular dynamics simulations.These simulations unveil the forma-tion of characteristic gas products and unstable surface species,which can undermine the cathode structure and reduce battery performance.By examining different solvent composi-tions,the simulations reveal that partial fluorination reduces oxidative degradation and gas evolution,thus offering a route to improve interface stability.Overall,this study provides an atomic-level perspective on preventing unwanted reactions and guiding the design of safer and more robust battery systems for high-voltage applications.展开更多
Hybrid electrolyte lithium-air batteries(HELABs)face challenges such as the high cathode overpotential,cycling instability,and catalyst degradation,limiting their widespread use in practical applications.This study em...Hybrid electrolyte lithium-air batteries(HELABs)face challenges such as the high cathode overpotential,cycling instability,and catalyst degradation,limiting their widespread use in practical applications.This study employs density functional theory(DFT)to analyze the oxygen reduction reaction(ORR)free energy profile,overpotential,and adsorption energy of two-dimensional Ti_(3)C_(2)T_(x) as a cathode catalyst.The optimal oxygen adsorption sites on Ti_(3)C_(2)T_(x) surfaces are identified,and the charge transfer,band structure,density of states,and bonding characteristics after oxygen adsorption are quantitatively analyzed.Results suggest that Ti_(3)C_(2)T_(x) exhibits low overpotentials when used as a HELAB cathode electrocatalyst,with oxygen preferentially adsorbing at the top and bridge sites of Ti_(3)C_(2) and Ti_(3)C_(2)F2,respectively.These findings offer valuable insights for the application of MXenes in HELABs.展开更多
In this study,the pure erosion behaviour of pure iron and its erosion-corrosion behaviour under different anodic polarization currents were investigated in various cathodic reactions(oxygen reduction,hydrogen ion redu...In this study,the pure erosion behaviour of pure iron and its erosion-corrosion behaviour under different anodic polarization currents were investigated in various cathodic reactions(oxygen reduction,hydrogen ion reduction,and water reduction)using a cylindrical stirring system.The corrosion-enhanced erosion(C-E)rates were determined for each condition.The results revealed that pure iron displayed similar pure erosion behaviour across all three cathodic reactions.When the cathodic reactions involve hydrogen ion reduction or water reduction,the erosion-corrosion of pure iron manifested as uniform damage,with the reduction in hardness being the main cause of the C-E in this case.Conversely,in the case of oxy-gen reduction reaction as the cathodic reaction,the erosion-corrosion presented as pitting damage,with the reduction in hardness resulting from localized concentration of anodic current and the formation of easily worn protruding flaky iron structures at the edges of the pits as the main mechanism of the C-E.Moreover,linear and exponential relationships were found between the C-E rate and the anodic current density for uniform damage and pitting damage,respectively.Finally,the concept of surface equivalent hardness was proposed,along with the establishment of a mathematical model for surface equivalent hardness based on the relationships between the C-E rate and the anodic current density.Utilizing the surface equivalent hardness enables the evaluation of the erosion rate on material surfaces considering the coupled effect.展开更多
PEO-based all-solid-state electrolytes are extensively utilized and researched owing to their exceptional safety,low-mass-density,and cost-effectiveness.However,the low oxidation potential of PEO makes the interface p...PEO-based all-solid-state electrolytes are extensively utilized and researched owing to their exceptional safety,low-mass-density,and cost-effectiveness.However,the low oxidation potential of PEO makes the interface problem with the high-voltage cathode extremely severe.In this work,the impedance of PEO-based all-solid-state batteries with high-voltage cathode(NCM811)was studied at different potentials.The Nyquist plots displayed a gyrate arc at low-frequencies for NCM811/PEO interface.Based on the kinetic modeling,it was deduced that there is a decomposition reaction of PEO-matrix in addition to de-embedded reaction of NCM811,and the PEO intermediate product(dehydra-PEO)adsorbed on the electrode surface leading to low-frequency inductive arcs.Furthermore,the distribution of relaxation time shows the dehydra-PEO results in the kinetic tardiness of the charge transfer process in the temporal dimension.Hence,an artificial interface layer(CEI_(x))was modified on the surface of NCM811 to regulate the potential of cathode/electrolyte interface to prevent the high-voltage deterioration of PEO.NCM/CEI_(x)/PEO batteries exhibit capacity retentions of 96.0%,84.6%,and 76.8%after undergoing 100 cycles at cut-off voltages of 4.1,4.2,and 4.3 V,respectively.Therefore,here the failure mechanism of high-voltage PEO electrolyte is investigated by EIS and a proposed solving strategy is presented.展开更多
