Li metal batteries using high-voltage layered oxides cathodes are of particular interest due to their high energy density.However,they suffer from short lifespan and extreme safety concerns,which are attributed to the...Li metal batteries using high-voltage layered oxides cathodes are of particular interest due to their high energy density.However,they suffer from short lifespan and extreme safety concerns,which are attributed to the degradation of layered oxides and the decomposition of electrolyte at high voltage,as well as the high reactivity of metallic Li.The key is the development of stable electrolytes against both highvoltage cathodes and Li with the formation of robust interphase films on the surfaces.Herein,we report a highly fluorinated ether,1,1,1-trifluoro-2-[(2,2,2-trifluoroethoxy)methoxy]ethane(TTME),as a cosolvent,which not only functions as a diluent forming a localized high concentration electrolyte(LHCE),but also participates in the construction of the inner solvation structure.The TTME-based electrolyte is stable itself at high voltage and induces the formation of a unique double-layer solid electrolyte interphase(SEI)film,which is embodied as one layer rich in crystalline structural components for enhanced mechanical strength and another amorphous layer with a higher concentration of organic components for enhanced flexibility.The Li||Cu cells display a noticeably high Coulombic efficiency of 99.28%after 300 cycles and Li symmetric cells maintain stable cycling more than 3200 h at 0.5 mA/cm^(2) and 1.0m Ah/cm^(2).In addition,lithium metal cells using LiNi_(0.8)Co_(0.1)Mn_(0.1)O_(2) and Li CoO_(2) cathodes(both loadings~3.0 m Ah/cm^(2))realize capacity retentions of>85%over 240 cycles with a charge cut-off voltage of 4.4 V and 90%for 170 cycles with a charge cut-off voltage of 4.5 V,respectively.This study offers a bifunctional ether-based electrolyte solvent beneficial for high-voltage Li metal batteries.展开更多
Weakly-solvated electrolytes(WSEs)utilizing solvents with weak coordination ability offer advantages for low-potential graphite anode owing to their facile desolvation process and anions-derived inorganic-rich solid e...Weakly-solvated electrolytes(WSEs)utilizing solvents with weak coordination ability offer advantages for low-potential graphite anode owing to their facile desolvation process and anions-derived inorganic-rich solid electrolyte interphase(SEI)film.However,these electrolytes face challenges in achieving a balance between the weak solvation affinity and high ionic conductivity,as well as between rigid inorganic-rich SEI and flexible SEI for long-term stability.Herein,we introduce 1,3-dioxolane(DOL)and lithium bis(trifluoromethanesulfonyl)-imide(LiTFSI)as functional additives into a WSE based on nonpolar cyclic ether(1,4-dioxane).The well-formulated WSE not only preserves the weakly solvated features and anion-dominated solvation sheath,but also utilizes DOL to contribute organic species for stabilizing the SEI layer.Benefitting from these merits,the optimized electrolyte enables graphite anode with excellent fast-charging performance(210 mAh/g at 5 C)and outstanding cycling stability(600 cycles with a capacity retention of 82.0%at room temperature and 400 cycles with a capacity retention of 80.4%at high temper-ature).Furthermore,the fabricated LiNi_(0.8)Co_(0.1)Mn_(0.1)O_(2)||graphite full cells demonstrate stable operation for 140 cycles with high capacity retention of 80.3%.This work highlights the potential of tailoring solvation sheath and interphase properties in WSEs for advanced electrolyte design in graphite-based lithium-ion batteries.展开更多
Ether-based solvents generally show better affinity for lithium metal,and thus ether-based electrolytes(EBEs)are more inclined to form a uniform and thin solid electrolyte interface(SEI),ensuring the long cycle stabil...Ether-based solvents generally show better affinity for lithium metal,and thus ether-based electrolytes(EBEs)are more inclined to form a uniform and thin solid electrolyte interface(SEI),ensuring the long cycle stability of the lithium metal batteries(LMBs).Nonetheless,EBEs still face the challenge of oxidative decomposition under high voltage,which will corrode the structure of cathodes,destroy the stability of the electrode−electrolyte interface,and even cause safety risks.Herein,the types and challenges of EBEs are reviewed,the strategies for improving the high voltage stability of EBEs and constructing stable electrode−electrolyte interfaces are discussed in detail.Finally,the future perspectives and potential directions for composition optimization of EBEs and electrolyte−electrode interface regulation of high-voltage LMBs are explored.展开更多
