To address the limitations of contemporary lithium-ion batteries,particularly their low energy density and safety concerns,all-solid-state lithium batteries equipped with solid-state electrolytes have been identified ...To address the limitations of contemporary lithium-ion batteries,particularly their low energy density and safety concerns,all-solid-state lithium batteries equipped with solid-state electrolytes have been identified as an up-and-coming alternative.Among the various SEs,organic–inorganic composite solid electrolytes(OICSEs)that combine the advantages of both polymer and inorganic materials demonstrate promising potential for large-scale applications.However,OICSEs still face many challenges in practical applications,such as low ionic conductivity and poor interfacial stability,which severely limit their applications.This review provides a comprehensive overview of recent research advancements in OICSEs.Specifically,the influence of inorganic fillers on the main functional parameters of OICSEs,including ionic conductivity,Li+transfer number,mechanical strength,electrochemical stability,electronic conductivity,and thermal stability are systematically discussed.The lithium-ion conduction mechanism of OICSE is thoroughly analyzed and concluded from the microscopic perspective.Besides,the classic inorganic filler types,including both inert and active fillers,are categorized with special emphasis on the relationship between inorganic filler structure design and the electrochemical performance of OICSEs.Finally,the advanced characterization techniques relevant to OICSEs are summarized,and the challenges and perspectives on the future development of OICSEs are also highlighted for constructing superior ASSLBs.展开更多
Lithium-ion batteries(LIBs)have greatly facilitated our daily lives since 1990s[1,2].To meet the ever-increasing demand on energy density,Li metal is seen as the ultimate anode because of its ultra-high specific capac...Lithium-ion batteries(LIBs)have greatly facilitated our daily lives since 1990s[1,2].To meet the ever-increasing demand on energy density,Li metal is seen as the ultimate anode because of its ultra-high specific capacity(3860 m Ah/g)and the lowest electrochemical potential(-3.04 V vs.the standard hydrogen electrode)[3–6].However,issues of Li metal anode,such as Li dendrite formation and large volume change during plating/stripping。展开更多
The insurmountable charge transfer impedance at the Li metal/solid polymer electrolytes(SPEs)interface at room temperature as well as the ascending risk of short circuits at the operating temperature higher than the m...The insurmountable charge transfer impedance at the Li metal/solid polymer electrolytes(SPEs)interface at room temperature as well as the ascending risk of short circuits at the operating temperature higher than the melting point,dominantly limits their applications in solid-state batteries(SSBs).Although the inorganic filler such as CeO_(2)nanoparticle content of composite solid polymer electrolytes(CSPEs)can significantly reduce the enormous charge transfer impedance at the Li metal/SPEs interface,we found that the required content of CeO_(2)nanoparticles in SPEs varies for achieving a decent interfacial charge transfer impedance and the bulk ionic conductivity in CSPEs.In this regard,a sandwich-type composited solid polymer electrolyte with a 10%CeO_(2)CSPEs interlayer sandwiched between two 50%CeO_(2)CSPEs thin layers(sandwiched CSPEs)is constructed to simultaneously achieve low charge transfer impedance and superior ionic conductivity at 30℃.The sandwiched CSPEs allow for stable cycling of Li plating and stripping for 1000 h with 129 mV polarized voltage at 0.1 mA cm^(-2)and 30℃.In addition,the LiFePO_(4)/Sandwiched CSPEs/Li cell also exhibits exceptional cycle performance at 30℃and even elevated120℃without short circuits.Constructing multi-layered CSPEs with optimized contents of the inorganic fillers can be an efficient method for developing all solid-state PEO-based batteries with high performance at a wide range of temperatures.展开更多
Recent advances in utilizing ^(17)O isotopic labeling methods for solid-state nuclear magnetic resonance(NMR)investigations of metal oxides for lithium-ion batteries have yielded extensive insights into their structur...Recent advances in utilizing ^(17)O isotopic labeling methods for solid-state nuclear magnetic resonance(NMR)investigations of metal oxides for lithium-ion batteries have yielded extensive insights into their structural and dynamic details.Herein,we commence with a brief introduction to recent research on lithium-ion battery oxide materials studied using ^(17)O solid-state NMR spectroscopy.Then we delve into a review of ^(17)O isotopic labeling methods for tagging oxygen sites in both the bulk and surfaces of metal oxides.At last,the unresolved problems and the future research directions for advancing the ^(17)O labeling technique are discussed.展开更多
Silicon(Si)is a promising anode material for rechargeable batteries due to its high theoretical capacity and abundance,but its practical application is hindered by the continuous growth of porous solid-electrolyte int...Silicon(Si)is a promising anode material for rechargeable batteries due to its high theoretical capacity and abundance,but its practical application is hindered by the continuous growth of porous solid-electrolyte interphase(SEI),leading to capacity fade.Herein,a LiF-Pie structured SEI is proposed,with LiF nanodomains encapsulated in the inner layer of the organic cross-linking silane matrix.A series of advanced techniques such as cryogenic electron microscopy,time-of-flight secondary ion mass spectrometry,and matrix-assisted laser desorption/ionization time-of-flight mass spectrometry have provided detailed insights into the formation mechanism,nanostructure,and chemical composition of the interface.With such SEI,the capacity retention of LiCoO_(2)||Si is significantly improved from 49.6%to 88.9%after 300 cycles at 100 mA g^(-1).These findings provide a desirable interfacial design principle with enhanced(electro)chemical and mechanical stability,which are crucial for sustaining Si anode functionality,thereby significantly advancing the reliability and practical application of Si-based anodes.展开更多
Supercapacitors,comprising electrical double-layer capacitors(EDLCs)and pseudocapa-citors,are widely acknowledged as high-power energy storage devices.However,their local structures and fundamental mechanisms remain p...Supercapacitors,comprising electrical double-layer capacitors(EDLCs)and pseudocapa-citors,are widely acknowledged as high-power energy storage devices.However,their local structures and fundamental mechanisms remain poorly understood,and suitable experimental techniques for investigation are also lacking.Recently,nuclear magnetic resonance(NMR)has emerged as a powerful tool for addressing these fundamental issues with high local sensitivity and non-invasiveness.In this paper,we first review the limi-tations of existing characterization methods and highlight the advantages of NMR in investigating mechanisms of supercapacitors.Subsequently,we introduce the basic prin-ciple of ring current effect,NMR-active nuclei,and various NMR techniques employed in exploring energy storage mechanisms including cross polarization(CP)magic angle spinning(MAS)NMR,multiple-quantum(MQ)MAS,two-dimensional exchange spec-troscopy(2D-EXSY)NMR,magnetic resonance imaging(MRI)and pulsed-field gradient(PFG)NMR.Based on this,recent progress in investigating energy storage mechanisms in EDLCs and pseudocapacitors through various NMR techniques is discussed.Finally,an outlook on future directions for NMR research in supercapacitors is offered.展开更多
