Fluoride-based electrolyte exhibits extraordinarily high oxidative stability in high-voltage lithium metal batteries(h-LMBs) due to the inherent low highest occupied molecular orbital(HOMO) of fiuorinated solvents. Ho...Fluoride-based electrolyte exhibits extraordinarily high oxidative stability in high-voltage lithium metal batteries(h-LMBs) due to the inherent low highest occupied molecular orbital(HOMO) of fiuorinated solvents. However, such fascinating properties do not bring long-term cyclability of h-LMBs. One of critical challenges is the interface instability in contacting with the Li metal anode, as fiuorinated solvents are highly susceptible to exceptionally reductive metallic Li attributed to its low lowest unoccupied molecular orbital(LUMO), which leads to significant consumption of the fiuorinated components upon cycling.Herein, attenuating reductive decomposition of fiuorinated electrolytes is proposed to circumvent rapid electrolyte consumption. Specifically, the vinylene carbonate(VC) is selected to tame the reduction decomposition by preferentially forming protective layer on the Li anode. This work, experimentally and computationally, demonstrates the importance of pre-passivation of Li metal anodes at high voltage to attenuate the decomposition of fiuoroethylene carbonate(FEC). It is expected to enrich the understanding of how VC attenuate the reactivity of FEC, thereby extending the cycle life of fiuorinated electrolytes in high-voltage Li-metal batteries.展开更多
This study shows that sulfide solid-state electrolytes,β-Li_(3)PS_(4)and Li_(6)PS_(5)Cl,are flammable solids.Both solid-state electrolytes release sulfur vapor in a dry,oxidizing environment at elevated temperature&l...This study shows that sulfide solid-state electrolytes,β-Li_(3)PS_(4)and Li_(6)PS_(5)Cl,are flammable solids.Both solid-state electrolytes release sulfur vapor in a dry,oxidizing environment at elevated temperature<300℃.Sulfur vapor is a highly flammable gas,which then auto-ignites to produce a flame.This behavior suggests that an O_(2)-S gas-gas reaction mechanism may contribute to all-solid-state battery thermal runaway.To improve all-solid-state battery safety,current work focuses on eliminating the O_(2)source by changing the cathode active material.The conclusion of this study suggests that all-solidstate battery safety can also be realized by the development of solid-state electrolytes with less susceptibility to sulfur volatilization.展开更多
This study focuses on the impact of Gd^(3+),Sm^(3+),Er^(3+).Y^(3+),and Bi^(3+)multi-doping on the crystal structure,microscopic surface features,and ionic conductivity of cerium dioxide in the Ce_(1-x)(Gd_(1/5)Sm_(1/5...This study focuses on the impact of Gd^(3+),Sm^(3+),Er^(3+).Y^(3+),and Bi^(3+)multi-doping on the crystal structure,microscopic surface features,and ionic conductivity of cerium dioxide in the Ce_(1-x)(Gd_(1/5)Sm_(1/5)Er_(1/5)Y_(1/)_5Bi_(1/5))_(x)O_(2-δ)(GSEYB)system.This system holds promise as a solid electrolyte material for low and medium-temperature solid oxide fuel cells.The powders of Ce_(1-x)(Gd_(1/5)Sm_(1/5)Er_(1/5)Y_(1/5)Bi_(1/5))_(x)O_(2-δ)(x=0,0.10,0.15,0.20,0.25,0.30)were synthesized using the solid-phase reaction method.The GSEYB electrolytes were comprehensively investigated for their phase structure,microstructure,oxygen vacancy concentration,and ionic conductivity using X-ray diffraction(XRD),scanning electron microscopy(SEM),energy dispersive spectroscopy(EDS),transmission electron microscopy(TEM),X-ray photoelectron spectroscopy(XPS),and impedance spectroscopy.XRD diffraction patterns confirm a cubic fluorite-type structure with Fm3m space groups in all multi-doped systems.After sintering at 1400℃for 10 h,the relative density of doped samples exceeds 96%.In terms of electrical properties,the Ce_(0.75)Gd_(0.05)Sm_(0.05)Er_(0.05)Y_(0.05)Bi_(0.05)O_(2-δ)(x=0.25)electrolyte exhibits the highest ionic conductivity(σ_(t)=4.45×10^(-2)S/cm)and the lowest activation energy(E_(a)=0.79 eV)at 800℃.The coefficient of thermal expansion of the developed electrolyte aligns well with that of the commonly used electrode materials.This compatibility positions it as a highly promising candidate for utilization as an electrolyte material in solid oxide fuel cells(SOFCs).展开更多
The deterioration of aqueous zinc-ion batteries(AZIBs)is confronted with challenges such as unregulated Zn^(2+)diffusion,dendrite growth and severe decay in battery performance under harsh environments.Here,a design c...The deterioration of aqueous zinc-ion batteries(AZIBs)is confronted with challenges such as unregulated Zn^(2+)diffusion,dendrite growth and severe decay in battery performance under harsh environments.Here,a design concept of eutectic electrolyte is presented by mixing long chain polymer molecules,polyethylene glycol dimethyl ether(PEGDME),with H_(2)O based on zinc trifluoromethyl sulfonate(Zn(OTf)2),to reconstruct the Zn^(2+)solvated structure and in situ modified the adsorption layer on Zn electrode surface.Molecular dynamics simulations(MD),density functional theory(DFT)calculations were combined with experiment to prove that the long-chain polymer-PEGDME could effectively reduce side reactions,change the solvation structure of the electrolyte and priority absorbed on Zn(002),achieving a stable dendrite-free Zn anode.Due to the comprehensive regulation of solvation structure and zinc deposition by PEGDME,it can stably cycle for over 3200 h at room temperature at 0.5 mA/cm^(2)and 0.5 mAh/cm^(2).Even at high-temperature environments of 60℃,it can steadily work for more than 800 cycles(1600 h).Improved cyclic stability and rate performance of aqueous Zn‖VO_(2)batteries in modified electrolyte were also achieved at both room and high temperatures.Beyond that,the demonstration of stable and high-capacity Zn‖VO_(2)pouch cells also implies its practical application.展开更多
Lithium-ion batteries are widely recognized as prime candidates for energy storage devices.Ethylene carbonate(EC)has become a critical component in conventional commercial electrolytes due to its exceptional film-form...Lithium-ion batteries are widely recognized as prime candidates for energy storage devices.Ethylene carbonate(EC)has become a critical component in conventional commercial electrolytes due to its exceptional film-forming properties and high dielectric constant.However,the elevated freezing point,high viscosity,and strong solvation energy of EC significantly hinder the transport rate of Li^(+)and the desolvation process at low temperatures.This leads to substantial capacity loss and even lithium plating on graphite anodes.Herein,we have developed an efficient electrolyte system specifically designed for lowtemperature conditions,which consists of 1.0 M lithium bis(fluorosulfonyl)imide(LiFSI)in isoxazole(IZ)with fluorobenzene(FB)as an uncoordinated solvent and fluoroethylene carbonate(FEC)as a filmforming co-solvent.This system effectively lowers the desolvation energy of Li^(+)through dipole-dipole interactions.The weak solvation capability allows more anions to enter the solvation sheath,promoting the formation of contact ion pairs(CIPs)and aggregates(AGGs)that enhance the transport rate of Li^(+)while maintaining high ionic conductivity across a broad temperature range.Moreover,the formation of inorganic-dominant interfacial phases on the graphite anode,induced by fluoroethylene carbonate,significantly enhances the kinetics of Li^(+)transport.At a low temperature of-20℃,this electrolyte system achieves an impressive reversible capacity of 200.9 mAh g^(-1)in graphite half-cell,which is nearly three times that observed with conventional EC-based electrolytes,demonstrating excellent stability throughout its operation.展开更多
