Polymer solid-state lithium batteries(SSLB)are regarded as a promising energy storage technology to meet growing demand due to their high energy density and safety.Ion conductivity,interface stability and battery asse...Polymer solid-state lithium batteries(SSLB)are regarded as a promising energy storage technology to meet growing demand due to their high energy density and safety.Ion conductivity,interface stability and battery assembly process are still the main challenges to hurdle the commercialization of SSLB.As the main component of SSLB,poly(1,3-dioxolane)(PDOL)-based solid polymer electrolytes polymerized in-situ are becoming a promising candidate solid elec-trolyte,for their high ion conductivity at room temperature,good battery elec-trochemical performances,and simple assembly process.This review analyzes opportunities and challenges of PDOL electrolytes toward practical application for polymer SSLB.The focuses include exploring the polymerization mechanism of DOL,the performance of PDOL composite electrolytes,and the application of PDOL.Furthermore,we provide a perspective on future research directions that need to be emphasized for commercialization of PDOL-based electrolytes in SSLB.The exploration of these schemes facilitates a comprehensive and profound understanding of PDOL-based polymer electrolyte and provides new research ideas to boost them toward practical application in solid-state batteries.展开更多
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
For the performance optimization strategies of hard carbon,heteroatom doping is an effective way to enhance the intrinsic transfer properties of sodium ions and electrons for accelerating the reaction kinetics.However...For the performance optimization strategies of hard carbon,heteroatom doping is an effective way to enhance the intrinsic transfer properties of sodium ions and electrons for accelerating the reaction kinetics.However,the previous work focuses mainly on the intrinsic physicochemical property changes of the material,but little attention has been paid to the resulting interfacial regulation of the electrode surface,namely the formation of solid electrolyte interphase(SEI)film.In this work,element F,which has the highest electronegativity,was chosen as the doping source to,more effectively,tune the electronic structure of the hard carbon.The effect of F-doping on the physicochemical properties of hard carbon was not only systematically analyzed but also investigated with spectroscopy,optics,and in situ characterization techniques to further verify that appropriate F-doping plays a positive role in constructing a homogenous and inorganic-rich SEI film.The experimentally demonstrated link between the electronic structure of the electrode and the SEI film properties can reframe the doping optimization strategy as well as provide a new idea for the design of electrode materials with low reduction kinetics to the electrolyte.As a result,the optimized sample with the appropriate F-doping content exhibits the best electrochemical performance with high capacity(434.53 mA h g^(-1)at 20mA g^(-1))and excellent rate capability(141 mAh g^(-1)at 400 mA g^(-1)).展开更多
Polymer solid electrolytes(SPEs)based on the[solvate-Li+]complex structure have promising prospects in lithium metal batteries(LMBs)due to their unique ion transport mechanism.However,the solvation structure may compr...Polymer solid electrolytes(SPEs)based on the[solvate-Li+]complex structure have promising prospects in lithium metal batteries(LMBs)due to their unique ion transport mechanism.However,the solvation structure may compromise the mechanical performance and safety,hindering practical application of SPEs.In this work,a composite solid electrolyte(CSE)is designed through the organic-inorganic syner-gistic interaction among N,N-dimethylformamide(DMF),polycarbonate(PC),and Mg_(2)B_(2)O_(5) in poly(vinylidene fluoride-co-hexafluoropropylene)(PVDF-HFP).Flame-retardant Mg_(2)B_(2)O_(5) nanowires provide non-flammability to the prepared CSEs,and the addition of PC improves the dispersion of Mg_(2)B_(2)O_(5) nanowires.Simultaneously,the organic-inorganic synergistic action of PC plasticizer and Mg_(2)B_(2)O_(5) nanowires pro-motes the dissociation degree of LiTFSI and reduces the crystallinity of PVDF-HFP,enabling rapid Li ion transport.Additionally,Raman spectroscopy and DFT calculations confirm the coordination between Mg atoms in Mg_(2)B_(2)O_(5) and N atoms in DMF,which exhibits Lewis base-like behavior attacking adjacent C-F and C-H bonds in PVDF-HFP while inducing dehydrofluorination of PVDF-HFP.Based on the syner-gistic coupling of Mg_(2)B_(2)O_(5),PC,and DMF in the PVDF-HFP matrix,the prepared CSE exhibits superior ion conductivity(9.78×10^(-4) s cm^(-1)).The assembled Li symmetric cells cycle stably for 3900 h at a current density of 0.1 mA cm^(-2) without short circuit.The LFP||Li cells assembled with PDL-Mg_(2)B_(2)O_(5)/PC CSEs show excellent rate capability and cycling performance,with a capacity retention of 83.3%after 1000 cycles at 0.5 C.This work provides a novel approach for the practical application of organic-inorganic Synergistic CSEs in LMBs.展开更多
Composite solid electrolytes(CSEs)have emerged as promising candidates for safe and high-energy–density solid-state lithium metal batteries(SSLMBs).However,concurrently achieving exceptional ionic conductivity and in...Composite solid electrolytes(CSEs)have emerged as promising candidates for safe and high-energy–density solid-state lithium metal batteries(SSLMBs).However,concurrently achieving exceptional ionic conductivity and interface compatibility between the electrolyte and electrode presents a significant challenge in the development of high-performance CSEs for SSLMBs.To overcome these challenges,we present a method involving the in-situ polymerization of a monomer within a self-supported porous Li_(6.4)La_(3)Zr_(1.4)Ta_(0.6)O_(12)(LLZT)to produce the CSE.The synergy of the continuous conductive LLZT network,well-organized polymer,and their interface can enhance the ionic conductivity of the CSE at room temperature.Furthermore,the in-situ polymerization process can also con-struct the integration and compatibility of the solid electrolyte–solid electrode interface.The synthesized CSE exhibited a high ionic conductivity of 1.117 mS cm^(-1),a significant lithium transference number of 0.627,and exhibited electrochemical stability up to 5.06 V vs.Li/Li+at 30℃.Moreover,the Li|CSE|LiNi_(0.8)Co_(0.1)Mn_(0.1)O_(2) cell delivered a discharge capacity of 105.1 mAh g^(-1) after 400 cycles at 0.5 C and 30℃,corresponding to a capacity retention of 61%.This methodology could be extended to a variety of ceramic,polymer electrolytes,or battery systems,thereby offering a viable strategy to improve the electrochemical properties of CSEs for high-energy–density SSLMBs.展开更多
Solid state lithium metal batteries(SSLMBs)are considered to be one of the most promising battery systems for achieving high energy density and excellent safety for energy storage in the future.However,current existed...Solid state lithium metal batteries(SSLMBs)are considered to be one of the most promising battery systems for achieving high energy density and excellent safety for energy storage in the future.However,current existed solid-state electrolytes(SSEs)are still difficult to meet the practical application requirements of SSLMBs.In this review,based on the analysis of main problems and challenges faced by the development of SSEs,the ingenious application and latest progresses including specific suggestions of various polymer fibers and their membrane products in solving these issues are emphatically reviewed.Firstly,the inherent defects of inorganic and organic electrolytes are pointed out.Then,the application strategies of polymer fibers/fiber membranes in strengthening strength,reducing thickness,enhancing thermal stability,increasing the film formability,improving ion conductivity and optimizing interface stability are discussed in detail from two aspects of improving physical structure properties and electrochemical performances.Finally,the researches and development trends of the intelligent applications of high-performance polymer fibers in SSEs is prospected.This review intends to provide timely and important guidance for the design and development of polymer fiber composite SSEs for SSLMBs.展开更多