The photocatalytic oxidative coupling of amines has emerged as a promising alternative for imine production.Nevertheless,enhancing the photocatalytic activity of conjugated organic polymers(COP)still faces significant...The photocatalytic oxidative coupling of amines has emerged as a promising alternative for imine production.Nevertheless,enhancing the photocatalytic activity of conjugated organic polymers(COP)still faces significant challenges,particularly in near-infrared(NIR)driven photocatalytic activity,charge separation efficiency,adsorption,and activation of amine molecules.Here,we tackled these challenges by modulating the internal electronic states of cobalt phthalocyanine polymers(C-CoPPc-x)through edgesubstituted modification with various electron-donating or electron-withdrawing groups.The built-in electric field(B-IEF)and Lewis acidity of metal sites are significantly influenced by such an edgesubstituted modification,which further results in an adjustable separation efficiency of photogenerated charges and the adsorption/activation behavior of benzylamine.By optimizing the surface catalytic reactions of COP,the methoxy-edge-modified polymer demonstrated a superior performance with an amine yield of 4.32 mmol g^(-1)under NIR irradiation,surpassing the performance of many reported photocatalysts even under ultraviolet(UV)or visible light.This work underscores the substantial impact of minor substituent modifications on both the separation of photogenerated charge carriers and the adsorption/activation of amine molecules in the photocatalytic process,and provides valuable insights for enhancing the photocatalytic performance of COP in diverse applications.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
Sodium metal batteries(SMBs)are promising candidates for next-generation energy storage devices owing to their excellent safety performance and natural abunda nce of sodium.However,the insurmountable obstacles of dend...Sodium metal batteries(SMBs)are promising candidates for next-generation energy storage devices owing to their excellent safety performance and natural abunda nce of sodium.However,the insurmountable obstacles of dendrite formation and quick capacity decay are caused by an unstable and inhomogeneous solid electrolyte interphase that resulted from the immediate interactions between the Na metal anode and organic liquid electrolyte.Herein,a customised glass fibre separator coupled with chitosan(CS@GF)was developed to modulate the sodium ion(Na^(+))flux.The CS@GF separator facilitates the Na+homogeneous deposition on the anode side through redistribution at the chitosan polyactive sites and by inhibiting the decomposition of the electrolyte to robust solid electrolyte interphase(SEI)formation.Multiphysics simulations show that chitosan incorporated into SMBs through the separator can make the local electric field around the anode uniform,thus facilitating the transfer of cations.Na|Na symmetric cells utilising a CS@GF separator exhibited an outstanding cycle stability of over 600 h(0.5 mA cm^(-2)).Meanwhile,the Na|Na_(3)V_(5)(PO_(4))_(3)full cell exhibited excellent fast-charging performance(93.47%capacity retention after 1500 cycles at 5C).This study presents a promising strategy for inhibiting dendrite growth and realizes stable Na metal batteries,which significantly boosts the development of high-performance SMBs.展开更多
In this paper,we report the design of ultrafine ordered PtFeZn ternary intermetallics uniformly supported on ZIF-8-derived Zn,N-codoped graphitic carbon(ZnNC)via a green aqueous impregnation method followed by a two-s...In this paper,we report the design of ultrafine ordered PtFeZn ternary intermetallics uniformly supported on ZIF-8-derived Zn,N-codoped graphitic carbon(ZnNC)via a green aqueous impregnation method followed by a two-step annealing protocol(H_(2)/Ar,600 and 800℃)to circumvent the sintering issues imposed by conventional thermodynamics.Physical characterizations(X-ray diffraction,high-angle annular dark-field scanning transmission electron microscopy,X-ray absorption spectroscopy)and theoretical calculations reveal that low-temperature annealing at 600℃stabilizes sub-nano disordered PtFe alloys via the strong metal-support interactions(SMSI)between Zn in ZnNC and Pt precursors,while high-temperature treatment at 800℃promotes Zn diffusion from the support into the alloy bulk and simultaneously triggers the disorder-to-order phase transition.The as-prepared ZnNC-15PtFeZn exhibits an initial mass activity of 0.769 mA/μgPt and retains 61.7%of its activity after 30000 cycles of accelerated stress testing(AST).Notably,when used as a cathode catalyst in MEA,ZnNC-15PtFeZn achieves superior power density(2.018 W/cm^(2)under H_(2)-O_(2))at half the Pt loading(0.05 mg/cm^(2))of state-of-the-art commercial Pt/C,highlighting its potential for low-Pt PEMFCs.Density functional theory confirms that Fe enhances ORR activity via ligand effects,while Zn strengthens Pt-Fe/Zn bonding(elevating vacancy formation energies),thereby improving structural stability.This mild,scalable aqueous impregnation strategy offers a general approach for synthesizing multi-component ordered alloys in electrocatalysis.展开更多
Achieving simultaneous fast-charging capabilities and low-temperature adaptability in graphite-based lithium-ion batteries(LIBs)with an acceptable cycle life remains challenging.Herein,an ether-based electrolyte with ...Achieving simultaneous fast-charging capabilities and low-temperature adaptability in graphite-based lithium-ion batteries(LIBs)with an acceptable cycle life remains challenging.Herein,an ether-based electrolyte with temperature-adaptive Li^(+)solvation structure is designed for graphite,and stable Li^(+)/solvent co-intercalation has been achieved at subzero.As revealed by in-situ variable temperature(-20℃)X-ray diffraction(XRD),the poor compatibility of graphite in ether-based electrolyte at 25℃is mainly due to the continuous electrolyte decomposition and the in-plane rearrangement below0.5 V.Former results in a significant irreversible capacity,while latter maintains graphite in a prolonged state of extreme expansion,ultimately leading to its exfoliation and failure.In contrast,low temperature triggers the rearra ngement of Li^(+)solvation structu re with stronger Li^(+)/solvent binding energy and sho rter Li^(+)-O bond length,which is conducive for reversible Li^(+)/solvent co-intercalation and reducing the time of graphite in an extreme expansion state.In addition,the co-intercalation of solvents minimizes the interaction between Li-ions and host graphite,endowing graphite with fast diffusion kinetics.As expected,the graphite anode delivers about 84%of the capacity at room temperature at-20℃.Moreover,within6 min,about 83%,73%,and 43%of the capacity could be charged at 25,-20,and-40℃,respectively.展开更多
Micrometer-sized silicon oxide(SiO)anodes encounter challenges in large-scale applications due to significant volume expansion during the alloy/de-alloy process.Herein,an innovative deep eutectic electrolyte derived f...Micrometer-sized silicon oxide(SiO)anodes encounter challenges in large-scale applications due to significant volume expansion during the alloy/de-alloy process.Herein,an innovative deep eutectic electrolyte derived from succinonitrile is introduced to enhance the cycling stability of SiO anodes.Density functional theory calculations validate a robust ion-dipole interaction between lithium ions(Li^(+))and succinonitrile(SN).The cosolvent fluoroethylene carbonate(FEC)optimizes the Li^(+)solvation structure in the SN-based electrolyte with its weakly solvating ability.Molecular dynamics simulations investigate the regulating mechanism of ion-dipole and cation-anion interaction.The unique Li^(+)solvation structure,enriched with FEC and TFSI^(-),facilitates the formation of an inorganic-organic composite solid electrolyte interphase on SiO anodes.Micro-CT further detects the inhibiting effect on the SiO volume expansion.As a result,the SiO|LiCoO_(2) full cells exhibit excellent electrochemical performance in deep eutectic-based electrolytes.This work presents an effective strategy for extending the cycle life of SiO anodes by designing a new SN-based deep eutectic electrolyte.展开更多
