Lithium-based montmorillonite(Li-MMT)was prepared by inorganic modification of sodiumbased montmorillonite(Na-MMT)using the ion-exchange method under microwave-enhanced conditions.The ionic conductivity of Li-MMT was ...Lithium-based montmorillonite(Li-MMT)was prepared by inorganic modification of sodiumbased montmorillonite(Na-MMT)using the ion-exchange method under microwave-enhanced conditions.The ionic conductivity of Li-MMT was explored at different temperatures,humidities,and exchange ratios.The results showed that the modified materials all exhibited temperature-and humidity-dependent changes in ionic conductivity.When the mass ratio of Na-MMT and anhydrous lithium chloride(LiCl)was 1∶1,Li-MMT exhibited excellent ionic conductivity,with an ionic conductivity of 9.81×10^(-5)S·cm^(-1)for Na-MMT at 40%RH(relative humidity)and 60℃,and ionic conductivity of 4.15×10^(-4)S·cm^(-1)for Li-MMT-1(exchange ratio of Na-MMT and anhydrous LiCl was 1∶1).This modification method is simple and inexpensive as well as provides an effective method to improve the electrical conductivity of Na-MMT.展开更多
The perovskite-type oxide solid solution Ba0.98Ce0.8Tm0.2O3-α was prepared by high temperature solid-state reaction and its single phase character was confirmed by X-ray diffraction. The conduction property of the sa...The perovskite-type oxide solid solution Ba0.98Ce0.8Tm0.2O3-α was prepared by high temperature solid-state reaction and its single phase character was confirmed by X-ray diffraction. The conduction property of the sample was investigated by alternating current impedance spectroscopy and gas concentration cell methods under different gases atmospheres in the temperature range of 500-900 ℃. The performance of the hydrogen-air fuel cell using the sample as solid electrolyte was measured. In wet hydrogen, the sample is a pure protonic conductor with the protonic transport number of 1 in the range of 500-600 ℃, a mixed conductor of proton and electron with the protonic transport number of 0.945-0.933 above 600 ℃. In wet air, the sample is a mixed conductor of proton, oxide ion, and electronic hole. The protonic transport numbers are 0.010-0.021, and the oxide ionic transport numbers are 0.471-0.382. In hydrogen-air fuel cell, the sample is a mixed conductor of proton, oxide ion and electron, the ionic transport numbers are 0.942 0.885. The fuel cell using Ba0.98Ce0.8Tm0.2O3-α as solid electrolyte can work stably. At 900 ℃, the maximum power output density is 110,2 mW/cm2, which is higher than that of our previous cell using Ba0.98Ce0.8Tm0.2O3-α （x〈≤1, RE=Y, Eu, Ho） as solid electrolyte.展开更多
BaxCe0.8Pr0.2O3-α (x=0.98-1.03) ceramics were prepared by high temperature solid-state reaction. X-ray diffraction (XRD) patterns showed that the materials were perovskite-type orthorhombic single phase. By using gas...BaxCe0.8Pr0.2O3-α (x=0.98-1.03) ceramics were prepared by high temperature solid-state reaction. X-ray diffraction (XRD) patterns showed that the materials were perovskite-type orthorhombic single phase. By using gas concentration cell and AC impedance spectroscopy methods, the electrical conduction behavior of the materials was investigated in different gases at 500-900 °C. The influence of non-stoichiometry in the materials with x≠1 on conduction properties was studied and compared with that in the material with x=1. The results indicated that Ba1.03Ce0.8Pr0.2O3-α was a pure protonic conductor, and Ba0.98Ce0.8Pr0.2O3-α was a mixed conductor of protons and electrons in wet hydrogen at 500-900 °C. BaCe0.8Pr0.2O3-α was a pure protonic conductor in 500-600 °C, and a mixed conductor of protons and electrons above 600 °C in wet hydrogen. In 500-900 °C, they were all mixed conductors of oxide ions and electronic holes in dry air, and mixed conductors of protons, oxide ions and electronic holes in wet air. Both the protonic and oxide ionic conductivities increased with increasing barium content in the materials in wet hydrogen, dry air and wet air, respectively.展开更多
Ringlike polar monomer maleic, anhydride (MAn) was copolymerized with oligo (oxyethylene) methacrylate (MEO_n), and its effect on ion conduction property of the corresponding polymer-salt complexes was studied. As a c...Ringlike polar monomer maleic, anhydride (MAn) was copolymerized with oligo (oxyethylene) methacrylate (MEO_n), and its effect on ion conduction property of the corresponding polymer-salt complexes was studied. As a consequence the introduction of MAn onto polymer chain retards crystallization of the ether pendants considerably, and improves the ion conductivity to a larger degree compared with other polar groups once investigated (σ_(max),25℃=8.5×10^(-5) S/cm). The structure-ion conduction relation in the polymer-salt matrix is also analyzed macroscopically through the correspondence between composition-dependences of polymerization conversion and isothermal ion conductivity, and microscopically through the measurements of cross polarized light and electron transmission.展开更多
Acrylamide was introduced onto the chain of poly[oligo(oxyethylene) methacrylate] as a polar constituent, and the effect of its presence on the mechanical strength and ionic conduction properties of Li-salt complex ba...Acrylamide was introduced onto the chain of poly[oligo(oxyethylene) methacrylate] as a polar constituent, and the effect of its presence on the mechanical strength and ionic conduction properties of Li-salt complex based on the resultant copolymer was investigated. The introduction of the polar constituent raises chain rigidity, retards crystallization of oligo(oxyethylene) domain and promotes the dissociation of lithium salt. The factors work on the mechanical and conduction properties synergistically, therefore both of the properties are improved simultaneously as the consequence of acrylamide-introduction.展开更多
Poly(pyridinium ethyl methacrylate)was synthesized.The blends of polymeric solid anion conductor,P(PyEMAClO+4)/P(MEO_(16)—AM),were prepared. The temperature—dependence of both the conductivity and anionic mobility i...Poly(pyridinium ethyl methacrylate)was synthesized.The blends of polymeric solid anion conductor,P(PyEMAClO+4)/P(MEO_(16)—AM),were prepared. The temperature—dependence of both the conductivity and anionic mobility in the blends obey Arrhenius relationship,the transport of perchlorate anion being of thermal activation mechanism.Perchlorate anion is a free anion in the blends.展开更多