Polyethylene oxide(PEO)-based solid polymer electrolytes(SPEs)with good electrochemical stability and excellent Li salt solubility are considered as one of the most promising SPEs for solid-state lithium metal batteri...Polyethylene oxide(PEO)-based solid polymer electrolytes(SPEs)with good electrochemical stability and excellent Li salt solubility are considered as one of the most promising SPEs for solid-state lithium metal batteries(SSLMBs).However,PEO-based SPEs suffer from low ionic conductivity at room temperature and high interfacial resistance with the electrodes due to poor interfacial contact,seriously hindering their practical applications.As an emerging technology,in-situ polymerization process has been widely used in PEO-based SPEs because it can effectively increase Li-ion transport at the interface and improve the interfacial contact between the electrolyte and electrodes.Herein,we review recent advances in design and fabrication of in-situ polymerized PEO-based SPEs to realize enhanced performance in LMBs.The merits and current challenges of various SPEs,as well as their stabilizing strategies are presented.Furthermore,various in-situ polymerization methods(such as free radical polymerization,cationic polymerization,anionic polymerization)for the preparation of PEO-based SPEs are summarized.In addition,the application of in-situ polymerization technology in PEO-based SPEs for adjustment of the functional units and addition of different functional filler materials was systematically discussed to explore the design concepts,methods and working mechanisms.Finally,the challenges and future prospects of in-situ polymerized PEO-based SPEs for SSLMBs are also proposed.展开更多
Lithium (Li) metal with an ultrahigh specific theoretical capacity and the lowest reduction potential is strongly considered as a promising anode for high-energy-density batteries. However, uncontrolled lithium dendri...Lithium (Li) metal with an ultrahigh specific theoretical capacity and the lowest reduction potential is strongly considered as a promising anode for high-energy-density batteries. However, uncontrolled lithium dendrites and infinite volume change during repeated plating/stripping cycles hinder its practical applications immensely. Herein, a house-like Li anode (housed Li) was designed to circumvent the above issues. The house matrix was composed of carbon fiber matrix and affords a stable structure to relieve the volume change. An artificial solid electrolyte layer was formed on composite Li metal, just like the roof of a house, which facilitates uniform Li ions diffusion and serves as a physical barrier against electrolyte corrosion. With the combination of solid electrolyte layer and matrix in the composite Li metal anode, both dendrite growth and volume expansion are remarkably inhibited. The housed Li|LiFePO4 batteries exhibited over 95% capacity retention after 500 cycles at 1.0 C in coin cell and 85% capacity retention after 80 cycles at 0.5 C in pouch cell. The rationally combination of solid electrolyte layer protection and housed framework in one Li metal anode sheds fresh insights on the design principle of a safe and long-lifespan Li metal anode for Li metal batteries.展开更多
The rapid development of new energy vehicles and 5G communication technologies has led to higher demands for the safety,energy density,and cycle performance of lithium-ion batteries as power sources.However,the curren...The rapid development of new energy vehicles and 5G communication technologies has led to higher demands for the safety,energy density,and cycle performance of lithium-ion batteries as power sources.However,the currently used liquid carbonate compounds in commercial lithium-ion battery electrolytes pose potential safety hazards such as leakage,swelling,corrosion,and flammability.Solid electrolytes can be used to mitigate these risks and create a safer lithium battery.Furthermore,high-energy density can be achieved by using solid electrolytes along with high-voltage cathode and metal lithium anode.Two types of solid electrolytes are generally used:inorganic solid electrolytes and polymer solid electrolytes.Inorganic solid electrolytes have high ionic conductivity,electrochemical stability window,and mechanical strength,but suffer from large solid/solid contact resistance between the electrode and electrolyte.Polymer solid electrolytes have good flexibility,processability,and contact interface properties,but low room temperature ionic conductivity,necessitating operation at elevated temperatures.Composite solid electrolytes(CSEs) are a promising alternative because they offer light weight and flexibility,like polymers,as well as the strength and stability of inorganic electrolytes.This paper presents a comprehensive review of recent advances in CSEs to help researchers optimize CSE composition and interactions for practical applications.It covers the development history of solid-state electrolytes,CSE properties with respect to nanofillers,morphology,and polymer types,and also discusses the lithium-ion transport mechanism of the composite electrolyte,and the methods of engineering interfaces with the positive and negative electrodes.Overall,the paper aims to provide an outlook on the potential applications of CSEs in solid-state lithium batteries,and to inspire further research aimed at the development of more systematic optimization strategies for CSEs.展开更多
We fabricated a silver ion emitter based on the solid state electrolyte film of RbAg4 I5 prepared by pulsed laser deposition. The RbAg4 I5 target for PLD process was mechano-chemically synthesized by high-energy ball ...We fabricated a silver ion emitter based on the solid state electrolyte film of RbAg4 I5 prepared by pulsed laser deposition. The RbAg4 I5 target for PLD process was mechano-chemically synthesized by high-energy ball milling in Ar atmosphere using β-AgI and RbI as raw materials. The ion-conducting properties of RbAg4 I5 were studied by alternating current(AC) impedance spectroscopy and the ionic conductivity at room temperature was estimated 0.21 S/m. The structure, morphology, and elemental composition of the RbAg4 I5 film were investigated. The Ag+ ion-conducting property of the prepared superioni-conductor film was exploited for ion–beam generation. The temperature and accelerating voltage dependences of the ion current were studied. Few nA current was obtained at the temperature of 196?C and the accelerating voltage of 10 kV.展开更多
Composite solid electrolytes(CSEs)with poly(ethylene oxide)(PEO)have become fairly prevalent for fabricating high-performance solid-state lithium metal batteries due to their high Li~+solvating capability,flexible pro...Composite solid electrolytes(CSEs)with poly(ethylene oxide)(PEO)have become fairly prevalent for fabricating high-performance solid-state lithium metal batteries due to their high Li~+solvating capability,flexible processability and low cost.However,unsatisfactory room-temperature ionic conductivity,weak interfacial compatibility and uncontrollable Li dendrite growth seriously hinder their progress.Enormous efforts have been devoted to combining PEO with ceramics either as fillers or major matrix with the rational design of two-phase architecture,spatial distribution and content,which is anticipated to hold the key to increasing ionic conductivity and resolving interfacial compatibility within CSEs and between CSEs/electrodes.Unfortunately,a comprehensive review exclusively discussing the design,preparation and application of PEO/ceramic-based CSEs is largely lacking,in spite of tremendous reviews dealing with a broad spectrum of polymers and ceramics.Consequently,this review targets recent advances in PEO/ceramicbased CSEs,starting with a brief introduction,followed by their ionic conduction mechanism,preparation methods,and then an emphasis on resolving ionic conductivity and interfacial compatibility.Afterward,their applications in solid-state lithium metal batteries with transition metal oxides and sulfur cathodes are summarized.Finally,a summary and outlook on existing challenges and future research directions are proposed.展开更多