Sodium-ion batteries are promising candidates for next-generation large-scale energy storage owing to their abundance and low cost.Biphasic intercalation reactions,constrained by kinetic limitations and structural ins...Sodium-ion batteries are promising candidates for next-generation large-scale energy storage owing to their abundance and low cost.Biphasic intercalation reactions,constrained by kinetic limitations and structural instability,fundamentally restrict the rate capability and cycle life of sodium ion batteries.However,precise regulation of these reactions to enhance kinetics remains challenging.Here,we propose a strategy of atomic-scale phase engineering to activate the metastable state and achieve a three-phase reaction through precise Mg^(2+)doping at V sites in Na_(3)V_(2)(PO_(4))_(3).The Mg^(2+)occupancy promotes the exchange between Na1 and Na2 sites,thereby stabilizing a Na_(2)V_(2)(PO_(4))_(3) intermediate.First-principles calculations indicate that Mg^(2+)occupation facilitates charge redistribution by weakening Na-O electrostatic interaction,stabilizing the formation of Na_(2)V_(2)(PO_(4))_(3)phase.The optimized cathode exhibits ultrahigh capacity retention(84.5%after 5000 cycles at 3.51 A g^(-1)),supports ultrafast charging within 120 s,and exceptional rate capability(96.2 mAh g^(-1)at 4.68 A g^(-1)).This work establishes a universal route to unlock hidden reaction pathways by redefining the role of dopants in phase transition control.展开更多
NASICON-type vanadium fluorophosphate is a promising cathode for sodium-ion batteries.Yet,the thermally-driven loss of undercoordinated dangling fluorine anions weakens its structural stability,which triggers severe f...NASICON-type vanadium fluorophosphate is a promising cathode for sodium-ion batteries.Yet,the thermally-driven loss of undercoordinated dangling fluorine anions weakens its structural stability,which triggers severe framework distortion from interconnected double-octahedral to isolated local octahedral units,as well as a degeneracy of t_(2g) electronic configuration of vanadium(V)3d orbit.In this work,it is clarified that such a degenerate state undergoes spontaneous lattice evolution to reduce the system energy,which causes a low crystalline symmetry and a parasitic V^(4+)/V^(3+)redox reaction in the low-voltage region.Herein,an anion-coordination regulation strategy is developed to suppress this degeneration by anchoring fluorine anions in the double-octahedral[V_(2)O_(8)F_(3)]framework.Density functional theory calculations and in-situ techniques track the F-anion-driven structural evolution and charge compensation mechanisms,revealing that this strategy mitigates detrimental phase segregation during the initial desodiation stage and enhances the Na^(+)diffusion kinetic rate over a factor of 100.Concurrently,this strategy releases the V^(4+)/V^(3+)redox kinetics by eliminating the parasitic low-voltage plateau.The full-cell assembled with the optimized fluorophosphate cathode delivers an increase of 50%in discharge capacity and stable two-voltage-plateau behavior,enabled by its double-octahedral[V_(2)O_(8)F_(3)]polyanionic structure that facilitates unimpeded three-dimensional(3D)Na^(+)transport.By correlating anion-coordination stability with orbital-level charge compensation,this work establishes a universal paradigm for highperformance polyanionic cathodes,positioning it as a competitive candidate for battery applications.展开更多
The NASICON-structured Na_(3)MnTi(PO_(4))_(3)(NMTP)cathode has attracted widespread attention due to its prominent thermal stability,stable 3D structure and rapid sodium ion transport channel.However,the poor cycling ...The NASICON-structured Na_(3)MnTi(PO_(4))_(3)(NMTP)cathode has attracted widespread attention due to its prominent thermal stability,stable 3D structure and rapid sodium ion transport channel.However,the poor cycling stability,limited electronic conductivity and phase transition represent significant obstacles to for its commercialization.Herein,an innovative mixed-conducting interphase,comprising amorphous carbon and Ti_(3)C_(2)-MXene,was developed for NMTP.NMTP particles are evenly dispersed on the MXene sheets through electrostatic adsorption,and MXenes can also regulate the growth of NMTP crystals and provide a large number of active sites in contact with the electrolyte.Furthermore,DFT calculations demonstrate that MXene enhances both electron and ion transport processes.Therefore,the mixedconducting interphase,forming an interconnected network on the NMTP surface,serves as an artificial cathode electrolyte interface,significantly enhancing the dynamic processes and cycle stability of the NMTP cathode.The NMTP/C@Ti_(3)C_(2)exhibits a fully reversible three-electron redox reaction and inhibited voltage hysteresis.An excellent reversible capacity of 158.2 mAh/g is achieved at 0.2 C,corresponding to an extremely high energy density of 466.6 Wh/kg.This study presents an effective approach for developing high-energy SIB cathodes.展开更多
Energy storage plays a critical role in sustainable development,with secondary batteries serving as vital technologies for efficient energy conversion and utilization.This review provides a comprehensive summary of re...Energy storage plays a critical role in sustainable development,with secondary batteries serving as vital technologies for efficient energy conversion and utilization.This review provides a comprehensive summary of recent advancements across various battery systems,including lithium-ion,sodium-ion,potassium-ion,and multivalent metal-ion batteries such as magnesium,zinc,calcium,and aluminum.Emerging technologies,including dual-ion,redox flow,and anion batteries,are also discussed.Particular attention is given to alkali metal rechargeable systems,such as lithium-sulfur,lithium-air,sodium-sulfur,sodium-selenium,potassium-sulfur,potassium-selenium,potassium-air,and zinc-air batteries,which have shown significant promise for high-energy applications.The optimization of key components—cathodes,anodes,electrolytes,and interfaces—is extensively analyzed,supported by advanced characterization techniques like time-of-flight secondary ion mass spectrometry(TOF-SIMS),synchrotron radiation,nuclear magnetic resonance(NMR),and in-situ spectroscopy.Moreover,sustainable strategies for recycling spent batteries,including pyrometallurgy,hydrometallurgy,and direct recycling,are critically evaluated to mitigate environmental impacts and resource scarcity.This review not only highlights the latest technological breakthroughs but also identifies key challenges in reaction mechanisms,material design,system integration,and waste battery recycling,and presents a roadmap for advancing high-performance and sustainable battery technologies.展开更多