Understanding the evolution of the solid electrolyte-electrode interface is currently one of the most challenging obstacles in the development of solid-state batteries(SSBs).Here,we develop an X-ray Photoelectron Spec...Understanding the evolution of the solid electrolyte-electrode interface is currently one of the most challenging obstacles in the development of solid-state batteries(SSBs).Here,we develop an X-ray Photoelectron Spectroscopy(XPS)that allows for operando measurement during cycling.Based on theoretical analysis and the modulated electrode and detector co-grounding mode,the displacement of binding energy can be correlated with the surface electrostatic potential of the material,revealing the charge distribution and composition evolution of the space charge layer between the cathode and the electrolyte.In the investigation of typical LiCoO_(2)(LCO)/Li6PS5Cl(LPSC)/Li-In batteries,we observed the static potential difference and oxidative decomposition between LPSC and LCO,and the effectiveness of the LiNbO3 coating in reducing potential difference and inhibiting the diffusion of Co and oxidation of S species.Furthermore,our study also revealed that the potential drop between LiNi0⋅8Co0⋅1Mn0⋅1O_(2) and LPSC is smaller than that of LCO,whilst that between Li3InCl6 and LCO remains near zero.The proposed operando XPS method offers a novel approach for real-time monitoring of interface potential and species formation,providing rational guidance for the interface engineering in SSBs.展开更多
Boosting the interfacial stability between electrolyte and Li-rich cathode material at high operating voltage is vital important to enhance the cycling stability of Li-rich cathode materials for high-performance Li-io...Boosting the interfacial stability between electrolyte and Li-rich cathode material at high operating voltage is vital important to enhance the cycling stability of Li-rich cathode materials for high-performance Li-ion batteries.In this work,vinyltrimethylsilane as a new type of organic silicon electrolyte additive is studied to address the interfacial instability of Li-rich cathode material at high operating voltage.The cells using vinyltrimethylsilane additive shows the high capacity retention of 73.9%after 300 cycles at 1 C,whereas the cells without this kind of additive only have the capacity retention of 58.9%.The improvement of stability is mainly attributed to the additive helping to form a more stable surface film for Li-rich cathode material,thus avoiding direct contact between the electrolyte and the cathode material,slowing down the dissolution of metal ions and the decomposition of the electrolyte under high operating voltage.Our findings in this work shed some light on the design of stable cycling performance of Li-rich cathode toward advanced Li-ion batteries.展开更多
Microstructural design and processing science of ceramics from materials to devices are critical to the present and future applications in various fields.They have profound effects on the mechanical and functional pro...Microstructural design and processing science of ceramics from materials to devices are critical to the present and future applications in various fields.They have profound effects on the mechanical and functional properties,as well as the reliability and lifetime of ceramics.The stability issue has been attracting more and more attentions,as many devices are pushed towards extreme service conditions to gain additional benefits such as energy density and efficiency.In this pespective article,we shall discuss on four selected topics of energy ceramic design,including the oxygen evolution issue of oxide battery cathodes under extreme charge voltages,the synthesis conundrum of single-crystalline battery cathodes,the metal/ceramic interface contact problem in all-solid-state lithium-metal batteries,and the nature of hole polarons in oxygen ion and protonic ceramic electrolytes.Our understanding and solutions to these challenging problems shall be discussed.The new fundamental insights and rationally optimized processing practices presented here could help to develop advanced interdisciplinary ceramics further,enabling exciting applications in the coming decades.展开更多
Owing to their high volumetric capacity,low cost and high safety,rechargeable aluminum batteries have become promising candidates for energy applications.However,the high charge density of Al^(3+)leads to strong coulo...Owing to their high volumetric capacity,low cost and high safety,rechargeable aluminum batteries have become promising candidates for energy applications.However,the high charge density of Al^(3+)leads to strong coulombic interactions between anions and the cathode,resulting in sluggish diffusion kinetics and irreversible collapse of the cathode structure.Furthermore,AlCl_(3)-based ionic liquids,which are commonly used as electrolytes in such batteries,corrode battery components and are prone to side reactions.The above problems lead to low capacity and poor cycling stability.Herein,we propose a reduced graphene oxide(rGO)cathode with a three-dimensional porous structure prepared using a simple and scalable method.The lamellar edges and oxygen-containing group defects of rGO synergistically provide abundant ion storage sites and enhance ion transfer kinetics.We matched the prepared rGO cathode with noncorrosive electrolyte 0.5 mol·L^(-1) Al(OTF)_(3)/[BMIM]OTF and Al metal to construct a high-performance battery,Al||rGO-150,with good cycling stability for 2700 cycles.Quasi-in-situ physicochemical characterization results show that the ion storage mechanism is codominated by diffusion and capacitance.The capacity consists of the insertion of Al-based species cations as well as synergistic adsorption of Al(OTF)_(x)^((3-x)+)(x<3)and[BMIM]+.The present study promotes the fundamental and applied research on rechargeable aluminum batteries.展开更多
基金National Natural Science Foundation of China(U2001220)the Local Innovative Research Teams Project of Guangdong Pearl River Talents Program(No.2017BT01N111)+1 种基金the Shenzhen Technical Plan Project(Nos.JCYJ20180508152210821,JCYJ20170817161221958,and JCYJ20180508152135822)the Shenzhen All-Solid-State Lithium Battery Electrolyte Engineering Research Center(XMHT20200203006).