Li metal has been regarded as one of the most promising anodes for high-energy-density storage systems due to its high theoretical capacity and lowest electrochemical potential.Unfortunately,an unstable and non-unifor...Li metal has been regarded as one of the most promising anodes for high-energy-density storage systems due to its high theoretical capacity and lowest electrochemical potential.Unfortunately,an unstable and non-uniform solid electrolyte interphase(SEI)deriving from the spontaneous reaction between Li metal anode and electrolyte causes uneven Li deposition,resulting in the growth of Li dendrites and low Coulombic efficiency,which have greatly hindered the practical application of Li metal batteries.Thus,the construction of a stable SEI is an effective approach to suppress the growth of Li dendrites and enhance the electrochemical performances of Li metal anode.In this review,we firstly introduce the formation process of inferior SEI of Li metal anode and the corresponding challenges caused by the unstable SEI.Next,recent progresses to modify SEI layer through the regulation of electrolyte compositions and exsitu protective coating are summarized.Finally,the remained issues,challenges,and perspectives are also proposed on the basis of current research status and progress.展开更多
The anodic stability and reversibility of Ca metal electrodeposition/dissolution have always been hampered by surface passivation and anion corrosion,especially in F-based carbonate ester electrolytes at high device v...The anodic stability and reversibility of Ca metal electrodeposition/dissolution have always been hampered by surface passivation and anion corrosion,especially in F-based carbonate ester electrolytes at high device voltages.To avoid direct Ca metal/electrolyte reactions,an artificial hybrid solid electrolyte layer(AHSEL),which is characteristic of sodium/calcium carbonate and calcium hydride nitride nanocrystals of size<10 nm encapsulated by amorphous C,N species,is constructed on calcium with good ion conductivity(≈0.01 mS cm^(-1))and uniform coating of thickness≈20μm.After cycling in the KPF_(6) electrolyte,AHSEL is transformed into Na/K/Ca hybrid solid electrolyte interphases(SEIs),which is a compact layer composed of monodisperse nanocrystals(mostly Ca_(2)NH)and small amorphous zones,thus greatly suppressing the fluoridation of the Ca deposit.Consequently,the plating/stripping performance of AHSEL-modified Ca(AHSEL-Ca)is markedly improved compared with that of pristine Ca,lasting for>1400 h at a polarization shift of<0.4 mV/h.The AHSEL-Ca anode also endows Ca batteries with superior anodic stability with a ceiling voltage of up to 5.0 V,a high discharge voltage(>3.3 V),a large capacity of≈80 mAh g^(-1)at 200 mA g^(-1),and an ultralong lifespan≈5000 cycles.展开更多
Silicon is an important high capacity anode material for the next generation Li-ion batteries.The electrochemical performances of the Si anode are influenced strongly by the properties of the solid electrolyte interph...Silicon is an important high capacity anode material for the next generation Li-ion batteries.The electrochemical performances of the Si anode are influenced strongly by the properties of the solid electrolyte interphase(SEI).It is well known that the addition of flouroethylene carbonate(FEC)in the carbonate electrolyte is helpful to improve the cyclic performance of the Si anode.The possible origin is suggested to relate to the modification of the SEI.However,detailed information is still absent.In this work,the structural and mechanical properties of the SEI on Si thin film anode in the ethylene-carbonate-based(EC-based)and FEC-based electrolytes at different discharging and charging states have been investigated using a scanning atomic force microscopy force spectroscopy(AFMFS)method.Single-layered,double-layered,and multi-layered SEI structures with various Young’s moduli have been visualized three dimensionally at nanoscale based on the hundreds of force curves in certain scanned area.The coverage of the SEI can be obtained quantitatively from the two-dimensional(2D)project plots.The related analysis indicates that more soft SEI layers are covered on the Si anode,and this could explain the benefits of the FEC additive.展开更多
Developing laminar composite solid electrolyte with ultrathin thickness and continuous conduction channels in vertical direction holds great promise for all-solid-state lithium batteries.Herein,a thin,laminar solid el...Developing laminar composite solid electrolyte with ultrathin thickness and continuous conduction channels in vertical direction holds great promise for all-solid-state lithium batteries.Herein,a thin,laminar solid electrolyte is synthesized by filtrating–NH 2 functionalized metal-organic framework nanosheets and then being threaded with poly(ethylene oxide)chains induced by the hydrogen-bonding interaction from–NH_(2) groups.It is demonstrated that the threaded poly(ethylene oxide)chains lock the adjacent metal-organic framework nanosheets,giving highly enhanced structural stability(Young’s modulus,1.3 GPa)to 7.5-μm-thick laminar composite solid electrolyte.Importantly,these poly(ethylene oxide)chains with stretching structure serve as continuous conduction pathways along the chains in pores.It makes the non-conduction laminar metal-organic framework electrolyte highly conductive:3.97×10^(−5) S cm^(−1) at 25℃,which is even over 25 times higher than that of pure poly(ethylene oxide)electrolyte.The assembled lithium cell,thus,acquires superior cycling stability,initial discharge capacity(148 mAh g^(−1) at 0.5 C and 60℃),and retention(94% after 150 cycles).Besides,the pore size of nanosheet is tailored(24.5–40.9˚A)to evaluate the mechanisms of chain conformation and ion transport in confined space.It shows that the confined pore only with proper size could facilitate the stretching of poly(ethylene oxide)chains,and meanwhile inhibit their disorder degree.Specifically,the pore size of 33.8˚A shows optimized confinement effect with trans-poly(ethylene oxide)and cis-poly(ethylene oxide)conformation,which offers great significance in ion conduction.Our design of poly(ethylene oxide)-threaded architecture provides a platform and paves a way to the rational design of next-generation high-performance porous electrolytes.展开更多
Developing effective strategies to improve the initial Coulombic efficiency(ICE)and cycling stability of hard carbon(HC)anodes for sodium-ion batteries is the key to promoting the commercial application of HC.In this ...Developing effective strategies to improve the initial Coulombic efficiency(ICE)and cycling stability of hard carbon(HC)anodes for sodium-ion batteries is the key to promoting the commercial application of HC.In this paper,homotype heterojunctions are designed on HC to induce the generation of stable solid electrolyte interfaces,which can effectively increase the ICE of HC from 64.7%to 81.1%.The results show that using a simple surface engineering strategy to construct a homotypic amorphous Al_(2)O_(3) layer on the HC could shield the active sites,and further inhibit electrolyte decomposition and side effects occurrence.Particularly,due to the suppression of continuous decomposition of NaPF 6 in ester-based electrolytes,the accumulation of NaF could be reduced,leading to the formation of thinner and denser solid electrolyte interface films and a decrease in the interface resistance.The HC anode can not only improve the ICE but elevate its sodium storage performance based on this homotype heterojunction composed of HC and Al_(2)O_(3).The optimized HC anode exhibits an outstanding reversible capacity of 321.5mAhg^(−1) at 50mAg^(−1).The cycling stability is also improved effectively,and the capacity retention rate is 86.9%after 2000 cycles at 1Ag^(−1) while that of the untreated HC is only 52.6%.More importantly,the improved sodium storage behaviors are explained by electrochemical kinetic analysis.展开更多