All-solid-state Li batteries(ASSLBs)using solid electrolytes(SEs)have gained significant attention in recent years considering the safety issue and their high energy density.Despite these advantages,the commercializat...All-solid-state Li batteries(ASSLBs)using solid electrolytes(SEs)have gained significant attention in recent years considering the safety issue and their high energy density.Despite these advantages,the commercialization of ASSLBs still faces challenges regarding the electrolyte/electrodes interfaces and growth of Li dendrites.Elemental doping is an effective and direct method to enhance the performance of SEs.Here,we report an Al-F co-doping strategy to improve the overall properties including ion conductivity,high voltage stability,and cathode and anode compatibility.Particularly,the Al-F co-doping enables the formation of a thin Li-Al alloy layer and fluoride interphases,thereby constructing a relatively stable interface and promoting uniform Li deposition.The similar merits of Al-F co-doping are also revealed in the Li-argyrodite series.ASSLBs assembled with these optimized electrolytes gain good electrochemical performance,demonstrating the universality of Al-F co-doping towards advanced SEs.展开更多
Solid-state electrolytes(SSEs),as the core component within the next generation of key energy storage technologies-solid-state lithium batteries(SSLBs)-are significantly leading the development of future energy storag...Solid-state electrolytes(SSEs),as the core component within the next generation of key energy storage technologies-solid-state lithium batteries(SSLBs)-are significantly leading the development of future energy storage systems.Among the numerous types of SSEs,inorganic oxide garnet-structured superionic conductors Li7La3Zr2O12(LLZO)crystallized with the cubic Iaˉ3d space group have received considerable attention owing to their highly advantageous intrinsic properties encompassing reasonable lithium-ion conductivity,wide electrochemical voltage window,high shear modulus,and excellent chemical stability with electrodes.However,no SSEs possess all the properties necessary for SSLBs,thus both the ionic conductivity at room temperature and stability in ambient air regarding cubic garnet-based electrolytes are still subject to further improvement.Hence,this review comprehensively covers the nine key structural factors affecting the ion conductivity of garnet-based electrolytes comprising Li concentration,Li vacancy concentration,Li carrier concentration and mobility,Li occupancy at available sites,lattice constant,triangle bottleneck size,oxygen vacancy defects,and Li-O bonding interactions.Furthermore,the general illustration of structures and fundamental features being crucial to chemical stability is examined,including Li concentration,Li-site occupation behavior,and Li-O bonding interactions.Insights into the composition-structure-property relations among cubic garnet-based oxide ionic conductors from the perspective of their crystal structures,revealing the potential compatibility conflicts between ionic transportation and chemical stability resulting from Li-O bonding interactions.We believe that this review will lay the foundation for future reasonable structural design of oxide-based or even other types of superionic conductors,thus assisting in promoting the rapid development of alternative green and sustainable technologies.展开更多
Rechargeable zinc(Zn)-ion batteries(RZIBs) with hydrogel electrolytes(HEs) have gained significant attention in the last decade owing to their high safety, low cost, sufficient material abundance, and superb environme...Rechargeable zinc(Zn)-ion batteries(RZIBs) with hydrogel electrolytes(HEs) have gained significant attention in the last decade owing to their high safety, low cost, sufficient material abundance, and superb environmental friendliness, which is extremely important for wearable energy storage applications. Given that HEs play a critical role in building flexible RZIBs, it is urgent to summarize the recent advances in this field and elucidate the design principles of HEs for practical applications. This review systematically presents the development history, recent advances in the material fundamentals, functional designs, challenges, and prospects of the HEs-based RZIBs. Firstly, the fundamentals, species, and flexible mechanisms of HEs are discussed, along with their compatibility with Zn anodes and various cathodes. Then, the functional designs of hydrogel electrolytes in harsh conditions are comprehensively discussed, including high/low/wide-temperature windows, mechanical deformations(e.g., bending, twisting, and straining), and damages(e.g., cutting, burning, and soaking). Finally, the remaining challenges and future perspectives for advancing HEs-based RZIBs are outlined.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
A critical challenge hindering the practical application of lithium–oxygen batteries(LOBs)is the inevitable problems associated with liquid electrolytes,such as evaporation and safety problems.Our study addresses the...A critical challenge hindering the practical application of lithium–oxygen batteries(LOBs)is the inevitable problems associated with liquid electrolytes,such as evaporation and safety problems.Our study addresses these problems by proposing a modified polyrotaxane(mPR)-based solid polymer electrolyte(SPE)design that simultaneously mitigates solvent-related problems and improves conductivity.mPR-SPE exhibits high ion conductivity(2.8×10^(−3)S cm^(−1)at 25℃)through aligned ion conduction pathways and provides electrode protection ability through hydrophobic chain dispersion.Integrating this mPR-SPE into solid-state LOBs resulted in stable potentials over 300 cycles.In situ Raman spectroscopy reveals the presence of an LiO_(2)intermediate alongside Li_(2)O_(2)during oxygen reactions.Ex situ X-ray diffraction confirm the ability of the SPE to hinder the permeation of oxygen and moisture,as demonstrated by the air permeability tests.The present study suggests that maintaining a low residual solvent while achieving high ionic conductivity is crucial for restricting the sub-reactions of solid-state LOBs.展开更多
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
Sodium-ion batteries hold great promise as next-generation energy storage systems.However,the high instability of the electrode/electrolyte interphase during cycling has seriously hindered the development of SIBs.In p...Sodium-ion batteries hold great promise as next-generation energy storage systems.However,the high instability of the electrode/electrolyte interphase during cycling has seriously hindered the development of SIBs.In particular,an unstable cathode–electrolyte interphase(CEI)leads to successive electrolyte side reactions,transition metal leaching and rapid capacity decay,which tends to be exacerbated under high-voltage conditions.Therefore,constructing dense and stable CEIs are crucial for high-performance SIBs.This work reports localized high-concentration electrolyte by incorporating a highly oxidation-resistant sulfolane solvent with non-solvent diluent 1H,1H,5H-octafluoropentyl-1,1,2,2-tetrafluoroethyl ether,which exhibited excellent oxidative stability and was able to form thin,dense and homogeneous CEI.The excellent CEI enabled the O3-type layered oxide cathode NaNi_(1/3)Mn_(1/3)Fe_(1/3)O_(2)(NaNMF)to achieve stable cycling,with a capacity retention of 79.48%after 300 cycles at 1 C and 81.15%after 400 cycles at 2 C with a high charging voltage of 4.2 V.In addition,its nonflammable nature enhances the safety of SIBs.This work provides a viable pathway for the application of sulfolane-based electrolytes on SIBs and the design of next-generation high-voltage electrolytes.展开更多