Novel cost-effective fuel cells have become more attractive due to the demands for rare and expensive platinum-group metal(PGM)catalysts for mitigating the sluggish kinetics of the oxygen reduction reaction(ORR).The h...Novel cost-effective fuel cells have become more attractive due to the demands for rare and expensive platinum-group metal(PGM)catalysts for mitigating the sluggish kinetics of the oxygen reduction reaction(ORR).The high-cost PGM catalyst in fuel cells can be replaced by earth-abundant transition-metalbased catalysts,that is,an Fe-N-C catalyst,which is considered one of the most promising alternatives.However,the performance of the Fe-N-C catalyst is hindered by the low catalytic activity and poor stability,which is caused by insufficient active sites and the lack of optimization of the triple-phase interface for mass transportation.Herein,a novel Fe–N–C catalyst consisting of mono-dispersed hierarchically mesoporous carbon sphere cores and single Fe atom-dispersed functional shells are presented.The synergistic effect between highly dispersed Fe-active sites and well-organized porous structures yields the combination of high ORR activity and high mass transfer performance.The half-wave potential of the catalyst in 0.1M H_(2)SO_(4) is 0.82 V versus reversible hydrogen electrode,and the peak power density is 812 mW·cm^(−2) in H_(2)–O_(2) fuel cells.Furthermore,it shows superior methanol tolerance,which is almost immune to methanol poisoning and generates up to 162 mW·cm^(−2) power density in direct methanol fuel cells.展开更多
As a promising solid electrolyte for thin-film lithium batteries,the amorphous Li_(0.33)La_(0.56)TiO_(3)(LLTO)thin film has gained great interest.However,enhancing ionic conductivity remains challenging in the field.H...As a promising solid electrolyte for thin-film lithium batteries,the amorphous Li_(0.33)La_(0.56)TiO_(3)(LLTO)thin film has gained great interest.However,enhancing ionic conductivity remains challenging in the field.Here,a systematical study was performed to improve the ionic conductivity of sputter-deposited LLTO thin films via the optimization of processing atmosphere and temperature.By combining the optimized oxygen partial pressure(30%),annealing temperature(300℃),and annealing atmosphere(air),an amorphous LLTO thin film with an ionic conductivity of 5.32910^(-5)·S·cm^(-1) at room temperature and activation energy of 0.26 eV was achieved.The results showed that,first,the oxygen partial pressure should be high enough to compensate for the oxygen loss,but low enough to avoid the abusive oxygen scattering effect on lithium precursors that results in a lithium-poor composition.The oxygen partial pressure needs to achieve a balance between lithium loss and oxygen defects to improve the ionic conductivity.Second,a proper annealing temperature reduces the oxygen defects of LLTO thin films while maintaining its amorphous state,which improves the ionic conductivity.Third,the highest ionic conductivity for the LLTO thin films that were annealed in air(a static space without a gas stream)occurs because of the decreased lithium loss and oxygen defects during annealing.These findings show that the lithium-ion concentration and oxygen defects affect the ionic conductivity for amorphous LLTO thin films,which provides insight into the optimization of LLTO thin-film solid electrolytes,and generates new opportunities for their application in thinfilm lithium batteries.展开更多
It is challenging for aqueous Zn-ion batteries(ZIBs)to achieve comparable low-temperature(low-T)performance due to the easy-frozen electrolyte and severe Zn dendrites.Herein,an aqueous electrolyte with a low freezing ...It is challenging for aqueous Zn-ion batteries(ZIBs)to achieve comparable low-temperature(low-T)performance due to the easy-frozen electrolyte and severe Zn dendrites.Herein,an aqueous electrolyte with a low freezing point and high ionic conductivity is proposed.Combined with molecular dynamics simulation and multi-scale interface analysis(time of flight secondary ion mass spectrometry threedimensional mapping and in-situ electrochemical impedance spectroscopy method),the temperature independence of the V_(2)O_(5)cathode and Zn anode is observed to be opposite.Surprisingly,dominated by the solvent structure of the designed electrolyte at low temperatures,vanadium dissolution/shuttle is significantly inhibited,and the zinc dendrites caused by this electrochemical crosstalk are greatly relieved,thus showing an abnormal temperature inversion effect.Through the disclosure and improvement of the above phenomena,the designed Zn||V_(2)O_(5)full cell delivers superior low-T performance,maintaining almost 99%capacity retention after 9500 cycles(working more than 2500 h)at-20°C.This work proposes a kind of electrolyte suitable for low-T ZIBs and reveals the inverse temperature dependence of the Zn anode,which might offer a novel perspective for the investigation of low-T aqueous battery systems.展开更多
Lithium-sulfur(Li-S)batteries have been considered as the next generation high energy storage devices.However,its commercialization has been hindered by several issues,especially the dissolution and shuttle of the sol...Lithium-sulfur(Li-S)batteries have been considered as the next generation high energy storage devices.However,its commercialization has been hindered by several issues,especially the dissolution and shuttle of the soluble lithium polysulfides(LiPSs)as well as the slow reaction kinetics of LiPSs which may make shuttling effect even worse.Herein,we report a strategy to address this issue by in-situ transformation of Co−N_(x) coordinations in cobalt polyphthalocyanine(CoPPc)into Co nanoparticles(Co NPs)embedded in carbon matrix and mono-dispersed on graphene flakes.The Co NPs can provide rich binding and catalytic sites,while graphene flakes act as ideally LiPSs transportation and electron conducting platform.With a remarkable enhanced reaction kinetics of LiPSs via these merits,the sulfur host with a sulfur content up to 70 wt%shows a high initial capacity of 1048 mA∙h/g at 0.2C,good rate capability up to 399 mA·h/g at 2C.展开更多
基金supported by the National Natural Science Foundation of China(Grant No.22075064,52302234,52272241)Zhejiang Provincial Natural Science Foundation of China under Grant No.LR24E020001+2 种基金Natural Science of Heilongjiang Province(No.LH2023B009)China Postdoctoral Science Foundation(2022M710950)Heilongjiang Postdoctoral Fund(LBH-Z21131),National Key Laboratory Projects(No.SYSKT20230056).
文摘To address the limitations of contemporary lithium-ion batteries,particularly their low energy density and safety concerns,all-solid-state lithium batteries equipped with solid-state electrolytes have been identified as an up-and-coming alternative.Among the various SEs,organic–inorganic composite solid electrolytes(OICSEs)that combine the advantages of both polymer and inorganic materials demonstrate promising potential for large-scale applications.However,OICSEs still face many challenges in practical applications,such as low ionic conductivity and poor interfacial stability,which severely limit their applications.This review provides a comprehensive overview of recent research advancements in OICSEs.Specifically,the influence of inorganic fillers on the main functional parameters of OICSEs,including ionic conductivity,Li+transfer number,mechanical strength,electrochemical stability,electronic conductivity,and thermal stability are systematically discussed.The lithium-ion conduction mechanism of OICSE is thoroughly analyzed and concluded from the microscopic perspective.Besides,the classic inorganic filler types,including both inert and active fillers,are categorized with special emphasis on the relationship between inorganic filler structure design and the electrochemical performance of OICSEs.Finally,the advanced characterization techniques relevant to OICSEs are summarized,and the challenges and perspectives on the future development of OICSEs are also highlighted for constructing superior ASSLBs.