Apatite-type lanthanum silicate with special conduction mechanism via interstitial oxygen has attracted considerable interest in recent years. In this work, pure powder of La9.33 2x/3MxSi6O26 （M=Mg, Ca, Sr） is prepa...Apatite-type lanthanum silicate with special conduction mechanism via interstitial oxygen has attracted considerable interest in recent years. In this work, pure powder of La9.33 2x/3MxSi6O26 （M=Mg, Ca, Sr） is prepared by the sol-gel method with sintering at 1000℃. The powder is characterized by X-ray diffraction （XRD） and scanning electron micrograph （SEM）. The apatite can be obtained at relatively low temperature as compared to the conventional solid-state reaction method. The measurements of conductivity of a series of doped samples La9.33-2x/3MxSi6O26 （M=Ca, Mg, Sr） indicate that the type of dopant and the amount have a significant effect on the conductivity. The greatest decrease in conductivity is observed for Mg doping, following the Ca and the Sr doped apatites. The effect is ultimately attributed to the amount of oxygen interstitials, which is affected by the crystal lattice distortion arising from cation vacancies.展开更多
Poly(ethylene oxide)(PEO)is a classic matrix model for solid polymer electrolyte which can not only dissociate lithium-ions(Li^(+)),but also can conduct Li^(+) through segmental motion in long-range.However,the crysta...Poly(ethylene oxide)(PEO)is a classic matrix model for solid polymer electrolyte which can not only dissociate lithium-ions(Li^(+)),but also can conduct Li^(+) through segmental motion in long-range.However,the crystal aggregation state of PEO restricts the conduction of Li^(+) especially at room temperature.In this work,an amorphous polymer electrolyte with ethylene oxide(EO)and propylene oxide(PO)block structure(B-PEG@DMC)synthesized by the transesterification is firstly obtained,showing an ionic conductivity value of 1.1×10^(5) S/cm at room temperature(25℃).According to the molecular dynamics(MD)simulation,the PO segments would lead to an inconsecutive and hampered conduction of Li^(+),which is not beneficial to the short range conduction of Li^(+).Thus the effect of transformation of aggregation state on the improveme nt of ionic conductivity is not eno ugh,it is n ecessary to further consider the differe nt coupled behaviours of EO and PO segments with Li^(+).In this way,we blend this amorphous polymer(B-PEG@DMC)with PEO to obtain a dual range ionic conductive solid polymer electrolyte(D-SPE)with further improved ionic conductivity promoted by constructing a dual range fast ionic conduction,which eventually shows a further improved ionic conductivity value of 2.3×10^(5) S/cm at room temperature.展开更多
In this study,powders of polyethylene oxide（PEO） and lithium perchlorate（Li Cl O4） were used as the raw materials for producing the ionic conduction polymer PEO–Li Cl O4 with different complex-ratios and used for...In this study,powders of polyethylene oxide（PEO） and lithium perchlorate（Li Cl O4） were used as the raw materials for producing the ionic conduction polymer PEO–Li Cl O4 with different complex-ratios and used for anodic bonding through high energy ball milling method,and meanwhile,X-ray diffraction,differential scanning calorimetry（DSC）,ultraviolet absorption spectrum test analysis,and other relevant methods were adopted to research the complexation mechanism of PEO and Li Cl O4 and the impact of the ionic conduction polymer with different complex-ratios on the anodic bonding process under the action of the strong static electric field.The research results showed that the crystallization of PEO could be effectively obstructed with increased addition of Li Cl O4,thus increasing the content of PEO–Li Cl O4 in amorphous area and continuously improving the complexation degree and the room-temperature conductivity thereof,and that the higher room-temperature conductivity enabled PEO–Li Cl O4 to better bond with metallic aluminum and have better bonding quality.As the new encapsulating material,such research results will promote the application of new polymer functional materials in micro-electromechanical system（MEMS） components.展开更多
The ac conductivities of Y2O3 or CaO-stabilized cubic zirconias were obtained from complex impedance measurements in the temperature range from 373 to 473 K. By analyzing the temperature-dependence of the resultant dc...The ac conductivities of Y2O3 or CaO-stabilized cubic zirconias were obtained from complex impedance measurements in the temperature range from 373 to 473 K. By analyzing the temperature-dependence of the resultant dc conductivities, it was shown that the activation energies for conduction are lower than those reported previously for the same materials at high temperatures. Comparing the activation energy data with the theoretically estimated values revealed that there may exist a certain, although very small, amount of free oxygen vacancies in the test samples at low temperatures and the conduction in the test samples is a result of the migration of these free oxygen vacancies.展开更多
1.INTRODUCTION Elevating energy density using high nickel oxide cathodes and lithium metal anode will aggravate the safety hazards of lithium batteries with flammable organic liquid electrolytes.Using solid electrolyt...1.INTRODUCTION Elevating energy density using high nickel oxide cathodes and lithium metal anode will aggravate the safety hazards of lithium batteries with flammable organic liquid electrolytes.Using solid electrolytes(SEs)instead to realize all-solid-state lithium batteries(ASSLBs)can ensure both energy density and safety,for which it is essential to apply SEs with good electrode compatibility and high ionic conductivity to enable stable cycling of ASSLBs at room temperature.展开更多
CONSPECTUS:The widespread deployment of solar and wind energy requires advanced energy storage technologies to address the intermittent energy output and the loading limit of the current power grid.Materials are of cr...CONSPECTUS:The widespread deployment of solar and wind energy requires advanced energy storage technologies to address the intermittent energy output and the loading limit of the current power grid.Materials are of critical importance for energy storage and conversion.Under such circumstances,development of the advanced energy storage materials featuring high capacity,large energy density,and good safety has been taking center stage in the research areas of physics,chemistry,and materials science.As a class of multifunctional materials,metal hydrides with great potential for energy-related applications such as rechargeable batteries,hydrogen energy storage,thermal storage,and ion conduction are one of the core focuses in the current development of advanced energy materials.展开更多