The development of low-temperature solid oxide fuel cells(LT-SOFCs)is of significant importance for realizing the widespread application of SOFCs.This has stimulated a substantial materials research effort in developi...The development of low-temperature solid oxide fuel cells(LT-SOFCs)is of significant importance for realizing the widespread application of SOFCs.This has stimulated a substantial materials research effort in developing high oxide-ion conductivity in the electrolyte layer of SOFCs.In this context,for the first time,a dielectric material,CaCu_(3)Ti_(4)O_(12)(CCTO)is designed for LT-SOFCs electrolyte application in this study.Both individual CCTO and its heterostructure materials with a p-type Ni_(0.8)Co_(0.15)Al_(0.05)LiO_(2−δ)(NCAL)semiconductor are evaluated as alternative electrolytes in LT-SOFC at 450–550℃.The single cell with the individual CCTO electrolyte exhibits a power output of approximately 263 mW cm^(-2) and an open-circuit voltage(OCV)of 0.95 V at 550℃,while the cell with the CCTO–NCAL heterostructure electrolyte capably delivers an improved power output of approximately 605 mW cm^(-2) along with a higher OCV over 1.0 V,which indicates the introduction of high hole-conducting NCAL into the CCTO could enhance the cell performance rather than inducing any potential short-circuiting risk.It is found that these promising outcomes are due to the interplay of the dielectric material,its structure,and overall properties that led to improve electrochemical mechanism in CCTO–NCAL.Furthermore,density functional theory calculations provide the detailed information about the electronic and structural properties of the CCTO and NCAL and their heterostructure CCTO–NCAL.Our study thus provides a new approach for developing new advanced electrolytes for LT-SOFCs.展开更多
Porous organic cages(POCs)with permanent porosity and excellent host–vip property hold great potentials in regulating ion transport behavior,yet their feasibility as solid-state electrolytes has never been testifie...Porous organic cages(POCs)with permanent porosity and excellent host–vip property hold great potentials in regulating ion transport behavior,yet their feasibility as solid-state electrolytes has never been testified in a practical battery.Herein,we design and fabricate a quasi-solid-state electrolyte(QSSE)based on a POC to enable the stable operation of Li-metal batteries(LMBs).Benefiting from the ordered channels and cavity-induced anion-trapping effect of POC,the resulting POC-based QSSE exhibits a high Li+transference number of 0.67 and a high ionic conductivity of 1.25×10^(−4) S cm^(−1) with a low activation energy of 0.17 eV.These allow for homogeneous Li deposition and highly reversible Li plating/stripping for over 2000 h.As a proof of concept,the LMB assembled with POC-based QSSE demonstrates extremely stable cycling performance with 85%capacity retention after 1000 cycles.Therefore,our work demonstrates the practical applicability of POC as SSEs for LMBs and could be extended to other energy-storage systems,such as Na and K batteries.展开更多
The risk of flammability is an unavoidable issue for gel polymer electrolytes(GPEs).Usually,flameretardant solvents are necessary to be used,but most of them would react with anode/cathode easily and cause serious int...The risk of flammability is an unavoidable issue for gel polymer electrolytes(GPEs).Usually,flameretardant solvents are necessary to be used,but most of them would react with anode/cathode easily and cause serious interfacial instability,which is a big challenge for design and application of nonflammable GPEs.Here,a nonflammable GPE(SGPE)is developed by in situ polymerizing trifluoroethyl methacrylate(TFMA)monomers with flame-retardant triethyl phosphate(TEP)solvents and LiTFSI–LiDFOB dual lithium salts.TEP is strongly anchored to PTFMA matrix via polarity interaction between-P=O and-CH_(2)CF_(3).It reduces free TEP molecules,which obviously mitigates interfacial reactions,and enhances flame-retardant performance of TEP surprisingly.Anchored TEP molecules are also inhibited in solvation of Li^(+),leading to anion-dominated solvation sheath,which creates inorganic-rich solid electrolyte interface/cathode electrolyte interface layers.Such coordination structure changes Li^(+)transport from sluggish vehicular to fast structural transport,raising ionic conductivity to 1.03 mS cm^(-1) and transfer number to 0.41 at 30℃.The Li|SGPE|Li cell presents highly reversible Li stripping/plating performance for over 1000 h at 0.1 mA cm^(−2),and 4.2 V LiCoO_(2)|SGPE|Li battery delivers high average specific capacity>120 mAh g^(−1) over 200 cycles.This study paves a new way to make nonflammable GPE that is compatible with Li metal anode.展开更多
Aqueous Zn-ion batteries(AZIBs)have been regarded as promising alternatives to Li-ion batteries due to their advantages,such as low cost,high safety,and environmental friendliness.However,AZIBs face significant challe...Aqueous Zn-ion batteries(AZIBs)have been regarded as promising alternatives to Li-ion batteries due to their advantages,such as low cost,high safety,and environmental friendliness.However,AZIBs face significant challenges in limited stability and lifetime owing to zinc dendrite growth and serious side reactions caused by water molecules in the aqueous electrolyte during cycling.To address these issues,a new eutectic electrolyte based on Zn(ClO_(4))_(2)·6H_(2)O-N-methylacetamide(ZN)is proposed in this work.Compared with aqueous electrolyte,the ZN eutectic electrolyte containing organic N-methylacetamide could regulate the solvated structure of Zn^(2+),effectively suppressing zinc dendrite growth and side reactions.As a result,the Zn//NH4 V4 O10 full cell with the eutectic ZN-1-3 electrolyte demonstrates significantly enhanced cycling stability after 1000 cycles at 1 A g^(-1).Therefore,this study not only presents a new eutectic electrolyte for zinc-ion batteries but also provides a deep understanding of the influence of Zn^(2+)solvation structure on the cycle stability,contributing to the exploration of novel electrolytes for high-performance AZIBs.展开更多
Aqueous zinc-halogen batteries are promising candidates for large-scale energy storage due to their abundant resources,intrinsic safety,and high theoretical capacity.Nevertheless,the uncontrollable zinc dendrite growt...Aqueous zinc-halogen batteries are promising candidates for large-scale energy storage due to their abundant resources,intrinsic safety,and high theoretical capacity.Nevertheless,the uncontrollable zinc dendrite growth and spontaneous shuttle effect of active species have prohibited their practical implementation.Herein,a double-layered protective film based on zinc-ethylenediamine tetramethylene phosphonic acid(ZEA)artificial film and ZnF2-rich solid electrolyte interphase(SEI)layer has been successfully fabricated on the zinc metal anode via electrode/electrolyte synergistic optimization.The ZEA-based artificial film shows strong affinity for the ZnF2-rich SEI layer,therefore effectively suppressing the SEI breakage and facilitating the construction of double-layered protective film on the zinc metal anode.Such double-layered architecture not only modulates Zn2+flux and suppresses the zinc dendrite growth,but also blocks the direct contact between the metal anode and electrolyte,thus mitigating the corrosion from the active species.When employing optimized metal anodes and electrolytes,the as-developed zinc-(dual)halogen batteries present high areal capacity and satisfactory cycling stability.This work provides a new avenue for developing aqueous zinc-(dual)halogen batteries.展开更多