基金financial support by the National Natural Science Foundation of China(No.51802224)“Shanghai Rising-Star Program”(19QA1409300)Shanghai Aerospace Science and Technology Innovation Fundation(SISP2018)。
文摘Lithium-ion batteries(LIBs)have greatly facilitated our daily lives since 1990s[1,2].To meet the ever-increasing demand on energy density,Li metal is seen as the ultimate anode because of its ultra-high specific capacity(3860 m Ah/g)and the lowest electrochemical potential(-3.04 V vs.the standard hydrogen electrode)[3–6].However,issues of Li metal anode,such as Li dendrite formation and large volume change during plating/stripping。
基金supported by the National Key R&D Program of China(2021YFB2400400)the National Natural Science Foundation of China(Grant No.22379120,22179085)+5 种基金the Key Research and Development Plan of Shanxi Province(China,Grant No.2018ZDXM-GY-135,2021JLM-36)the National Natural Science Foundation of China(Grant No.22108218)the“Young Talent Support Plan”of Xi’an Jiaotong University(71211201010723)the Qinchuangyuan Innovative Talent Project(QCYRCXM-2022-137)the“Young Talent Support Plan”of Xi’an Jiaotong University(HG6J003)the“1000-Plan program”of Shaanxi Province。
文摘The insurmountable charge transfer impedance at the Li metal/solid polymer electrolytes(SPEs)interface at room temperature as well as the ascending risk of short circuits at the operating temperature higher than the melting point,dominantly limits their applications in solid-state batteries(SSBs).Although the inorganic filler such as CeO_(2)nanoparticle content of composite solid polymer electrolytes(CSPEs)can significantly reduce the enormous charge transfer impedance at the Li metal/SPEs interface,we found that the required content of CeO_(2)nanoparticles in SPEs varies for achieving a decent interfacial charge transfer impedance and the bulk ionic conductivity in CSPEs.In this regard,a sandwich-type composited solid polymer electrolyte with a 10%CeO_(2)CSPEs interlayer sandwiched between two 50%CeO_(2)CSPEs thin layers(sandwiched CSPEs)is constructed to simultaneously achieve low charge transfer impedance and superior ionic conductivity at 30℃.The sandwiched CSPEs allow for stable cycling of Li plating and stripping for 1000 h with 129 mV polarized voltage at 0.1 mA cm^(-2)and 30℃.In addition,the LiFePO_(4)/Sandwiched CSPEs/Li cell also exhibits exceptional cycle performance at 30℃and even elevated120℃without short circuits.Constructing multi-layered CSPEs with optimized contents of the inorganic fillers can be an efficient method for developing all solid-state PEO-based batteries with high performance at a wide range of temperatures.
基金supported by National Key R&D Program of China(2021YFA1502803)the National Natural Science Foundation of China(NSFC)(21972066,91745202)+3 种基金NSFC-Royal Society Joint Program(21661130149)L.P.thanks the Royal Society and Newton Fund for a Royal Society-Newton Advanced Fellowshipsupported by the Research Funds for the Frontiers Science Centre for Critical Earth Material Cycling,Nanjing Universitya Project Funded by the Priority Academic Program Development of Jiangsu Higher Education Institutions.
文摘Recent advances in utilizing ^(17)O isotopic labeling methods for solid-state nuclear magnetic resonance(NMR)investigations of metal oxides for lithium-ion batteries have yielded extensive insights into their structural and dynamic details.Herein,we commence with a brief introduction to recent research on lithium-ion battery oxide materials studied using ^(17)O solid-state NMR spectroscopy.Then we delve into a review of ^(17)O isotopic labeling methods for tagging oxygen sites in both the bulk and surfaces of metal oxides.At last,the unresolved problems and the future research directions for advancing the ^(17)O labeling technique are discussed.
基金supported by the National Key Research and Development Program of China(Grant No.2022YFB2502200)the National Natural Science Foundation of China(NSFC nos.52172257 and 22409211)+2 种基金the China Postdoctoral Science Foundation(No.2023M743739)the Postdoctoral Fellowship Program of CPSF(No.GZC20232939)CAS Youth Interdisciplinary Team。
文摘Silicon(Si)is a promising anode material for rechargeable batteries due to its high theoretical capacity and abundance,but its practical application is hindered by the continuous growth of porous solid-electrolyte interphase(SEI),leading to capacity fade.Herein,a LiF-Pie structured SEI is proposed,with LiF nanodomains encapsulated in the inner layer of the organic cross-linking silane matrix.A series of advanced techniques such as cryogenic electron microscopy,time-of-flight secondary ion mass spectrometry,and matrix-assisted laser desorption/ionization time-of-flight mass spectrometry have provided detailed insights into the formation mechanism,nanostructure,and chemical composition of the interface.With such SEI,the capacity retention of LiCoO_(2)||Si is significantly improved from 49.6%to 88.9%after 300 cycles at 100 mA g^(-1).These findings provide a desirable interfacial design principle with enhanced(electro)chemical and mechanical stability,which are crucial for sustaining Si anode functionality,thereby significantly advancing the reliability and practical application of Si-based anodes.
基金supported by the National Natural Science Foundation of China(Grant No.22075064)National Key Laboratory Projects(No.SYSKT20230056).
文摘Supercapacitors,comprising electrical double-layer capacitors(EDLCs)and pseudocapa-citors,are widely acknowledged as high-power energy storage devices.However,their local structures and fundamental mechanisms remain poorly understood,and suitable experimental techniques for investigation are also lacking.Recently,nuclear magnetic resonance(NMR)has emerged as a powerful tool for addressing these fundamental issues with high local sensitivity and non-invasiveness.In this paper,we first review the limi-tations of existing characterization methods and highlight the advantages of NMR in investigating mechanisms of supercapacitors.Subsequently,we introduce the basic prin-ciple of ring current effect,NMR-active nuclei,and various NMR techniques employed in exploring energy storage mechanisms including cross polarization(CP)magic angle spinning(MAS)NMR,multiple-quantum(MQ)MAS,two-dimensional exchange spec-troscopy(2D-EXSY)NMR,magnetic resonance imaging(MRI)and pulsed-field gradient(PFG)NMR.Based on this,recent progress in investigating energy storage mechanisms in EDLCs and pseudocapacitors through various NMR techniques is discussed.Finally,an outlook on future directions for NMR research in supercapacitors is offered.