Solid-state electrolytes(SSEs),as the core component within the next generation of key energy storage technologies-solid-state lithium batteries(SSLBs)-are significantly leading the development of future energy storag...Solid-state electrolytes(SSEs),as the core component within the next generation of key energy storage technologies-solid-state lithium batteries(SSLBs)-are significantly leading the development of future energy storage systems.Among the numerous types of SSEs,inorganic oxide garnet-structured superionic conductors Li7La3Zr2O12(LLZO)crystallized with the cubic Iaˉ3d space group have received considerable attention owing to their highly advantageous intrinsic properties encompassing reasonable lithium-ion conductivity,wide electrochemical voltage window,high shear modulus,and excellent chemical stability with electrodes.However,no SSEs possess all the properties necessary for SSLBs,thus both the ionic conductivity at room temperature and stability in ambient air regarding cubic garnet-based electrolytes are still subject to further improvement.Hence,this review comprehensively covers the nine key structural factors affecting the ion conductivity of garnet-based electrolytes comprising Li concentration,Li vacancy concentration,Li carrier concentration and mobility,Li occupancy at available sites,lattice constant,triangle bottleneck size,oxygen vacancy defects,and Li-O bonding interactions.Furthermore,the general illustration of structures and fundamental features being crucial to chemical stability is examined,including Li concentration,Li-site occupation behavior,and Li-O bonding interactions.Insights into the composition-structure-property relations among cubic garnet-based oxide ionic conductors from the perspective of their crystal structures,revealing the potential compatibility conflicts between ionic transportation and chemical stability resulting from Li-O bonding interactions.We believe that this review will lay the foundation for future reasonable structural design of oxide-based or even other types of superionic conductors,thus assisting in promoting the rapid development of alternative green and sustainable technologies.展开更多
Solid electrolytes face challenges in solid-state sodium batteries(SSSBs)because of limited ionic conductivity,increased interfacial resistance,and sodium dendrite issues.In this study,we adopted a unique Sn4+doping s...Solid electrolytes face challenges in solid-state sodium batteries(SSSBs)because of limited ionic conductivity,increased interfacial resistance,and sodium dendrite issues.In this study,we adopted a unique Sn4+doping strategy for Na_(3.2)Zr_(2)Si_(2.2)P_(0.8)O_(12)(NZSP)that caused a partial structural transition from the monoclinic(C2/c)phase to the rhombohedral(R-3c)phase in Na_(3.2)Zr_(1.9)Sn_(0.1)Si_(2.2)P_(0.8)O_(12)(NZSnSP1).X-ray diffraction(XRD)patterns and high-resolution transmission electron microscopy analyses were used to confirm this transition,where rhombohedral NZSnSP1 showed an increase in the Na2-O bond length compared with monoclinic NZSnSP1,increasing its triangular bottleneck areas and noticeably enhancing Na+ionic conductivity,a higher Na transference number,and lower electronic conductivity.NZSnSP1 also showed exceptionally high compatibility with Na metal with an increased critical current density,as evidenced by symmetric cell tests.The SSSB,fabricated using Na_(0.9)Zn_(0.22)Fe_(0.3)Mn_(0.48)O_(2)(NZFMO),Na metal,and NZSnSP1 as the cathode,anode,and the solid electrolyte and separator,respectively,maintains 65.86%of retention in the reversible capacity over 300 cycles within a voltage range of 2.0-4.0 V at 25℃ at 0.1 C.The in-situ X-ray diffraction and X-ray absorption analyses of the P and Zr K-edges confirmed that NZSnSP1 remained highly stable before and after electrochemical cycling.This crystal structure modification strategy enables the synthesis of ideal solid electrolytes for practical SSSBs.展开更多
Fiber-shaped energy storage devices(FSESDs)with exceptional flexibility for wearable power sources should be applied with solid electrolytes over liquid electrolytes due to short circuits and leakage issue during defo...Fiber-shaped energy storage devices(FSESDs)with exceptional flexibility for wearable power sources should be applied with solid electrolytes over liquid electrolytes due to short circuits and leakage issue during deformation.Among the solid options,polymer electrolytes are particularly preferred due to their robustness and flexibility,although their low ionic conductivity remains a significant challenge.Here,we present a redox polymer electrolyte(HT_RPE)with 4-hydroxy-2,2,6,6-tetramethylpiperidine-1-oxyl(HT)as a multi-functional additive.HT acts as a plasticizer that transforms the glassy state into the rubbery state for improved chain mobility and provides distinctive ion conduction pathway by the self-exchange reaction between radical and oxidized species.These synergetic effects lead to high ionic conductivity(73.5 mS cm−1)based on a lower activation energy of 0.13 eV than other redox additives.Moreover,HT_RPE with a pseudocapacitive characteristic by HT enables an outstanding electrochemical performance of the symmetric FSESDs using carbon-based fiber electrodes(energy density of 25.4 W h kg^(−1) at a power density of 25,000 W kg^(−1))without typical active materials,along with excellent stability(capacitance retention of 91.2%after 8,000 bending cycles).This work highlights a versatile HT_RPE that utilizes the unique functionality of HT for both the high ionic conductivity and improved energy storage capability,providing a promising pathway for next-generation flexible energy storage devices.展开更多
Solid polymer electrolytes(SPEs)are considered one of the most promising materials for all-solid-state lithium metal batteries(ASSLMBs)due to their facile processability.However,developing SPEs with both high ionic co...Solid polymer electrolytes(SPEs)are considered one of the most promising materials for all-solid-state lithium metal batteries(ASSLMBs)due to their facile processability.However,developing SPEs with both high ionic conductivity and interfacial stability remains a challenge.Here,a donor-acceptor(D-A)like solid plasticizer,tris(pentafluorophenyl)borane(TPFPB),containing electron-rich F atoms and electrondeficient B sites,was introduced to regulate the ion transport behavior and interfacial chemistry of polyethylene oxide(PEO)-based SPEs.Owing to the multiple ion-dipole interactions(F Li^(+)TFSI^(-)and B TFSI^(-)Li^(+))between the TPFPB molecule and Li salts,a multimodal electrolyte environment featuring more free Li^(+)and trapped TFSI^(-)anions was generated,which cooperates with the reduced crystallinity of PEO,significantly facilitating the rapid migration of Li^(+).More importantly,TPFPB tends to be preferentially reduced to form a stable inorganic-rich solid electrolyte interphase on the Li-metal anode,ensuring uniform Li plating/stripping behavior.Thus,the TPFPB-modulated SPEs system achieves a high Li^(+)conductivity of 0.74 m S cm^(-1)and effectively suppresses dendrite growth,which enables a long-cycle dendrite-free Li/Li symmetric cell for over 5000 h,and remarkable electrochemical performance has been further validated in operational ASSLMBs.The findings in this work would inspire efforts to develop highperformance SPEs for all-solid-state alkali-metal batteries.展开更多
