The solid-state electrolyte in a solid-state battery acts as an electrons'barrier and an ions'bridge between the two electrodes.As solid-state electrolyte does not store the mobile ions,it is necessary to achi...The solid-state electrolyte in a solid-state battery acts as an electrons'barrier and an ions'bridge between the two electrodes.As solid-state electrolyte does not store the mobile ions,it is necessary to achieve a thin solid-state electrolyte to reduce the internal resistance and enhance the energy density.In this work,a thin NASICON solid-state electrolyte,with a stoichiometry of Na_(3)Zr_(2)Si_(2)PO_(12),is fabricated by the tape-casting method and its thickness can be easily controlled by the gap between substrate and scraper.The areal-specific resistance and the flexural strength increase with the electrolyte thickness.A solid-state sodium metal battery with 86 pm thick Na_(3)Zr_(2)Si_(2)PO_(12)exhibits a reversible specific capacity of 73-78 mAh g^(-1)with a redox potential of 3.4 V at 0.2 C.This work presents the importance of electrolyte thickness to reduce internal resistance and achieve a high energy density for sodium batteries.展开更多
Halide electrolytes,renowned for their excellent electrochemical stability and wide voltage window,exhibit significant potential in the development of high energy density solid-state batteries featuring high voltage c...Halide electrolytes,renowned for their excellent electrochemical stability and wide voltage window,exhibit significant potential in the development of high energy density solid-state batteries featuring high voltage cathode materials.In this study,we present the development and synthesis of a 0.6Li_(2)S-ZrCl_(4)solid electrolyte,demonstrating an ion conductivity of 1.9×10^(–3)S/cm at 25°C.Under a pressure of 500 MPa,the relative density of the electrolyte can reach 97.37%,showcasing its commendable compressibility.0.6Li_(2)S-ZrCl_(4)served as the electrolyte,and we assembled batteries utilizing a LiCoO_(2)(LCO)positive electrode,Li_(9.54)Si_(1.74)P_(1.44)S_(11.7)Cl_(0.3)(LSPSCl)coating,and Li-In negative electrode for laboratory testing.At 25°C,this all-solid-state battery demonstrated an impressive discharge capacity retention rate of86.99%(with a final discharge specific capacity of 110.5 m Ah/g)after 250 cycles at 24 m A/g and 100 MPa stack pressure.Upon substituting the positive electrode material with LiNi_(0.8)Mn_(0.1)Co_(0.1)O_(2)(NMC811)and assembling an all-solid-state battery,it demonstrated a discharge capacity retention rate of 74.17%after200 cycles at 3.6 m A/g and 100 MPa stack pressure in an environment at 25°C(with a final discharge specific capacity of 103.3 m A/g).Our findings hold significant implications for the design of novel superionic conductors,thereby contributing to the advancement of all-solid-state battery technology.展开更多
Rechargeable batteries based on solid-state electrolytes are of great interest and importance for the next-generation energy storage due to their high energy output and improved safety.For building the solid-state bat...Rechargeable batteries based on solid-state electrolytes are of great interest and importance for the next-generation energy storage due to their high energy output and improved safety.For building the solid-state batteries,Na_(3)Zr_(2)Si_(2)PO_(12)(NZSP)represents a promising candidate as it features high chemical stability against air exposure and a high Na^(+)conductivity.NZSP pellets were usually calcined at a high temperature,and the high volatility of Na and P elements easily led to the formation of impurity phase.In this work,the effects of calcination temperature and stoichiometry on the phase purity and ionic conductivity of the NZSP electrolyte were studied.At an elevated sintering temperature,the NZSP electrolyte showed a high ionic conductivity owing to decreased porosity,and the highest ionic conductivity at 30℃was observed to be 2.75×10^(-5)S·cm^(-1)with an activation energy of 0.41 eV.For the stoichiometry,the introduction of 5 mol%excessive P results in formation of more Na_(3)PO_(4) and glass-like phase at the grain boundary,which caused the blurred grain boundary and reduced grain barrier,and effectively suppressed Na dendrite growth,then accounted for improved cycling performance of a Na‖Na symmetric cell.Our work provided insights on reasonable design and preparation of NZSP electrolyte towards practical realization of solid-state Na-metal batteries.展开更多
Solid-state electrolytes in rechargeable all-solidstate Li-metal batteries,which have better safety and higher specific capacity than conventional rechargeable Liion batteries with liquid electrolytes,are limited by t...Solid-state electrolytes in rechargeable all-solidstate Li-metal batteries,which have better safety and higher specific capacity than conventional rechargeable Liion batteries with liquid electrolytes,are limited by the low Li-ion conductivity of the solid electrolyte and the large electrolyte/electrode interfacial resistance.Here,we report a new rhombohedral NAS ICON structure Li1.4Sr0.2Hf1.8(PO4)3 with a high Li-ion conductivity of 1.62×10-5 S·cm-1 at 25℃,and its conductivity can be improved to 3.4×10-5 S·cm-1 after the densification of the pellet by hot pressing.Li1.4Sr0.2Hf1.8(PO4)3 coated by a thin layer of polymer electrolyte showed a stable lowimpedance dendrite-free plating/stripping process in a symmetric Li/Li cell for 100 h;moreover,the Li1.4Sr0.2Hf1.8(PO4)3 electrolyte had a small interfacial resistance in all-solid-state Li/LiFePO4 cell,which allows a high Coulombic efficiency and good cycling of the cell.展开更多