基金supported by the National Natural Science Foundation of China(52172278)the Natural Science Foundation of Heilongjiang Province(LH2022E050)。
文摘The photocatalytic oxidative coupling of amines has emerged as a promising alternative for imine production.Nevertheless,enhancing the photocatalytic activity of conjugated organic polymers(COP)still faces significant challenges,particularly in near-infrared(NIR)driven photocatalytic activity,charge separation efficiency,adsorption,and activation of amine molecules.Here,we tackled these challenges by modulating the internal electronic states of cobalt phthalocyanine polymers(C-CoPPc-x)through edgesubstituted modification with various electron-donating or electron-withdrawing groups.The built-in electric field(B-IEF)and Lewis acidity of metal sites are significantly influenced by such an edgesubstituted modification,which further results in an adjustable separation efficiency of photogenerated charges and the adsorption/activation behavior of benzylamine.By optimizing the surface catalytic reactions of COP,the methoxy-edge-modified polymer demonstrated a superior performance with an amine yield of 4.32 mmol g^(-1)under NIR irradiation,surpassing the performance of many reported photocatalysts even under ultraviolet(UV)or visible light.This work underscores the substantial impact of minor substituent modifications on both the separation of photogenerated charge carriers and the adsorption/activation of amine molecules in the photocatalytic process,and provides valuable insights for enhancing the photocatalytic performance of COP in diverse applications.
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funded by the Key Research and Development Program of Shandong Province(2023CXPT069)Opening Funds of the State Key Laboratory of Building Safety and Built Environment(BSBE2022-EET-06)Innovation Project of Guangwei Group Academician Workstation(GWYS-2022-04)。
文摘Sodium metal batteries(SMBs)are promising candidates for next-generation energy storage devices owing to their excellent safety performance and natural abunda nce of sodium.However,the insurmountable obstacles of dendrite formation and quick capacity decay are caused by an unstable and inhomogeneous solid electrolyte interphase that resulted from the immediate interactions between the Na metal anode and organic liquid electrolyte.Herein,a customised glass fibre separator coupled with chitosan(CS@GF)was developed to modulate the sodium ion(Na^(+))flux.The CS@GF separator facilitates the Na+homogeneous deposition on the anode side through redistribution at the chitosan polyactive sites and by inhibiting the decomposition of the electrolyte to robust solid electrolyte interphase(SEI)formation.Multiphysics simulations show that chitosan incorporated into SMBs through the separator can make the local electric field around the anode uniform,thus facilitating the transfer of cations.Na|Na symmetric cells utilising a CS@GF separator exhibited an outstanding cycle stability of over 600 h(0.5 mA cm^(-2)).Meanwhile,the Na|Na_(3)V_(5)(PO_(4))_(3)full cell exhibited excellent fast-charging performance(93.47%capacity retention after 1500 cycles at 5C).This study presents a promising strategy for inhibiting dendrite growth and realizes stable Na metal batteries,which significantly boosts the development of high-performance SMBs.
文摘In this paper,we report the design of ultrafine ordered PtFeZn ternary intermetallics uniformly supported on ZIF-8-derived Zn,N-codoped graphitic carbon(ZnNC)via a green aqueous impregnation method followed by a two-step annealing protocol(H_(2)/Ar,600 and 800℃)to circumvent the sintering issues imposed by conventional thermodynamics.Physical characterizations(X-ray diffraction,high-angle annular dark-field scanning transmission electron microscopy,X-ray absorption spectroscopy)and theoretical calculations reveal that low-temperature annealing at 600℃stabilizes sub-nano disordered PtFe alloys via the strong metal-support interactions(SMSI)between Zn in ZnNC and Pt precursors,while high-temperature treatment at 800℃promotes Zn diffusion from the support into the alloy bulk and simultaneously triggers the disorder-to-order phase transition.The as-prepared ZnNC-15PtFeZn exhibits an initial mass activity of 0.769 mA/μgPt and retains 61.7%of its activity after 30000 cycles of accelerated stress testing(AST).Notably,when used as a cathode catalyst in MEA,ZnNC-15PtFeZn achieves superior power density(2.018 W/cm^(2)under H_(2)-O_(2))at half the Pt loading(0.05 mg/cm^(2))of state-of-the-art commercial Pt/C,highlighting its potential for low-Pt PEMFCs.Density functional theory confirms that Fe enhances ORR activity via ligand effects,while Zn strengthens Pt-Fe/Zn bonding(elevating vacancy formation energies),thereby improving structural stability.This mild,scalable aqueous impregnation strategy offers a general approach for synthesizing multi-component ordered alloys in electrocatalysis.
基金financially supported by the National Natural Science Foundation of China(52372191)the Natural Science Foundation of Fujian Province(2023J05047)+1 种基金the Natural Science Foundation of Xiamen,China(3502Z202372036)the support of the High-Performance Computing Center(HPCC)at Harbin Institute of Technology on first-principles calculations.
文摘Achieving simultaneous fast-charging capabilities and low-temperature adaptability in graphite-based lithium-ion batteries(LIBs)with an acceptable cycle life remains challenging.Herein,an ether-based electrolyte with temperature-adaptive Li^(+)solvation structure is designed for graphite,and stable Li^(+)/solvent co-intercalation has been achieved at subzero.As revealed by in-situ variable temperature(-20℃)X-ray diffraction(XRD),the poor compatibility of graphite in ether-based electrolyte at 25℃is mainly due to the continuous electrolyte decomposition and the in-plane rearrangement below0.5 V.Former results in a significant irreversible capacity,while latter maintains graphite in a prolonged state of extreme expansion,ultimately leading to its exfoliation and failure.In contrast,low temperature triggers the rearra ngement of Li^(+)solvation structu re with stronger Li^(+)/solvent binding energy and sho rter Li^(+)-O bond length,which is conducive for reversible Li^(+)/solvent co-intercalation and reducing the time of graphite in an extreme expansion state.In addition,the co-intercalation of solvents minimizes the interaction between Li-ions and host graphite,endowing graphite with fast diffusion kinetics.As expected,the graphite anode delivers about 84%of the capacity at room temperature at-20℃.Moreover,within6 min,about 83%,73%,and 43%of the capacity could be charged at 25,-20,and-40℃,respectively.
基金supported by the National Natural Science Foundation of China(22279026)the National Key Research and Development Program of China(2022YFE0138900)+2 种基金the Young Elite Scientist sponsorship program by CAST(no.20200148)the Natural Science Funds of Heilongjiang Province(YQ2021B003)the Fundamental Research Funds for the Central Universities(grant no.HIT.OCEF.2022017).
文摘Micrometer-sized silicon oxide(SiO)anodes encounter challenges in large-scale applications due to significant volume expansion during the alloy/de-alloy process.Herein,an innovative deep eutectic electrolyte derived from succinonitrile is introduced to enhance the cycling stability of SiO anodes.Density functional theory calculations validate a robust ion-dipole interaction between lithium ions(Li^(+))and succinonitrile(SN).The cosolvent fluoroethylene carbonate(FEC)optimizes the Li^(+)solvation structure in the SN-based electrolyte with its weakly solvating ability.Molecular dynamics simulations investigate the regulating mechanism of ion-dipole and cation-anion interaction.The unique Li^(+)solvation structure,enriched with FEC and TFSI^(-),facilitates the formation of an inorganic-organic composite solid electrolyte interphase on SiO anodes.Micro-CT further detects the inhibiting effect on the SiO volume expansion.As a result,the SiO|LiCoO_(2) full cells exhibit excellent electrochemical performance in deep eutectic-based electrolytes.This work presents an effective strategy for extending the cycle life of SiO anodes by designing a new SN-based deep eutectic electrolyte.