The resourceful and inexpensive red phosphorus has emerged as a promising anode material of potassium-ion batteries(PIBs) for its large theoretical capacities and low redox potentials in the multielectron alloying/dea...The resourceful and inexpensive red phosphorus has emerged as a promising anode material of potassium-ion batteries(PIBs) for its large theoretical capacities and low redox potentials in the multielectron alloying/dealloying reactions,yet chronically suffering from the huge volume expansion/shrinkage with a sluggish reaction kinetics and an unsatisfactory interfacial stability against volatile electrolytes.Herein,we systematically developed a series of localized high-concentration electrolytes(LHCE) through diluting high-concentration ether electrolytes with a non-solvating fluorinated ether to regulate the formation/evolution of solid electrolyte interphases(SEI) on phosphorus/carbon(P/C) anodes for PIBs.Benefitting from the improved mechanical strength and structural stability of a robust/uniform SEI thin layer derived from a composition-optimized LHCE featured with a unique solvation structure and a superior K+migration capability,the P/C anode with noticeable pseudocapacitive behaviors could achieve a large reversible capacity of 760 mA h g^(-1)at 100 mA g^(-1),a remarkable capacity retention rate of 92.6% over 200 cycles at 800 mA g^(-1),and an exceptional rate capability of 334 mA h g^(-1)at8000 mA g^(-1).Critically,a suppressed reduction of ether solvents with a preferential decomposition of potassium salts in anion-derived interfacial reactions on P/C anode for LHCE could enable a rational construction of an outer organic-rich and inner inorganic-dominant SEI thin film with remarkable mechanical strength/flexibility to buffer huge volume variations and abundant K+diffusion channels to accelerate reaction kinetics.Additionally,the highly reversible/durable full PIBs coupling P/C anodes with annealed organic cathodes further verified an excellent practical applicability of LHCE.This encouraging work on electrolytes regulating SEI formation/evolution would advance the development of P/C anodes for high-performance PIBs.展开更多
High ionic conductivity and superior interfacial stability of solid electrolytes at the electrodes are crucial factors for high-performance all-solid-state sodium batteries. Herein, a composite solid electrolyte Na3PS...High ionic conductivity and superior interfacial stability of solid electrolytes at the electrodes are crucial factors for high-performance all-solid-state sodium batteries. Herein, a composite solid electrolyte Na3PS4-polyethylene oxide is synthesized by the solution-phase reaction method with an improved ionic conductivity up to 9.4 × 10-5 S/cm at room temperature. Moreover, polyethylene oxide polymer layer is wrapped homogeneously on the surface of Na3PS4 particles, which could effectively avoid the direct contact between Na3PS4 electrolyte and sodium metal, thus alleviate their side reactions. We demonstrate that all-solid-state battery SnS2/Na with the composite solid electrolyte Na3PS4-polyethylene oxide delivers an enhanced electrochemical performance with 230 m Ah/g after 40 cycles.展开更多
Lithium metal anode is a promising electrode with high theoretical specific capacity and low electrode potential.However,its unstable interface and low Coulombic efficiency,resulting from the dendritic growth of lithi...Lithium metal anode is a promising electrode with high theoretical specific capacity and low electrode potential.However,its unstable interface and low Coulombic efficiency,resulting from the dendritic growth of lithium,limits its commercial application.PIM-1(PIM:polymer of intrinsic microporosity),which is a polymer with abundant micropores,exhibits high rigidity and flexibility with contorted spirocenters in the backbone,and is an ideal candidate for artificial solid electrolyte interphases(SEI).In this work,a PIM-1 membrane was synthesized and fabricated as a protective membrane on the surface of an electrode to facilitate the uniform flux of Li ions and act as a stable interface for the lithium plating/stripping process.Nodule-like lithium with rounded edges was observed under the PIM-1 membrane.The Li@PIM-1 electrode delivered a high average Coulombic efficiency(99.7%),excellent cyclability(80%capacity retention rate after 600 cycles at 1 C),and superior rate capability(125.3 m Ah g-1 at 10 C).Electrochemical impedance spectrum(EIS)showed that the PIM-1 membrane could lower the diffusion rate of Li+significantly and change the rate-determining step from charge transfer to Li+diffusion.Thus,the PIM-1 membrane is proven to act as an artificial SEI to facilitate uniform and stable deposition of lithium,in favor of obtaining a compact and dense Li-plating pattern.This work extends the application of PIMs in the field of lithium batteries and provides ideas for the construction of artificial SEI.展开更多
Lithium sulfur batteries are regarded as a promising candidate for high-energy-density energy storage devices.However,the lithium metal anode in lithium-sulfur batteries encounters the problem of lithium dendrites and...Lithium sulfur batteries are regarded as a promising candidate for high-energy-density energy storage devices.However,the lithium metal anode in lithium-sulfur batteries encounters the problem of lithium dendrites and lithium metal consumption caused by polysulfide corrosion.Herein we design a dualfunction PMMA/PPC/LiNO3composite as an artificial solid electrolyte interphase(PMCN-SEI)to protect Li metal anode.This SEI offers multiple sites of C=O for polysulfide anchoring to constrain corrosion of Li metal anode.The lithiated polymer group and Li3N in PMCN-SEI can homogenize lithium-ion deposition behavior to achieve a dendrite-free anode.As a result,the PMCN-SEI protected Li metal anode enables the Li||Li symmetric batteries to maintain over 300 cycles(1300 h)at a capacity of 5 m Ah cm^(-2),corresponding to a cumulative capacity of 3.25 Ah cm^(-2).Moreover,Li-S batteries assembled with 20μm of Li metal anode(N/P=1.67)still deliver an initial capacity of 1166 m A h g-1at 0.5C.Hence,introducing polycarbonate polymer/inorganic composite SEI on Li provides a new solution for achieving the high energy density of Li-S batteries.展开更多
基金We express our sincere appreciation to the National Natural Science Foundation of China(No.51474113(M.Jing),22279070[L.Wang]and U21A20170[X.He])the Ministry of Science and Technology of China(No.2019YFA0705703[L.Wang]).And we would like to thank the“Explorer 100”cluster system of Tsinghua National Laboratory for Information Science and Technology for facility support.
文摘Polymer solid-state lithium batteries(SSLB)are regarded as a promising energy storage technology to meet growing demand due to their high energy density and safety.Ion conductivity,interface stability and battery assembly process are still the main challenges to hurdle the commercialization of SSLB.As the main component of SSLB,poly(1,3-dioxolane)(PDOL)-based solid polymer electrolytes polymerized in-situ are becoming a promising candidate solid elec-trolyte,for their high ion conductivity at room temperature,good battery elec-trochemical performances,and simple assembly process.This review analyzes opportunities and challenges of PDOL electrolytes toward practical application for polymer SSLB.The focuses include exploring the polymerization mechanism of DOL,the performance of PDOL composite electrolytes,and the application of PDOL.Furthermore,we provide a perspective on future research directions that need to be emphasized for commercialization of PDOL-based electrolytes in SSLB.The exploration of these schemes facilitates a comprehensive and profound understanding of PDOL-based polymer electrolyte and provides new research ideas to boost them toward practical application in solid-state batteries.