A new series of Zr1-xInxP2O7 （x=0.03, 0.06, 0.09, 0.12） samples were prepared by a solid state reaction method. XRD patterns indicated that the samples of x=0.03–0.09 exhibited a single cubic phase structure, and t...A new series of Zr1-xInxP2O7 （x=0.03, 0.06, 0.09, 0.12） samples were prepared by a solid state reaction method. XRD patterns indicated that the samples of x=0.03–0.09 exhibited a single cubic phase structure, and the doping limit of In3＋ in ZrP2O7 was x=0.09. The conduction behavior was investigated in wet hydrogen using various electrochemical methods including AC impedance spectroscopy, isotope effect, gas concentration cells at intermediate temperatures （373–573 K）. The conductivities were affected by the doping levels, and increased in the order： σ （x=0.03）〈σ （x=0.12）〈σ （x=0.06）〈σ （x=0.09）. The highest conductivity was observed for the sample Zr0.91In0.09P2O7 to be 1.59×10-2 S·cm-1 in wet hydrogen at 573 K. The isotope effect also confirmed the proton conduction of the sample under water vapor-containing atmosphere. It was found that in wet hydrogen atmosphere Zr0.91In0.09P2O7 was almost pure ionic conductor, the ionic conduction was contributed mainly to proton and partially to oxide ionic. The H2/air fuel cell using x=0.09 sample as electrolyte （thickness： 1.73 mm） generated a maximum power density of 13.5 mW·cm？2 at 423 K and 16.9 mW·cm？2 at 448 K, respectively.展开更多
Carbon was used as electronic conductive agent, and metasilicic acid lithium (Li<sub>2</sub>SiO<sub>3</sub>) as ionic conductive agent, the two factors were investigated cooperatively. We evalu...Carbon was used as electronic conductive agent, and metasilicic acid lithium (Li<sub>2</sub>SiO<sub>3</sub>) as ionic conductive agent, the two factors were investigated cooperatively. We evaluated their effect by using spherical spinel LiMn<sub>2</sub>O<sub>4</sub> which prepared ourselves as cathode material. Then Li<sub>2</sub>SiO<sub><sub></sub>3</sub>/carbon surface coating on LiMn<sub><sub></sub>2</sub>O<sub>4</sub> (LMO/C/LSO) which Li<sub><sub></sub>2</sub>SiO<sub><sub></sub>3</sub> inside and carbon/Li<sub><sub></sub>2</sub>SiO<sub><sub></sub>3</sub> coated LiMn<sub><sub></sub>2</sub>O<sub><sub></sub>4</sub> (LMO/LSO/C) were prepared, All of materials were characterized by X-ray diffraction (XRD) and electrochemical test;spherical LiMn<sub></sub>2O<sub></sub>4 was characterized by scanning electron microscopy (SEM);and coated materials were characterized by transmission electron microscopy (TEM). While uncoated spinel LiMn<sub><sub></sub>2</sub>O<sub><sub></sub>4</sub> maintained 72% of capacity in 60 cycles by the rate of 0.2C, and LMO/LSO/C showed the best electrochemical performance, 89% of the initial capacity remained after 75 cycles at 0.2C. Furthermore, the rate performance of LMO/LSO/C also improved obviously, about 30 mAh·g<sup>-1</sup> of capacity attained at the rate of 5C, higher than LMO/C/LSO and bare LiMn<sub><sub></sub>2</sub>O<sub><sub></sub>4</sub>.展开更多
A composite solid electrolyte comprising a Cu-Al bimetallic metal-organic framework(CAB),lithium salt(LiTFSI)and polyethylene oxide(PEO)was fabricated through molecular grafting to enhance the ionic conductivity of th...A composite solid electrolyte comprising a Cu-Al bimetallic metal-organic framework(CAB),lithium salt(LiTFSI)and polyethylene oxide(PEO)was fabricated through molecular grafting to enhance the ionic conductivity of the PEO-based electrolytes.Experimental and molecular dynamics simulation results indicated that the electrolyte with 10 wt.%CAB(PL-CAB-10%)exhibits high ionic conductivity(8.42×10~(-4)S/cm at 60℃),high Li+transference number(0.46),wide electrochemical window(4.91 V),good thermal stability,and outstanding mechanical properties.Furthermore,PL-CAB-10%exhibits excellent cycle stability in both Li-Li symmetric battery and Li/PL-CAB-10%/LiFePO4 asymmetric battery setups.These enhanced performances are primarily attributable to the introduction of the versatile CAB.The abundant metal sites in CAB can react with TFSI~-and PEO through Lewis acid-base interactions,promoting LiTFSI dissociation and improving ionic conductivity.Additionally,regular pores in CAB provide uniformly distributed sites for cation plating during cycling.展开更多
Argyrodites,Li_(6)PS_(5)X(X=Cl,Br,I),have piqued the interest of researchers by offering promising lithium ionic conductivity for their application in all-solid-state batteries(ASSBs).However,other than Li_(6)PS_(5)Cl...Argyrodites,Li_(6)PS_(5)X(X=Cl,Br,I),have piqued the interest of researchers by offering promising lithium ionic conductivity for their application in all-solid-state batteries(ASSBs).However,other than Li_(6)PS_(5)Cl(651Cl)and Li_(6)PS_(5)Br(651Br),Li_(6)PS_(5)I(651I)shows poor ionic conductivity(10^(-7)S cm^(-1)at 298 K).Herein,we present Al-doped 651I with I^(-)/S^(2-)site disordering to lower activation energy(Ea)and improve ionic conductivity.They formed argyrodite-type solid solutions with a composition of(Li_(6–3x)Al_(x))PS_(5)I in 0≤x≤0.10,and structural analysis revealed that Al^(3+)is located at Li sites.Also,the Al-doped samples contained anion I^(-)/S^(2-)site disorders in the crystal structures and smaller lattice parameters than the non-doped samples.Impedance spectroscopy measurements indicated that Al-doping reduced the ionic diffusion barrier,Ea,and increased the ionic conductivity to 10^(-5)S cm^(-1);the(Li5.7Al0.1)PS5I had the highest ionic conductivity in the studied system,at 2.6×10^(-5)S cm^(-1).In a lab-scale ASSB,with(Li_(5.7)Al_(0.1))PS_(5)I functioned as a solid electrolyte,demonstrating the characteristics of a pure ionic conductor with negligible electronic conductivity.The evaluated ionic conduction is due to decreased Li+content and I^(-)/S^(2-)disorder formation.Li-site cation doping enables an in-depth understanding of the structure and provides an additional approach to designing betterperforming SEs in the argyrodite system.展开更多
基金supported by the National Natural Science Foundation of China(22322102)Science and Technology Project of State Grid Jilin Electric Power Co.,Ltd(2023-07).