Application of sodium-ion batteries is suppressed due to the lack of appropriate electrolytes matching cathode and anode simultaneously.Ether-based electrolytes,preference of anode materials,cannot match with high-pot...Application of sodium-ion batteries is suppressed due to the lack of appropriate electrolytes matching cathode and anode simultaneously.Ether-based electrolytes,preference of anode materials,cannot match with high-potential cathodes failing to apply in full cells.Herein,vinylene carbonate(VC)as an additive into NaCF_(3) SO_(3)-Diglyme(DGM)could make sodium-ion full cells applicable without preactivation of cathode and anode.The assembled FeS@C||Na3 V2(PO_(4))_(3)@C full cell with this electrolyte exhibits long term cycling stability and high capacity retention.The deduced reason is additive VC,whose HOMO level value is close to that of DGM,not only change the solvent sheath structure of Na^(+),but also is synergistically oxidized with DGM to form integrity and consecutive cathode electrolyte interphase on Na3 V2(PO_(4))_(3)@C cathode,which could effectively improve the oxidative stability of electrolyte and prevent the electrolyte decomposition.This work displays a new way to optimize the sodium-ion full cell seasily with bright practical application potential.展开更多
Compared with graphite,the lower sodiation potential and larger discharge capacity of hard carbon(HC)makes it the most promising anode material for sodium-ion battery.Utilizing ether-based electrolyte rather than conv...Compared with graphite,the lower sodiation potential and larger discharge capacity of hard carbon(HC)makes it the most promising anode material for sodium-ion battery.Utilizing ether-based electrolyte rather than conventional carbonate-based electrolyte,HC achieves superior electrochemical performance.Nevertheless,the mechanism by which ether-based electrolyte improves the properties of HC is still controversial,primarily focusing on whether it forms solid electrolyte interphase(SEI)film.In this work,according to the sodium storage mechanisms in HC at low voltage(<0.1 V),including Na^(+)-diglyme co-interaction into the carbon layer(SEI forbidden)and desolvated Na^(+)insertion in the irregular carbon holes(SEI required),the NaPF6concentration in ether-based electrolyte was regulated,so as to construct a discontinuous-SEI on the surface of the HC anode,which significantly enhances the electrochemical performances of HC.Specifically,with 0.2 M NaPF6ether-based electrolyte,HC deliverers a discharge capacity of 459.7 mA h g^(-1)at 0.1 C and stays at 357.2 mA h g^(-1)after 500 cycles at 1 C,which is substantially higher than that of higher/lower salt concentration electrolytes.展开更多
Organic materials, especially the carbonyl compounds, are promising anode materials for room temperature sodium-ion batteries owing to their high reversible capacity, structural diversity as well as eco-friendly synth...Organic materials, especially the carbonyl compounds, are promising anode materials for room temperature sodium-ion batteries owing to their high reversible capacity, structural diversity as well as eco-friendly synthesis from bio-mass. Herein, we report a novel anthraquinone derivative, C_(14)H_6 O_4 Na_2 composited with carbon nanotube(C_(14)H_6 O_4 Na_2-CNT), used as an anode material for sodium-ion batteries in etherbased electrolyte. The C_(14)H_6 O_4 Na_2-CNT electrode delivers a reversible capacity of 173 mAh g^(-1) and an ultra-high initial Coulombic efficiency of 98% at the rate of 0.1 C. The capacity retention is 82% after 50 cycles at 0.2 C and a good rate capability is displayed at 2 C.Furthermore, the average Na insertion voltage of 1.27 V vs. Na^+/Na makes it a unique and safety battery material, which would avoid Na plating and formation of solid electrolyte interface. Our contribution provides new insights for designing developed organic anode materials with high initial Coulombic efficiency and improved safety capability for sodium-ion batteries.展开更多