文摘Security risks of flammability and explosion represent major problems with the use of conventional lithium rechargeable batteries using a liquid electrolyte.The application of solid-state electrolytes could effectively help to avoid these safety concerns.However,integrating the solid-state electrolytes into the all-solid-state lithium batteries is still a huge challenge mainly due to the high interfacial resistance present in the entire battery,especially at the interface between the cathode and the solid-state electrolyte pellet and the interfaces inside the cathode.Herein,recent progress made from investigations of cathode/solid-state electrolyte interfacial behaviors including the contact problem,the interlayer diffusion issue,the space-charge layer effect,and electrochemical compatibility is presented according to the classification of oxide-,sulfide-,and polymer-based solid-state electrolytes.We also propose strategies for the construction of ideal next-generation cathode/solid-state electrolyte interfaces with high room-temperature ionic conductivity,stable interfacial contact during long cycling,free formation of the space-charge region,and good compatibility with high-voltage cathodes.
基金Funded by the National Natural Science Foundation of China(Nos.51772314,51532002,51771222 and 51702346)the Natural Science Foundation of Shanghai City(17ZR1434600)。
文摘Li/garnet/LiFePO_(4) solid-state battery was fabricated.The cathode contains LiFePO_(4),Ketjen black,poly(vinylidene fluoride):LiTFSI polymer as active material,electric conductor and Li-ion conducting binder,respectively.Polyvinylpyrrolidone was added into the cathode to improve cathode/electrolyte interfacial performance.When combined with polyvinylpyrrolidone additive,poly(vinylidene fluoride):polyvinylpyrrol idone:LiTFSI blend forms,and the cathode/electrolyte interfacial resistance reduces from 10.7 kΩto 3.2 kΩ.The Li/garnet/LiFePO_(4) solid-state battery shows 80%capacity retention after 100 cycles at 30℃and 0.05 C.This study offers a general strategy to improve cathode/electrolyte interfacial performance and may enable the practical application of solid-state Li-metal batteries.
基金supported by the National Natural Science Foundation of China(52372249)support by the Program of Shanghai Academic Research Leader(21XD1424400)。
文摘Vanadium pentoxide(V_(2)O_(5))displays the characteristics of high theoretical specific capacity,high operating voltage,and adjustable layered structure,possessing the considerable potential as cathode in magnesium metal batteries(MMBs).Nevertheless,the large charge-radius ratio of Mg^(2+)induces the strong interactions of Mg^(2+)with solvent molecules of electrolyte and anionic framework of cathode,resulting in a notable voltage polarization and structural deterioration during cycling process.Herein,an in-situ multi-scale structural engineering is proposed to activate the interlayer-expanded V_(2)O_(5)cathode(pillared by tetrabutylammonium cation)via adding hexadecyltrimethylammonium bromide(CTAB)additive into electrolyte.During cycling,the in-situ incorporation of CTA^(+)not only enhances the electrostatic shielding effect and Mg species migration,but also stabilizes the interlayer spacing.Besides,CTA^(+)is prone to be adsorbed on cathode surface and induces the loss-free pulverization and amorphization of electroactive grains,leading to the pronounced effect of intercalation pseudocapacitance.CTAB additive also enables to scissor the Mg^(2+)solvation sheath and tailor the insertion mode of Mg species,further endowing V_(2)O_(5)cathode with fast reaction kinetics.Based on these merits,the corresponding V2O5‖Mg full cells exhibit the remarkable rate performance with capacities as high as 317.6,274.4,201.1,and 132.7 mAh g^(-1)at the high current densities of 0.1,0.2,0.5,and 1 A g^(-1),respectively.Moreover,after 1000 cycles,the capacity is still preserved to be 90,4 mAh g^(-1)at 1 A g^(-1)with an average coulombic efficiency of~100%.Our strategy of synergetic modulations of cathode host and electrolyte solvation structures provides new guidance for the development of high-rate,large-capacity,and long-life MMBs.