Solid-state Na metal batteries(SSNBs),known for the low cost,high safety,and high energy density,hold a significant position in the next generation of rechargeable batteries.However,the urgent challenge of poor interf...Solid-state Na metal batteries(SSNBs),known for the low cost,high safety,and high energy density,hold a significant position in the next generation of rechargeable batteries.However,the urgent challenge of poor interfacial contact in solid-state electrolytes has hindered the commercialization of SSNBs.Driven by the concept of intimate electrode-electrolyte interface design,this study employs a combination of sodium-potassium(NaK)alloy and carbon nanotubes to prepare a semi-solid NaK(NKC)anode.Unlike traditional Na anodes,the paintable paste-like NKC anode exhibits superior adhesion and interface compatibility with both current collectors and gel electrolytes,significantly enhancing the physical contact of the electrode-electrolyte interface.Additionally,the filling of SiO_(2) nanoparticles improves the wettability of NaK alloy on gel polymer electrolytes,further achieving a conformal interface contact.Consequently,the overpotential of the NKC symmetric cell is markedly lower than that of the Na symmetric cell when subjected to a long cycle of 300 hrs.The full cell coupled with Na_(3)V_(2)(PO_(4))_(2) cathodes had an initial discharge capacity of 106.8 mAh·g^(-1) with a capacity retention of 89.61%after 300 cycles,and a high discharge capacity of 88.1 mAh·g^(-1) even at a high rate of 10 C.The outstanding electrochemical performance highlights the promising application potential of the NKC electrode.展开更多
Lithium-oxygen batteries attract considerable attention due to exceptionally high theoretical energy density,while the development remains in its early stage.As is widely suggested,the solution mechanism induces great...Lithium-oxygen batteries attract considerable attention due to exceptionally high theoretical energy density,while the development remains in its early stage.As is widely suggested,the solution mechanism induces greater discharge capacity,while the surface mechanism induces greater cycle stability.Therefore,battery performance can be improved by adjusting the reaction mechanism.Previous studies predominantly focus on extremely thin or flat electrodes.In contrast,this work utilizes thick electrodes,emphasizing the importance of mass transport.Given that the electrolyte solvent is the main site of mass transport,the effects of two typical solvents on mass transport and battery performance are investigated:dimethyl sulfoxide with low viscosity and a high O_(2) diffusion rate and tetraethylene glycol dimethyl ether with high O_(2) solubility and high Li+transport capability.The results reveal a novel pathway for reaction mechanism induction where the mechanism varies with the spatial position of the electrode.As the spatial distribution of the electrode progresses,a layered appearance of solution mechanism products,transition state products,and surface mechanism products emerges,which is attributed to the increase in the mass transfer resistance.This work presents a distinct perspective on the way solvents influence reaction pathways and offers a new approach to regulating reaction pathways.展开更多
Compared to currently commercialized lithium-ion batteries,which use flammable organic liquid electrolytes and low-energy-density graphite anodes,solid-state lithium-metal batteries(SSLMBs)offer enhanced energy densit...Compared to currently commercialized lithium-ion batteries,which use flammable organic liquid electrolytes and low-energy-density graphite anodes,solid-state lithium-metal batteries(SSLMBs)offer enhanced energy density and improved safety,making them promising alternatives for next-generation rechargeable batteries[1].As a crucial component of these batteries,solid-state electrolytes—divided into inorganic solid ceramic electrolytes(SCEs)and organic solid polymer electrolytes(SPEs)—are vital for lithium-ion transport and inhibiting lithium dendrite growth.Among them,SCEs exhibit high ionic conductivity,excellent mechanical properties,and outstanding electrochemical and thermal stability.Nevertheless,their brittleness,interfacial challenges with electrodes,and the requirement for high stacking pressure during battery operation significantly hinder their scalable application.In comparison,SPEs are more favourable for manufacturing due to their flexibility and good interfacial compatibility with electrodes[2].Despite these advantages,SPEs still face significant challenges in achieving practical application.Firstly,typical SPEs,such as poly(ethylene oxide)(PEO),poly(vinylidene fluoride)(PVDF),and poly(ethylene glycol)diacrylate(PEGDA),are characterized by high crystallinity,which causes polymer chains to be tightly packed and rigid.This restricts the segmental motion within the SPEs,resulting in low ionic conductivity.Secondly,compared to lithium ions,anions with large ionic radii and low charge density typically form weaker interactions with the polymer chains,which facilitates their mobility and results in a low lithium-ion transference number(tt).Thirdly,the weak interactions between polymer chains in typical SPEs lead to a low elastic modulus,which in turn compromises their poor mechanical strength.展开更多
基金supported by the National Natural Science Foundation of China (Nos. 22379121, 62005216)Basic Public Welfare Research Program of Zhejiang (No. LQ22F050013)+1 种基金Zhejiang Province Key Laboratory of Flexible Electronics Open Fund (2023FE005)Shenzhen Foundation Research Program (No. JCYJ20220530112812028)。
文摘Fluoride-based electrolyte exhibits extraordinarily high oxidative stability in high-voltage lithium metal batteries(h-LMBs) due to the inherent low highest occupied molecular orbital(HOMO) of fiuorinated solvents. However, such fascinating properties do not bring long-term cyclability of h-LMBs. One of critical challenges is the interface instability in contacting with the Li metal anode, as fiuorinated solvents are highly susceptible to exceptionally reductive metallic Li attributed to its low lowest unoccupied molecular orbital(LUMO), which leads to significant consumption of the fiuorinated components upon cycling.Herein, attenuating reductive decomposition of fiuorinated electrolytes is proposed to circumvent rapid electrolyte consumption. Specifically, the vinylene carbonate(VC) is selected to tame the reduction decomposition by preferentially forming protective layer on the Li anode. This work, experimentally and computationally, demonstrates the importance of pre-passivation of Li metal anodes at high voltage to attenuate the decomposition of fiuoroethylene carbonate(FEC). It is expected to enrich the understanding of how VC attenuate the reactivity of FEC, thereby extending the cycle life of fiuorinated electrolytes in high-voltage Li-metal batteries.