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National Key R&D Program of China,Grant/Award Number:2022YFB4000120Fundamental Research Funds for the Central Universities,Grant/Award Number:2022ZYGXZR101。
文摘For the performance optimization strategies of hard carbon,heteroatom doping is an effective way to enhance the intrinsic transfer properties of sodium ions and electrons for accelerating the reaction kinetics.However,the previous work focuses mainly on the intrinsic physicochemical property changes of the material,but little attention has been paid to the resulting interfacial regulation of the electrode surface,namely the formation of solid electrolyte interphase(SEI)film.In this work,element F,which has the highest electronegativity,was chosen as the doping source to,more effectively,tune the electronic structure of the hard carbon.The effect of F-doping on the physicochemical properties of hard carbon was not only systematically analyzed but also investigated with spectroscopy,optics,and in situ characterization techniques to further verify that appropriate F-doping plays a positive role in constructing a homogenous and inorganic-rich SEI film.The experimentally demonstrated link between the electronic structure of the electrode and the SEI film properties can reframe the doping optimization strategy as well as provide a new idea for the design of electrode materials with low reduction kinetics to the electrolyte.As a result,the optimized sample with the appropriate F-doping content exhibits the best electrochemical performance with high capacity(434.53 mA h g^(-1)at 20mA g^(-1))and excellent rate capability(141 mAh g^(-1)at 400 mA g^(-1)).
基金supported by the National Natural Science Foundation of China(Grant Nos.51604089,51874110,22173066,and 21903058)Natural Science Foundation of Heilongjiang Province(Grant No.YQ2021B004).
文摘Polymer solid electrolytes(SPEs)based on the[solvate-Li+]complex structure have promising prospects in lithium metal batteries(LMBs)due to their unique ion transport mechanism.However,the solvation structure may compromise the mechanical performance and safety,hindering practical application of SPEs.In this work,a composite solid electrolyte(CSE)is designed through the organic-inorganic syner-gistic interaction among N,N-dimethylformamide(DMF),polycarbonate(PC),and Mg_(2)B_(2)O_(5) in poly(vinylidene fluoride-co-hexafluoropropylene)(PVDF-HFP).Flame-retardant Mg_(2)B_(2)O_(5) nanowires provide non-flammability to the prepared CSEs,and the addition of PC improves the dispersion of Mg_(2)B_(2)O_(5) nanowires.Simultaneously,the organic-inorganic synergistic action of PC plasticizer and Mg_(2)B_(2)O_(5) nanowires pro-motes the dissociation degree of LiTFSI and reduces the crystallinity of PVDF-HFP,enabling rapid Li ion transport.Additionally,Raman spectroscopy and DFT calculations confirm the coordination between Mg atoms in Mg_(2)B_(2)O_(5) and N atoms in DMF,which exhibits Lewis base-like behavior attacking adjacent C-F and C-H bonds in PVDF-HFP while inducing dehydrofluorination of PVDF-HFP.Based on the syner-gistic coupling of Mg_(2)B_(2)O_(5),PC,and DMF in the PVDF-HFP matrix,the prepared CSE exhibits superior ion conductivity(9.78×10^(-4) s cm^(-1)).The assembled Li symmetric cells cycle stably for 3900 h at a current density of 0.1 mA cm^(-2) without short circuit.The LFP||Li cells assembled with PDL-Mg_(2)B_(2)O_(5)/PC CSEs show excellent rate capability and cycling performance,with a capacity retention of 83.3%after 1000 cycles at 0.5 C.This work provides a novel approach for the practical application of organic-inorganic Synergistic CSEs in LMBs.
基金supported by the National Research Foundation of Korea (NRF) grant funded by the MSIT,Korea (No. 2018R1A5A1025224 and No. 2019R1A2C1084020)this research received funding support from a grant from the Korea Planning&Evaluation Institute of Industrial Technology (KEIT),funded by the MOTIE of Korea (No. 10077287)。
文摘Composite solid electrolytes(CSEs)have emerged as promising candidates for safe and high-energy–density solid-state lithium metal batteries(SSLMBs).However,concurrently achieving exceptional ionic conductivity and interface compatibility between the electrolyte and electrode presents a significant challenge in the development of high-performance CSEs for SSLMBs.To overcome these challenges,we present a method involving the in-situ polymerization of a monomer within a self-supported porous Li_(6.4)La_(3)Zr_(1.4)Ta_(0.6)O_(12)(LLZT)to produce the CSE.The synergy of the continuous conductive LLZT network,well-organized polymer,and their interface can enhance the ionic conductivity of the CSE at room temperature.Furthermore,the in-situ polymerization process can also con-struct the integration and compatibility of the solid electrolyte–solid electrode interface.The synthesized CSE exhibited a high ionic conductivity of 1.117 mS cm^(-1),a significant lithium transference number of 0.627,and exhibited electrochemical stability up to 5.06 V vs.Li/Li+at 30℃.Moreover,the Li|CSE|LiNi_(0.8)Co_(0.1)Mn_(0.1)O_(2) cell delivered a discharge capacity of 105.1 mAh g^(-1) after 400 cycles at 0.5 C and 30℃,corresponding to a capacity retention of 61%.This methodology could be extended to a variety of ceramic,polymer electrolytes,or battery systems,thereby offering a viable strategy to improve the electrochemical properties of CSEs for high-energy–density SSLMBs.
基金supported by the National Natural Science Foundation of China(52203066,51973157,61904123)Tianjin Natural Science Foundation(18JCQNJC02900)+3 种基金Tianjin Research Innovation Project for Postgraduate Students(2021YJSB234)Science and Technology Plans of Tianjin(19PTSYJC00010)Science&Technology Development Fund of Tianjin Education Commission for Higher Education(Grant No.2018KJ196)State Key Laboratory of Membrane and Membrane Separation,Tiangong University。
文摘Solid state lithium metal batteries(SSLMBs)are considered to be one of the most promising battery systems for achieving high energy density and excellent safety for energy storage in the future.However,current existed solid-state electrolytes(SSEs)are still difficult to meet the practical application requirements of SSLMBs.In this review,based on the analysis of main problems and challenges faced by the development of SSEs,the ingenious application and latest progresses including specific suggestions of various polymer fibers and their membrane products in solving these issues are emphatically reviewed.Firstly,the inherent defects of inorganic and organic electrolytes are pointed out.Then,the application strategies of polymer fibers/fiber membranes in strengthening strength,reducing thickness,enhancing thermal stability,increasing the film formability,improving ion conductivity and optimizing interface stability are discussed in detail from two aspects of improving physical structure properties and electrochemical performances.Finally,the researches and development trends of the intelligent applications of high-performance polymer fibers in SSEs is prospected.This review intends to provide timely and important guidance for the design and development of polymer fiber composite SSEs for SSLMBs.