Single-ion conducting solid polymer electrolytes are expected to play a vital role in the realization of solid-state Li metal batteries.In this work,a lithiated Nafion(Li-Nafion)-garnet ceramic Li6.25La3 Zr2 Al0.25O12...Single-ion conducting solid polymer electrolytes are expected to play a vital role in the realization of solid-state Li metal batteries.In this work,a lithiated Nafion(Li-Nafion)-garnet ceramic Li6.25La3 Zr2 Al0.25O12(LLZAO)composite solid electrolyte(CSE)membrane with 30μm thickness was prepared for the first time.By employing X-ray photoelectron spectroscopy and transmission electron microscope,the interaction between LLZAO and Li-Nafion was investigated.It is found that the LLZAO interacts with the Li-Nafion to form a space charge layer at the interface between LLZAO and Li-Nafion.The space charge layer reduces the migration barrier of Li-ions and improves the ionic conductivity of the CSE membrane.The CSE membrane containing 10 wt%LLZAO exhibits the highest ionic conductivity of2.26×10-4 S cm-1 at 30℃among the pristine Li-Nafion membrane,the membrane containing 5 wt%,20 wt%,and 30 wt%LLZAO,respectively.It also exhibits a high Li-ion transference number of 0.92,and a broader electrochemical window of 0-+4.8 V vs.Li+/Li than that of 0-+4.0 V vs.Li+/Li for the pristine Li-Nafion membrane.It is observed that the CSE membrane not only inhibits the growth of Li dendrites but also keeps excellent electrochemical stability with the Li electrode.Benefitting from the above merits,the solid-state LiFePO4/Li cell fabricated with the CSE membrane was practically charged and discharged at 30℃.The cell exhibits an initial reversible discharge specific capacity of 160 mAh g-1 with 97%capacity retention after 100 cycles at 0.2 C,and maintains discharge specific capacity of 126 mAh g-1 after500 cycles at 1 C.The CSE membrane prepared with Li-Nafion and LLZAO is proved to be a promising solid electrolyte for advanced solid-state Li metal batteries.展开更多
A solid-state electrolyte(SSE),which is a solid ionic conductor and electroninsulating material,is known to play a crucial role in adapting a lithium metal anode to a high-capacity cathode in a solid-state battery.Amo...A solid-state electrolyte(SSE),which is a solid ionic conductor and electroninsulating material,is known to play a crucial role in adapting a lithium metal anode to a high-capacity cathode in a solid-state battery.Among the various SSEs,the single Li-ion conductor has advantages in terms of enhancing the ion conductivity,eliminating interfacial side reactions,and broadening the electrochemical window.Covalent organic frameworks(COFs)are optimal platforms for achieving single Li-ion conduction behavior because of wellordered one-dimensional channels and precise chemical modification features.Herein,we study in depth three types of Li-carboxylate COFs(denoted LiOOC-COFn,n=1,2,and 3)as single Li-ion conducting SSEs.Benefiting from well-ordered directional ion channels,the single Li-ion conductor LiOOC-COF3 shows an exceptional ion conductivity of 1.36×10^(-5) S cm^(-1) at room temperature and a high transference number of 0.91.Moreover,it shows excellent electrochemical performance with long-term cycling,high-capacity output,and no dendrites in the quasi-solid-state organic battery,with the organic small molecule cyclohexanehexone(C_(6)O_(6))as the cathode and the Li metal as the anode,and enables effectively avoiding dissolution of the organic electrode by the liquid electrolyte.展开更多
One of the major obstacles to the application of potassium-ion batteries in large-scale energy storage is the lack of safe and effective electrolytes.KNH_(2),a new potassium-ion solid electrolyte has been developed in...One of the major obstacles to the application of potassium-ion batteries in large-scale energy storage is the lack of safe and effective electrolytes.KNH_(2),a new potassium-ion solid electrolyte has been developed in this study.Its ionic conductivity reaches 4.84×10^(-5)S cm^(-1)at 150°C and can reach3.56×10^(-4)S cm^(-1)after mechanochemical treatment.The result from electron paramagnetic resonance(EPR) measurement shows that the increment of ionic conductivity is dependent on the concentration of nitrogen defects in the KNH_(2) electrolyte.To the best of our knowledge,this is the first report that adopts inorganic amide as an electrolyte for potassium-ion battery and initiates the search for a new amidebased solid electrolyte for an all-solid-state potassium-ion battery.展开更多
Composite solid-state electrolytes have received significant attention due to their combined advantages as inorganic and polymer electrolytes.However,conventional ceramic fillers offer limited ion conductivity enhance...Composite solid-state electrolytes have received significant attention due to their combined advantages as inorganic and polymer electrolytes.However,conventional ceramic fillers offer limited ion conductivity enhancement for composite solid-state electrolytes due to the space-charge layer between the polymer matrix and ceramic phase.In this study,we develop a ferroelectric ceramic ion conductor(LiTaO_(3))as a func-tional filler to simultaneously alleviate the space-charge layer and provide an extra Li+transport pathway.The obtained composite solid-state electrolyte comprising LiTaO_(3)filler and poly(vinylidene difluoride)matrix(P-LTO15)achieves an ionic conductivity of 4.90×10^(−4)S cm−1 and a Li+transference number of 0.45.The polar-ized ferroelectric LiTaO_(3)creates a uniform electric field and promotes homogenous Li plating/stripping,providing the Li symmetrical batteries with an ultrastable cycle life for 4000 h at 0.1 mA cm^(−2)and a low polar-ization overpotential(~50 mV).Furthermore,the solid-state NCM811/P-LTO15/Li full batteries achieve an ultralong cycling performance(1400 cycles)at 1 C and a high discharge capacity of 102.1 mAh g^(−1)at 5 C.This work sheds light on the design of functional ceramic fillers for composite solid-state electrolytes to effec-tively enhance ion conductivity and battery performance.展开更多
All-solid-state lithium-ion batteries(LIBs)using ceramic electrolytes are considered the ideal form of rechargeable batteries due to their high energy density and safety.However,in the pursuit of all-solid-state LIBs,...All-solid-state lithium-ion batteries(LIBs)using ceramic electrolytes are considered the ideal form of rechargeable batteries due to their high energy density and safety.However,in the pursuit of all-solid-state LIBs,the issue of lithium resource availability is selectively overlooked.Considering that the amount of lithium required for all-solidstate LIBs is not sustainable with current lithium resources,another system that also offers the dual advantages of high energy density and safetydall-solid-state sodium-ion batteries(SIBs)dholds significant sustainable advantages and is likely to be the strong contender in the competition for developing next-generation high-energy-density batteries.This article briefly introduces the research status of all-solid-state SIBs,explains the sources of their advantages,and discusses potential approaches to the development of solid sodium-ion conductors,aiming to spark the interest of researchers and attract more attention to the field of all-solid-state SIBs.展开更多