基金supported by the National Key Research and Development Program of China(2022YFB3803400)。
文摘High-nickel cathode LiNi_(0.8)Co_(0.1)Mn_(0.1)O_(2)(NCM811)could enable lithium-ion batteries(LIBs)with high energy density.However,excessive decomposition of the electrolyte would happen in the high operating voltage range.In addition,the utilization of flammable organic solvents would increase safety risks in the high temperature environment.Herein,an electrolyte consisting of flame-retardant solvents with lower highest occupied molecular orbital(HOMO)level and LiDFOB salt is proposed to address above two issues.As a result,a thin and robust cathode-electrolyte interface containing rich LiF and Li-B-O compounds is formed on the cathode to effectively suppress electrolyte decomposition in the high operating voltage.The NCM811||Li cell paired with this designed electrolyte possesses a capacity retention of 72%after 300 cycles at 55℃.This work provides insights into developing electrolyte for stable high-nickel cathode operated in the high temperature.
基金the financial support received from the National Natural Science Foundation of China(22378426,22138013)the Natural Science Foundation of Shandong Province(ZR2022MB088)the Taishan Scholar Project(ts201712020)。
文摘High-voltage dual-ion batteries(DIBs)face significant challenges,including graphite cathode degradation,cathode-electrolyte interphase(CEI)instability,and the thermodynamic instability of conventional carbonate-based electrolytes,particularly at extreme temperatures.In this study,we develop a stable electrolyte incorporating lithium difluorophosphate(LiDFP)as an additive to enhance the electrochemical performance of DIBs over a wide temperature range.LiDFP preferentially decomposes to form a rapid anion-transporting,mechanically robust CEI layer on graphite,which provides better protection by suppressing graphite's volume expansion,preventing electrolyte oxidative decomposition,and enhancing reaction kinetics.As a result,Li||graphite half cells using LiDFP electrolyte exhibit outstanding rate performance(90.8% capacity retention at 30 C)and excellent cycle stability(82.2% capacity retention after 5000 cycles)at room temperature.Moreover,graphite||graphite full cells with LiDFP electrolyte demonstrate stable discharge capacity across a temperature range of-20 to 40℃,expanding the potential applications of LiDFP.This work establishes a novel strategy for optimizing the interphase through electrolyte design,paving the way for all-climate DIBs with improved performance and stability.
基金financially supported by the National Natural Science Foundation of China(52072036,52272187)the China Petroleum&Chemical Corporation(SINOPEC)project(223128).
文摘All-solid-state batteries(ASSBs)assembled with sulfide solid electrolytes(SSEs)and nickel(Ni)-rich oxide cathode materials are expected to achieve high energy density and safety,representing potential candidates for the next-generation energy storage systems.However,interfacial issues between SSEs and Nirich oxide cathode materials,attributed to space charge layer,interfacial side reactions,and mechanical contact failure,significantly restrict the performances of ASSBs.The interface degradation is closely related to the components of the composite cathode and the process of electrode fabrication.Focusing on the influencing factors of interface compatibility between SSEs and Ni-rich oxide cathode,this article systematically discusses how cathode active materials(CAMs),electrolytes,conductive additives,binders,and electrode fabrication impact the interface compatibility.In addition,the strategies for the compatibility modification are reviewed.Furthermore,the challenges and prospects of intensive research on the degradation and modification of the SSE/Ni-rich cathode material interface are discussed.This review is intended to inspire the development of high-energy-density and high-safety all-solid-state batteries.
基金supported by the National Key Research and Development Program of China(2021YFF0500600)National Natural Science Foundation of China(Nos.U2001220,52203298 and 523B2022)+2 种基金National Science Fund for Distinguished Young Scholars(No.52325206)Shenzhen Technical Plan Project(Nos.RCJC20200714114436091,JCYJ20220530143012027,JCYJ20220818101003008 and JCYJ20220818101003007)Tsinghua Shenzhen International Graduate School-Shenzhen Pengrui Young Faculty Program of Shenzhen Pengrui Foundation(No.SZPR2023006).
