Black phosphorus(BP)is recognized as a promising anode for sodium-ion batteries(SIBs)due to its high safety and theoretical capacity.However,traditional ball milling methodologies for fabricating BP composite anodes h...Black phosphorus(BP)is recognized as a promising anode for sodium-ion batteries(SIBs)due to its high safety and theoretical capacity.However,traditional ball milling methodologies for fabricating BP composite anodes have not satisfactorily addressed the challenges of poor rate performance and short cycle life.To fill this scientific gap,we herein pioneer incorporating the sodium fast ionic conductorβ"-Al_(2)O_(3)into ball-milled BP with carbon,which facilitates the formation of three-dimensional mass transfer channels in the resulting composite.To stabilize these channels,we develop a novel and environmentally friendly functional binder that outperforms traditional binders in thermal stability,wettability,and mechanical properties.The newly established binder is capable of remarkably mitigating volume expansion and interfacial side reactions in the BP/β"-Al_(2)O_(3)/C composite anode.Additionally,we identify synergistic effects of the binder interacting with the BP/β"-Al_(2)O_(3)/C composite during cycling,characterized by the in-situ formation of P-O-C bonds,which is the first instance of a strong,durable chemical bond between the binder and the active material to the best of our knowledge.These advancements allow the composite electrode to exhibit exceptional sodium storage,including high initial Coulombic efficiency and long-term cycling stability,which surpasses most previous phosphorus-based anodes fabricated via traditional approaches.Notably,when paired with a Na_(4)Fe_(3)(PO_(4))_(2)P_(2)O_7(NFPP)cathode,the full cell exhibits unexpectedly high energy and power densities,highlighting the BP potential in SIBs.The findings presented in the present work contribute to the promotion of economical and efficient applications of phosphorus-based anode materials.展开更多
La9.335i6O26 oxygen ionic conductor was synthesized by solid state reaction method. Its structure was deter- mined by single-crystal X-ray diffraction analysis at room temperature. The results showed that La9.33Si6O26...La9.335i6O26 oxygen ionic conductor was synthesized by solid state reaction method. Its structure was deter- mined by single-crystal X-ray diffraction analysis at room temperature. The results showed that La9.33Si6O26 oxide has the apatite structure with space group P63/m. AC impedance measurements indicated that the oxides sintered in nitrogen have much higher conductivity than those sintered in air. The effects of grain boundaries on the conductivity were discussed.展开更多
Apatite-lanthanum silicate has attracted considerable interest in recent years due to its high oxide ion conductivity.In this paper,V-doped samples La10-xVx(SiO4) 6O3+x(0≤x≤1.5) were prepared by sol-gel method and t...Apatite-lanthanum silicate has attracted considerable interest in recent years due to its high oxide ion conductivity.In this paper,V-doped samples La10-xVx(SiO4) 6O3+x(0≤x≤1.5) were prepared by sol-gel method and the influences of V-dopant content on calcining temperature and conductivity were reported.The samples were characterized by thermal analysis(TG-DSC) ,X-ray diffraction(XRD) and scanning electron micrograph(SEM) . The apatite was obtained at 800°C,a relatively low temperature in comparison to 1500°C with the conventional solid-state method.The ceramic pellets sintered at 1200°C for 5 h showed a higher relative density than La9.33Si6O26 pellets sintered at 1400°C for 20 h.The conductivities of samples were measured by electrochemical impedance spectroscopy.The conductivity was improved with the increase of V-dopant content on La site.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
A theoretical model is developed for predicting both conduction and diffusion in thin-film ionic conductors or cables. With the linearized Poisson-Nernst-Planck(PNP)theory, the two-dimensional(2D) equations for thin i...A theoretical model is developed for predicting both conduction and diffusion in thin-film ionic conductors or cables. With the linearized Poisson-Nernst-Planck(PNP)theory, the two-dimensional(2D) equations for thin ionic conductor films are obtained from the three-dimensional(3D) equations by power series expansions in the film thickness coordinate, retaining the lower-order equations. The thin-film equations for ionic conductors are combined with similar equations for one thin dielectric film to derive the 2D equations of thin sandwich films composed of a dielectric layer and two ionic conductor layers. A sandwich film in the literature, as an ionic cable, is analyzed as an example of the equations obtained in this paper. The numerical results show the effect of diffusion in addition to the conduction treated in the literature. The obtained theoretical model including both conduction and diffusion phenomena can be used to investigate the performance of ionic-conductor devices with any frequency.展开更多