The development of electrolytes with high ionic conductivity and stable electrode–electrolyte interfaces is crucial for the practical realization of solid-state sodium batteries.In this study,the effect of heteroatom...The development of electrolytes with high ionic conductivity and stable electrode–electrolyte interfaces is crucial for the practical realization of solid-state sodium batteries.In this study,the effect of heteroatom doping in a von-Alpen-type Na super ionic conductor(NASICON)was investigated by substituting Zr^(4+)with Mg^(2+),Zn^(2+),and La^(3+)to enhance its material properties and evaluate its potential for solid-state sodium battery applications.Computational chemistry was employed to predict the thermodynamic stability influenced by dopant introduction and the changes in ionic conductivity arising from crystal structure distortion,with the predictions validated by experiments.The optimized Zn^(2+)-doped NASICON(Zn-NZSP0.07)exhibited the highest total ionic conductivity of 2.74×10^(−3)S∙cm^(−1),representing a 4.5-fold increase compared with undoped NASICON(6.00×10−4 S∙cm^(−1)).The material also showed a high relative density of 99.1%,indicating a compact and well-sintered microstructure,as confirmed by a three-point bending test.Furthermore,a high critical current density of 1.4 mA∙cm^(−2)was achieved in symmetric cell testing.Additionally,a Na_(3)V_(2)(PO_(4))_(3)||Zn-NZSP0.07||Na cell delivered an initial capacity of 103.9 mAh∙g^(−1)at 0.1 A∙g^(−1)and retained 73.4%of its capacity after 200 cycles.These results demonstrate that optimal heteroatom doping is crucial for enhancing the performance of NASICON.展开更多
Solid-state batteries(SSBs)are considered as the next-generation battery technology,poised to deliver both high energy and enhanced safety.Nonetheless,their transition from laboratory to market is impeded by several c...Solid-state batteries(SSBs)are considered as the next-generation battery technology,poised to deliver both high energy and enhanced safety.Nonetheless,their transition from laboratory to market is impeded by several critical challenges.Among these,the solid–solid interfaces within SSBs represent a bottleneck,characterized by issues such as poor physical contact,side reactions,temporal separation,and sluggish charge carrier transfer.Developing key materials to construct the efficient solid–solid interface is critical for building high-performance SSBs.Organic mixed ionic–electronic conductors(OMIECs)have emerged as a promising alternative to conventional conductors in addressing the abovementioned issues owing to their intrinsic properties,including the capability of conducting both ions and electrons,mechanical flexibility,and structural designability.This review will first elucidate the necessity of the integration of OMIECs in SSBs.Next,a comprehensive exploration of the composition,preparation methods,key advantages,and basic characterizations of OMIECs is presented.This review then delves into recent research progress on OMIECs in SSBs,with a special focus on their application in cathode coating layers,the creation of a 3D mixed conductive framework for Li hosting,and their integration as inner layers in Li anodes.Conclusively,potential future applications and innovative designs of OMIECs are discussed.展开更多
The low ionic conductivity of solid-state electrolytes(SSEs)and the inferior interfacial reliability between SSEs and solid-state electrodes are two urgent challenges hindering the application of solid-state sodium ba...The low ionic conductivity of solid-state electrolytes(SSEs)and the inferior interfacial reliability between SSEs and solid-state electrodes are two urgent challenges hindering the application of solid-state sodium batteries(SSSBs).Herein,sodium(Na)super ionic conductor(NASICON)-type SSEs with a nominal composition of Na_(3+2x)Zr_(2-x)MgxSi_(2)PO_(12) were synthesized using a facile two-step solid-state method,among which Na_(3.3)Zr_(1.85)Mg_(0.15)Si_(2)PO_(12)(x=0.15,NZSP-Mg_(0.15))showed the highest ionic conductivity of 3.54mS∙cm^(-1) at 25℃.By means of a thorough investigation,it was verified that the composition of the grain boundary plays a crucial role in determining the total ionic conductivity of NASICON.Furthermore,due to a lack of examination in the literature regarding whether NASICON can provide enough anodic electrochemical stability to enable high-voltage SSSBs,we first adopted a high-voltage Na_(3)(VOPO_(4))2F(NVOPF)cathode to verify its compatibility with the optimized NZSP-Mg_(0.15) SSE.By comparing the electrochemical performance of cells with different configurations(low-voltage cathode vs high-voltage cathode,liquid electrolytes vs SSEs),along with an X-ray photoelectron spectroscopy evaluation of the after-cycled NZSP-Mg_(0.15),it was demonstrated that the NASICON SSEs are not stable enough under high voltage,suggesting the importance of investigating the interface between the NASICON SSEs and high-voltage cathodes.Furthermore,by coating NZSP-Mg_(0.15) NASICON powder onto a polyethylene(PE)separator(PE@NASICON),a 2.42 A∙h non-aqueous Na-ion cell of carbon|PE@NASICON|NaNi_(2/9)Cu_(1/9)Fe_(1/3)Mn_(1/3)O_(2) was found to deliver an excellent cycling performance with an 88%capacity retention after 2000 cycles,thereby demonstrating the high reliability of SSEs with NASICON-coated separator.展开更多
