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
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
Solid polymer electrolytes(SPEs)have attracted extensive attention by virtue of lightweight and flexible processability for solidstate lithium metal batteries(LMBs)with high energy density and intrinsic safety.However...Solid polymer electrolytes(SPEs)have attracted extensive attention by virtue of lightweight and flexible processability for solidstate lithium metal batteries(LMBs)with high energy density and intrinsic safety.However,the SPEs suffer from the trade-off effect between ionic conductivity and mechanical strength.Herein,we report an ionic solid-like conductor with high Li+conductivity and good thermal stability as the conductive phase of polymer electrolytes for advanced LMBs.Using poly(vinylidene fluoride-co-hexafluoropropylene)(PVDF-HFP)as the polymer matrix,the ionic solid-like conductor can be regarded as a solid plasticizer due to its advantages of non-fluidity and non-leakage.It increases the amorphous region and the dissociation degree of lithium salts in SPEs,while minimizing the loss of mechanical properties.As a result,the Li+conductivity of SPEs incorporating the ionic solid-like conductor is enhanced by four orders of magnitude compared to the blank PVDF-HFPbased electrolyte.The optimized SPE membranes can be processed as thin as 50μm with a high Young's modulus of 16.8 MPa,therefore ensuring stable long-term cycling of solid-state LMBs.The Li/Li symmetric cells stably cycled for more than 750 h without short circuits,and the LiFePO_(4)/Li solid-state batteries demonstrate excellent electrochemical performance over 350cycles with a capacity retention of 82.5%.This work provides a new strategy for designing ionic solid-like conductors as solid plasticizers for high-performance polymer electrolytes.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
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
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
Covalent organic frameworks(COFs) are attractive porous crystalline materials with extremely high stability, easy functionalization, and open channels, which are expected to be unique ion conductors/transporters in li...Covalent organic frameworks(COFs) are attractive porous crystalline materials with extremely high stability, easy functionalization, and open channels, which are expected to be unique ion conductors/transporters in lithium ion batteries(LIBs). Despite recent advances, low ion conductivity and low transference number, resulting in low charging/discharging rate, low energy density, and short battery life, are the main issues that limit their direct application as solid electrolytes in LIBs. Here, we designed and synthesized a novel polyimide COF, namely, TAPA-PDI-COF, with abundant C=O groups, which has been successfully employed as high-performance solid electrolytes by doping TAPA-PDI-COF and succinonitrile(SN). Both the well-defined nanochannels of COFs and SN confined in the well-aligned channels restricted the free migration of anions, while C=O on COFs and CN groups of SN enhanced Li^(+) transport, thus achieving a high ion conductivity of 0.102 m S cm^(-1)at 80 °C and a high lithium-ion transference number of 0.855 at room temperature. According to density functional theory(DFT)calculations, Li-ion migration mainly adopted in-plane transport rather than the axial pathway, which may be due to the shorter hopping distances in the planar pathway. The results suggest an effective strategy for the design and development of all-solidstate ionic conductors for achieving high-performance LIBs.展开更多
Solid-state electrolytes are critical for the development of next-generation high-energy and high-safety rechargeable batteries.Among all the candidates,sodium(Na)superionic conductors(NASICONs)are highly promising be...Solid-state electrolytes are critical for the development of next-generation high-energy and high-safety rechargeable batteries.Among all the candidates,sodium(Na)superionic conductors(NASICONs)are highly promising because of their evident advantages in high ionic conductivity and high chemical/electrochemical stability.The concept of NASICONs was proposed by Hong and Goodenough et al.in 1976 by reporting the synthesis and characterization