Strategy of Sb-substitution is carried out on the template structure Na4Sn0.67M0.33S4(M=Si,Ge),which affords a series of quinary sulfide-based sodium fast ionic conductors formulated as Na4-x[Sn0.67M0.33]1-xSbxS4(M=Si...Strategy of Sb-substitution is carried out on the template structure Na4Sn0.67M0.33S4(M=Si,Ge),which affords a series of quinary sulfide-based sodium fast ionic conductors formulated as Na4-x[Sn0.67M0.33]1-xSbxS4(M=Si,x=0.1,0.2,0.3;M=Ge,x=0.2.).Among them,the highest ambient ionic conductivity(1.75×10^-4 S cm^-1)is achieved when M=Si and x=0.2.The new fast ionic conductor Na3.8[Sn0.67Si0.33]0.8Sb0.2S4 is isostructural to its structure template Na4Sn0.67Si0.33S4 and thus crystallizes in the space group of I41/acd.It is shown that the incorporation of Sb improves the ionic conductivity.The study of lattice parameters shows that the improvement of the ion conductivity by Sbsubstitution is mainly due to the enlarged crystal lattice.Furthermore,using Na3.8[Sn0.67Si0.33]0.8Sb0.2S4as solid electrolytes,room temperature all-solid-state sodium battery of Se0.05S0.95@pPAN/Na3Sn is realized,which proves the novel fast ionic conductor a potential candidate to apply in sodium solid state battery.This work not only extends the scope of Na4[Sn0.67Si0.33]S4,the I41/acd space group template,but also deepens the understanding of the lattice size effect on the structure and property relationship by aliovalent substitution.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
The system of LiH-LiF-P_2O_5 ionic conductor glass is prepared in neutral atmosphere and glass -forming region is given. The structure and coor- dination of glass are analyzed by IR spectra. Raman spectra and RDF(r). ...The system of LiH-LiF-P_2O_5 ionic conductor glass is prepared in neutral atmosphere and glass -forming region is given. The structure and coor- dination of glass are analyzed by IR spectra. Raman spectra and RDF(r). The result indicates that the (PO_4), (PO_3F) and (LiF_4) tetrahedra are basical structure units of glass network and the coordina- tion number of Li is 4. The coordination number of P is 4. The glass random network structure model is given. The study on structure shows that Li^+, H^- and partial F^- are charge carriers in glass system.展开更多
Na_(5+x) YAl_x Si_(4-x) O_(12) polycrystalline solid electrolytes are prepared by solid reactions. By the analyses of X-ray, TG and DTA, infrared spectu re, and SEM, the variasion of their density with the composition...Na_(5+x) YAl_x Si_(4-x) O_(12) polycrystalline solid electrolytes are prepared by solid reactions. By the analyses of X-ray, TG and DTA, infrared spectu re, and SEM, the variasion of their density with the composition X are discussed Their electric conductivity in the temperature range of R. T. to 300℃ are determined with electric brigde, and their variasions with the compositions X and temperature are studied. Their activations in the tem- perature range 140℃ to 300℃ are calculated, and their variation with the compositons X are discussed.展开更多
Ion-dipole interaction is a type of electrostatic force between ions and molecular dipoles.It plays the key role in governing the mechanical and electrical performances of flexible ionic conductors for energy storage,...Ion-dipole interaction is a type of electrostatic force between ions and molecular dipoles.It plays the key role in governing the mechanical and electrical performances of flexible ionic conductors for energy storage,wearable electronics,and soft robotics.Due to the inherently weak and highly dynamic nature of conventional ion-dipole interactions,flexible ionic conductors are generally vulnerable to mechanical stress,moisture,and heat,greatly restricting their application.In the past five years,this key challenge has been successfully conquered through understanding the fundamental nature of ion-dipole interactions and designing new building blocks.This review aims to unravel the origin of the instability of flexible ionic conductors at the interaction level.It also summarizes strategies for stabilizing ion-dipole interactions under extreme conditions,covering aspects from fundamental understanding and material preparation to device fabrication.Given these optimized ion-dipole systems,we present state-ofthe-art flexible ionic conductors that exhibit extreme mechanical properties and robust performance underwater and at high temperatures.Finally,we highlight the scientific problems that remain to be addressed and discuss future prospects for ion-dipole interactions in next-generation ionotronic and energy devices.展开更多