基金This work was supported by the Major Science and Technology Projects of Henan Province(221100230200)the National Key Research and Development Program of China(2020YFB1713500)Open Fund of State Key Laboratory of Advanced Refractories(No.SKLAR202210).
文摘Polyethylene oxide(PEO)-based solid polymer electrolytes(SPEs)with good electrochemical stability and excellent Li salt solubility are considered as one of the most promising SPEs for solid-state lithium metal batteries(SSLMBs).However,PEO-based SPEs suffer from low ionic conductivity at room temperature and high interfacial resistance with the electrodes due to poor interfacial contact,seriously hindering their practical applications.As an emerging technology,in-situ polymerization process has been widely used in PEO-based SPEs because it can effectively increase Li-ion transport at the interface and improve the interfacial contact between the electrolyte and electrodes.Herein,we review recent advances in design and fabrication of in-situ polymerized PEO-based SPEs to realize enhanced performance in LMBs.The merits and current challenges of various SPEs,as well as their stabilizing strategies are presented.Furthermore,various in-situ polymerization methods(such as free radical polymerization,cationic polymerization,anionic polymerization)for the preparation of PEO-based SPEs are summarized.In addition,the application of in-situ polymerization technology in PEO-based SPEs for adjustment of the functional units and addition of different functional filler materials was systematically discussed to explore the design concepts,methods and working mechanisms.Finally,the challenges and future prospects of in-situ polymerized PEO-based SPEs for SSLMBs are also proposed.
基金supported by the National Key Research and Development Program (2016YFA0202500, 2015CB932500, and 2016YFA0200102)the National Natural Science Foundation of China (21676160, 21825501, 21805161, and 21808125)China Postdoctoral Science Foundation (2017M620773, 2018M631480, and BX201700125)
文摘Lithium (Li) metal with an ultrahigh specific theoretical capacity and the lowest reduction potential is strongly considered as a promising anode for high-energy-density batteries. However, uncontrolled lithium dendrites and infinite volume change during repeated plating/stripping cycles hinder its practical applications immensely. Herein, a house-like Li anode (housed Li) was designed to circumvent the above issues. The house matrix was composed of carbon fiber matrix and affords a stable structure to relieve the volume change. An artificial solid electrolyte layer was formed on composite Li metal, just like the roof of a house, which facilitates uniform Li ions diffusion and serves as a physical barrier against electrolyte corrosion. With the combination of solid electrolyte layer and matrix in the composite Li metal anode, both dendrite growth and volume expansion are remarkably inhibited. The housed Li|LiFePO4 batteries exhibited over 95% capacity retention after 500 cycles at 1.0 C in coin cell and 85% capacity retention after 80 cycles at 0.5 C in pouch cell. The rationally combination of solid electrolyte layer protection and housed framework in one Li metal anode sheds fresh insights on the design principle of a safe and long-lifespan Li metal anode for Li metal batteries.
基金the support of the Zhejiang Provincial Natural Science Foundation of China (LR20E020002, LD22E020006)the National Natural Science Foundation of China (NSFC) (U20A20253, 21972127, 22279116)。
文摘The rapid development of new energy vehicles and 5G communication technologies has led to higher demands for the safety,energy density,and cycle performance of lithium-ion batteries as power sources.However,the currently used liquid carbonate compounds in commercial lithium-ion battery electrolytes pose potential safety hazards such as leakage,swelling,corrosion,and flammability.Solid electrolytes can be used to mitigate these risks and create a safer lithium battery.Furthermore,high-energy density can be achieved by using solid electrolytes along with high-voltage cathode and metal lithium anode.Two types of solid electrolytes are generally used:inorganic solid electrolytes and polymer solid electrolytes.Inorganic solid electrolytes have high ionic conductivity,electrochemical stability window,and mechanical strength,but suffer from large solid/solid contact resistance between the electrode and electrolyte.Polymer solid electrolytes have good flexibility,processability,and contact interface properties,but low room temperature ionic conductivity,necessitating operation at elevated temperatures.Composite solid electrolytes(CSEs) are a promising alternative because they offer light weight and flexibility,like polymers,as well as the strength and stability of inorganic electrolytes.This paper presents a comprehensive review of recent advances in CSEs to help researchers optimize CSE composition and interactions for practical applications.It covers the development history of solid-state electrolytes,CSE properties with respect to nanofillers,morphology,and polymer types,and also discusses the lithium-ion transport mechanism of the composite electrolyte,and the methods of engineering interfaces with the positive and negative electrodes.Overall,the paper aims to provide an outlook on the potential applications of CSEs in solid-state lithium batteries,and to inspire further research aimed at the development of more systematic optimization strategies for CSEs.
基金Project supported by the National Natural Science Foundation of China(Grant No.11875210)China Postdoctoral Science Foundation(Grant No.2018M640724)+1 种基金the International Cooperation Program of Guangdong Provincial Science and Technology Plan Project(Grant No.2018A050506082)the Talent Project of Lingnan Normal University,China(Grant No.ZL1931)
文摘We fabricated a silver ion emitter based on the solid state electrolyte film of RbAg4 I5 prepared by pulsed laser deposition. The RbAg4 I5 target for PLD process was mechano-chemically synthesized by high-energy ball milling in Ar atmosphere using β-AgI and RbI as raw materials. The ion-conducting properties of RbAg4 I5 were studied by alternating current(AC) impedance spectroscopy and the ionic conductivity at room temperature was estimated 0.21 S/m. The structure, morphology, and elemental composition of the RbAg4 I5 film were investigated. The Ag+ ion-conducting property of the prepared superioni-conductor film was exploited for ion–beam generation. The temperature and accelerating voltage dependences of the ion current were studied. Few nA current was obtained at the temperature of 196?C and the accelerating voltage of 10 kV.
基金financially supported by National Key R&D Program for International Cooperation(No.2021YFE0115100)the project of the National Natural Science Foundation of China(Nos.51872240,51972270 and 52172101)+4 种基金Key Research and Development Program of Shaanxi Province(No.2021ZDLGY14-08 and 2022KWZ-04)Natural Science Foundation of Shaanxi Province(2020JZ-07)the Research Fund of the State Key Laboratory of Solidification Processing(NPU),China(2021-TS-03)the Fundamental Research Funds for the Central Universities(No.3102019JC005 and G2022KY0604)the Research Fund of the State Key Laboratory of Solid Lubrication(CAS),China(LSL-2007)。
文摘Composite solid electrolytes(CSEs)with poly(ethylene oxide)(PEO)have become fairly prevalent for fabricating high-performance solid-state lithium metal batteries due to their high Li~+solvating capability,flexible processability and low cost.However,unsatisfactory room-temperature ionic conductivity,weak interfacial compatibility and uncontrollable Li dendrite growth seriously hinder their progress.Enormous efforts have been devoted to combining PEO with ceramics either as fillers or major matrix with the rational design of two-phase architecture,spatial distribution and content,which is anticipated to hold the key to increasing ionic conductivity and resolving interfacial compatibility within CSEs and between CSEs/electrodes.Unfortunately,a comprehensive review exclusively discussing the design,preparation and application of PEO/ceramic-based CSEs is largely lacking,in spite of tremendous reviews dealing with a broad spectrum of polymers and ceramics.Consequently,this review targets recent advances in PEO/ceramicbased CSEs,starting with a brief introduction,followed by their ionic conduction mechanism,preparation methods,and then an emphasis on resolving ionic conductivity and interfacial compatibility.Afterward,their applications in solid-state lithium metal batteries with transition metal oxides and sulfur cathodes are summarized.Finally,a summary and outlook on existing challenges and future research directions are proposed.