Ether-based electrolytes with relatively high stability are widely used in Li-O_(2) batteries (LOBs) with high energy density.However,they are still prone to be attacked by reactive oxygen species.Understanding the de...Ether-based electrolytes with relatively high stability are widely used in Li-O_(2) batteries (LOBs) with high energy density.However,they are still prone to be attacked by reactive oxygen species.Understanding the degradation chemistry of ether-based solvent induced by reactive oxygen species is significant importance toward selection of stable electrolytes for LOBs.Herein,we demonstrate that a great amount of H_(2) gas evolves on the Li anode during the long-term discharge process of LOBs,which is due to the electrolyte decomposition at the oxygen cathode.By coupling with in-situ and ex-situ characterization techniques,it is demonstrated that O_(2)^(-) induces the H-abstraction of tetraethylene glycol dimethyl ether(TEGDME) to produce a large amount of H_(2)O at cathode,and this H_(2)O migrates to Li anode and produce H_(2) gas.Based on the established experiments and spectra,a possible decomposition pathway of TEGDME caused by O_(2)^(-)at the discharge process is proposed.And moreover,three types of strategies are discussed to inhibit the decomposition of ether-based electrolytes,which should be highly important for the fundamental and technical advancement for LOBs.展开更多
Heteroatom doping is a universal approach to improve rate capability for various carbon anodes of sodium-ion batteries(SIBs)owing to the interlayer spacing expansion and pseudocapacitive enhancement.However,there is s...Heteroatom doping is a universal approach to improve rate capability for various carbon anodes of sodium-ion batteries(SIBs)owing to the interlayer spacing expansion and pseudocapacitive enhancement.However,there is still a limitation for ion adsorption of internal voids and dopants in the bulk phase of carbon materials due to the sluggish intercalation kinetics of large-size sodium ions.In this work,the highly sulfur-doped carbon nanosheets are synthesized and investigated as the anode of SIBs.It shows that the electrochemical performance in ether-based electrolytes significantly outperforms that in ester-based electrolytes.The carbon anodes exhibit a specific capacity of 617 mAh·g^(-1) at 100 mA·g^(-1) after 300 cycles,especially an outstanding rate performance of delivering specific capacities of 305 and 191 mAh·g^(-1) at current densities of 10 and 50 A·g^(-1),respectively.It is speculated that the ion-storage kinetics was greatly enhanced in ether-based electrolytes owing to the better accessibility of sodium-ion diffusion from electrode interfaces to internal hosts.As a result,the carbon nanovoids and sulfur dopants in the bulk phase are efficiently activated for ion storage.This work provides a new insight into the ion-storage mechanism optimization of carbon materials for SIBs.展开更多
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
基金the financial supports from the KeyArea Research and Development Program of Guangdong Province (2020B090919001)the National Natural Science Foundation of China (22078144)the Guangdong Natural Science Foundation for Basic and Applied Basic Research (2021A1515010138 and 2023A1515010686)。
文摘Li metal batteries using high-voltage layered oxides cathodes are of particular interest due to their high energy density.However,they suffer from short lifespan and extreme safety concerns,which are attributed to the degradation of layered oxides and the decomposition of electrolyte at high voltage,as well as the high reactivity of metallic Li.The key is the development of stable electrolytes against both highvoltage cathodes and Li with the formation of robust interphase films on the surfaces.Herein,we report a highly fluorinated ether,1,1,1-trifluoro-2-[(2,2,2-trifluoroethoxy)methoxy]ethane(TTME),as a cosolvent,which not only functions as a diluent forming a localized high concentration electrolyte(LHCE),but also participates in the construction of the inner solvation structure.The TTME-based electrolyte is stable itself at high voltage and induces the formation of a unique double-layer solid electrolyte interphase(SEI)film,which is embodied as one layer rich in crystalline structural components for enhanced mechanical strength and another amorphous layer with a higher concentration of organic components for enhanced flexibility.The Li||Cu cells display a noticeably high Coulombic efficiency of 99.28%after 300 cycles and Li symmetric cells maintain stable cycling more than 3200 h at 0.5 mA/cm^(2) and 1.0m Ah/cm^(2).In addition,lithium metal cells using LiNi_(0.8)Co_(0.1)Mn_(0.1)O_(2) and Li CoO_(2) cathodes(both loadings~3.0 m Ah/cm^(2))realize capacity retentions of>85%over 240 cycles with a charge cut-off voltage of 4.4 V and 90%for 170 cycles with a charge cut-off voltage of 4.5 V,respectively.This study offers a bifunctional ether-based electrolyte solvent beneficial for high-voltage Li metal batteries.
基金support from the National Key Research and Development Program of China(No.2022YFB2402200)National Natural Science Foundation of China(No.22109028)+1 种基金Natural Science Foundation of Shanghai(No.22ZR1404400)Chenguang Program sponsored by Shanghai Education Development Foundation and Shanghai Municipal Education Commission(No.19CG01).