文摘This study shows that sulfide solid-state electrolytes,β-Li_(3)PS_(4)and Li_(6)PS_(5)Cl,are flammable solids.Both solid-state electrolytes release sulfur vapor in a dry,oxidizing environment at elevated temperature<300℃.Sulfur vapor is a highly flammable gas,which then auto-ignites to produce a flame.This behavior suggests that an O_(2)-S gas-gas reaction mechanism may contribute to all-solid-state battery thermal runaway.To improve all-solid-state battery safety,current work focuses on eliminating the O_(2)source by changing the cathode active material.The conclusion of this study suggests that all-solidstate battery safety can also be realized by the development of solid-state electrolytes with less susceptibility to sulfur volatilization.
基金supported by the Guangdong Provincial Basic and Applied Basic Research Foundation(2021A1515010671,2020A1515011221)the Guangdong Provincial Key Discipline Research Capacity Enhancement Project(2021ZDJS071)the Guangdong Provincial College Innovation Project(2021KTSCX122,2022KQNCX077)。
文摘This study focuses on the impact of Gd^(3+),Sm^(3+),Er^(3+).Y^(3+),and Bi^(3+)multi-doping on the crystal structure,microscopic surface features,and ionic conductivity of cerium dioxide in the Ce_(1-x)(Gd_(1/5)Sm_(1/5)Er_(1/5)Y_(1/)_5Bi_(1/5))_(x)O_(2-δ)(GSEYB)system.This system holds promise as a solid electrolyte material for low and medium-temperature solid oxide fuel cells.The powders of Ce_(1-x)(Gd_(1/5)Sm_(1/5)Er_(1/5)Y_(1/5)Bi_(1/5))_(x)O_(2-δ)(x=0,0.10,0.15,0.20,0.25,0.30)were synthesized using the solid-phase reaction method.The GSEYB electrolytes were comprehensively investigated for their phase structure,microstructure,oxygen vacancy concentration,and ionic conductivity using X-ray diffraction(XRD),scanning electron microscopy(SEM),energy dispersive spectroscopy(EDS),transmission electron microscopy(TEM),X-ray photoelectron spectroscopy(XPS),and impedance spectroscopy.XRD diffraction patterns confirm a cubic fluorite-type structure with Fm3m space groups in all multi-doped systems.After sintering at 1400℃for 10 h,the relative density of doped samples exceeds 96%.In terms of electrical properties,the Ce_(0.75)Gd_(0.05)Sm_(0.05)Er_(0.05)Y_(0.05)Bi_(0.05)O_(2-δ)(x=0.25)electrolyte exhibits the highest ionic conductivity(σ_(t)=4.45×10^(-2)S/cm)and the lowest activation energy(E_(a)=0.79 eV)at 800℃.The coefficient of thermal expansion of the developed electrolyte aligns well with that of the commonly used electrode materials.This compatibility positions it as a highly promising candidate for utilization as an electrolyte material in solid oxide fuel cells(SOFCs).
基金supported by the National Natural Science Foundation of China(Nos.22208221,22178221)the Natural Science Foundation of Guangdong Province(Nos.2024A1515011078,2024A1515011507)+1 种基金the Shenzhen Science and Technology Program(Nos.JCYJ20220818095805012,JCYJ20230808105109019)the Start-up Research Funding of Shenzhen University(No.868-000001032522).
文摘The deterioration of aqueous zinc-ion batteries(AZIBs)is confronted with challenges such as unregulated Zn^(2+)diffusion,dendrite growth and severe decay in battery performance under harsh environments.Here,a design concept of eutectic electrolyte is presented by mixing long chain polymer molecules,polyethylene glycol dimethyl ether(PEGDME),with H_(2)O based on zinc trifluoromethyl sulfonate(Zn(OTf)2),to reconstruct the Zn^(2+)solvated structure and in situ modified the adsorption layer on Zn electrode surface.Molecular dynamics simulations(MD),density functional theory(DFT)calculations were combined with experiment to prove that the long-chain polymer-PEGDME could effectively reduce side reactions,change the solvation structure of the electrolyte and priority absorbed on Zn(002),achieving a stable dendrite-free Zn anode.Due to the comprehensive regulation of solvation structure and zinc deposition by PEGDME,it can stably cycle for over 3200 h at room temperature at 0.5 mA/cm^(2)and 0.5 mAh/cm^(2).Even at high-temperature environments of 60℃,it can steadily work for more than 800 cycles(1600 h).Improved cyclic stability and rate performance of aqueous Zn‖VO_(2)batteries in modified electrolyte were also achieved at both room and high temperatures.Beyond that,the demonstration of stable and high-capacity Zn‖VO_(2)pouch cells also implies its practical application.
基金financial support from the Department of Science and Technology of Jilin Province(20240304104SF,20240304103SF)the Research and Innovation Fund of the Beihua University for the Graduate Student(Major Project 2023012)。
文摘Lithium-ion batteries are widely recognized as prime candidates for energy storage devices.Ethylene carbonate(EC)has become a critical component in conventional commercial electrolytes due to its exceptional film-forming properties and high dielectric constant.However,the elevated freezing point,high viscosity,and strong solvation energy of EC significantly hinder the transport rate of Li^(+)and the desolvation process at low temperatures.This leads to substantial capacity loss and even lithium plating on graphite anodes.Herein,we have developed an efficient electrolyte system specifically designed for lowtemperature conditions,which consists of 1.0 M lithium bis(fluorosulfonyl)imide(LiFSI)in isoxazole(IZ)with fluorobenzene(FB)as an uncoordinated solvent and fluoroethylene carbonate(FEC)as a filmforming co-solvent.This system effectively lowers the desolvation energy of Li^(+)through dipole-dipole interactions.The weak solvation capability allows more anions to enter the solvation sheath,promoting the formation of contact ion pairs(CIPs)and aggregates(AGGs)that enhance the transport rate of Li^(+)while maintaining high ionic conductivity across a broad temperature range.Moreover,the formation of inorganic-dominant interfacial phases on the graphite anode,induced by fluoroethylene carbonate,significantly enhances the kinetics of Li^(+)transport.At a low temperature of-20℃,this electrolyte system achieves an impressive reversible capacity of 200.9 mAh g^(-1)in graphite half-cell,which is nearly three times that observed with conventional EC-based electrolytes,demonstrating excellent stability throughout its operation.