of Na1+xZr2(SixP3−x)O12(0≤x≤3),which has attracted tremendous attention on the NASICONs-type solid-state electrolytes.In this review,we are committed to describing the development history of NASICONs-type solid-state electrolytes and elucidating the contribution of Goodenough as a tribute to him.We summarize the correlations and differences between lithium-based and sodium-based NASICONs electrolytes,such as their preparation methods,structures,ionic conductivities,and the mechanisms of ion transportation.Critical challenges of NASICONs-structured electrolytes are discussed,and several research directions are proposed to tackle the obstacles toward practical applications.展开更多
As a novel class of porous crystalline solids,covalent organic frameworks(COFs)based electrolyte can combine the advantages of both inorganic and polymer electrolytes,leading to such as higher structural stability to ...As a novel class of porous crystalline solids,covalent organic frameworks(COFs)based electrolyte can combine the advantages of both inorganic and polymer electrolytes,leading to such as higher structural stability to inhibit lithium dendrites and better processing facility for improving interfacial contact.However,the ionic components of Li salt tend to be closely associated in the form of ion pairs or even ionic aggregates in the channel of COFs due to strong coulombic interactions,thus resulting in slow ionic diffusion dynamics and low ionic conductivity.Herein,we successfully designed and synthesized a novel single-ion conducting nitrogen hybrid conjugated skeleton(NCS)as all solid electrolyte,whose backbone is consisted with triazine and piperazine rings.A loose bonding between the triazine rings and cations would lower the energy barrier during ions transfer,and electrostatic forces with piperazine rings could“anchor”anions to increase the selectivity during ions transfer.Thus,the NCSelectrolyte exhibits excellent room temperature lithium-ion conductivity up to 1.49 mS·cm−1 and high transference number of 0.84 without employing any solvent,which to the best of our knowledge is one of the highest COF-based electrolytes so far.Moreover,the fabricated all-solid-state lithium metal batteries demonstrate highly attractive properties with quite stable cycling performance over 100 cycles with 82%capacity reservation at 0.5 C.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 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supported by the National Key Research and Development Program of China(2023YFB2503700,and 2023YFC3008804)the National Natural Science Foundation of China(22071133)+1 种基金Beijing Municipal Science&Technology Commission(Z231100006123003)the Science Foundation of China Academy of Safety Science and Technology(2023JBKY17)。
文摘Solid polymer electrolytes(SPEs)have attracted extensive attention by virtue of lightweight and flexible processability for solidstate lithium metal batteries(LMBs)with high energy density and intrinsic safety.However,the SPEs suffer from the trade-off effect between ionic conductivity and mechanical strength.Herein,we report an ionic solid-like conductor with high Li+conductivity and good thermal stability as the conductive phase of polymer electrolytes for advanced LMBs.Using poly(vinylidene fluoride-co-hexafluoropropylene)(PVDF-HFP)as the polymer matrix,the ionic solid-like conductor can be regarded as a solid plasticizer due to its advantages of non-fluidity and non-leakage.It increases the amorphous region and the dissociation degree of lithium salts in SPEs,while minimizing the loss of mechanical properties.As a result,the Li+conductivity of SPEs incorporating the ionic solid-like conductor is enhanced by four orders of magnitude compared to the blank PVDF-HFPbased electrolyte.The optimized SPE membranes can be processed as thin as 50μm with a high Young's modulus of 16.8 MPa,therefore ensuring stable long-term cycling of solid-state LMBs.The Li/Li symmetric cells stably cycled for more than 750 h without short circuits,and the LiFePO_(4)/Li solid-state batteries demonstrate excellent electrochemical performance over 350cycles with a capacity retention of 82.5%.This work provides a new strategy for designing ionic solid-like conductors as solid plasticizers for high-performance polymer electrolytes.