Highly durable and stretchable ionic conductors are indispensable components of flexible electronics.However,fabricating such ionic conductors that are also non-toxic and biodegradable remains a challenge.In this stud...Highly durable and stretchable ionic conductors are indispensable components of flexible electronics.However,fabricating such ionic conductors that are also non-toxic and biodegradable remains a challenge.In this study,highly stretchable,elastic,healable,and ultra-durable ionic conductors capable of non-hazardous disposal are conveniently fabricated by complexation of vanillin-grafted polyvinyl alcohol(VPVA)and ionic liquids(ILs)(denoted as VPVA-IL).展开更多
A typical approach involving Pechini method and spark plasma sintering （SPS） method was presented for the preparation of high density Li5＋xSrxLa3_xBi2012 （x = 0, 1） ceramics. Phase formation, microstructure, grai...A typical approach involving Pechini method and spark plasma sintering （SPS） method was presented for the preparation of high density Li5＋xSrxLa3_xBi2012 （x = 0, 1） ceramics. Phase formation, microstructure, grain size and electrical properties of the specimens were examined using XRD, SEM and alternating current impedance spectro- scopy （ACIS）. Dense LisLa3Bi2012 and LisSrLa2Bi2012 ceramics with pure garnet-like phase, relative density of 97% and average grain size of about 5 pm were fabricated using this approach. The total conductivities at 298 K of Li5La3Bi2012 and LisSrLa2Bi2O12 ceramics prepared by the SPS method are 5.1 Qian-Feng FANG105 and 6.810SS/cm, respectively, 2 times higher than that of samples prepared by the conventional sintering method.展开更多
The ceramic composite separators coated with silica or alumina particles have been used in power batteries due to their better electrolyte wettability and better thermal stability compared with bare polymer separators...The ceramic composite separators coated with silica or alumina particles have been used in power batteries due to their better electrolyte wettability and better thermal stability compared with bare polymer separators.However,these oxide ceramics are Liþion insulators,which increase internal resistance and hinder the improvement of rate capability of batteries.Herein,we report a strategy to further improving the performance of lithium-ion batteries(LIBs)by using fast ionic conductor ceramic composite separator as an alternative to traditional ceramic coated separators.Lithium lanthanum titanate(LLTO),a fast ionic conductor with excellent room temperature bulk conductivity,are coated on the common polyethylene(PE)separators.Our results demonstrate that such a novel LLTO-coated separator possess excellent electrolyte wettability and thermal stability;and the assembled NCM523/graphite lithium-ion pouch cells with LLTO-coated separator show better rate capability and cyclic performance with 88.7%capacity retention after 1000 cycles at room temperature compared with the pouch cells with Al2O_(3)-coated separators.The fast ionic conductor ceramic composite separators will be a potential competitor to the next-generation novel separators for high-performance Li-ion power batteries.展开更多
Due to its low electronegativity and light weight, if lithium is used as negative electrode material for electrochemical devices, the cell voltage and energy density may be enhanced. In recent years, the search for a ...Due to its low electronegativity and light weight, if lithium is used as negative electrode material for electrochemical devices, the cell voltage and energy density may be enhanced. In recent years, the search for a new lithium conductor increased obviously with the increasing interest in all solid state lithium cell. LISICON is a three-dimensional lithium conductor with high conductivity, but its chemical stability is not good, and its conductivity at room temper-展开更多
The cubic and/or tetragonal ZrO<sub>2</sub> solid solution polycrystalline ceramics obtained byaddition of appropriate amounts of oxides asCaO, Y<sub>2</sub>O<sub>3</sub>, MgO or ra...The cubic and/or tetragonal ZrO<sub>2</sub> solid solution polycrystalline ceramics obtained byaddition of appropriate amounts of oxides asCaO, Y<sub>2</sub>O<sub>3</sub>, MgO or rare earth oxides to zirconiahas ioinc conductivity and is used as fast ionicconductor for new ceramic fuel cells and sensors.For MgO-stabilized zirconia the MgO content展开更多