LiBH_(4) and Mg(BH_(4))_(2) with high theoretical hydrogen mass capacity receive significant attentions for hy-drogen storage.Also,these compounds can be potentially applied as solid-state electrolytes with their high...LiBH_(4) and Mg(BH_(4))_(2) with high theoretical hydrogen mass capacity receive significant attentions for hy-drogen storage.Also,these compounds can be potentially applied as solid-state electrolytes with their high ionic conductivity.However,their applications are hindered by the poor kinetics and reversibility for hydrogen storage and low ionic conductivity at room temperature,respectively.To address these challenges,effective strategies towards engineering the hydrogen storage properties and the emerging solid-state electrolytes with improved performances have been summarized.The focuses are on the state-of-the-art developments of Li/Mg-based borohydrides with a parallel comparison of similar methods ap-plied in both hydrogen storage and solid-state electrolytes,particularly on the phase,structure,and thermal properties changes of Li/Mg-based borohydrides induced by milling,ion substitution,coordination,adding additives/catalysts,and hydrides.The similarities and differences between the strategies towards two kinds of applications are also discussed and prospected.The review will shed light on the future development of Li/Mg-based borohydrides for hydrogen storage and solid-state electrolytes.展开更多
Na superionic conductor（NASICON） nanoparticles were synthesized by a modified sol-gel method and sintered at a temperature range of 800--1000℃. The performance of the samples was characterized by the analysis metho...Na superionic conductor（NASICON） nanoparticles were synthesized by a modified sol-gel method and sintered at a temperature range of 800--1000℃. The performance of the samples was characterized by the analysis methods of X-ray diffraction（XRD）, Fourier transform infrared spectroscopy（FTIR）, and transmission electron microscopy（TEM） as well as conductivity measurement. Compared with those sintered at other temperatures, the NASICON material sintered at 900 ℃ had the best crystalline structure and higher conductivity.展开更多
The inferior ionic conductivity of composite polymer electrolytes(CPEs)caused by grain boundary impedance is one of the critical issues.Adjustable ion transport channels at the molecular level can improve ionic conduc...The inferior ionic conductivity of composite polymer electrolytes(CPEs)caused by grain boundary impedance is one of the critical issues.Adjustable ion transport channels at the molecular level can improve ionic conductivity and lithium-ion transference number.Herein,UIO-66-NSO_(2)CF_(3)LiLi_(6.4)La_(3)Zr_(1.4)Ta_(0.6)O_(12)(UIOLiTF-LLZTO)ionic conductor derived from metal-organic frameworks(MOFs)was designed by a covalent grafted strategy of trifluoromethylsulfonyl(TF)group on UIOLiTF and a doping process of LLZTO,showing two new lithium-ion transfer channels driven by molecular coordinationdoping engineering.The first channel along UIOLiTF-UIOLiTF was constructed due to the existence of the TF group on UIOLiTF.The second channel along UIOLiTF-LLZTO was constructed due to the direct nanometer contact interface between the opened channel of UIOLiTF and LLZTO.Then TF group acts as“claws”to capture and transfer lithium-ion along the different channels,facilitating improving ionic conductivity and reducing grain boundary impedance.Benefiting from the molecular coordination-doping engineering,UIOLiTF-LLZTO exhibits high ionic conductivity of 9.86×10^(-4)S cm^(-1),a large lithium-ion transference number of 0.79,and a wide electrochemical window of 5.35 V.Meanwhile,all-solid-state Li|UIOLiTF-LLZTO|LiFePO4 batteries show a high specific capacity of 164.5 mAh g^(-1)and 155.6 mAh g^(-1)at 0.2 C and 0.5 C,respectively.Therefore,UIOLiTF-LLZTO demonstrates the way towards the development of MOFs-based CPEs for all-solid-state lithium batteries with high performance.展开更多
In recent years,the development and research of electrochemical energy storage systems that can efficiently transform chemical energy into electrical energy with a long service life have become a key area of study.Sod...In recent years,the development and research of electrochemical energy storage systems that can efficiently transform chemical energy into electrical energy with a long service life have become a key area of study.Sodium-ion batteries,leveraging their chemical similarity to lithium-ion batteries,along with their abundant resources and low cost,are seen as a viable alternative to lithium-ion batteries.Additionally,all-solid-state sodium-ion batteries have drawn significant attention due to safety considerations.Among the solid electrolytes for all-solid-state sodium-ion batteries,the NASICON solid-state electrolyte emerges as one of the most promising choices for sodium battery solid electrolytes.However,to date,there has not been a comprehensive review summarizing the existing problems of NASICON electrolyte materials and the corresponding specific modification methods.This review simply summarizes the present issues of NASICON for all-solid-state sodium-ion batteries,such as,the low ionic conductivity,the poor interface stability and compatibility,and the dendrite formation.Then,the corresponding solutions to address these issues are discussed,including the ion doping,the interface modification,the sintering parameters optimization,and the composite electrolytes regulation.Finally,the perspectives of NASICON solid-state electrolyte are discussed.展开更多
基金Agency for Science,Technology and Research for its funding(U21-M1-019AR).
文摘The solid-state electrolyte in a solid-state battery acts as an electrons'barrier and an ions'bridge between the two electrodes.As solid-state electrolyte does not store the mobile ions,it is necessary to achieve a thin solid-state electrolyte to reduce the internal resistance and enhance the energy density.In this work,a thin NASICON solid-state electrolyte,with a stoichiometry of Na_(3)Zr_(2)Si_(2)PO_(12),is fabricated by the tape-casting method and its thickness can be easily controlled by the gap between substrate and scraper.The areal-specific resistance and the flexural strength increase with the electrolyte thickness.A solid-state sodium metal battery with 86 pm thick Na_(3)Zr_(2)Si_(2)PO_(12)exhibits a reversible specific capacity of 73-78 mAh g^(-1)with a redox potential of 3.4 V at 0.2 C.This work presents the importance of electrolyte thickness to reduce internal resistance and achieve a high energy density for sodium batteries.