文摘Nickel(Ni)-rich layered oxides have drawn great attention as cathode for lithium batteries due to their high capacity,high working voltage and competitive cost.Unfortunately,the operation of Ni-rich cathodes suffers from the notorious structural degradation and interfacial side reactions with electrolytes and thus incurs premature failure,especially at high charge cut-off voltages(≥4.4 V).For this,various structural and interphase regulation strategies(such as coating modification,element doping,and electrolyte engineering)are developed to enhance the cycling survivability of Ni-rich cathodes.Among them,electrolyte engineering by changing solvation structure and introducing additives has been considered an efficient method for constructing robust cathode-electrolyte interphases(CEI),inhibiting the formation of harmful species(such as HF and H_(2)O)or restraining the dissolution of transition metal ions.However,there is still an absence of systematic guidelines for selecting and designing competitive electrolyte systems for Ni-rich layered cathodes.In this review,we comprehensively summarize the recent research progress on electrolyte engineering for Ni-rich layered cathodes according to their working mechanisms.Moreover,we propose future perspectives of improving the electrolyte performance,which will provide new insights for designing novel electrolytes toward high-performance Ni-rich layered cathodes.
文摘Lithium-rich manganese-based oxides(LRMOs;xLi_(2)MnO_(3)(1−x)LiMO_(2);M=transition metal,0<x<1)with excellent specific capacity(>300 mAh/g)and high operating voltage(≥4.8V)are the preferred cathode materials for high-specific-energy lithium metal batteries(LMBs)[1].However,LRMOs face a series of serious problems such as irreversible lattice oxygen loss,transition metal(TM)migration,phase transfer,and interfacial side reactions at high voltages,resulting in rapid decay of capacity and voltage[2,3].In situ generating well-functional CEI through electrolyte engineering can effectively address these challenges[4].
基金financially supported by the Scientific Research Innovation Project of Graduate School of South China Normal University (No. 2024KYLX081)。
文摘As a potential candidate for high-energy lithium-ion batteries (LIBs),nickel-rich cathodes encounter significant challenges due to structural instability arising from interphases.In this work,tris(ethenyl)-tris(ethenyl)silyloxysilane (HVDS) with Si–O bonds and unsaturated bonds is introduced as additive designing functional electrolyte to enhance the long-cycle stability of LiNi_(0.8)Co_(0.1)Mn_(0.1)O_(2)(NCM811)/graphite LIBs at elevated temperature.The preferential oxidization and component of HVDS facilitate the generation of an extremely robust and ultra-thin cathode electrolyte interphase (CEI) comprising a chemically bonded silane polymer.This interphase effectively suppresses side-reactions of electrolyte,mitigates HF erosion,and reduces irreversible phase transitions.Benefiting from the above merits,the batteries’capacity retention shows a remarkable increase from 20% to 92% after nearly 1550 cycles conducted at room temperature.And under elevated temperature conditions (45℃),the capacity retention remains 80%after 670 cycles,in comparison to a drop to 80%after only 250 cycles with the blank electrolyte.These findings highlight HVDS’s potential to functionalize the electrolyte,marking a breakthrough in improving the longevity and reliability of NCM811/graphite LIBs under challenging conditions.
基金funding support from the Macao Science and Technology Development Fund(0013/2021/AMJ and 0082/2022/A2)support from the Multi-Year Research Grants(MYRG2022-00266-IAPME,and MYRG-GRG2023-00224-IAPME)provided by the Research&Development Office at the University of Macao+2 种基金the National Natural Science Foundation of China(52202328)the Shanghai Sailing Program(22YF1455500)the Shanghai Magnolia Talent Plan Pujiang Project(24PJD128)for their financial support。
文摘Iron-based Prussian white(PW)materials have attracted considerable attention as promising cathodes for potassium-ion batteries(PIBs)due to their high capacity,easy preparation,and economic merits.However,the intrinsic iron dissolution and uncontrollable cathode-electrolyte interface(CEI)formation in conventional organic electrolytes severely hinder their long-term cycling stability.Herein,we employ succinonitrile(SN),a bifunctional electrolyte additive,to suppress the iron dissolution and promote thin,uniform,and stable CEI formation of the PW cathode,thus improving its structural stability.Benefited from the coordination between the cyano groups in SN and iron atoms,this molecule can preferentially adsorb on the surface of PW to mitigate iron dissolution.SN also facilitates the decomposition of anions in potassium salt rather than organic solvents in electrolyte due to the attractive reaction between SN and anions.Consequently,the PW cathode with SN additive provides better electrochemical reversibility,showing capacity retention of 93.6%after 3000 cycles at 5C.In comparison,without SN,the capacity retention is only 87.4%after 1000 cycles under the same conditions.Moreover,the full cells of PW matched with commercial graphite(Gr)achieve stable cycling for 3500 cycles at a high rate of 20C,with an exceptional capacity decay of only 0.005%per cycle,surpassing the majority of recently reported results in literature.