基金financially supported by the National Natural Science Foundation of China(Grant no.51678182)China Postdoctoral Science Foundation(Grant no.2019M650663)Start-up Grant of Harbin Institute of Technology,Shenzhen。
文摘Li metal has been regarded as one of the most promising anodes for high-energy-density storage systems due to its high theoretical capacity and lowest electrochemical potential.Unfortunately,an unstable and non-uniform solid electrolyte interphase(SEI)deriving from the spontaneous reaction between Li metal anode and electrolyte causes uneven Li deposition,resulting in the growth of Li dendrites and low Coulombic efficiency,which have greatly hindered the practical application of Li metal batteries.Thus,the construction of a stable SEI is an effective approach to suppress the growth of Li dendrites and enhance the electrochemical performances of Li metal anode.In this review,we firstly introduce the formation process of inferior SEI of Li metal anode and the corresponding challenges caused by the unstable SEI.Next,recent progresses to modify SEI layer through the regulation of electrolyte compositions and exsitu protective coating are summarized.Finally,the remained issues,challenges,and perspectives are also proposed on the basis of current research status and progress.
基金support from the National Natural Science Foundation of China(Nos.51872339,91963210,and U1801255)the Key Research and Development Program of Guangdong Province(No.2020B0101690001)。
文摘The anodic stability and reversibility of Ca metal electrodeposition/dissolution have always been hampered by surface passivation and anion corrosion,especially in F-based carbonate ester electrolytes at high device voltages.To avoid direct Ca metal/electrolyte reactions,an artificial hybrid solid electrolyte layer(AHSEL),which is characteristic of sodium/calcium carbonate and calcium hydride nitride nanocrystals of size<10 nm encapsulated by amorphous C,N species,is constructed on calcium with good ion conductivity(≈0.01 mS cm^(-1))and uniform coating of thickness≈20μm.After cycling in the KPF_(6) electrolyte,AHSEL is transformed into Na/K/Ca hybrid solid electrolyte interphases(SEIs),which is a compact layer composed of monodisperse nanocrystals(mostly Ca_(2)NH)and small amorphous zones,thus greatly suppressing the fluoridation of the Ca deposit.Consequently,the plating/stripping performance of AHSEL-modified Ca(AHSEL-Ca)is markedly improved compared with that of pristine Ca,lasting for>1400 h at a polarization shift of<0.4 mV/h.The AHSEL-Ca anode also endows Ca batteries with superior anodic stability with a ceiling voltage of up to 5.0 V,a high discharge voltage(>3.3 V),a large capacity of≈80 mAh g^(-1)at 200 mA g^(-1),and an ultralong lifespan≈5000 cycles.
基金Project supported by the State Grid Technology Project,China(Grant No.DG71-17-010)。
文摘Silicon is an important high capacity anode material for the next generation Li-ion batteries.The electrochemical performances of the Si anode are influenced strongly by the properties of the solid electrolyte interphase(SEI).It is well known that the addition of flouroethylene carbonate(FEC)in the carbonate electrolyte is helpful to improve the cyclic performance of the Si anode.The possible origin is suggested to relate to the modification of the SEI.However,detailed information is still absent.In this work,the structural and mechanical properties of the SEI on Si thin film anode in the ethylene-carbonate-based(EC-based)and FEC-based electrolytes at different discharging and charging states have been investigated using a scanning atomic force microscopy force spectroscopy(AFMFS)method.Single-layered,double-layered,and multi-layered SEI structures with various Young’s moduli have been visualized three dimensionally at nanoscale based on the hundreds of force curves in certain scanned area.The coverage of the SEI can be obtained quantitatively from the two-dimensional(2D)project plots.The related analysis indicates that more soft SEI layers are covered on the Si anode,and this could explain the benefits of the FEC additive.
基金The authors would like to acknowledge the financial support from National Nat-ural Science Foundation of China (U2004199)Excellent Youth Foundation of Henan Province (202300410373)+2 种基金China Postdoctoral Science Foundation (2021T140615 and 2020M672281)Natural Science Foundation of Henan Province (212300410285)Young Talent Support Project of Henan Province(2021HYTP028).
文摘Developing laminar composite solid electrolyte with ultrathin thickness and continuous conduction channels in vertical direction holds great promise for all-solid-state lithium batteries.Herein,a thin,laminar solid electrolyte is synthesized by filtrating–NH 2 functionalized metal-organic framework nanosheets and then being threaded with poly(ethylene oxide)chains induced by the hydrogen-bonding interaction from–NH_(2) groups.It is demonstrated that the threaded poly(ethylene oxide)chains lock the adjacent metal-organic framework nanosheets,giving highly enhanced structural stability(Young’s modulus,1.3 GPa)to 7.5-μm-thick laminar composite solid electrolyte.Importantly,these poly(ethylene oxide)chains with stretching structure serve as continuous conduction pathways along the chains in pores.It makes the non-conduction laminar metal-organic framework electrolyte highly conductive:3.97×10^(−5) S cm^(−1) at 25℃,which is even over 25 times higher than that of pure poly(ethylene oxide)electrolyte.The assembled lithium cell,thus,acquires superior cycling stability,initial discharge capacity(148 mAh g^(−1) at 0.5 C and 60℃),and retention(94% after 150 cycles).Besides,the pore size of nanosheet is tailored(24.5–40.9˚A)to evaluate the mechanisms of chain conformation and ion transport in confined space.It shows that the confined pore only with proper size could facilitate the stretching of poly(ethylene oxide)chains,and meanwhile inhibit their disorder degree.Specifically,the pore size of 33.8˚A shows optimized confinement effect with trans-poly(ethylene oxide)and cis-poly(ethylene oxide)conformation,which offers great significance in ion conduction.Our design of poly(ethylene oxide)-threaded architecture provides a platform and paves a way to the rational design of next-generation high-performance porous electrolytes.
基金supported by the National Natural Science Foundation of China(grant nos.21975026 and 22005033)the National Postdoctoral Program of China(no.BX20180037)+1 种基金China Postdoctoral Science Foundation(no.2018M640077)the Beijing Institute of Technology Research Fund Program for Young Scholars(no.XSQD-202108005).