基金financially supported by Natural Science Foundation of Hebei Province(Nos.B2020203037,F2021203097)Science Research Project of Hebei Education Department(No.JZX2024022)National Natural Science Foundation of China(Nos.52022088,51971245)。
文摘Halide electrolytes,renowned for their excellent electrochemical stability and wide voltage window,exhibit significant potential in the development of high energy density solid-state batteries featuring high voltage cathode materials.In this study,we present the development and synthesis of a 0.6Li_(2)S-ZrCl_(4)solid electrolyte,demonstrating an ion conductivity of 1.9×10^(–3)S/cm at 25°C.Under a pressure of 500 MPa,the relative density of the electrolyte can reach 97.37%,showcasing its commendable compressibility.0.6Li_(2)S-ZrCl_(4)served as the electrolyte,and we assembled batteries utilizing a LiCoO_(2)(LCO)positive electrode,Li_(9.54)Si_(1.74)P_(1.44)S_(11.7)Cl_(0.3)(LSPSCl)coating,and Li-In negative electrode for laboratory testing.At 25°C,this all-solid-state battery demonstrated an impressive discharge capacity retention rate of86.99%(with a final discharge specific capacity of 110.5 m Ah/g)after 250 cycles at 24 m A/g and 100 MPa stack pressure.Upon substituting the positive electrode material with LiNi_(0.8)Mn_(0.1)Co_(0.1)O_(2)(NMC811)and assembling an all-solid-state battery,it demonstrated a discharge capacity retention rate of 74.17%after200 cycles at 3.6 m A/g and 100 MPa stack pressure in an environment at 25°C(with a final discharge specific capacity of 103.3 m A/g).Our findings hold significant implications for the design of novel superionic conductors,thereby contributing to the advancement of all-solid-state battery technology.
基金financially supported by the National Natural Science Foundation of China(Nos.51902238 and 52172234)the Fundamental Research Funds for the Central Universities(Nos.2020IVA069,2020IVB043 and 2021IVA020B)
文摘Rechargeable batteries based on solid-state electrolytes are of great interest and importance for the next-generation energy storage due to their high energy output and improved safety.For building the solid-state batteries,Na_(3)Zr_(2)Si_(2)PO_(12)(NZSP)represents a promising candidate as it features high chemical stability against air exposure and a high Na^(+)conductivity.NZSP pellets were usually calcined at a high temperature,and the high volatility of Na and P elements easily led to the formation of impurity phase.In this work,the effects of calcination temperature and stoichiometry on the phase purity and ionic conductivity of the NZSP electrolyte were studied.At an elevated sintering temperature,the NZSP electrolyte showed a high ionic conductivity owing to decreased porosity,and the highest ionic conductivity at 30℃was observed to be 2.75×10^(-5)S·cm^(-1)with an activation energy of 0.41 eV.For the stoichiometry,the introduction of 5 mol%excessive P results in formation of more Na_(3)PO_(4) and glass-like phase at the grain boundary,which caused the blurred grain boundary and reduced grain barrier,and effectively suppressed Na dendrite growth,then accounted for improved cycling performance of a Na‖Na symmetric cell.Our work provided insights on reasonable design and preparation of NZSP electrolyte towards practical realization of solid-state Na-metal batteries.
基金financially supported by the National Natural Science Foundation of China(No.51504127)。
文摘Solid-state electrolytes in rechargeable all-solidstate Li-metal batteries,which have better safety and higher specific capacity than conventional rechargeable Liion batteries with liquid electrolytes,are limited by the low Li-ion conductivity of the solid electrolyte and the large electrolyte/electrode interfacial resistance.Here,we report a new rhombohedral NAS ICON structure Li1.4Sr0.2Hf1.8(PO4)3 with a high Li-ion conductivity of 1.62×10-5 S·cm-1 at 25℃,and its conductivity can be improved to 3.4×10-5 S·cm-1 after the densification of the pellet by hot pressing.Li1.4Sr0.2Hf1.8(PO4)3 coated by a thin layer of polymer electrolyte showed a stable lowimpedance dendrite-free plating/stripping process in a symmetric Li/Li cell for 100 h;moreover,the Li1.4Sr0.2Hf1.8(PO4)3 electrolyte had a small interfacial resistance in all-solid-state Li/LiFePO4 cell,which allows a high Coulombic efficiency and good cycling of the cell.
基金financially supported by the National Key R&D Program of China(Grant no.2016YFB0100100)Strategic Priority Research Program of the Chinese Academy of Sciences(Grant no.XDA17020404)+2 种基金Strategic Priority Research Program of the Chinese Academy of Sciences(Grant no.XDA09010203)R&D Projects in Key Areas of Guangdong Province(Grant no.2019B090908001)DICP&QIBEBT(Grant no.DICP&QIBEBT UN201702)。
文摘Single-ion conducting solid polymer electrolytes are expected to play a vital role in the realization of solid-state Li metal batteries.In this work,a lithiated Nafion(Li-Nafion)-garnet ceramic Li6.25La3 Zr2 Al0.25O12(LLZAO)composite solid electrolyte(CSE)membrane with 30μm thickness was prepared for the first time.By employing X-ray photoelectron spectroscopy and transmission electron microscope,the interaction between LLZAO and Li-Nafion was investigated.It is found that the LLZAO interacts with the Li-Nafion to form a space charge layer at the interface between LLZAO and Li-Nafion.The space charge layer reduces the migration barrier of Li-ions and improves the ionic conductivity of the CSE membrane.The CSE membrane containing 10 wt%LLZAO exhibits the highest ionic conductivity of2.26×10-4 S cm-1 at 30℃among the pristine Li-Nafion membrane,the membrane containing 5 wt%,20 wt%,and 30 wt%LLZAO,respectively.It also exhibits a high Li-ion transference number of 0.92,and a broader electrochemical window of 0-+4.8 V vs.Li+/Li than that of 0-+4.0 V vs.Li+/Li for the pristine Li-Nafion membrane.It is observed that the CSE membrane not only inhibits the growth of Li dendrites but also keeps excellent electrochemical stability with the Li electrode.Benefitting from the above merits,the solid-state LiFePO4/Li cell fabricated with the CSE membrane was practically charged and discharged at 30℃.The cell exhibits an initial reversible discharge specific capacity of 160 mAh g-1 with 97%capacity retention after 100 cycles at 0.2 C,and maintains discharge specific capacity of 126 mAh g-1 after500 cycles at 1 C.The CSE membrane prepared with Li-Nafion and LLZAO is proved to be a promising solid electrolyte for advanced solid-state Li metal batteries.