基金supported by the National Natural Science Foundation of China(nos.22309027 and 52374301)the Shijiazhuang Basic Research Project(nos.241790667A and 241790907A)+3 种基金the Fundamental Research Funds for the Central Universities(no.N2523050)the Natural Science Foundation of Hebei Province(no.E2024501010)the Performance subsidy fund for Key Laboratory of Dielectric and Electrolyte Functional Material Hebei Province(no.22567627H)the 2024 Hebei Provincial Postgraduate Student Innovation Ability Training Funding Project(no.CXZZSS2025162)。
文摘Halide solid-state electrolytes(SSEs)have become a new research focus for all-solid-state batteries because of their significant safety advantages,high ionic conductivity,high-voltage stability,and good ductility.Nonetheless,stability issues are a key barrier to their practical application.In past reports,the analysis of halide electrolyte stability and its enhancement methods lacked relevance,which limited the design and optimization of halide solid electrolytes.This review focus on stability issues from a chemical,electrochemical,and interfacial point of view,with particular emphasis on the interaction of halide SSEs with anode and cathode interfaces.By focusing on innovative strategies to address the stability issue,this paper aims to further deepen the understanding and development of halide all-solid-state batteries by proposing to focus research efforts on improving their stability in order to address their inherent challenges and match higher voltage cathodes,paving the way for their wider application in the next generation of energy storage technologies.
基金support from Generalitat Valenciana under Pla Complementari“Programa de Materials Avanc¸ats”,2022(grant number MFA/2022/030)Ministerio de Ciencia,Innovaci´on y Universidades(Spain)(grant number MCIN/AEI/10.13039/501100011033)+1 种基金support from UJI(UJI-2023-16 and GACUJIMC/2023/08)Generalitat Valenciana through FPI Fellowship Program(grant numbers ACIF/2020/294 and CIACIF/2021/050).
文摘This study demonstrates the successful fabrication of solid-state bilayers using LiFePO_(4)(LFP)cathodes and Li_(1.3)Al_(0.3)Ti_(1.7)(PO_(4))_(3)(LATP)-based Composite Solid Electrolytes(CSEs)via Cold Sintering Process(CSP).By optimizing the sintering pressure,it is achieved an intimate contact between the cathode and the solid electrolyte,leading to an enhanced electrochemical performance.Bilayers cold sintered at 300 MPa and a low-sintering temperature of 150℃exhibit high ionic conductivities(0.5 mS cm^(-1))and stable specific capacities at room temperature(160.1 mAh g^(-1)LFP at C/10 and 75.8 mAh g^(-1)_(LFP)at 1 C).Moreover,an operando electrochemical impedance spectroscopy(EIS)technique is employed to identify limiting factors of the bilayer kinetics and to anticipate the overall electrochemical behavior.Results suggest that capacity fading can occur in samples prepared with high sintering pressures due to a volume reduction in the LFP crystalline cell.This work demonstrates the potential of CSP to produce straightforward high-performance bilayers and introduces a valuable non-destructive instrument for understanding and avoiding degradation in solid-state lithium-based batteries.
基金support from the National Key Research and Development Program of China(No.2022YFB2502200)the Natural Science Foun-dation of Jiangsu Province(BK20230065)+2 种基金the Key Laboratory of Functional Nano&Soft Materials,the Collaborative Innovation Center of Suzhou Nano Sci-ence&Technology,the Priority Academic Program Development of Jiangsu Higher Education Institutions(PAPD)the 111 Project,Joint International Research Laboratory of Carbon-Based Functional Materials and Devices,Yue Liu acknowledges support from the National Natural Science Foundation of China(22303058)the Natural Science Foundation of Jiangsu Province(BK20230475).
文摘Batteries power numerous technolo-gies,yet higher energy density de-mands push lithium cobalt oxide(Li-CoO_(2)referred as LCO)cathodes to higher voltages,triggering unwanted chemical reactions.In this work,we in-vestigate how carbonate-based elec-trolytes degrade on deeply delithiated LCO surfaces via extensive reactive molecular dynamics simulations.These simulations unveil the forma-tion of characteristic gas products and unstable surface species,which can undermine the cathode structure and reduce battery performance.By examining different solvent composi-tions,the simulations reveal that partial fluorination reduces oxidative degradation and gas evolution,thus offering a route to improve interface stability.Overall,this study provides an atomic-level perspective on preventing unwanted reactions and guiding the design of safer and more robust battery systems for high-voltage applications.