基金supported by the National Natural Science Foundation of China(Nos.52172243,52371215)。
文摘All-solid-state Li batteries(ASSLBs)using solid electrolytes(SEs)have gained significant attention in recent years considering the safety issue and their high energy density.Despite these advantages,the commercialization of ASSLBs still faces challenges regarding the electrolyte/electrodes interfaces and growth of Li dendrites.Elemental doping is an effective and direct method to enhance the performance of SEs.Here,we report an Al-F co-doping strategy to improve the overall properties including ion conductivity,high voltage stability,and cathode and anode compatibility.Particularly,the Al-F co-doping enables the formation of a thin Li-Al alloy layer and fluoride interphases,thereby constructing a relatively stable interface and promoting uniform Li deposition.The similar merits of Al-F co-doping are also revealed in the Li-argyrodite series.ASSLBs assembled with these optimized electrolytes gain good electrochemical performance,demonstrating the universality of Al-F co-doping towards advanced SEs.
基金supported by the National Natural Science Foundation of China(Nos.22171102 and 22090044)the National Key R&D Program of China(Nos.2021YFF0500502 and 2023YFA1506304)+2 种基金the Jilin Province Science and Technology Development Plan(No.20230101024JC)the"Medicine+X"crossinnovation team of Bethune Medical Department of Jilin University"Leading the Charge with Open Competition"construction project(No.2022JBGS04)the Jilin University Graduate Training Office(Nos.2021JGZ08 and 2022YJSJIP20).
文摘Solid-state electrolytes(SSEs),as the core component within the next generation of key energy storage technologies-solid-state lithium batteries(SSLBs)-are significantly leading the development of future energy storage systems.Among the numerous types of SSEs,inorganic oxide garnet-structured superionic conductors Li7La3Zr2O12(LLZO)crystallized with the cubic Iaˉ3d space group have received considerable attention owing to their highly advantageous intrinsic properties encompassing reasonable lithium-ion conductivity,wide electrochemical voltage window,high shear modulus,and excellent chemical stability with electrodes.However,no SSEs possess all the properties necessary for SSLBs,thus both the ionic conductivity at room temperature and stability in ambient air regarding cubic garnet-based electrolytes are still subject to further improvement.Hence,this review comprehensively covers the nine key structural factors affecting the ion conductivity of garnet-based electrolytes comprising Li concentration,Li vacancy concentration,Li carrier concentration and mobility,Li occupancy at available sites,lattice constant,triangle bottleneck size,oxygen vacancy defects,and Li-O bonding interactions.Furthermore,the general illustration of structures and fundamental features being crucial to chemical stability is examined,including Li concentration,Li-site occupation behavior,and Li-O bonding interactions.Insights into the composition-structure-property relations among cubic garnet-based oxide ionic conductors from the perspective of their crystal structures,revealing the potential compatibility conflicts between ionic transportation and chemical stability resulting from Li-O bonding interactions.We believe that this review will lay the foundation for future reasonable structural design of oxide-based or even other types of superionic conductors,thus assisting in promoting the rapid development of alternative green and sustainable technologies.
基金supported by the National Natural Science Foundation of China (22379038)Science Research Project of Hebei Education Department (JZX2024015)+4 种基金Shijiazhuang Science and Technology Plan Project (241791357A)Central Guidance for Local Science and Technology Development Funds Project (246Z4408G)Excellent Youth Research Innovation Team of Hebei University (QNTD202410)High-level Talents Research Start-Up Project of Hebei University (521100224223)Hebei Province Innovation Capability Enhancement Plan Project (22567620H)。
文摘Rechargeable zinc(Zn)-ion batteries(RZIBs) with hydrogel electrolytes(HEs) have gained significant attention in the last decade owing to their high safety, low cost, sufficient material abundance, and superb environmental friendliness, which is extremely important for wearable energy storage applications. Given that HEs play a critical role in building flexible RZIBs, it is urgent to summarize the recent advances in this field and elucidate the design principles of HEs for practical applications. This review systematically presents the development history, recent advances in the material fundamentals, functional designs, challenges, and prospects of the HEs-based RZIBs. Firstly, the fundamentals, species, and flexible mechanisms of HEs are discussed, along with their compatibility with Zn anodes and various cathodes. Then, the functional designs of hydrogel electrolytes in harsh conditions are comprehensively discussed, including high/low/wide-temperature windows, mechanical deformations(e.g., bending, twisting, and straining), and damages(e.g., cutting, burning, and soaking). Finally, the remaining challenges and future perspectives for advancing HEs-based RZIBs are outlined.
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 a National Research Foundation of Korea(NRF)Grant funded by the Ministry of Science and ICT(2021R1A2C1014294,2022R1A2C3003319)the BK21 FOUR(Fostering Outstanding Universities for Research)through the National Research Foundation(NRF)of Korea.
文摘A critical challenge hindering the practical application of lithium–oxygen batteries(LOBs)is the inevitable problems associated with liquid electrolytes,such as evaporation and safety problems.Our study addresses these problems by proposing a modified polyrotaxane(mPR)-based solid polymer electrolyte(SPE)design that simultaneously mitigates solvent-related problems and improves conductivity.mPR-SPE exhibits high ion conductivity(2.8×10^(−3)S cm^(−1)at 25℃)through aligned ion conduction pathways and provides electrode protection ability through hydrophobic chain dispersion.Integrating this mPR-SPE into solid-state LOBs resulted in stable potentials over 300 cycles.In situ Raman spectroscopy reveals the presence of an LiO_(2)intermediate alongside Li_(2)O_(2)during oxygen reactions.Ex situ X-ray diffraction confirm the ability of the SPE to hinder the permeation of oxygen and moisture,as demonstrated by the air permeability tests.The present study suggests that maintaining a low residual solvent while achieving high ionic conductivity is crucial for restricting the sub-reactions of solid-state LOBs.
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 National Natural Science Foundation(NNSF)of China(Nos.52202269,52002248,U23B2069,22309162)Shenzhen Science and Technology program(No.20220810155330003)+1 种基金Shenzhen Basic Research Project(No.JCYJ20190808163005631)Xiangjiang Lab(22XJ01007).