In this paper, 1,2,4-triazolium methanesulfonate （C_2H_4N_3^＋-CH_3SO_3^-, [Tri][MS]）, an ionic conductor, was successfully synthesized. It exhibited high ionic conductivity of 18.60 mS·cm^-1 at 140 ℃ and reac...In this paper, 1,2,4-triazolium methanesulfonate （C_2H_4N_3^＋-CH_3SO_3^-, [Tri][MS]）, an ionic conductor, was successfully synthesized. It exhibited high ionic conductivity of 18.60 mS·cm^-1 at 140 ℃ and reached up to 36.51 mS·cm^-1 at 190 ℃. [Tri][MS] was first applied to modify Nation membrane to fabricate [Tri][MS]/Nafion membrane by impregnation method at 150 ℃. The prepared composite membrane showed high thermal stability with decomposed temperature above 200 ℃ in air atmosphere. In addition, the membrane indicated good ionic conductivity with 3.67 mS·cm^-1 at 140 ℃ and reached up to 13.23 mS·cm^-1 at 180 ℃. The structure of the [Tri][MS] and the composite membrane were characterized by FTIR and the compatibility of [Tri][MS] and Pt/C catalyst was studied by a cyclic voltammetry （CV） method. Besides, the [Tri][MS]/Nafion membrane （thickness of 65 μm） was evaluated with single fuel cell at high temperature and without humidification. The highest power density of [Tri][MS]/Nafion membrane was 3.20 mW·cm^-2 at 140 ℃ and 4.90 mW·cm^-2 at 150 ℃, which was much higher than that of Nation membrane.展开更多
Although solid-state lithium electrolytes have the potential to reduce the safety issues associated with organic liquid electrolytes,disadvantages such as low total conductivity,large interface impedance,and delaminat...Although solid-state lithium electrolytes have the potential to reduce the safety issues associated with organic liquid electrolytes,disadvantages such as low total conductivity,large interface impedance,and delamination of the interface due to cyclic stress still need to be addressed.The solid-state lithium-ion conductor Li_(0.33)La_(0.56)TiO_(3)(LLTO) was prepared via a hydrothermal route by using CTAB as templates in this paper.Perovskite LLTO with micro-porous channels was obtained and the total conductivity is comparable to the non-porous LLTO.Porous LLTO pellets are infiltrated with the non-porous LLTO precursor solution,and the total conductivities of the infiltrated porous LLTO are all higher than those without infiltration.After infiltration,the porous LLTO calcined at 600℃ achieves the highest total conductivity,7.88×10^(-5) S/cm.The fracture toughness of the infiltrated LLTO is higher than that of the non-porous LLTO.The results demonstrate a new way to prepare solid-state lithium-ion conductors with high ionic conductivity and great tolerance to cyclic stress.展开更多
A new concept of forming solid electrolyte interphases（SEI） in situ in an ionic conducting Li（1.5）Al（0.5）Ge（1.5）（PO4）3-polypropylene（LAGP-PP） based separator during charging and discharging is proposed and...A new concept of forming solid electrolyte interphases（SEI） in situ in an ionic conducting Li（1.5）Al（0.5）Ge（1.5）（PO4）3-polypropylene（LAGP-PP） based separator during charging and discharging is proposed and demonstrated. This unique structure shows a high ionic conductivity, low interface resistance with electrode, and can suppress the growth of lithium dendrite. The features of forming the SEI in situ are investigated by scanning electron microscopy（SEM） and x-ray photoelectron spectroscopy（XPS）. The results confirm that SEI films mainly consist of lithium fluoride and carbonates with various alkyl contents. The cell assembled by using the LAGP-coated separator demonstrates a good cycling performance even at high charging rates, and the lithium dendrites were not observed on the lithium metal electrode. Therefore, the SEI-LAGP-PP separator can be used as a promising flexible solid electrolyte for solid state lithium batteries.展开更多
Ionic conductivity values for segmented polyether polyurethaneurea (PEUU) complexes with LiClO_4 were determined and values as high as～1.1×10^(-4) S·cm^(-1) at 353K and～1.0×10^(-5)S·cm^(-1) at 30...Ionic conductivity values for segmented polyether polyurethaneurea (PEUU) complexes with LiClO_4 were determined and values as high as～1.1×10^(-4) S·cm^(-1) at 353K and～1.0×10^(-5)S·cm^(-1) at 306K were achieved. The ionic conductivity data were analyzed using the VTF (Vogel-Tamman-Fulcher) equation and WLF (Williams-Landel-Ferry) type equation. Values have been estimated for the 'apparent' activation energies of ion transport from VTF equation and they lie in the range 2.70—5.53 kJ·mol^(-1).展开更多