文摘Lithium-based montmorillonite(Li-MMT)was prepared by inorganic modification of sodiumbased montmorillonite(Na-MMT)using the ion-exchange method under microwave-enhanced conditions.The ionic conductivity of Li-MMT was explored at different temperatures,humidities,and exchange ratios.The results showed that the modified materials all exhibited temperature-and humidity-dependent changes in ionic conductivity.When the mass ratio of Na-MMT and anhydrous lithium chloride(LiCl)was 1∶1,Li-MMT exhibited excellent ionic conductivity,with an ionic conductivity of 9.81×10^(-5)S·cm^(-1)for Na-MMT at 40%RH(relative humidity)and 60℃,and ionic conductivity of 4.15×10^(-4)S·cm^(-1)for Li-MMT-1(exchange ratio of Na-MMT and anhydrous LiCl was 1∶1).This modification method is simple and inexpensive as well as provides an effective method to improve the electrical conductivity of Na-MMT.
文摘The perovskite-type oxide solid solution Ba0.98Ce0.8Tm0.2O3-α was prepared by high temperature solid-state reaction and its single phase character was confirmed by X-ray diffraction. The conduction property of the sample was investigated by alternating current impedance spectroscopy and gas concentration cell methods under different gases atmospheres in the temperature range of 500-900 ℃. The performance of the hydrogen-air fuel cell using the sample as solid electrolyte was measured. In wet hydrogen, the sample is a pure protonic conductor with the protonic transport number of 1 in the range of 500-600 ℃, a mixed conductor of proton and electron with the protonic transport number of 0.945-0.933 above 600 ℃. In wet air, the sample is a mixed conductor of proton, oxide ion, and electronic hole. The protonic transport numbers are 0.010-0.021, and the oxide ionic transport numbers are 0.471-0.382. In hydrogen-air fuel cell, the sample is a mixed conductor of proton, oxide ion and electron, the ionic transport numbers are 0.942 0.885. The fuel cell using Ba0.98Ce0.8Tm0.2O3-α as solid electrolyte can work stably. At 900 ℃, the maximum power output density is 110,2 mW/cm2, which is higher than that of our previous cell using Ba0.98Ce0.8Tm0.2O3-α （x〈≤1, RE=Y, Eu, Ho） as solid electrolyte.
基金Project supported by the National Natural Science Foundation of China (20771079)Qing Lan Project and the Natural Science Foundation of Education Department of Jiangsu Province (07KJB150126 and 08KJD150008)
文摘BaxCe0.8Pr0.2O3-α (x=0.98-1.03) ceramics were prepared by high temperature solid-state reaction. X-ray diffraction (XRD) patterns showed that the materials were perovskite-type orthorhombic single phase. By using gas concentration cell and AC impedance spectroscopy methods, the electrical conduction behavior of the materials was investigated in different gases at 500-900 °C. The influence of non-stoichiometry in the materials with x≠1 on conduction properties was studied and compared with that in the material with x=1. The results indicated that Ba1.03Ce0.8Pr0.2O3-α was a pure protonic conductor, and Ba0.98Ce0.8Pr0.2O3-α was a mixed conductor of protons and electrons in wet hydrogen at 500-900 °C. BaCe0.8Pr0.2O3-α was a pure protonic conductor in 500-600 °C, and a mixed conductor of protons and electrons above 600 °C in wet hydrogen. In 500-900 °C, they were all mixed conductors of oxide ions and electronic holes in dry air, and mixed conductors of protons, oxide ions and electronic holes in wet air. Both the protonic and oxide ionic conductivities increased with increasing barium content in the materials in wet hydrogen, dry air and wet air, respectively.
文摘Ringlike polar monomer maleic, anhydride (MAn) was copolymerized with oligo (oxyethylene) methacrylate (MEO_n), and its effect on ion conduction property of the corresponding polymer-salt complexes was studied. As a consequence the introduction of MAn onto polymer chain retards crystallization of the ether pendants considerably, and improves the ion conductivity to a larger degree compared with other polar groups once investigated (σ_(max),25℃=8.5×10^(-5) S/cm). The structure-ion conduction relation in the polymer-salt matrix is also analyzed macroscopically through the correspondence between composition-dependences of polymerization conversion and isothermal ion conductivity, and microscopically through the measurements of cross polarized light and electron transmission.
文摘Acrylamide was introduced onto the chain of poly[oligo(oxyethylene) methacrylate] as a polar constituent, and the effect of its presence on the mechanical strength and ionic conduction properties of Li-salt complex based on the resultant copolymer was investigated. The introduction of the polar constituent raises chain rigidity, retards crystallization of oligo(oxyethylene) domain and promotes the dissociation of lithium salt. The factors work on the mechanical and conduction properties synergistically, therefore both of the properties are improved simultaneously as the consequence of acrylamide-introduction.
文摘Poly(pyridinium ethyl methacrylate)was synthesized.The blends of polymeric solid anion conductor,P(PyEMAClO+4)/P(MEO_(16)—AM),were prepared. The temperature—dependence of both the conductivity and anionic mobility in the blends obey Arrhenius relationship,the transport of perchlorate anion being of thermal activation mechanism.Perchlorate anion is a free anion in the blends.
基金Supported by the Natural Science Foundation of Guangdong PrOvince （06025657） and Guangdong Provincial Green Chemicals.
文摘Apatite-type lanthanum silicate with special conduction mechanism via interstitial oxygen has attracted considerable interest in recent years. In this work, pure powder of La9.33 2x/3MxSi6O26 （M=Mg, Ca, Sr） is prepared by the sol-gel method with sintering at 1000℃. The powder is characterized by X-ray diffraction （XRD） and scanning electron micrograph （SEM）. The apatite can be obtained at relatively low temperature as compared to the conventional solid-state reaction method. The measurements of conductivity of a series of doped samples La9.33-2x/3MxSi6O26 （M=Ca, Mg, Sr） indicate that the type of dopant and the amount have a significant effect on the conductivity. The greatest decrease in conductivity is observed for Mg doping, following the Ca and the Sr doped apatites. The effect is ultimately attributed to the amount of oxygen interstitials, which is affected by the crystal lattice distortion arising from cation vacancies.