文摘Sodium-ion batteries hold great promise as next-generation energy storage systems.However,the high instability of the electrode/electrolyte interphase during cycling has seriously hindered the development of SIBs.In particular,an unstable cathode–electrolyte interphase(CEI)leads to successive electrolyte side reactions,transition metal leaching and rapid capacity decay,which tends to be exacerbated under high-voltage conditions.Therefore,constructing dense and stable CEIs are crucial for high-performance SIBs.This work reports localized high-concentration electrolyte by incorporating a highly oxidation-resistant sulfolane solvent with non-solvent diluent 1H,1H,5H-octafluoropentyl-1,1,2,2-tetrafluoroethyl ether,which exhibited excellent oxidative stability and was able to form thin,dense and homogeneous CEI.The excellent CEI enabled the O3-type layered oxide cathode NaNi_(1/3)Mn_(1/3)Fe_(1/3)O_(2)(NaNMF)to achieve stable cycling,with a capacity retention of 79.48%after 300 cycles at 1 C and 81.15%after 400 cycles at 2 C with a high charging voltage of 4.2 V.In addition,its nonflammable nature enhances the safety of SIBs.This work provides a viable pathway for the application of sulfolane-based electrolytes on SIBs and the design of next-generation high-voltage electrolytes.
基金National Natural Science Foundation of China(NSFC)supported this work under Grant No.32250410309,11674086,51736006,and 51772080funding from Science and Technology Department of Jiangsu Province under Grant No.BE2022029Shenzhen University under Grant No.86902/000248 also supported part of this work.
文摘The development of low-temperature solid oxide fuel cells(LT-SOFCs)is of significant importance for realizing the widespread application of SOFCs.This has stimulated a substantial materials research effort in developing high oxide-ion conductivity in the electrolyte layer of SOFCs.In this context,for the first time,a dielectric material,CaCu_(3)Ti_(4)O_(12)(CCTO)is designed for LT-SOFCs electrolyte application in this study.Both individual CCTO and its heterostructure materials with a p-type Ni_(0.8)Co_(0.15)Al_(0.05)LiO_(2−δ)(NCAL)semiconductor are evaluated as alternative electrolytes in LT-SOFC at 450–550℃.The single cell with the individual CCTO electrolyte exhibits a power output of approximately 263 mW cm^(-2) and an open-circuit voltage(OCV)of 0.95 V at 550℃,while the cell with the CCTO–NCAL heterostructure electrolyte capably delivers an improved power output of approximately 605 mW cm^(-2) along with a higher OCV over 1.0 V,which indicates the introduction of high hole-conducting NCAL into the CCTO could enhance the cell performance rather than inducing any potential short-circuiting risk.It is found that these promising outcomes are due to the interplay of the dielectric material,its structure,and overall properties that led to improve electrochemical mechanism in CCTO–NCAL.Furthermore,density functional theory calculations provide the detailed information about the electronic and structural properties of the CCTO and NCAL and their heterostructure CCTO–NCAL.Our study thus provides a new approach for developing new advanced electrolytes for LT-SOFCs.
基金supported by the National Natural Science Foundation of China(No.92372123)Guangdong Basic and Applied Basic Research Foundation(No.2022A1515012057,2022B1515020005,2023B1515130004)Guangzhou Basic and Applied Basic Research Foundation(No.202201011342).
文摘Porous organic cages(POCs)with permanent porosity and excellent host–vip property hold great potentials in regulating ion transport behavior,yet their feasibility as solid-state electrolytes has never been testified in a practical battery.Herein,we design and fabricate a quasi-solid-state electrolyte(QSSE)based on a POC to enable the stable operation of Li-metal batteries(LMBs).Benefiting from the ordered channels and cavity-induced anion-trapping effect of POC,the resulting POC-based QSSE exhibits a high Li+transference number of 0.67 and a high ionic conductivity of 1.25×10^(−4) S cm^(−1) with a low activation energy of 0.17 eV.These allow for homogeneous Li deposition and highly reversible Li plating/stripping for over 2000 h.As a proof of concept,the LMB assembled with POC-based QSSE demonstrates extremely stable cycling performance with 85%capacity retention after 1000 cycles.Therefore,our work demonstrates the practical applicability of POC as SSEs for LMBs and could be extended to other energy-storage systems,such as Na and K batteries.
基金supported by the National Natural Science Foundation of China(Nos.52172214,52272221,52171182)the Postdoctoral Innovation Project of Shandong Province(No.202102003)+2 种基金The Key Research and Development Program of Shandong Province(2021ZLGX01)the Qilu Young Scholar ProgramHPC Cloud Platform of Shandong University are also thanked.
文摘The risk of flammability is an unavoidable issue for gel polymer electrolytes(GPEs).Usually,flameretardant solvents are necessary to be used,but most of them would react with anode/cathode easily and cause serious interfacial instability,which is a big challenge for design and application of nonflammable GPEs.Here,a nonflammable GPE(SGPE)is developed by in situ polymerizing trifluoroethyl methacrylate(TFMA)monomers with flame-retardant triethyl phosphate(TEP)solvents and LiTFSI–LiDFOB dual lithium salts.TEP is strongly anchored to PTFMA matrix via polarity interaction between-P=O and-CH_(2)CF_(3).It reduces free TEP molecules,which obviously mitigates interfacial reactions,and enhances flame-retardant performance of TEP surprisingly.Anchored TEP molecules are also inhibited in solvation of Li^(+),leading to anion-dominated solvation sheath,which creates inorganic-rich solid electrolyte interface/cathode electrolyte interface layers.Such coordination structure changes Li^(+)transport from sluggish vehicular to fast structural transport,raising ionic conductivity to 1.03 mS cm^(-1) and transfer number to 0.41 at 30℃.The Li|SGPE|Li cell presents highly reversible Li stripping/plating performance for over 1000 h at 0.1 mA cm^(−2),and 4.2 V LiCoO_(2)|SGPE|Li battery delivers high average specific capacity>120 mAh g^(−1) over 200 cycles.This study paves a new way to make nonflammable GPE that is compatible with Li metal anode.
基金supported by the Natural Science Foundation of Henan Province(No.242300420021)the Major Science and Technology Projects of Henan Province(No.221100230200)+4 种基金the Open Fund of State Key Laboratory of Advanced Refractories(No.SKLAR202210)the Key Science and Technology Program of Henan Province(No.232102241020)the Undergraduate Innovation and Entrepreneurship Training Program of Henan Province(No.S202310464012)the Ph.D.Research Startup Foundation of Henan University of Science and Technology(No.400613480015)the Postdoctoral Research Startup Foundation of Henan University of Science and Technology(No.400613554001).
文摘Aqueous Zn-ion batteries(AZIBs)have been regarded as promising alternatives to Li-ion batteries due to their advantages,such as low cost,high safety,and environmental friendliness.However,AZIBs face significant challenges in limited stability and lifetime owing to zinc dendrite growth and serious side reactions caused by water molecules in the aqueous electrolyte during cycling.To address these issues,a new eutectic electrolyte based on Zn(ClO_(4))_(2)·6H_(2)O-N-methylacetamide(ZN)is proposed in this work.Compared with aqueous electrolyte,the ZN eutectic electrolyte containing organic N-methylacetamide could regulate the solvated structure of Zn^(2+),effectively suppressing zinc dendrite growth and side reactions.As a result,the Zn//NH4 V4 O10 full cell with the eutectic ZN-1-3 electrolyte demonstrates significantly enhanced cycling stability after 1000 cycles at 1 A g^(-1).Therefore,this study not only presents a new eutectic electrolyte for zinc-ion batteries but also provides a deep understanding of the influence of Zn^(2+)solvation structure on the cycle stability,contributing to the exploration of novel electrolytes for high-performance AZIBs.