The polysiloxane containing propylene carbonate side group and several lithium poly-meric salts were synthesized. The structure were confirmed by IR, NMR and XPS. Theblending systems of polysiloxane containing propyle...The polysiloxane containing propylene carbonate side group and several lithium poly-meric salts were synthesized. The structure were confirmed by IR, NMR and XPS. Theblending systems of polysiloxane containing propylene carbonate group with different lithiumpolymeric salts were studied by ion conductivity XPS and DSC. Different lithium poly-meric salts in the blending system lead to conductivity arranged in the following sequence:poly(lithium ethylenebenzene sulfonate methylsiloxane)>poly(lithium propionate methyl-siloxane)>poly(lithium propylsulfonate methylsiloxane)>poly(lithium styrenesulfonate).In the blending system the best single ion conductivity was close to 10^(-5) Scm^(-1) at roomtemperature. XPS showed that at low lithium salt concentration the conductivity increasedwith the increasing content of lithium salt, in consequence of the increase of free ion andsolvent separated ion pair. At high lithium salt concentration the free ion was absent andthe solvent-separated ion pair functioned as carrier.展开更多
基金supported by the National Key R&D Program of China(2022YFB3807700)the National Natural Science Foundation of China(52072217,22179071,51772169,and 52104313)+3 种基金the Hubei Provincial Natural Science Foundation of China(2023AFB618 and 2024AFB993)the Hubei Natural Science Foundation Innovation Group Project(2022CFA020)the Joint Funds of the Hubei Natural Science Foundation Innovation and Development(2022CFD034)the Major Technological Innovation Project of Hubei Science and Technology Department(2019AAA164)。
文摘Black phosphorus(BP)is recognized as a promising anode for sodium-ion batteries(SIBs)due to its high safety and theoretical capacity.However,traditional ball milling methodologies for fabricating BP composite anodes have not satisfactorily addressed the challenges of poor rate performance and short cycle life.To fill this scientific gap,we herein pioneer incorporating the sodium fast ionic conductorβ"-Al_(2)O_(3)into ball-milled BP with carbon,which facilitates the formation of three-dimensional mass transfer channels in the resulting composite.To stabilize these channels,we develop a novel and environmentally friendly functional binder that outperforms traditional binders in thermal stability,wettability,and mechanical properties.The newly established binder is capable of remarkably mitigating volume expansion and interfacial side reactions in the BP/β"-Al_(2)O_(3)/C composite anode.Additionally,we identify synergistic effects of the binder interacting with the BP/β"-Al_(2)O_(3)/C composite during cycling,characterized by the in-situ formation of P-O-C bonds,which is the first instance of a strong,durable chemical bond between the binder and the active material to the best of our knowledge.These advancements allow the composite electrode to exhibit exceptional sodium storage,including high initial Coulombic efficiency and long-term cycling stability,which surpasses most previous phosphorus-based anodes fabricated via traditional approaches.Notably,when paired with a Na_(4)Fe_(3)(PO_(4))_(2)P_(2)O_7(NFPP)cathode,the full cell exhibits unexpectedly high energy and power densities,highlighting the BP potential in SIBs.The findings presented in the present work contribute to the promotion of economical and efficient applications of phosphorus-based anode materials.
文摘La9.335i6O26 oxygen ionic conductor was synthesized by solid state reaction method. Its structure was deter- mined by single-crystal X-ray diffraction analysis at room temperature. The results showed that La9.33Si6O26 oxide has the apatite structure with space group P63/m. AC impedance measurements indicated that the oxides sintered in nitrogen have much higher conductivity than those sintered in air. The effects of grain boundaries on the conductivity were discussed.
基金Supported by the Joint Funds of NSFC-Guangdong of China(U0834004)the Natural Science Foundation of Guangdong Province(06025657)
文摘Apatite-lanthanum silicate has attracted considerable interest in recent years due to its high oxide ion conductivity.In this paper,V-doped samples La10-xVx(SiO4) 6O3+x(0≤x≤1.5) were prepared by sol-gel method and the influences of V-dopant content on calcining temperature and conductivity were reported.The samples were characterized by thermal analysis(TG-DSC) ,X-ray diffraction(XRD) and scanning electron micrograph(SEM) . The apatite was obtained at 800°C,a relatively low temperature in comparison to 1500°C with the conventional solid-state method.The ceramic pellets sintered at 1200°C for 5 h showed a higher relative density than La9.33Si6O26 pellets sintered at 1400°C for 20 h.The conductivities of samples were measured by electrochemical impedance spectroscopy.The conductivity was improved with the increase of V-dopant content on La site.