基金support from the National Natural Science Foundation of China[22021001,21875195]the Fundamental Research Funds for the Central Universities[20720190040]the Key Project of Science and Technology of Xiamen[3502Z20201013]。
文摘Poly(ethylene oxide)(PEO)is a classic matrix model for solid polymer electrolyte which can not only dissociate lithium-ions(Li^(+)),but also can conduct Li^(+) through segmental motion in long-range.However,the crystal aggregation state of PEO restricts the conduction of Li^(+) especially at room temperature.In this work,an amorphous polymer electrolyte with ethylene oxide(EO)and propylene oxide(PO)block structure(B-PEG@DMC)synthesized by the transesterification is firstly obtained,showing an ionic conductivity value of 1.1×10^(5) S/cm at room temperature(25℃).According to the molecular dynamics(MD)simulation,the PO segments would lead to an inconsecutive and hampered conduction of Li^(+),which is not beneficial to the short range conduction of Li^(+).Thus the effect of transformation of aggregation state on the improveme nt of ionic conductivity is not eno ugh,it is n ecessary to further consider the differe nt coupled behaviours of EO and PO segments with Li^(+).In this way,we blend this amorphous polymer(B-PEG@DMC)with PEO to obtain a dual range ionic conductive solid polymer electrolyte(D-SPE)with further improved ionic conductivity promoted by constructing a dual range fast ionic conduction,which eventually shows a further improved ionic conductivity value of 2.3×10^(5) S/cm at room temperature.
基金supported by the National Natural Science Foundation of China (No.51275332)the Natural Science Foundation for Young Scientists of Shanxi Province,China (No.2014021025-2)
文摘In this study,powders of polyethylene oxide（PEO） and lithium perchlorate（Li Cl O4） were used as the raw materials for producing the ionic conduction polymer PEO–Li Cl O4 with different complex-ratios and used for anodic bonding through high energy ball milling method,and meanwhile,X-ray diffraction,differential scanning calorimetry（DSC）,ultraviolet absorption spectrum test analysis,and other relevant methods were adopted to research the complexation mechanism of PEO and Li Cl O4 and the impact of the ionic conduction polymer with different complex-ratios on the anodic bonding process under the action of the strong static electric field.The research results showed that the crystallization of PEO could be effectively obstructed with increased addition of Li Cl O4,thus increasing the content of PEO–Li Cl O4 in amorphous area and continuously improving the complexation degree and the room-temperature conductivity thereof,and that the higher room-temperature conductivity enabled PEO–Li Cl O4 to better bond with metallic aluminum and have better bonding quality.As the new encapsulating material,such research results will promote the application of new polymer functional materials in micro-electromechanical system（MEMS） components.
基金supported by the State Key Laboratory of New Ceramics and Fine Processing,Tsinghua University,Chinathe supports of K.CWong Education Foundatio,Hong KongChina Postdoctorl Science Foundation
文摘The ac conductivities of Y2O3 or CaO-stabilized cubic zirconias were obtained from complex impedance measurements in the temperature range from 373 to 473 K. By analyzing the temperature-dependence of the resultant dc conductivities, it was shown that the activation energies for conduction are lower than those reported previously for the same materials at high temperatures. Comparing the activation energy data with the theoretically estimated values revealed that there may exist a certain, although very small, amount of free oxygen vacancies in the test samples at low temperatures and the conduction in the test samples is a result of the migration of these free oxygen vacancies.
基金financial support from the National Natural Science Foundation of China(Grant No.22475235,22325505,52073271,22305236)the USTC Research Funds of the Double First-Class Initiative(YD2060002034)+1 种基金the Collaborative Innovation Program of Hefei Science Center,CAS(Grant No.2022HSC-CIP018)the China Postdoctoral Science Foundation(Grant No.2023M733375 and 2023T160619).
文摘1.INTRODUCTION Elevating energy density using high nickel oxide cathodes and lithium metal anode will aggravate the safety hazards of lithium batteries with flammable organic liquid electrolytes.Using solid electrolytes(SEs)instead to realize all-solid-state lithium batteries(ASSLBs)can ensure both energy density and safety,for which it is essential to apply SEs with good electrode compatibility and high ionic conductivity to enable stable cycling of ASSLBs at room temperature.
基金support received from the National Key R&D Program of China(2023YFB2504000)the National Outstanding Youth Foundation of China(52125104)+2 种基金the National Natural Science Foundation of China(52001277)the Fundamental Research Funds for the Central Universities(2021FZZX001-09,226-2022-00246)the National Youth Top-Notch Talent Support Program.
文摘CONSPECTUS:The widespread deployment of solar and wind energy requires advanced energy storage technologies to address the intermittent energy output and the loading limit of the current power grid.Materials are of critical importance for energy storage and conversion.Under such circumstances,development of the advanced energy storage materials featuring high capacity,large energy density,and good safety has been taking center stage in the research areas of physics,chemistry,and materials science.As a class of multifunctional materials,metal hydrides with great potential for energy-related applications such as rechargeable batteries,hydrogen energy storage,thermal storage,and ion conduction are one of the core focuses in the current development of advanced energy materials.
基金supported by the National Natural Science Foundation of China(Nos.22171102 and 22090044)the National Key R&D Program of China(Nos.2021YFF0500502 and 2023YFA1506304)+2 种基金the Jilin Province Science and Technology Development Plan(No.20230101024JC)the"Medicine+X"crossinnovation team of Bethune Medical Department of Jilin University"Leading the Charge with Open Competition"construction project(No.2022JBGS04)the Jilin University Graduate Training Office(Nos.2021JGZ08 and 2022YJSJIP20).