文摘Developing effective strategies to improve the initial Coulombic efficiency(ICE)and cycling stability of hard carbon(HC)anodes for sodium-ion batteries is the key to promoting the commercial application of HC.In this paper,homotype heterojunctions are designed on HC to induce the generation of stable solid electrolyte interfaces,which can effectively increase the ICE of HC from 64.7%to 81.1%.The results show that using a simple surface engineering strategy to construct a homotypic amorphous Al_(2)O_(3) layer on the HC could shield the active sites,and further inhibit electrolyte decomposition and side effects occurrence.Particularly,due to the suppression of continuous decomposition of NaPF 6 in ester-based electrolytes,the accumulation of NaF could be reduced,leading to the formation of thinner and denser solid electrolyte interface films and a decrease in the interface resistance.The HC anode can not only improve the ICE but elevate its sodium storage performance based on this homotype heterojunction composed of HC and Al_(2)O_(3).The optimized HC anode exhibits an outstanding reversible capacity of 321.5mAhg^(−1) at 50mAg^(−1).The cycling stability is also improved effectively,and the capacity retention rate is 86.9%after 2000 cycles at 1Ag^(−1) while that of the untreated HC is only 52.6%.More importantly,the improved sodium storage behaviors are explained by electrochemical kinetic analysis.
基金supported by the National Key Research and Development Program of China(2021YFB2400200)the National Natural Science Foundation of China(52104313,22172117,52072298)the Scientific Research Program of Shaanxi Provincial Education Department(21JK0808)。
文摘The resourceful and inexpensive red phosphorus has emerged as a promising anode material of potassium-ion batteries(PIBs) for its large theoretical capacities and low redox potentials in the multielectron alloying/dealloying reactions,yet chronically suffering from the huge volume expansion/shrinkage with a sluggish reaction kinetics and an unsatisfactory interfacial stability against volatile electrolytes.Herein,we systematically developed a series of localized high-concentration electrolytes(LHCE) through diluting high-concentration ether electrolytes with a non-solvating fluorinated ether to regulate the formation/evolution of solid electrolyte interphases(SEI) on phosphorus/carbon(P/C) anodes for PIBs.Benefitting from the improved mechanical strength and structural stability of a robust/uniform SEI thin layer derived from a composition-optimized LHCE featured with a unique solvation structure and a superior K+migration capability,the P/C anode with noticeable pseudocapacitive behaviors could achieve a large reversible capacity of 760 mA h g^(-1)at 100 mA g^(-1),a remarkable capacity retention rate of 92.6% over 200 cycles at 800 mA g^(-1),and an exceptional rate capability of 334 mA h g^(-1)at8000 mA g^(-1).Critically,a suppressed reduction of ether solvents with a preferential decomposition of potassium salts in anion-derived interfacial reactions on P/C anode for LHCE could enable a rational construction of an outer organic-rich and inner inorganic-dominant SEI thin film with remarkable mechanical strength/flexibility to buffer huge volume variations and abundant K+diffusion channels to accelerate reaction kinetics.Additionally,the highly reversible/durable full PIBs coupling P/C anodes with annealed organic cathodes further verified an excellent practical applicability of LHCE.This encouraging work on electrolytes regulating SEI formation/evolution would advance the development of P/C anodes for high-performance PIBs.
基金funding support from 1000 Talent Plan program(NO.31370086963030)research projects from Shandong Province(2018JMRH0211,2017CXGC1010 and 2016GGX104001)+2 种基金Taishan Scholar Program(11370085961006)the National Science Foundation of Shandong Province(ZR2017MEM002)the Fundamental Research Funds of Shandong University(201810422046,2017JC010,2017JC042,and 2016JC005)。
文摘High ionic conductivity and superior interfacial stability of solid electrolytes at the electrodes are crucial factors for high-performance all-solid-state sodium batteries. Herein, a composite solid electrolyte Na3PS4-polyethylene oxide is synthesized by the solution-phase reaction method with an improved ionic conductivity up to 9.4 × 10-5 S/cm at room temperature. Moreover, polyethylene oxide polymer layer is wrapped homogeneously on the surface of Na3PS4 particles, which could effectively avoid the direct contact between Na3PS4 electrolyte and sodium metal, thus alleviate their side reactions. We demonstrate that all-solid-state battery SnS2/Na with the composite solid electrolyte Na3PS4-polyethylene oxide delivers an enhanced electrochemical performance with 230 m Ah/g after 40 cycles.
基金supported by the Opening Project(SKLACPS-C-21)of the State Key Laboratory of Advanced Chemical Power Source,Guizhou Meiling Power Sources Co.,Ltd.the Program for Innovative and Entrepreneurial team in Zhuhai(ZH01110405160007PWC).
文摘Lithium metal anode is a promising electrode with high theoretical specific capacity and low electrode potential.However,its unstable interface and low Coulombic efficiency,resulting from the dendritic growth of lithium,limits its commercial application.PIM-1(PIM:polymer of intrinsic microporosity),which is a polymer with abundant micropores,exhibits high rigidity and flexibility with contorted spirocenters in the backbone,and is an ideal candidate for artificial solid electrolyte interphases(SEI).In this work,a PIM-1 membrane was synthesized and fabricated as a protective membrane on the surface of an electrode to facilitate the uniform flux of Li ions and act as a stable interface for the lithium plating/stripping process.Nodule-like lithium with rounded edges was observed under the PIM-1 membrane.The Li@PIM-1 electrode delivered a high average Coulombic efficiency(99.7%),excellent cyclability(80%capacity retention rate after 600 cycles at 1 C),and superior rate capability(125.3 m Ah g-1 at 10 C).Electrochemical impedance spectrum(EIS)showed that the PIM-1 membrane could lower the diffusion rate of Li+significantly and change the rate-determining step from charge transfer to Li+diffusion.Thus,the PIM-1 membrane is proven to act as an artificial SEI to facilitate uniform and stable deposition of lithium,in favor of obtaining a compact and dense Li-plating pattern.This work extends the application of PIMs in the field of lithium batteries and provides ideas for the construction of artificial SEI.
基金supported by the Jilin Province Science and Technology Department Program(YDZJ202201ZYTS304)the Science and Technology Project of Jilin Provincial Education Department(JJKH20220428KJ)+3 种基金the Jilin Province Science and Technology Department Program(YDZJ202101ZYTS047)the National Natural Science Foundation of China(21905110,21905041,22279045,22102020)the Special foundation of Jilin Province Industrial Technology Research and Development(2019C042)the Fundamental Research Funds for the Central Universities(2412020FZ008)。
文摘Lithium sulfur batteries are regarded as a promising candidate for high-energy-density energy storage devices.However,the lithium metal anode in lithium-sulfur batteries encounters the problem of lithium dendrites and lithium metal consumption caused by polysulfide corrosion.Herein we design a dualfunction PMMA/PPC/LiNO3composite as an artificial solid electrolyte interphase(PMCN-SEI)to protect Li metal anode.This SEI offers multiple sites of C=O for polysulfide anchoring to constrain corrosion of Li metal anode.The lithiated polymer group and Li3N in PMCN-SEI can homogenize lithium-ion deposition behavior to achieve a dendrite-free anode.As a result,the PMCN-SEI protected Li metal anode enables the Li||Li symmetric batteries to maintain over 300 cycles(1300 h)at a capacity of 5 m Ah cm^(-2),corresponding to a cumulative capacity of 3.25 Ah cm^(-2).Moreover,Li-S batteries assembled with 20μm of Li metal anode(N/P=1.67)still deliver an initial capacity of 1166 m A h g-1at 0.5C.Hence,introducing polycarbonate polymer/inorganic composite SEI on Li provides a new solution for achieving the high energy density of Li-S batteries.