文摘Weakly-solvated electrolytes(WSEs)utilizing solvents with weak coordination ability offer advantages for low-potential graphite anode owing to their facile desolvation process and anions-derived inorganic-rich solid electrolyte interphase(SEI)film.However,these electrolytes face challenges in achieving a balance between the weak solvation affinity and high ionic conductivity,as well as between rigid inorganic-rich SEI and flexible SEI for long-term stability.Herein,we introduce 1,3-dioxolane(DOL)and lithium bis(trifluoromethanesulfonyl)-imide(LiTFSI)as functional additives into a WSE based on nonpolar cyclic ether(1,4-dioxane).The well-formulated WSE not only preserves the weakly solvated features and anion-dominated solvation sheath,but also utilizes DOL to contribute organic species for stabilizing the SEI layer.Benefitting from these merits,the optimized electrolyte enables graphite anode with excellent fast-charging performance(210 mAh/g at 5 C)and outstanding cycling stability(600 cycles with a capacity retention of 82.0%at room temperature and 400 cycles with a capacity retention of 80.4%at high temper-ature).Furthermore,the fabricated LiNi_(0.8)Co_(0.1)Mn_(0.1)O_(2)||graphite full cells demonstrate stable operation for 140 cycles with high capacity retention of 80.3%.This work highlights the potential of tailoring solvation sheath and interphase properties in WSEs for advanced electrolyte design in graphite-based lithium-ion batteries.
基金financial support from the Natural Science Foundation of Hunan Province,China (No.2023JJ40759)the State Key Laboratory of Powder Metallurgy in Central South University,China。
文摘Ether-based solvents generally show better affinity for lithium metal,and thus ether-based electrolytes(EBEs)are more inclined to form a uniform and thin solid electrolyte interface(SEI),ensuring the long cycle stability of the lithium metal batteries(LMBs).Nonetheless,EBEs still face the challenge of oxidative decomposition under high voltage,which will corrode the structure of cathodes,destroy the stability of the electrode−electrolyte interface,and even cause safety risks.Herein,the types and challenges of EBEs are reviewed,the strategies for improving the high voltage stability of EBEs and constructing stable electrode−electrolyte interfaces are discussed in detail.Finally,the future perspectives and potential directions for composition optimization of EBEs and electrolyte−electrode interface regulation of high-voltage LMBs are explored.
基金supported by the National Natural Science Foundation of China(Nos.U1804129,21771164,21671205,U1804126)Zhongyuan Youth Talent Support Program of Henan ProvinceZhengzhou University Youth Innovation Program。
文摘Application of sodium-ion batteries is suppressed due to the lack of appropriate electrolytes matching cathode and anode simultaneously.Ether-based electrolytes,preference of anode materials,cannot match with high-potential cathodes failing to apply in full cells.Herein,vinylene carbonate(VC)as an additive into NaCF_(3) SO_(3)-Diglyme(DGM)could make sodium-ion full cells applicable without preactivation of cathode and anode.The assembled FeS@C||Na3 V2(PO_(4))_(3)@C full cell with this electrolyte exhibits long term cycling stability and high capacity retention.The deduced reason is additive VC,whose HOMO level value is close to that of DGM,not only change the solvent sheath structure of Na^(+),but also is synergistically oxidized with DGM to form integrity and consecutive cathode electrolyte interphase on Na3 V2(PO_(4))_(3)@C cathode,which could effectively improve the oxidative stability of electrolyte and prevent the electrolyte decomposition.This work displays a new way to optimize the sodium-ion full cell seasily with bright practical application potential.
基金supported by the National Natural Science Foundation of China(No.21972049)。
文摘Compared with graphite,the lower sodiation potential and larger discharge capacity of hard carbon(HC)makes it the most promising anode material for sodium-ion battery.Utilizing ether-based electrolyte rather than conventional carbonate-based electrolyte,HC achieves superior electrochemical performance.Nevertheless,the mechanism by which ether-based electrolyte improves the properties of HC is still controversial,primarily focusing on whether it forms solid electrolyte interphase(SEI)film.In this work,according to the sodium storage mechanisms in HC at low voltage(<0.1 V),including Na^(+)-diglyme co-interaction into the carbon layer(SEI forbidden)and desolvated Na^(+)insertion in the irregular carbon holes(SEI required),the NaPF6concentration in ether-based electrolyte was regulated,so as to construct a discontinuous-SEI on the surface of the HC anode,which significantly enhances the electrochemical performances of HC.Specifically,with 0.2 M NaPF6ether-based electrolyte,HC deliverers a discharge capacity of 459.7 mA h g^(-1)at 0.1 C and stays at 357.2 mA h g^(-1)after 500 cycles at 1 C,which is substantially higher than that of higher/lower salt concentration electrolytes.