文摘Hybrid electrolyte lithium-air batteries(HELABs)face challenges such as the high cathode overpotential,cycling instability,and catalyst degradation,limiting their widespread use in practical applications.This study employs density functional theory(DFT)to analyze the oxygen reduction reaction(ORR)free energy profile,overpotential,and adsorption energy of two-dimensional Ti_(3)C_(2)T_(x) as a cathode catalyst.The optimal oxygen adsorption sites on Ti_(3)C_(2)T_(x) surfaces are identified,and the charge transfer,band structure,density of states,and bonding characteristics after oxygen adsorption are quantitatively analyzed.Results suggest that Ti_(3)C_(2)T_(x) exhibits low overpotentials when used as a HELAB cathode electrocatalyst,with oxygen preferentially adsorbing at the top and bridge sites of Ti_(3)C_(2) and Ti_(3)C_(2)F2,respectively.These findings offer valuable insights for the application of MXenes in HELABs.
基金supported by the National Key Research and Development Program(No.2022YFC2806200)the National Key Research and Development Program(No.2023YFC2810800)the Natural Science Foundation of China(No.52001055).
文摘In this study,the pure erosion behaviour of pure iron and its erosion-corrosion behaviour under different anodic polarization currents were investigated in various cathodic reactions(oxygen reduction,hydrogen ion reduction,and water reduction)using a cylindrical stirring system.The corrosion-enhanced erosion(C-E)rates were determined for each condition.The results revealed that pure iron displayed similar pure erosion behaviour across all three cathodic reactions.When the cathodic reactions involve hydrogen ion reduction or water reduction,the erosion-corrosion of pure iron manifested as uniform damage,with the reduction in hardness being the main cause of the C-E in this case.Conversely,in the case of oxy-gen reduction reaction as the cathodic reaction,the erosion-corrosion presented as pitting damage,with the reduction in hardness resulting from localized concentration of anodic current and the formation of easily worn protruding flaky iron structures at the edges of the pits as the main mechanism of the C-E.Moreover,linear and exponential relationships were found between the C-E rate and the anodic current density for uniform damage and pitting damage,respectively.Finally,the concept of surface equivalent hardness was proposed,along with the establishment of a mathematical model for surface equivalent hardness based on the relationships between the C-E rate and the anodic current density.Utilizing the surface equivalent hardness enables the evaluation of the erosion rate on material surfaces considering the coupled effect.
基金financially supported by the National Natural Science Foundation of China (Nos. 51972023, 11210304)
文摘PEO-based all-solid-state electrolytes are extensively utilized and researched owing to their exceptional safety,low-mass-density,and cost-effectiveness.However,the low oxidation potential of PEO makes the interface problem with the high-voltage cathode extremely severe.In this work,the impedance of PEO-based all-solid-state batteries with high-voltage cathode(NCM811)was studied at different potentials.The Nyquist plots displayed a gyrate arc at low-frequencies for NCM811/PEO interface.Based on the kinetic modeling,it was deduced that there is a decomposition reaction of PEO-matrix in addition to de-embedded reaction of NCM811,and the PEO intermediate product(dehydra-PEO)adsorbed on the electrode surface leading to low-frequency inductive arcs.Furthermore,the distribution of relaxation time shows the dehydra-PEO results in the kinetic tardiness of the charge transfer process in the temporal dimension.Hence,an artificial interface layer(CEI_(x))was modified on the surface of NCM811 to regulate the potential of cathode/electrolyte interface to prevent the high-voltage deterioration of PEO.NCM/CEI_(x)/PEO batteries exhibit capacity retentions of 96.0%,84.6%,and 76.8%after undergoing 100 cycles at cut-off voltages of 4.1,4.2,and 4.3 V,respectively.Therefore,here the failure mechanism of high-voltage PEO electrolyte is investigated by EIS and a proposed solving strategy is presented.
基金the financial support from the National Natural Science Foundation of China(No.12174057,22179020)Natural Science Foundation of Fujian Province(Grant No.2021L3011).
文摘Understanding the evolution of the solid electrolyte-electrode interface is currently one of the most challenging obstacles in the development of solid-state batteries(SSBs).Here,we develop an X-ray Photoelectron Spectroscopy(XPS)that allows for operando measurement during cycling.Based on theoretical analysis and the modulated electrode and detector co-grounding mode,the displacement of binding energy can be correlated with the surface electrostatic potential of the material,revealing the charge distribution and composition evolution of the space charge layer between the cathode and the electrolyte.In the investigation of typical LiCoO_(2)(LCO)/Li6PS5Cl(LPSC)/Li-In batteries,we observed the static potential difference and oxidative decomposition between LPSC and LCO,and the effectiveness of the LiNbO3 coating in reducing potential difference and inhibiting the diffusion of Co and oxidation of S species.Furthermore,our study also revealed that the potential drop between LiNi0⋅8Co0⋅1Mn0⋅1O_(2) and LPSC is smaller than that of LCO,whilst that between Li3InCl6 and LCO remains near zero.The proposed operando XPS method offers a novel approach for real-time monitoring of interface potential and species formation,providing rational guidance for the interface engineering in SSBs.