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 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 National Key R&D Program of China (2023YFB3608904)the National Natural Science Foundation of China (62004106, 62274097, 21835003, 62005126)+7 种基金the Natural Science Foundation of Jiangsu Province (BE2019120,BK20210601)the Foundation of Key Laboratory of Flexible Electronics of Zhejiang Province (2023FE002)Program for Jiangsu Specially-Appointed Professors (RK030STP15001)the Excellent Scientific and Technological Innovative Teams of Jiangsu Higher Education Institutions (TJ217038)the Six Talent Peaks Project of Jiangsu Province (TD-XCL-009)the 333 Project of Jiangsu Province (BRA2017402)the Project of State Key Laboratory of Organic Electronics and Information Displays,NJUPT (GZR2023-010016)Natural Science Foundation of NJUPT (NY223079)。
文摘Covalent organic frameworks(COFs) are attractive porous crystalline materials with extremely high stability, easy functionalization, and open channels, which are expected to be unique ion conductors/transporters in lithium ion batteries(LIBs). Despite recent advances, low ion conductivity and low transference number, resulting in low charging/discharging rate, low energy density, and short battery life, are the main issues that limit their direct application as solid electrolytes in LIBs. Here, we designed and synthesized a novel polyimide COF, namely, TAPA-PDI-COF, with abundant C=O groups, which has been successfully employed as high-performance solid electrolytes by doping TAPA-PDI-COF and succinonitrile(SN). Both the well-defined nanochannels of COFs and SN confined in the well-aligned channels restricted the free migration of anions, while C=O on COFs and CN groups of SN enhanced Li^(+) transport, thus achieving a high ion conductivity of 0.102 m S cm^(-1)at 80 °C and a high lithium-ion transference number of 0.855 at room temperature. According to density functional theory(DFT)calculations, Li-ion migration mainly adopted in-plane transport rather than the axial pathway, which may be due to the shorter hopping distances in the planar pathway. The results suggest an effective strategy for the design and development of all-solidstate ionic conductors for achieving high-performance LIBs.
基金National Key Research and Development Program of China,Grant/Award Number:2020YFA0715000National Natural Science Foundation of China,Grant/Award Numbers:51902238,52127816,52172234Fundamental Research Funds for the Central Universities,Grant/Award Numbers:WUT:2020IVA069,2020IVB043,2021IVA020B。
文摘Solid-state electrolytes are critical for the development of next-generation high-energy and high-safety rechargeable batteries.Among all the candidates,sodium(Na)superionic conductors(NASICONs)are highly promising because of their evident advantages in high ionic conductivity and high chemical/electrochemical stability.The concept of NASICONs was proposed by Hong and Goodenough et al.in 1976 by reporting the synthesis and characterization of Na1+xZr2(SixP3−x)O12(0≤x≤3),which has attracted tremendous attention on the NASICONs-type solid-state electrolytes.In this review,we are committed to describing the development history of NASICONs-type solid-state electrolytes and elucidating the contribution of Goodenough as a tribute to him.We summarize the correlations and differences between lithium-based and sodium-based NASICONs electrolytes,such as their preparation methods,structures,ionic conductivities,and the mechanisms of ion transportation.Critical challenges of NASICONs-structured electrolytes are discussed,and several research directions are proposed to tackle the obstacles toward practical applications.
基金We thank the financial support from the Natural Science Foundation of Shandong(Nos.ZR2020JQ21 and ZR2021ZD24)National Natural Science Foundation of China(Nos.51873231 and 22138013)+1 种基金Taishan Scholar Project(No.tsqn201909062)the Technology Foundation of Shandong Energy Group Co.,LTD.(YKZB2020-176,YKKJ2019AJ08JG-R63)。
文摘As a novel class of porous crystalline solids,covalent organic frameworks(COFs)based electrolyte can combine the advantages of both inorganic and polymer electrolytes,leading to such as higher structural stability to inhibit lithium dendrites and better processing facility for improving interfacial contact.However,the ionic components of Li salt tend to be closely associated in the form of ion pairs or even ionic aggregates in the channel of COFs due to strong coulombic interactions,thus resulting in slow ionic diffusion dynamics and low ionic conductivity.Herein,we successfully designed and synthesized a novel single-ion conducting nitrogen hybrid conjugated skeleton(NCS)as all solid electrolyte,whose backbone is consisted with triazine and piperazine rings.A loose bonding between the triazine rings and cations would lower the energy barrier during ions transfer,and electrostatic forces with piperazine rings could“anchor”anions to increase the selectivity during ions transfer.Thus,the NCSelectrolyte exhibits excellent room temperature lithium-ion conductivity up to 1.49 mS·cm−1 and high transference number of 0.84 without employing any solvent,which to the best of our knowledge is one of the highest COF-based electrolytes so far.Moreover,the fabricated all-solid-state lithium metal batteries demonstrate highly attractive properties with quite stable cycling performance over 100 cycles with 82%capacity reservation at 0.5 C.