文摘Solid-state electrolytes(SSEs),as the core component within the next generation of key energy storage technologies-solid-state lithium batteries(SSLBs)-are significantly leading the development of future energy storage systems.Among the numerous types of SSEs,inorganic oxide garnet-structured superionic conductors Li7La3Zr2O12(LLZO)crystallized with the cubic Iaˉ3d space group have received considerable attention owing to their highly advantageous intrinsic properties encompassing reasonable lithium-ion conductivity,wide electrochemical voltage window,high shear modulus,and excellent chemical stability with electrodes.However,no SSEs possess all the properties necessary for SSLBs,thus both the ionic conductivity at room temperature and stability in ambient air regarding cubic garnet-based electrolytes are still subject to further improvement.Hence,this review comprehensively covers the nine key structural factors affecting the ion conductivity of garnet-based electrolytes comprising Li concentration,Li vacancy concentration,Li carrier concentration and mobility,Li occupancy at available sites,lattice constant,triangle bottleneck size,oxygen vacancy defects,and Li-O bonding interactions.Furthermore,the general illustration of structures and fundamental features being crucial to chemical stability is examined,including Li concentration,Li-site occupation behavior,and Li-O bonding interactions.Insights into the composition-structure-property relations among cubic garnet-based oxide ionic conductors from the perspective of their crystal structures,revealing the potential compatibility conflicts between ionic transportation and chemical stability resulting from Li-O bonding interactions.We believe that this review will lay the foundation for future reasonable structural design of oxide-based or even other types of superionic conductors,thus assisting in promoting the rapid development of alternative green and sustainable technologies.
基金supported by the National Research Foundation of Korea(RS-2024-00404414)the National Research Council of Science&Technology(NST,No.GTL24011-000)funded by the Ministry of Science and ICTsupported by the KIST Institutional Program(Project No.2E33270).
文摘Solid electrolytes face challenges in solid-state sodium batteries(SSSBs)because of limited ionic conductivity,increased interfacial resistance,and sodium dendrite issues.In this study,we adopted a unique Sn4+doping strategy for Na_(3.2)Zr_(2)Si_(2.2)P_(0.8)O_(12)(NZSP)that caused a partial structural transition from the monoclinic(C2/c)phase to the rhombohedral(R-3c)phase in Na_(3.2)Zr_(1.9)Sn_(0.1)Si_(2.2)P_(0.8)O_(12)(NZSnSP1).X-ray diffraction(XRD)patterns and high-resolution transmission electron microscopy analyses were used to confirm this transition,where rhombohedral NZSnSP1 showed an increase in the Na2-O bond length compared with monoclinic NZSnSP1,increasing its triangular bottleneck areas and noticeably enhancing Na+ionic conductivity,a higher Na transference number,and lower electronic conductivity.NZSnSP1 also showed exceptionally high compatibility with Na metal with an increased critical current density,as evidenced by symmetric cell tests.The SSSB,fabricated using Na_(0.9)Zn_(0.22)Fe_(0.3)Mn_(0.48)O_(2)(NZFMO),Na metal,and NZSnSP1 as the cathode,anode,and the solid electrolyte and separator,respectively,maintains 65.86%of retention in the reversible capacity over 300 cycles within a voltage range of 2.0-4.0 V at 25℃ at 0.1 C.The in-situ X-ray diffraction and X-ray absorption analyses of the P and Zr K-edges confirmed that NZSnSP1 remained highly stable before and after electrochemical cycling.This crystal structure modification strategy enables the synthesis of ideal solid electrolytes for practical SSSBs.
基金supported by Korea Institute of Science and Technology(KIST)Institutional Program and Open Research Program(ORP)This work was also supported by grant from the National Research Foundation(NRF)of Korea government(RS-2024-00433159 and RS-2023-00208313)from ITECH R&D program of MOTIE/KEIT(RS-2023-00257573).
文摘Fiber-shaped energy storage devices(FSESDs)with exceptional flexibility for wearable power sources should be applied with solid electrolytes over liquid electrolytes due to short circuits and leakage issue during deformation.Among the solid options,polymer electrolytes are particularly preferred due to their robustness and flexibility,although their low ionic conductivity remains a significant challenge.Here,we present a redox polymer electrolyte(HT_RPE)with 4-hydroxy-2,2,6,6-tetramethylpiperidine-1-oxyl(HT)as a multi-functional additive.HT acts as a plasticizer that transforms the glassy state into the rubbery state for improved chain mobility and provides distinctive ion conduction pathway by the self-exchange reaction between radical and oxidized species.These synergetic effects lead to high ionic conductivity(73.5 mS cm−1)based on a lower activation energy of 0.13 eV than other redox additives.Moreover,HT_RPE with a pseudocapacitive characteristic by HT enables an outstanding electrochemical performance of the symmetric FSESDs using carbon-based fiber electrodes(energy density of 25.4 W h kg^(−1) at a power density of 25,000 W kg^(−1))without typical active materials,along with excellent stability(capacitance retention of 91.2%after 8,000 bending cycles).This work highlights a versatile HT_RPE that utilizes the unique functionality of HT for both the high ionic conductivity and improved energy storage capability,providing a promising pathway for next-generation flexible energy storage devices.
基金supported by the National Natural Science Foundation of China(No.52203261,No.52473213)。
文摘Solid polymer electrolytes(SPEs)are considered one of the most promising materials for all-solid-state lithium metal batteries(ASSLMBs)due to their facile processability.However,developing SPEs with both high ionic conductivity and interfacial stability remains a challenge.Here,a donor-acceptor(D-A)like solid plasticizer,tris(pentafluorophenyl)borane(TPFPB),containing electron-rich F atoms and electrondeficient B sites,was introduced to regulate the ion transport behavior and interfacial chemistry of polyethylene oxide(PEO)-based SPEs.Owing to the multiple ion-dipole interactions(F Li^(+)TFSI^(-)and B TFSI^(-)Li^(+))between the TPFPB molecule and Li salts,a multimodal electrolyte environment featuring more free Li^(+)and trapped TFSI^(-)anions was generated,which cooperates with the reduced crystallinity of PEO,significantly facilitating the rapid migration of Li^(+).More importantly,TPFPB tends to be preferentially reduced to form a stable inorganic-rich solid electrolyte interphase on the Li-metal anode,ensuring uniform Li plating/stripping behavior.Thus,the TPFPB-modulated SPEs system achieves a high Li^(+)conductivity of 0.74 m S cm^(-1)and effectively suppresses dendrite growth,which enables a long-cycle dendrite-free Li/Li symmetric cell for over 5000 h,and remarkable electrochemical performance has been further validated in operational ASSLMBs.The findings in this work would inspire efforts to develop highperformance SPEs for all-solid-state alkali-metal batteries.