基金National Natural Science Foundation of China,Grant/Award Number:52064049Key National Natural Science Foundation of Yunnan Province,Grant/Award Numbers:2018FA028,2019FY003023+1 种基金International Joint Research Center for Advanced Energy Materials of Yunnan Province,Grant/Award Number:202003AE140001Key Laboratory of Solid State Ions for Green Energy of Yunnan University,Grant/Award Number:2019。
文摘A solid-state electrolyte(SSE),which is a solid ionic conductor and electroninsulating material,is known to play a crucial role in adapting a lithium metal anode to a high-capacity cathode in a solid-state battery.Among the various SSEs,the single Li-ion conductor has advantages in terms of enhancing the ion conductivity,eliminating interfacial side reactions,and broadening the electrochemical window.Covalent organic frameworks(COFs)are optimal platforms for achieving single Li-ion conduction behavior because of wellordered one-dimensional channels and precise chemical modification features.Herein,we study in depth three types of Li-carboxylate COFs(denoted LiOOC-COFn,n=1,2,and 3)as single Li-ion conducting SSEs.Benefiting from well-ordered directional ion channels,the single Li-ion conductor LiOOC-COF3 shows an exceptional ion conductivity of 1.36×10^(-5) S cm^(-1) at room temperature and a high transference number of 0.91.Moreover,it shows excellent electrochemical performance with long-term cycling,high-capacity output,and no dendrites in the quasi-solid-state organic battery,with the organic small molecule cyclohexanehexone(C_(6)O_(6))as the cathode and the Li metal as the anode,and enables effectively avoiding dissolution of the organic electrode by the liquid electrolyte.
基金supported by the Key R&D Program of Shandong Province China (2020CXGC010402)the National Natural Science Foundation of China (51801197)+3 种基金the Youth Innovation Promotion Association CAS (2019189)the Liaoning Revitalization Talents Program (XLYC2002076)the Dalian High-level Talents Program (2019RD09)the K.C. Wong Education Foundation (GJTD2018-06)。
文摘One of the major obstacles to the application of potassium-ion batteries in large-scale energy storage is the lack of safe and effective electrolytes.KNH_(2),a new potassium-ion solid electrolyte has been developed in this study.Its ionic conductivity reaches 4.84×10^(-5)S cm^(-1)at 150°C and can reach3.56×10^(-4)S cm^(-1)after mechanochemical treatment.The result from electron paramagnetic resonance(EPR) measurement shows that the increment of ionic conductivity is dependent on the concentration of nitrogen defects in the KNH_(2) electrolyte.To the best of our knowledge,this is the first report that adopts inorganic amide as an electrolyte for potassium-ion battery and initiates the search for a new amidebased solid electrolyte for an all-solid-state potassium-ion battery.
基金supported by the National Natural Science Foundation of China(No.52325206,U2001220 and 52203298)Key-Area Research and Development Program of Guangdong Province(No.2020B090919001)+2 种基金Shenzhen.Shenzhen Outstanding Talents Training FundAll-Solid-State Lithium Battery Electrolyte Engineering Research Center(XMHT20200203006)Shenzhen Technical Plan Project(Nos.RCJC20200714114436091,YJ20220530143012027,JCYJ20220818101003007,JCYJ20220818101003008).
文摘Composite solid-state electrolytes have received significant attention due to their combined advantages as inorganic and polymer electrolytes.However,conventional ceramic fillers offer limited ion conductivity enhancement for composite solid-state electrolytes due to the space-charge layer between the polymer matrix and ceramic phase.In this study,we develop a ferroelectric ceramic ion conductor(LiTaO_(3))as a func-tional filler to simultaneously alleviate the space-charge layer and provide an extra Li+transport pathway.The obtained composite solid-state electrolyte comprising LiTaO_(3)filler and poly(vinylidene difluoride)matrix(P-LTO15)achieves an ionic conductivity of 4.90×10^(−4)S cm−1 and a Li+transference number of 0.45.The polar-ized ferroelectric LiTaO_(3)creates a uniform electric field and promotes homogenous Li plating/stripping,providing the Li symmetrical batteries with an ultrastable cycle life for 4000 h at 0.1 mA cm^(−2)and a low polar-ization overpotential(~50 mV).Furthermore,the solid-state NCM811/P-LTO15/Li full batteries achieve an ultralong cycling performance(1400 cycles)at 1 C and a high discharge capacity of 102.1 mAh g^(−1)at 5 C.This work sheds light on the design of functional ceramic fillers for composite solid-state electrolytes to effec-tively enhance ion conductivity and battery performance.
基金the support of the Grant-in-Aid for JSPS Research Fellow.
文摘All-solid-state lithium-ion batteries(LIBs)using ceramic electrolytes are considered the ideal form of rechargeable batteries due to their high energy density and safety.However,in the pursuit of all-solid-state LIBs,the issue of lithium resource availability is selectively overlooked.Considering that the amount of lithium required for all-solidstate LIBs is not sustainable with current lithium resources,another system that also offers the dual advantages of high energy density and safetydall-solid-state sodium-ion batteries(SIBs)dholds significant sustainable advantages and is likely to be the strong contender in the competition for developing next-generation high-energy-density batteries.This article briefly introduces the research status of all-solid-state SIBs,explains the sources of their advantages,and discusses potential approaches to the development of solid sodium-ion conductors,aiming to spark the interest of researchers and attract more attention to the field of all-solid-state SIBs.