基金supported by funding from the National Key Technologies R&D Program (2016YFB0901500)the NSFC (11234013 and 51421002)the One Hundred Talent Project of the Chinese Academy of Sciences
文摘Organic materials, especially the carbonyl compounds, are promising anode materials for room temperature sodium-ion batteries owing to their high reversible capacity, structural diversity as well as eco-friendly synthesis from bio-mass. Herein, we report a novel anthraquinone derivative, C_(14)H_6 O_4 Na_2 composited with carbon nanotube(C_(14)H_6 O_4 Na_2-CNT), used as an anode material for sodium-ion batteries in etherbased electrolyte. The C_(14)H_6 O_4 Na_2-CNT electrode delivers a reversible capacity of 173 mAh g^(-1) and an ultra-high initial Coulombic efficiency of 98% at the rate of 0.1 C. The capacity retention is 82% after 50 cycles at 0.2 C and a good rate capability is displayed at 2 C.Furthermore, the average Na insertion voltage of 1.27 V vs. Na^+/Na makes it a unique and safety battery material, which would avoid Na plating and formation of solid electrolyte interface. Our contribution provides new insights for designing developed organic anode materials with high initial Coulombic efficiency and improved safety capability for sodium-ion batteries.
基金the National Natural Science Foundation of China (21773055, U1604122, 22005085)。
文摘Ether-based electrolytes with relatively high stability are widely used in Li-O_(2) batteries (LOBs) with high energy density.However,they are still prone to be attacked by reactive oxygen species.Understanding the degradation chemistry of ether-based solvent induced by reactive oxygen species is significant importance toward selection of stable electrolytes for LOBs.Herein,we demonstrate that a great amount of H_(2) gas evolves on the Li anode during the long-term discharge process of LOBs,which is due to the electrolyte decomposition at the oxygen cathode.By coupling with in-situ and ex-situ characterization techniques,it is demonstrated that O_(2)^(-) induces the H-abstraction of tetraethylene glycol dimethyl ether(TEGDME) to produce a large amount of H_(2)O at cathode,and this H_(2)O migrates to Li anode and produce H_(2) gas.Based on the established experiments and spectra,a possible decomposition pathway of TEGDME caused by O_(2)^(-)at the discharge process is proposed.And moreover,three types of strategies are discussed to inhibit the decomposition of ether-based electrolytes,which should be highly important for the fundamental and technical advancement for LOBs.
基金supported by the National Natural Science Foundation of China(Nos.52307243 and 52272213)the Natural Science Foundation of Jiangsu Province(No.BK20230537)+2 种基金the China Postdoctoral Science Foundation(No.2023M741451)the Natural Science Foundation of the Jiangsu Higher Education Institutions of China(No.23KJB140003)the Jiangsu University Advanced Talent Research Startup Fund(No.22JDG052).
文摘Heteroatom doping is a universal approach to improve rate capability for various carbon anodes of sodium-ion batteries(SIBs)owing to the interlayer spacing expansion and pseudocapacitive enhancement.However,there is still a limitation for ion adsorption of internal voids and dopants in the bulk phase of carbon materials due to the sluggish intercalation kinetics of large-size sodium ions.In this work,the highly sulfur-doped carbon nanosheets are synthesized and investigated as the anode of SIBs.It shows that the electrochemical performance in ether-based electrolytes significantly outperforms that in ester-based electrolytes.The carbon anodes exhibit a specific capacity of 617 mAh·g^(-1) at 100 mA·g^(-1) after 300 cycles,especially an outstanding rate performance of delivering specific capacities of 305 and 191 mAh·g^(-1) at current densities of 10 and 50 A·g^(-1),respectively.It is speculated that the ion-storage kinetics was greatly enhanced in ether-based electrolytes owing to the better accessibility of sodium-ion diffusion from electrode interfaces to internal hosts.As a result,the carbon nanovoids and sulfur dopants in the bulk phase are efficiently activated for ion storage.This work provides a new insight into the ion-storage mechanism optimization of carbon materials for SIBs.
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.