基金finally supported by the National Natural Science Foundation of China(NSFC Grants 52074098)the Major Science and Technology R&D Special Project in Jiangxi Province(104 Ah high specific energy and fast charging function lithium-ion battery system development and application project 20233AAE02009)the Cospowers Technology Co.,Ltd.,Technology Project Funding(research on key materials and battery technologies for sodium ion batteries,KYDY2022003)。
文摘Sodium-ion batteries are promising candidates for next-generation large-scale energy storage owing to their abundance and low cost.Biphasic intercalation reactions,constrained by kinetic limitations and structural instability,fundamentally restrict the rate capability and cycle life of sodium ion batteries.However,precise regulation of these reactions to enhance kinetics remains challenging.Here,we propose a strategy of atomic-scale phase engineering to activate the metastable state and achieve a three-phase reaction through precise Mg^(2+)doping at V sites in Na_(3)V_(2)(PO_(4))_(3).The Mg^(2+)occupancy promotes the exchange between Na1 and Na2 sites,thereby stabilizing a Na_(2)V_(2)(PO_(4))_(3) intermediate.First-principles calculations indicate that Mg^(2+)occupation facilitates charge redistribution by weakening Na-O electrostatic interaction,stabilizing the formation of Na_(2)V_(2)(PO_(4))_(3)phase.The optimized cathode exhibits ultrahigh capacity retention(84.5%after 5000 cycles at 3.51 A g^(-1)),supports ultrafast charging within 120 s,and exceptional rate capability(96.2 mAh g^(-1)at 4.68 A g^(-1)).This work establishes a universal route to unlock hidden reaction pathways by redefining the role of dopants in phase transition control.
基金supported by the National Key Research and Development Program of China(2023YFB2406100)the National Natural Science Foundation of China(Grant No.22075062 and U23A20573)+6 种基金the Heilongjiang Touyan Team(Grant No.HITTY20190033)the Heilongjiang Postdoctoral Financial Assistance(Grant No.LBH-Z23137)the Postdoctoral Fellowship Program of CPSF(Grant No.GZC20233448)the China Postdoctoral Science Foundation(Grant No.2024M754198)the Shenzhen Science and Technology Program(KCXST20221021111216037)the Fundamental Research Funds for the Central Universities(Grant No.FRFCU5710051922)the program of “Open bidding for selecting the best candidates”(Grant No.2023JCA06)from Jiangxi Fuzhou Municipal Government。
文摘NASICON-type vanadium fluorophosphate is a promising cathode for sodium-ion batteries.Yet,the thermally-driven loss of undercoordinated dangling fluorine anions weakens its structural stability,which triggers severe framework distortion from interconnected double-octahedral to isolated local octahedral units,as well as a degeneracy of t_(2g) electronic configuration of vanadium(V)3d orbit.In this work,it is clarified that such a degenerate state undergoes spontaneous lattice evolution to reduce the system energy,which causes a low crystalline symmetry and a parasitic V^(4+)/V^(3+)redox reaction in the low-voltage region.Herein,an anion-coordination regulation strategy is developed to suppress this degeneration by anchoring fluorine anions in the double-octahedral[V_(2)O_(8)F_(3)]framework.Density functional theory calculations and in-situ techniques track the F-anion-driven structural evolution and charge compensation mechanisms,revealing that this strategy mitigates detrimental phase segregation during the initial desodiation stage and enhances the Na^(+)diffusion kinetic rate over a factor of 100.Concurrently,this strategy releases the V^(4+)/V^(3+)redox kinetics by eliminating the parasitic low-voltage plateau.The full-cell assembled with the optimized fluorophosphate cathode delivers an increase of 50%in discharge capacity and stable two-voltage-plateau behavior,enabled by its double-octahedral[V_(2)O_(8)F_(3)]polyanionic structure that facilitates unimpeded three-dimensional(3D)Na^(+)transport.By correlating anion-coordination stability with orbital-level charge compensation,this work establishes a universal paradigm for highperformance polyanionic cathodes,positioning it as a competitive candidate for battery applications.
基金supported by the National Natural Science Foundation of China(Nos.51604089,51874110 and 22479035)Natural Science Foundation of Heilongjiang Province(No.YQ2021B004)。
文摘The NASICON-structured Na_(3)MnTi(PO_(4))_(3)(NMTP)cathode has attracted widespread attention due to its prominent thermal stability,stable 3D structure and rapid sodium ion transport channel.However,the poor cycling stability,limited electronic conductivity and phase transition represent significant obstacles to for its commercialization.Herein,an innovative mixed-conducting interphase,comprising amorphous carbon and Ti_(3)C_(2)-MXene,was developed for NMTP.NMTP particles are evenly dispersed on the MXene sheets through electrostatic adsorption,and MXenes can also regulate the growth of NMTP crystals and provide a large number of active sites in contact with the electrolyte.Furthermore,DFT calculations demonstrate that MXene enhances both electron and ion transport processes.Therefore,the mixedconducting interphase,forming an interconnected network on the NMTP surface,serves as an artificial cathode electrolyte interface,significantly enhancing the dynamic processes and cycle stability of the NMTP cathode.The NMTP/C@Ti_(3)C_(2)exhibits a fully reversible three-electron redox reaction and inhibited voltage hysteresis.An excellent reversible capacity of 158.2 mAh/g is achieved at 0.2 C,corresponding to an extremely high energy density of 466.6 Wh/kg.This study presents an effective approach for developing high-energy SIB cathodes.
基金supported by the National Natural Science Foundation of China(Nos.U21A20311 and 22409147)。
文摘Energy storage plays a critical role in sustainable development,with secondary batteries serving as vital technologies for efficient energy conversion and utilization.This review provides a comprehensive summary of recent advancements across various battery systems,including lithium-ion,sodium-ion,potassium-ion,and multivalent metal-ion batteries such as magnesium,zinc,calcium,and aluminum.Emerging technologies,including dual-ion,redox flow,and anion batteries,are also discussed.Particular attention is given to alkali metal rechargeable systems,such as lithium-sulfur,lithium-air,sodium-sulfur,sodium-selenium,potassium-sulfur,potassium-selenium,potassium-air,and zinc-air batteries,which have shown significant promise for high-energy applications.The optimization of key components—cathodes,anodes,electrolytes,and interfaces—is extensively analyzed,supported by advanced characterization techniques like time-of-flight secondary ion mass spectrometry(TOF-SIMS),synchrotron radiation,nuclear magnetic resonance(NMR),and in-situ spectroscopy.Moreover,sustainable strategies for recycling spent batteries,including pyrometallurgy,hydrometallurgy,and direct recycling,are critically evaluated to mitigate environmental impacts and resource scarcity.This review not only highlights the latest technological breakthroughs but also identifies key challenges in reaction mechanisms,material design,system integration,and waste battery recycling,and presents a roadmap for advancing high-performance and sustainable battery technologies.