基金supported by Korea Research Institute for defense Technology planning and advancement(KRIT)grant funded by the Korea government(Defense Acquisition Program Administration(DAPA))(No.21-107-D00-009,Design and development of core materials and unit cells for seawater secondary batteries,2025).
文摘The development of electrolytes with high ionic conductivity and stable electrode–electrolyte interfaces is crucial for the practical realization of solid-state sodium batteries.In this study,the effect of heteroatom doping in a von-Alpen-type Na super ionic conductor(NASICON)was investigated by substituting Zr^(4+)with Mg^(2+),Zn^(2+),and La^(3+)to enhance its material properties and evaluate its potential for solid-state sodium battery applications.Computational chemistry was employed to predict the thermodynamic stability influenced by dopant introduction and the changes in ionic conductivity arising from crystal structure distortion,with the predictions validated by experiments.The optimized Zn^(2+)-doped NASICON(Zn-NZSP0.07)exhibited the highest total ionic conductivity of 2.74×10^(−3)S∙cm^(−1),representing a 4.5-fold increase compared with undoped NASICON(6.00×10−4 S∙cm^(−1)).The material also showed a high relative density of 99.1%,indicating a compact and well-sintered microstructure,as confirmed by a three-point bending test.Furthermore,a high critical current density of 1.4 mA∙cm^(−2)was achieved in symmetric cell testing.Additionally,a Na_(3)V_(2)(PO_(4))_(3)||Zn-NZSP0.07||Na cell delivered an initial capacity of 103.9 mAh∙g^(−1)at 0.1 A∙g^(−1)and retained 73.4%of its capacity after 200 cycles.These results demonstrate that optimal heteroatom doping is crucial for enhancing the performance of NASICON.
基金supported by the National Key R&D Program of China(grant no.2021YFB3800300)the National Natural Science Foundation of China(grant nos.22179143,22309201,and 22309202)the Jiangsu Funding Program for Excellent Postdoctoral Talent,and the Gusu Leading Talents Program(grant no.ZXL2023190).
文摘Solid-state batteries(SSBs)are considered as the next-generation battery technology,poised to deliver both high energy and enhanced safety.Nonetheless,their transition from laboratory to market is impeded by several critical challenges.Among these,the solid–solid interfaces within SSBs represent a bottleneck,characterized by issues such as poor physical contact,side reactions,temporal separation,and sluggish charge carrier transfer.Developing key materials to construct the efficient solid–solid interface is critical for building high-performance SSBs.Organic mixed ionic–electronic conductors(OMIECs)have emerged as a promising alternative to conventional conductors in addressing the abovementioned issues owing to their intrinsic properties,including the capability of conducting both ions and electrons,mechanical flexibility,and structural designability.This review will first elucidate the necessity of the integration of OMIECs in SSBs.Next,a comprehensive exploration of the composition,preparation methods,key advantages,and basic characterizations of OMIECs is presented.This review then delves into recent research progress on OMIECs in SSBs,with a special focus on their application in cathode coating layers,the creation of a 3D mixed conductive framework for Li hosting,and their integration as inner layers in Li anodes.Conclusively,potential future applications and innovative designs of OMIECs are discussed.
基金the National Key Technologies Research and Development Program,China(2016YFB0901500)the Opening Project of the Key Laboratory of Optoelectronic Chemical Materials and Devices,Ministry of Education,Jianghan University(JDGD-201703)+2 种基金the National Natural Science Foundation of China(51725206 and 51421002)the Strategic Priority Research Program of the Chinese Academy of Sciences(XDA21070500)the Youth Innovation Promotion Association,Chinese Academy of Sciences(2020006).
文摘The low ionic conductivity of solid-state electrolytes(SSEs)and the inferior interfacial reliability between SSEs and solid-state electrodes are two urgent challenges hindering the application of solid-state sodium batteries(SSSBs).Herein,sodium(Na)super ionic conductor(NASICON)-type SSEs with a nominal composition of Na_(3+2x)Zr_(2-x)MgxSi_(2)PO_(12) were synthesized using a facile two-step solid-state method,among which Na_(3.3)Zr_(1.85)Mg_(0.15)Si_(2)PO_(12)(x=0.15,NZSP-Mg_(0.15))showed the highest ionic conductivity of 3.54mS∙cm^(-1) at 25℃.By means of a thorough investigation,it was verified that the composition of the grain boundary plays a crucial role in determining the total ionic conductivity of NASICON.Furthermore,due to a lack of examination in the literature regarding whether NASICON can provide enough anodic electrochemical stability to enable high-voltage SSSBs,we first adopted a high-voltage Na_(3)(VOPO_(4))2F(NVOPF)cathode to verify its compatibility with the optimized NZSP-Mg_(0.15) SSE.By comparing the electrochemical performance of cells with different configurations(low-voltage cathode vs high-voltage cathode,liquid electrolytes vs SSEs),along with an X-ray photoelectron spectroscopy evaluation of the after-cycled NZSP-Mg_(0.15),it was demonstrated that the NASICON SSEs are not stable enough under high voltage,suggesting the importance of investigating the interface between the NASICON SSEs and high-voltage cathodes.Furthermore,by coating NZSP-Mg_(0.15) NASICON powder onto a polyethylene(PE)separator(PE@NASICON),a 2.42 A∙h non-aqueous Na-ion cell of carbon|PE@NASICON|NaNi_(2/9)Cu_(1/9)Fe_(1/3)Mn_(1/3)O_(2) was found to deliver an excellent cycling performance with an 88%capacity retention after 2000 cycles,thereby demonstrating the high reliability of SSEs with NASICON-coated separator.