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Project supported by the National Natural Science Foundation of China(Nos.11672265,11202182,and 11621062)the Fundamental Research Funds for the Central Universities(Nos.2016QNA4026 and2016XZZX001-05)the Open Foundation of Zhejiang Provincial Top Key Discipline of Mechanical Engineering
文摘A theoretical model is developed for predicting both conduction and diffusion in thin-film ionic conductors or cables. With the linearized Poisson-Nernst-Planck(PNP)theory, the two-dimensional(2D) equations for thin ionic conductor films are obtained from the three-dimensional(3D) equations by power series expansions in the film thickness coordinate, retaining the lower-order equations. The thin-film equations for ionic conductors are combined with similar equations for one thin dielectric film to derive the 2D equations of thin sandwich films composed of a dielectric layer and two ionic conductor layers. A sandwich film in the literature, as an ionic cable, is analyzed as an example of the equations obtained in this paper. The numerical results show the effect of diffusion in addition to the conduction treated in the literature. The obtained theoretical model including both conduction and diffusion phenomena can be used to investigate the performance of ionic-conductor devices with any frequency.
基金supported by the National Natural Science Foundation of China(21975087 and 51902116)。
文摘Strategy of Sb-substitution is carried out on the template structure Na4Sn0.67M0.33S4(M=Si,Ge),which affords a series of quinary sulfide-based sodium fast ionic conductors formulated as Na4-x[Sn0.67M0.33]1-xSbxS4(M=Si,x=0.1,0.2,0.3;M=Ge,x=0.2.).Among them,the highest ambient ionic conductivity(1.75×10^-4 S cm^-1)is achieved when M=Si and x=0.2.The new fast ionic conductor Na3.8[Sn0.67Si0.33]0.8Sb0.2S4 is isostructural to its structure template Na4Sn0.67Si0.33S4 and thus crystallizes in the space group of I41/acd.It is shown that the incorporation of Sb improves the ionic conductivity.The study of lattice parameters shows that the improvement of the ion conductivity by Sbsubstitution is mainly due to the enlarged crystal lattice.Furthermore,using Na3.8[Sn0.67Si0.33]0.8Sb0.2S4as solid electrolytes,room temperature all-solid-state sodium battery of Se0.05S0.95@pPAN/Na3Sn is realized,which proves the novel fast ionic conductor a potential candidate to apply in sodium solid state battery.This work not only extends the scope of Na4[Sn0.67Si0.33]S4,the I41/acd space group template,but also deepens the understanding of the lattice size effect on the structure and property relationship by aliovalent substitution.
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.
文摘The system of LiH-LiF-P_2O_5 ionic conductor glass is prepared in neutral atmosphere and glass -forming region is given. The structure and coor- dination of glass are analyzed by IR spectra. Raman spectra and RDF(r). The result indicates that the (PO_4), (PO_3F) and (LiF_4) tetrahedra are basical structure units of glass network and the coordina- tion number of Li is 4. The coordination number of P is 4. The glass random network structure model is given. The study on structure shows that Li^+, H^- and partial F^- are charge carriers in glass system.
文摘Na_(5+x) YAl_x Si_(4-x) O_(12) polycrystalline solid electrolytes are prepared by solid reactions. By the analyses of X-ray, TG and DTA, infrared spectu re, and SEM, the variasion of their density with the composition X are discussed Their electric conductivity in the temperature range of R. T. to 300℃ are determined with electric brigde, and their variasions with the compositions X and temperature are studied. Their activations in the tem- perature range 140℃ to 300℃ are calculated, and their variation with the compositons X are discussed.
基金the National Natural Science Foundation of China(grant no.22425504)for the financial support.
文摘Ion-dipole interaction is a type of electrostatic force between ions and molecular dipoles.It plays the key role in governing the mechanical and electrical performances of flexible ionic conductors for energy storage,wearable electronics,and soft robotics.Due to the inherently weak and highly dynamic nature of conventional ion-dipole interactions,flexible ionic conductors are generally vulnerable to mechanical stress,moisture,and heat,greatly restricting their application.In the past five years,this key challenge has been successfully conquered through understanding the fundamental nature of ion-dipole interactions and designing new building blocks.This review aims to unravel the origin of the instability of flexible ionic conductors at the interaction level.It also summarizes strategies for stabilizing ion-dipole interactions under extreme conditions,covering aspects from fundamental understanding and material preparation to device fabrication.Given these optimized ion-dipole systems,we present state-ofthe-art flexible ionic conductors that exhibit extreme mechanical properties and robust performance underwater and at high temperatures.Finally,we highlight the scientific problems that remain to be addressed and discuss future prospects for ion-dipole interactions in next-generation ionotronic and energy devices.