基金supported partially by State Key Laboratory of Alternate Electrical Power System with Renewable Energy Sources(Nos.LAPS_(2)1004,LAPS_(2)02114)National Natural Science Foundation of China(Nos.52272200,51972110,52102245 and 52072121)+6 种基金Beijing Science and Technology Project(No.Z211100004621010)Beijing Natural Science Foundation(Nos.2222076,2222077)Hebei Natural Science Foundation(No.E2022502022)Huaneng Group Headquarters Science and Technology Project(No.HNKJ20-H88)2022 Strategic Research Key Project of Science and Technology Commission of the Ministry of Education,China Postdoctoral Science Foundation(No.2022M721129)the Fundamental Research Funds for the Central Universities(Nos.2022MS030,2021MS028,2020MS023,2020MS028)the NCEPU"Double First-Class"Program and the State Key Laboratory of Alternate Electrical Power System with Renewable Energy Sources(No.LAPS22005).
文摘Boosting the interfacial stability between electrolyte and Li-rich cathode material at high operating voltage is vital important to enhance the cycling stability of Li-rich cathode materials for high-performance Li-ion batteries.In this work,vinyltrimethylsilane as a new type of organic silicon electrolyte additive is studied to address the interfacial instability of Li-rich cathode material at high operating voltage.The cells using vinyltrimethylsilane additive shows the high capacity retention of 73.9%after 300 cycles at 1 C,whereas the cells without this kind of additive only have the capacity retention of 58.9%.The improvement of stability is mainly attributed to the additive helping to form a more stable surface film for Li-rich cathode material,thus avoiding direct contact between the electrolyte and the cathode material,slowing down the dissolution of metal ions and the decomposition of the electrolyte under high operating voltage.Our findings in this work shed some light on the design of stable cycling performance of Li-rich cathode toward advanced Li-ion batteries.
基金supported by National Key Research and Development Program of China(grant no.2023YFB3812000).
文摘Microstructural design and processing science of ceramics from materials to devices are critical to the present and future applications in various fields.They have profound effects on the mechanical and functional properties,as well as the reliability and lifetime of ceramics.The stability issue has been attracting more and more attentions,as many devices are pushed towards extreme service conditions to gain additional benefits such as energy density and efficiency.In this pespective article,we shall discuss on four selected topics of energy ceramic design,including the oxygen evolution issue of oxide battery cathodes under extreme charge voltages,the synthesis conundrum of single-crystalline battery cathodes,the metal/ceramic interface contact problem in all-solid-state lithium-metal batteries,and the nature of hole polarons in oxygen ion and protonic ceramic electrolytes.Our understanding and solutions to these challenging problems shall be discussed.The new fundamental insights and rationally optimized processing practices presented here could help to develop advanced interdisciplinary ceramics further,enabling exciting applications in the coming decades.
基金supported by the National Natural Science Foundation of China(Grant Nos.52222213,U23A20572)the Fundamental Research Funds for the Central Universities of China(Grant No.22lgqb01).
文摘Owing to their high volumetric capacity,low cost and high safety,rechargeable aluminum batteries have become promising candidates for energy applications.However,the high charge density of Al^(3+)leads to strong coulombic interactions between anions and the cathode,resulting in sluggish diffusion kinetics and irreversible collapse of the cathode structure.Furthermore,AlCl_(3)-based ionic liquids,which are commonly used as electrolytes in such batteries,corrode battery components and are prone to side reactions.The above problems lead to low capacity and poor cycling stability.Herein,we propose a reduced graphene oxide(rGO)cathode with a three-dimensional porous structure prepared using a simple and scalable method.The lamellar edges and oxygen-containing group defects of rGO synergistically provide abundant ion storage sites and enhance ion transfer kinetics.We matched the prepared rGO cathode with noncorrosive electrolyte 0.5 mol·L^(-1) Al(OTF)_(3)/[BMIM]OTF and Al metal to construct a high-performance battery,Al||rGO-150,with good cycling stability for 2700 cycles.Quasi-in-situ physicochemical characterization results show that the ion storage mechanism is codominated by diffusion and capacitance.The capacity consists of the insertion of Al-based species cations as well as synergistic adsorption of Al(OTF)_(x)^((3-x)+)(x<3)and[BMIM]+.The present study promotes the fundamental and applied research on rechargeable aluminum batteries.