基金H.S.acknowledges the Guangdong-Hong Kong-Macao Joint Laboratory (Grant No.2019B121205001),Macao Sci-ence and Technology Development Fund (FDCT) (Project No.0098/2020/A2),National Key Research and Development Program (No.2022YFE0206400),Natural Science Foundation of Guang-dong Province (No.2023A1515010765)and FDCT-MOST joint project (Grant No.0026/2022/AMJ)for funding.We also acknowl-edge the support of the National Natural Science Foundation of China (Grant No.52104309)Natural Science Foundation of Hubei Province (No.2021CFB011)+1 种基金“Macao Young Scholars Program”China (No.AM2020004)FDCT Funding Scheme for Postdoctoral Researchers (No.0026/APD/2021).
文摘LiBH_(4) and Mg(BH_(4))_(2) with high theoretical hydrogen mass capacity receive significant attentions for hy-drogen storage.Also,these compounds can be potentially applied as solid-state electrolytes with their high ionic conductivity.However,their applications are hindered by the poor kinetics and reversibility for hydrogen storage and low ionic conductivity at room temperature,respectively.To address these challenges,effective strategies towards engineering the hydrogen storage properties and the emerging solid-state electrolytes with improved performances have been summarized.The focuses are on the state-of-the-art developments of Li/Mg-based borohydrides with a parallel comparison of similar methods ap-plied in both hydrogen storage and solid-state electrolytes,particularly on the phase,structure,and thermal properties changes of Li/Mg-based borohydrides induced by milling,ion substitution,coordination,adding additives/catalysts,and hydrides.The similarities and differences between the strategies towards two kinds of applications are also discussed and prospected.The review will shed light on the future development of Li/Mg-based borohydrides for hydrogen storage and solid-state electrolytes.
基金Supported by the Major International Collaborative Project of the National Natural Science Foundation of China(No. 60574096)the Distinguished Young Scholars(No.60625301).
文摘Na superionic conductor（NASICON） nanoparticles were synthesized by a modified sol-gel method and sintered at a temperature range of 800--1000℃. The performance of the samples was characterized by the analysis methods of X-ray diffraction（XRD）, Fourier transform infrared spectroscopy（FTIR）, and transmission electron microscopy（TEM） as well as conductivity measurement. Compared with those sintered at other temperatures, the NASICON material sintered at 900 ℃ had the best crystalline structure and higher conductivity.
基金the National Natural Science Foundation of China(No.52002227)Postdoctoral Research Foundation of China(2022M721971)+1 种基金National Natural Science Foundation of China(No.51872173)Scientific Research Foundation of Shandong University of Science and Technology for Recruited Talents,and Key Laboratory of Photochemical Conversion and Optoelectronic Materials,TIPC,CAS.
文摘The inferior ionic conductivity of composite polymer electrolytes(CPEs)caused by grain boundary impedance is one of the critical issues.Adjustable ion transport channels at the molecular level can improve ionic conductivity and lithium-ion transference number.Herein,UIO-66-NSO_(2)CF_(3)LiLi_(6.4)La_(3)Zr_(1.4)Ta_(0.6)O_(12)(UIOLiTF-LLZTO)ionic conductor derived from metal-organic frameworks(MOFs)was designed by a covalent grafted strategy of trifluoromethylsulfonyl(TF)group on UIOLiTF and a doping process of LLZTO,showing two new lithium-ion transfer channels driven by molecular coordinationdoping engineering.The first channel along UIOLiTF-UIOLiTF was constructed due to the existence of the TF group on UIOLiTF.The second channel along UIOLiTF-LLZTO was constructed due to the direct nanometer contact interface between the opened channel of UIOLiTF and LLZTO.Then TF group acts as“claws”to capture and transfer lithium-ion along the different channels,facilitating improving ionic conductivity and reducing grain boundary impedance.Benefiting from the molecular coordination-doping engineering,UIOLiTF-LLZTO exhibits high ionic conductivity of 9.86×10^(-4)S cm^(-1),a large lithium-ion transference number of 0.79,and a wide electrochemical window of 5.35 V.Meanwhile,all-solid-state Li|UIOLiTF-LLZTO|LiFePO4 batteries show a high specific capacity of 164.5 mAh g^(-1)and 155.6 mAh g^(-1)at 0.2 C and 0.5 C,respectively.Therefore,UIOLiTF-LLZTO demonstrates the way towards the development of MOFs-based CPEs for all-solid-state lithium batteries with high performance.
基金Projects(52204378,22309209)supported by the National Natural Science Foundation of ChinaProject(2023JJ40709)supported by the Natural Science Foundation of Hunan Province,China。
文摘In recent years,the development and research of electrochemical energy storage systems that can efficiently transform chemical energy into electrical energy with a long service life have become a key area of study.Sodium-ion batteries,leveraging their chemical similarity to lithium-ion batteries,along with their abundant resources and low cost,are seen as a viable alternative to lithium-ion batteries.Additionally,all-solid-state sodium-ion batteries have drawn significant attention due to safety considerations.Among the solid electrolytes for all-solid-state sodium-ion batteries,the NASICON solid-state electrolyte emerges as one of the most promising choices for sodium battery solid electrolytes.However,to date,there has not been a comprehensive review summarizing the existing problems of NASICON electrolyte materials and the corresponding specific modification methods.This review simply summarizes the present issues of NASICON for all-solid-state sodium-ion batteries,such as,the low ionic conductivity,the poor interface stability and compatibility,and the dendrite formation.Then,the corresponding solutions to address these issues are discussed,including the ion doping,the interface modification,the sintering parameters optimization,and the composite electrolytes regulation.Finally,the perspectives of NASICON solid-state electrolyte are discussed.