文摘A new series of Zr1-xInxP2O7 （x=0.03, 0.06, 0.09, 0.12） samples were prepared by a solid state reaction method. XRD patterns indicated that the samples of x=0.03–0.09 exhibited a single cubic phase structure, and the doping limit of In3＋ in ZrP2O7 was x=0.09. The conduction behavior was investigated in wet hydrogen using various electrochemical methods including AC impedance spectroscopy, isotope effect, gas concentration cells at intermediate temperatures （373–573 K）. The conductivities were affected by the doping levels, and increased in the order： σ （x=0.03）〈σ （x=0.12）〈σ （x=0.06）〈σ （x=0.09）. The highest conductivity was observed for the sample Zr0.91In0.09P2O7 to be 1.59×10-2 S·cm-1 in wet hydrogen at 573 K. The isotope effect also confirmed the proton conduction of the sample under water vapor-containing atmosphere. It was found that in wet hydrogen atmosphere Zr0.91In0.09P2O7 was almost pure ionic conductor, the ionic conduction was contributed mainly to proton and partially to oxide ionic. The H2/air fuel cell using x=0.09 sample as electrolyte （thickness： 1.73 mm） generated a maximum power density of 13.5 mW·cm？2 at 423 K and 16.9 mW·cm？2 at 448 K, respectively.
文摘Carbon was used as electronic conductive agent, and metasilicic acid lithium (Li<sub>2</sub>SiO<sub>3</sub>) as ionic conductive agent, the two factors were investigated cooperatively. We evaluated their effect by using spherical spinel LiMn<sub>2</sub>O<sub>4</sub> which prepared ourselves as cathode material. Then Li<sub>2</sub>SiO<sub><sub></sub>3</sub>/carbon surface coating on LiMn<sub><sub></sub>2</sub>O<sub>4</sub> (LMO/C/LSO) which Li<sub><sub></sub>2</sub>SiO<sub><sub></sub>3</sub> inside and carbon/Li<sub><sub></sub>2</sub>SiO<sub><sub></sub>3</sub> coated LiMn<sub><sub></sub>2</sub>O<sub><sub></sub>4</sub> (LMO/LSO/C) were prepared, All of materials were characterized by X-ray diffraction (XRD) and electrochemical test;spherical LiMn<sub></sub>2O<sub></sub>4 was characterized by scanning electron microscopy (SEM);and coated materials were characterized by transmission electron microscopy (TEM). While uncoated spinel LiMn<sub><sub></sub>2</sub>O<sub><sub></sub>4</sub> maintained 72% of capacity in 60 cycles by the rate of 0.2C, and LMO/LSO/C showed the best electrochemical performance, 89% of the initial capacity remained after 75 cycles at 0.2C. Furthermore, the rate performance of LMO/LSO/C also improved obviously, about 30 mAh·g<sup>-1</sup> of capacity attained at the rate of 5C, higher than LMO/C/LSO and bare LiMn<sub><sub></sub>2</sub>O<sub><sub></sub>4</sub>.
基金supported by the National Natural Science Foundation of China(No.21501015)the Hunan Provincial Natural Science Foundation,China(No.2022JJ30604)Hunan Provincial Key Laboratory of Materials Protection for Electric Power and Transportation,China(No.2022CL01)。
文摘A composite solid electrolyte comprising a Cu-Al bimetallic metal-organic framework(CAB),lithium salt(LiTFSI)and polyethylene oxide(PEO)was fabricated through molecular grafting to enhance the ionic conductivity of the PEO-based electrolytes.Experimental and molecular dynamics simulation results indicated that the electrolyte with 10 wt.%CAB(PL-CAB-10%)exhibits high ionic conductivity(8.42×10~(-4)S/cm at 60℃),high Li+transference number(0.46),wide electrochemical window(4.91 V),good thermal stability,and outstanding mechanical properties.Furthermore,PL-CAB-10%exhibits excellent cycle stability in both Li-Li symmetric battery and Li/PL-CAB-10%/LiFePO4 asymmetric battery setups.These enhanced performances are primarily attributable to the introduction of the versatile CAB.The abundant metal sites in CAB can react with TFSI~-and PEO through Lewis acid-base interactions,promoting LiTFSI dissociation and improving ionic conductivity.Additionally,regular pores in CAB provide uniformly distributed sites for cation plating during cycling.
基金supported by the Hundred-Talent Project of Hubei Province,China(Grant No.2021HG01)the Huanggang Young Talent+2 种基金China(Grant No.HRZF2022-5)the Pearl Scholars Research Programs(Grant Nos.P20190218,P20190219)Young Scholars Start-up Research Programs of Huanggang Normal University,China(Grant Nos.Y20190218,Y20190219)。
文摘Argyrodites,Li_(6)PS_(5)X(X=Cl,Br,I),have piqued the interest of researchers by offering promising lithium ionic conductivity for their application in all-solid-state batteries(ASSBs).However,other than Li_(6)PS_(5)Cl(651Cl)and Li_(6)PS_(5)Br(651Br),Li_(6)PS_(5)I(651I)shows poor ionic conductivity(10^(-7)S cm^(-1)at 298 K).Herein,we present Al-doped 651I with I^(-)/S^(2-)site disordering to lower activation energy(Ea)and improve ionic conductivity.They formed argyrodite-type solid solutions with a composition of(Li_(6–3x)Al_(x))PS_(5)I in 0≤x≤0.10,and structural analysis revealed that Al^(3+)is located at Li sites.Also,the Al-doped samples contained anion I^(-)/S^(2-)site disorders in the crystal structures and smaller lattice parameters than the non-doped samples.Impedance spectroscopy measurements indicated that Al-doping reduced the ionic diffusion barrier,Ea,and increased the ionic conductivity to 10^(-5)S cm^(-1);the(Li5.7Al0.1)PS5I had the highest ionic conductivity in the studied system,at 2.6×10^(-5)S cm^(-1).In a lab-scale ASSB,with(Li_(5.7)Al_(0.1))PS_(5)I functioned as a solid electrolyte,demonstrating the characteristics of a pure ionic conductor with negligible electronic conductivity.The evaluated ionic conduction is due to decreased Li+content and I^(-)/S^(2-)disorder formation.Li-site cation doping enables an in-depth understanding of the structure and provides an additional approach to designing betterperforming SEs in the argyrodite system.