基金supported by the National Natural Science Foundation of China(NSFC grant nos.21935004 and 21774049).
文摘Highly durable and stretchable ionic conductors are indispensable components of flexible electronics.However,fabricating such ionic conductors that are also non-toxic and biodegradable remains a challenge.In this study,highly stretchable,elastic,healable,and ultra-durable ionic conductors capable of non-hazardous disposal are conveniently fabricated by complexation of vanillin-grafted polyvinyl alcohol(VPVA)and ionic liquids(ILs)(denoted as VPVA-IL).
文摘A typical approach involving Pechini method and spark plasma sintering （SPS） method was presented for the preparation of high density Li5＋xSrxLa3_xBi2012 （x = 0, 1） ceramics. Phase formation, microstructure, grain size and electrical properties of the specimens were examined using XRD, SEM and alternating current impedance spectro- scopy （ACIS）. Dense LisLa3Bi2012 and LisSrLa2Bi2012 ceramics with pure garnet-like phase, relative density of 97% and average grain size of about 5 pm were fabricated using this approach. The total conductivities at 298 K of Li5La3Bi2012 and LisSrLa2Bi2O12 ceramics prepared by the SPS method are 5.1 Qian-Feng FANG105 and 6.810SS/cm, respectively, 2 times higher than that of samples prepared by the conventional sintering method.
文摘The ceramic composite separators coated with silica or alumina particles have been used in power batteries due to their better electrolyte wettability and better thermal stability compared with bare polymer separators.However,these oxide ceramics are Liþion insulators,which increase internal resistance and hinder the improvement of rate capability of batteries.Herein,we report a strategy to further improving the performance of lithium-ion batteries(LIBs)by using fast ionic conductor ceramic composite separator as an alternative to traditional ceramic coated separators.Lithium lanthanum titanate(LLTO),a fast ionic conductor with excellent room temperature bulk conductivity,are coated on the common polyethylene(PE)separators.Our results demonstrate that such a novel LLTO-coated separator possess excellent electrolyte wettability and thermal stability;and the assembled NCM523/graphite lithium-ion pouch cells with LLTO-coated separator show better rate capability and cyclic performance with 88.7%capacity retention after 1000 cycles at room temperature compared with the pouch cells with Al2O_(3)-coated separators.The fast ionic conductor ceramic composite separators will be a potential competitor to the next-generation novel separators for high-performance Li-ion power batteries.
文摘Due to its low electronegativity and light weight, if lithium is used as negative electrode material for electrochemical devices, the cell voltage and energy density may be enhanced. In recent years, the search for a new lithium conductor increased obviously with the increasing interest in all solid state lithium cell. LISICON is a three-dimensional lithium conductor with high conductivity, but its chemical stability is not good, and its conductivity at room temper-
基金Project supported by Tianjin Higher Education Bureau and National Laboratory of Laser Technology.
文摘The cubic and/or tetragonal ZrO<sub>2</sub> solid solution polycrystalline ceramics obtained byaddition of appropriate amounts of oxides asCaO, Y<sub>2</sub>O<sub>3</sub>, MgO or rare earth oxides to zirconiahas ioinc conductivity and is used as fast ionicconductor for new ceramic fuel cells and sensors.For MgO-stabilized zirconia the MgO content
基金financially supported by the National Basic Research Program of China(973 ProgramGrant 2012CB215504)the National Natural Science Foundation of China(21203191 and 21306190)
文摘In this paper, 1,2,4-triazolium methanesulfonate （C_2H_4N_3^＋-CH_3SO_3^-, [Tri][MS]）, an ionic conductor, was successfully synthesized. It exhibited high ionic conductivity of 18.60 mS·cm^-1 at 140 ℃ and reached up to 36.51 mS·cm^-1 at 190 ℃. [Tri][MS] was first applied to modify Nation membrane to fabricate [Tri][MS]/Nafion membrane by impregnation method at 150 ℃. The prepared composite membrane showed high thermal stability with decomposed temperature above 200 ℃ in air atmosphere. In addition, the membrane indicated good ionic conductivity with 3.67 mS·cm^-1 at 140 ℃ and reached up to 13.23 mS·cm^-1 at 180 ℃. The structure of the [Tri][MS] and the composite membrane were characterized by FTIR and the compatibility of [Tri][MS] and Pt/C catalyst was studied by a cyclic voltammetry （CV） method. Besides, the [Tri][MS]/Nafion membrane （thickness of 65 μm） was evaluated with single fuel cell at high temperature and without humidification. The highest power density of [Tri][MS]/Nafion membrane was 3.20 mW·cm^-2 at 140 ℃ and 4.90 mW·cm^-2 at 150 ℃, which was much higher than that of Nation membrane.