基金support from the National Natural Science Foundation of China(22209089,22178187)Natural Science Foundation of Shandong Province(ZR2022QB048,ZR2021MB006)+2 种基金Excellent Youth Science Foundation of Shandong Province(Overseas)(2023HWYQ-089)the Taishan Scholars Program of Shandong Province(tsqn201909091)Open Research Fund of School of Chemistry and Chemical Engineering,Henan Normal University.
文摘Aqueous zinc-halogen batteries are promising candidates for large-scale energy storage due to their abundant resources,intrinsic safety,and high theoretical capacity.Nevertheless,the uncontrollable zinc dendrite growth and spontaneous shuttle effect of active species have prohibited their practical implementation.Herein,a double-layered protective film based on zinc-ethylenediamine tetramethylene phosphonic acid(ZEA)artificial film and ZnF2-rich solid electrolyte interphase(SEI)layer has been successfully fabricated on the zinc metal anode via electrode/electrolyte synergistic optimization.The ZEA-based artificial film shows strong affinity for the ZnF2-rich SEI layer,therefore effectively suppressing the SEI breakage and facilitating the construction of double-layered protective film on the zinc metal anode.Such double-layered architecture not only modulates Zn2+flux and suppresses the zinc dendrite growth,but also blocks the direct contact between the metal anode and electrolyte,thus mitigating the corrosion from the active species.When employing optimized metal anodes and electrolytes,the as-developed zinc-(dual)halogen batteries present high areal capacity and satisfactory cycling stability.This work provides a new avenue for developing aqueous zinc-(dual)halogen batteries.
基金National Natural Science Foundation of China (52073253)。
文摘Solid-state Na metal batteries(SSNBs),known for the low cost,high safety,and high energy density,hold a significant position in the next generation of rechargeable batteries.However,the urgent challenge of poor interfacial contact in solid-state electrolytes has hindered the commercialization of SSNBs.Driven by the concept of intimate electrode-electrolyte interface design,this study employs a combination of sodium-potassium(NaK)alloy and carbon nanotubes to prepare a semi-solid NaK(NKC)anode.Unlike traditional Na anodes,the paintable paste-like NKC anode exhibits superior adhesion and interface compatibility with both current collectors and gel electrolytes,significantly enhancing the physical contact of the electrode-electrolyte interface.Additionally,the filling of SiO_(2) nanoparticles improves the wettability of NaK alloy on gel polymer electrolytes,further achieving a conformal interface contact.Consequently,the overpotential of the NKC symmetric cell is markedly lower than that of the Na symmetric cell when subjected to a long cycle of 300 hrs.The full cell coupled with Na_(3)V_(2)(PO_(4))_(2) cathodes had an initial discharge capacity of 106.8 mAh·g^(-1) with a capacity retention of 89.61%after 300 cycles,and a high discharge capacity of 88.1 mAh·g^(-1) even at a high rate of 10 C.The outstanding electrochemical performance highlights the promising application potential of the NKC electrode.
基金supported by the National Natural Science Foundation of China(52376080 and 52306122)the Anhui Provincial Natural Science Foundation(2308085QE174)+3 种基金the China Postdoctoral Science Foundation(2023TQ0346)the Postdoctoral Fellowship Program of CPSF(GZC20232522)the Fundamental Research Funds for the Central Universities(WK2090000057)the Students’Innovation and Entrepreneurship Foundation of USTC(CY2023C008).
文摘Lithium-oxygen batteries attract considerable attention due to exceptionally high theoretical energy density,while the development remains in its early stage.As is widely suggested,the solution mechanism induces greater discharge capacity,while the surface mechanism induces greater cycle stability.Therefore,battery performance can be improved by adjusting the reaction mechanism.Previous studies predominantly focus on extremely thin or flat electrodes.In contrast,this work utilizes thick electrodes,emphasizing the importance of mass transport.Given that the electrolyte solvent is the main site of mass transport,the effects of two typical solvents on mass transport and battery performance are investigated:dimethyl sulfoxide with low viscosity and a high O_(2) diffusion rate and tetraethylene glycol dimethyl ether with high O_(2) solubility and high Li+transport capability.The results reveal a novel pathway for reaction mechanism induction where the mechanism varies with the spatial position of the electrode.As the spatial distribution of the electrode progresses,a layered appearance of solution mechanism products,transition state products,and surface mechanism products emerges,which is attributed to the increase in the mass transfer resistance.This work presents a distinct perspective on the way solvents influence reaction pathways and offers a new approach to regulating reaction pathways.
基金supported by the University of Wollongong,Wollongong,Australiafinancial support from the National Natural Science Foundation of China(22272086)Natural Science Foundation of Sichuan Province(2023NSFSC0009).
文摘Compared to currently commercialized lithium-ion batteries,which use flammable organic liquid electrolytes and low-energy-density graphite anodes,solid-state lithium-metal batteries(SSLMBs)offer enhanced energy density and improved safety,making them promising alternatives for next-generation rechargeable batteries[1].As a crucial component of these batteries,solid-state electrolytes—divided into inorganic solid ceramic electrolytes(SCEs)and organic solid polymer electrolytes(SPEs)—are vital for lithium-ion transport and inhibiting lithium dendrite growth.Among them,SCEs exhibit high ionic conductivity,excellent mechanical properties,and outstanding electrochemical and thermal stability.Nevertheless,their brittleness,interfacial challenges with electrodes,and the requirement for high stacking pressure during battery operation significantly hinder their scalable application.In comparison,SPEs are more favourable for manufacturing due to their flexibility and good interfacial compatibility with electrodes[2].Despite these advantages,SPEs still face significant challenges in achieving practical application.Firstly,typical SPEs,such as poly(ethylene oxide)(PEO),poly(vinylidene fluoride)(PVDF),and poly(ethylene glycol)diacrylate(PEGDA),are characterized by high crystallinity,which causes polymer chains to be tightly packed and rigid.This restricts the segmental motion within the SPEs,resulting in low ionic conductivity.Secondly,compared to lithium ions,anions with large ionic radii and low charge density typically form weaker interactions with the polymer chains,which facilitates their mobility and results in a low lithium-ion transference number(tt).Thirdly,the weak interactions between polymer chains in typical SPEs lead to a low elastic modulus,which in turn compromises their poor mechanical strength.