基金We gratefully acknowledge support from the National Natural Science Foundation of China(Grant Nos.21905220,51772240,21503158,51425301,U1601214,21703184)the China Postdoctoral Science Foundation(2020M673408)+5 种基金the Key Research and Development Plan of Shaanxi Province,China(Grant No.2018ZDXM-GY-135)the Fundamental Research Funds for“Young Talent Support Plan”of Xi'an Jiaotong University(HG6J003)the“1000‐Plan program”of Shaanxi Province,the Promotion Program for Young and Middle-Aged Teacher in Science and Technology Research of Huaqiao University(ZQN-PY506)the Scientific Research Funds of Huaqiao University(17BS405)the State Key Laboratory for Mechanical Behavior of Materials(20192101)the Natural Science Foundation Committee of Jiangsu Province(BK20201190).
文摘Novel cost-effective fuel cells have become more attractive due to the demands for rare and expensive platinum-group metal(PGM)catalysts for mitigating the sluggish kinetics of the oxygen reduction reaction(ORR).The high-cost PGM catalyst in fuel cells can be replaced by earth-abundant transition-metalbased catalysts,that is,an Fe-N-C catalyst,which is considered one of the most promising alternatives.However,the performance of the Fe-N-C catalyst is hindered by the low catalytic activity and poor stability,which is caused by insufficient active sites and the lack of optimization of the triple-phase interface for mass transportation.Herein,a novel Fe–N–C catalyst consisting of mono-dispersed hierarchically mesoporous carbon sphere cores and single Fe atom-dispersed functional shells are presented.The synergistic effect between highly dispersed Fe-active sites and well-organized porous structures yields the combination of high ORR activity and high mass transfer performance.The half-wave potential of the catalyst in 0.1M H_(2)SO_(4) is 0.82 V versus reversible hydrogen electrode,and the peak power density is 812 mW·cm^(−2) in H_(2)–O_(2) fuel cells.Furthermore,it shows superior methanol tolerance,which is almost immune to methanol poisoning and generates up to 162 mW·cm^(−2) power density in direct methanol fuel cells.
基金This study was financially supported by the National Natural Science Funds of China(No.21905040)the Startup Funds from the University of Electronic Science and Technology of China,the National Key Research and Development Program of China(Nos.2017YFB0702802 and 2018YFB0905400)Shanghai Venus Project(No.18QB1402600).
文摘As a promising solid electrolyte for thin-film lithium batteries,the amorphous Li_(0.33)La_(0.56)TiO_(3)(LLTO)thin film has gained great interest.However,enhancing ionic conductivity remains challenging in the field.Here,a systematical study was performed to improve the ionic conductivity of sputter-deposited LLTO thin films via the optimization of processing atmosphere and temperature.By combining the optimized oxygen partial pressure(30%),annealing temperature(300℃),and annealing atmosphere(air),an amorphous LLTO thin film with an ionic conductivity of 5.32910^(-5)·S·cm^(-1) at room temperature and activation energy of 0.26 eV was achieved.The results showed that,first,the oxygen partial pressure should be high enough to compensate for the oxygen loss,but low enough to avoid the abusive oxygen scattering effect on lithium precursors that results in a lithium-poor composition.The oxygen partial pressure needs to achieve a balance between lithium loss and oxygen defects to improve the ionic conductivity.Second,a proper annealing temperature reduces the oxygen defects of LLTO thin films while maintaining its amorphous state,which improves the ionic conductivity.Third,the highest ionic conductivity for the LLTO thin films that were annealed in air(a static space without a gas stream)occurs because of the decreased lithium loss and oxygen defects during annealing.These findings show that the lithium-ion concentration and oxygen defects affect the ionic conductivity for amorphous LLTO thin films,which provides insight into the optimization of LLTO thin-film solid electrolytes,and generates new opportunities for their application in thinfilm lithium batteries.
基金financially supported by the National Natural Science Foundation of China(52372191)the Natural Science Foundation of Xiamen,China(3502Z202372036)+1 种基金the China Postdoctoral Science Foundation(2022TQ0282)the support of the High-Performance Computing Center(HPCC)at Harbin Institute of Technology on first-principles calculations。
文摘It is challenging for aqueous Zn-ion batteries(ZIBs)to achieve comparable low-temperature(low-T)performance due to the easy-frozen electrolyte and severe Zn dendrites.Herein,an aqueous electrolyte with a low freezing point and high ionic conductivity is proposed.Combined with molecular dynamics simulation and multi-scale interface analysis(time of flight secondary ion mass spectrometry threedimensional mapping and in-situ electrochemical impedance spectroscopy method),the temperature independence of the V_(2)O_(5)cathode and Zn anode is observed to be opposite.Surprisingly,dominated by the solvent structure of the designed electrolyte at low temperatures,vanadium dissolution/shuttle is significantly inhibited,and the zinc dendrites caused by this electrochemical crosstalk are greatly relieved,thus showing an abnormal temperature inversion effect.Through the disclosure and improvement of the above phenomena,the designed Zn||V_(2)O_(5)full cell delivers superior low-T performance,maintaining almost 99%capacity retention after 9500 cycles(working more than 2500 h)at-20°C.This work proposes a kind of electrolyte suitable for low-T ZIBs and reveals the inverse temperature dependence of the Zn anode,which might offer a novel perspective for the investigation of low-T aqueous battery systems.
基金Project(21905220) supported by the National Natural Science Foundation of ChinaProject(BK20201190) supported by the Jiangsu Provincial Department of Science and Technology,China+2 种基金Projects(2018ZDXM-GY-135,2021JLM-36) supported by the Key Research and Development Plan of Shaanxi Province,ChinaProject(HG6J003) supported by the Fundamental Research Funds for “Young Talent Support Plan” of Xi’ an Jiaotong University,ChinaProject supported by the “1000-Plan program” of Shaanxi Province,China。
文摘Lithium-sulfur(Li-S)batteries have been considered as the next generation high energy storage devices.However,its commercialization has been hindered by several issues,especially the dissolution and shuttle of the soluble lithium polysulfides(LiPSs)as well as the slow reaction kinetics of LiPSs which may make shuttling effect even worse.Herein,we report a strategy to address this issue by in-situ transformation of Co−N_(x) coordinations in cobalt polyphthalocyanine(CoPPc)into Co nanoparticles(Co NPs)embedded in carbon matrix and mono-dispersed on graphene flakes.The Co NPs can provide rich binding and catalytic sites,while graphene flakes act as ideally LiPSs transportation and electron conducting platform.With a remarkable enhanced reaction kinetics of LiPSs via these merits,the sulfur host with a sulfur content up to 70 wt%shows a high initial capacity of 1048 mA∙h/g at 0.2C,good rate capability up to 399 mA·h/g at 2C.