基金Project supported by the Natural Science Foundation of Hebei Province,China(E2021502013)Key Research and Development Projects of Hebei Province.China(21373805D)。
文摘Although solid-state lithium electrolytes have the potential to reduce the safety issues associated with organic liquid electrolytes,disadvantages such as low total conductivity,large interface impedance,and delamination of the interface due to cyclic stress still need to be addressed.The solid-state lithium-ion conductor Li_(0.33)La_(0.56)TiO_(3)(LLTO) was prepared via a hydrothermal route by using CTAB as templates in this paper.Perovskite LLTO with micro-porous channels was obtained and the total conductivity is comparable to the non-porous LLTO.Porous LLTO pellets are infiltrated with the non-porous LLTO precursor solution,and the total conductivities of the infiltrated porous LLTO are all higher than those without infiltration.After infiltration,the porous LLTO calcined at 600℃ achieves the highest total conductivity,7.88×10^(-5) S/cm.The fracture toughness of the infiltrated LLTO is higher than that of the non-porous LLTO.The results demonstrate a new way to prepare solid-state lithium-ion conductors with high ionic conductivity and great tolerance to cyclic stress.
基金Project supported by the Beijing Science and Technology ProjectChina(Grant No.Z13111000340000)+1 种基金the National Basic Research Program of China(Grant No.2012CB932900)the National Natural Science Foundation of China(Grant Nos.51325206 and 51421002)
文摘A new concept of forming solid electrolyte interphases（SEI） in situ in an ionic conducting Li（1.5）Al（0.5）Ge（1.5）（PO4）3-polypropylene（LAGP-PP） based separator during charging and discharging is proposed and demonstrated. This unique structure shows a high ionic conductivity, low interface resistance with electrode, and can suppress the growth of lithium dendrite. The features of forming the SEI in situ are investigated by scanning electron microscopy（SEM） and x-ray photoelectron spectroscopy（XPS）. The results confirm that SEI films mainly consist of lithium fluoride and carbonates with various alkyl contents. The cell assembled by using the LAGP-coated separator demonstrates a good cycling performance even at high charging rates, and the lithium dendrites were not observed on the lithium metal electrode. Therefore, the SEI-LAGP-PP separator can be used as a promising flexible solid electrolyte for solid state lithium batteries.
文摘Ionic conductivity values for segmented polyether polyurethaneurea (PEUU) complexes with LiClO_4 were determined and values as high as～1.1×10^(-4) S·cm^(-1) at 353K and～1.0×10^(-5)S·cm^(-1) at 306K were achieved. The ionic conductivity data were analyzed using the VTF (Vogel-Tamman-Fulcher) equation and WLF (Williams-Landel-Ferry) type equation. Values have been estimated for the 'apparent' activation energies of ion transport from VTF equation and they lie in the range 2.70—5.53 kJ·mol^(-1).
基金This work was supported by the National Natural Science Foundation of China.
文摘The polysiloxane containing propylene carbonate side group and several lithium poly-meric salts were synthesized. The structure were confirmed by IR, NMR and XPS. Theblending systems of polysiloxane containing propylene carbonate group with different lithiumpolymeric salts were studied by ion conductivity XPS and DSC. Different lithium poly-meric salts in the blending system lead to conductivity arranged in the following sequence:poly(lithium ethylenebenzene sulfonate methylsiloxane)>poly(lithium propionate methyl-siloxane)>poly(lithium propylsulfonate methylsiloxane)>poly(lithium styrenesulfonate).In the blending system the best single ion conductivity was close to 10^(-5) Scm^(-1) at roomtemperature. XPS showed that at low lithium salt concentration the conductivity increasedwith the increasing content of lithium salt, in consequence of the increase of free ion andsolvent separated ion pair. At high lithium salt concentration the free ion was absent andthe solvent-separated ion pair functioned as carrier.
