In the current aera of rapid development in the field of electric vehicles and electrochemical energy storage,solid-state battery technology is attracting much research and attention.Solid-state electrolytes,as the ke...In the current aera of rapid development in the field of electric vehicles and electrochemical energy storage,solid-state battery technology is attracting much research and attention.Solid-state electrolytes,as the key component of next-generation battery technology,are favored for their high safety,high energy density,and long life.However,finding high-performance solid-state electrolytes is the primary challenge for solid-state battery applications.Focusing on inorganic solid-state electrolytes,this work highlights the need for ideal solid-state electrolytes to have low electronic conductivity,good thermal stability,and structural and phase stability.Traditional experimental and theoretical computational methods suffer from inefficiency,thus machine learning methods become a novel path to intelligently predict material properties by analyzing a large number of inorganic structural properties and characteristics.Through the gradient descent-based XGBoost algorithm,we successfully predicted the energy band structure and stability of the materials,and screened out only 194 ideal solid-state electrolyte structures from more than 6000 structures that satisfy the requirements of low electronic conductivity and stability simultaneously,which greatly accelerated the development of solid-state batteries.展开更多
Li_(1.5)Ga_(0.5)Ti_(1.5)PO_(4))_(3)(LGTP)is recognized as a promising solid electrolyte material for lithium ions.In this work,LGTP solid electrolyte materials were prepared under different process conditions to explo...Li_(1.5)Ga_(0.5)Ti_(1.5)PO_(4))_(3)(LGTP)is recognized as a promising solid electrolyte material for lithium ions.In this work,LGTP solid electrolyte materials were prepared under different process conditions to explore the effects of sintering temperature and holding time on relative density,phase composition,microstructure,bulk conductivity,and total conductivity.In the impedance test under frequency of 1-10^(6) Hz,the bulk conductivity of the samples increased with increasing sintering temperature,and the total conductivity first increased and then decreased.SEM results showed that the average grain size in the ceramics was controlled by the sintering temperature,which increased from(0.54±0.01)μm to(1.21±0.01)μm when the temperature changed from 750 to 950°C.The relative density of the ceramics increased and then decreased with increasing temperature as the porosity increased.The holding time had little effect on the grain size growth or sample density,but an extended holding time resulted in crack generation that served to reduce the conductivity of the solid electrolyte.展开更多
Ce0.8Sm0.2O1.9-δ-La0.9Sr0.1Ga0.8Mg0.2O3-δ(SDC-LSGM)is prepared by the glycine-nitrate process(GNP).SDC-LSGM composite electrolyte samples with different weight ratios are prepared by the co-combustion method so ...Ce0.8Sm0.2O1.9-δ-La0.9Sr0.1Ga0.8Mg0.2O3-δ(SDC-LSGM)is prepared by the glycine-nitrate process(GNP).SDC-LSGM composite electrolyte samples with different weight ratios are prepared by the co-combustion method so as to obtain homogeneous nano-sized precursor powders. The X-ray diffraction (XRD) and the scan electron microscope (SEM) are used to investigate the phases and microstructures. The measurements and analyses of oxygen ionic conductivity of SDC-LSGM are carried out through the four-terminal direct current (DC) method and the electrochemical impendence spectroscopy, respectively. The optimum weight ratio of SDC-LSGM is 8∶2, of which the ionic conductivity is 0.113 S/cm at 800℃ and the conductivity activation energy is 0.620 eV. The impendence spectra shows that the grain boundary resistance becomes the main barrier for the ionic conductivity of electrolyte at lower temperatures. The appropriate introduction of LSGM to the electrolyte SDC can not only decrease the electronic conductivity but also improve the conditions of the grain and grain boundary, which is advantageous to cause an increase in oxygen ionic conductivity.展开更多
Through orthogonal experiment, a new type of LiClO4-LiNO3-LiBr eutectic salt with optimum mole ratio of n(LiClO4)∶n(LiNO3)∶n(LiBr)=1.6∶3.8∶1.0 was prepared. The poly(lithium acrylate-acrylonitrile)/LiClO4-...Through orthogonal experiment, a new type of LiClO4-LiNO3-LiBr eutectic salt with optimum mole ratio of n(LiClO4)∶n(LiNO3)∶n(LiBr)=1.6∶3.8∶1.0 was prepared. The poly(lithium acrylate-acrylonitrile)/LiClO4-LiNO3-LiBr solid polymer electrolytes were prepared with poly(lithium acrylate-acrylonitrile) and (LiClO4-LiNO3-LiBr) eutectic salts. The effect of LiClO4-LiNO3-LiBr eutectic salts content on the conductivity of solid polymer electrolytes was studied by alternating current impedance method, and the structures of eutectic salts and solid polymer electrolytes were characterized by differential thermal analysis, infrared spectroscopy and X-ray diffractometry. The results show that the room temperature conductivity of LiClO4-LiNO3-LiBr eutectic salts reaches (3.11×10-4 S·cm-1.) The poly(lithium acrylate-acrylonitrile)/LiClO4-LiNO3-LiBr solid polymer electrolytes possess the highest room temperature conductivity at 70% LiClO4-LiNO3-LiBr eutectic salts content, and exhibit lower glass transition temperature of 75 ℃ compared with that of poly(lithium acrylate-acrylonitrile) of 105 ℃. A complex may be formed in the solid polymer electrolytes from the differential thermal analysis and infrared spectroscopy analysis. X-ray diffraction results show that the poly(lithium acrylate-acrylonitrile) can suppress the crystallization of eutectic salts in this system.展开更多
Ionic conductivity is one of the crucial parameters for inorganic solid-state electrolytes.To explore the relationship between porosity and ionic conductivity,a series of Li_(6.4)Ga_(0.2)La_(3)Zr_(2)O_(12) garnet type...Ionic conductivity is one of the crucial parameters for inorganic solid-state electrolytes.To explore the relationship between porosity and ionic conductivity,a series of Li_(6.4)Ga_(0.2)La_(3)Zr_(2)O_(12) garnet type solid-state electrolytes with different porosities were prepared via solid-state reaction.Based on the quantified data,an empirical decay relationship was summarized and discussed by means of mathematical model and dimensional analysis method.It suggests that open porosity causes ionic conductivity to decrease exponentially.The pre-exponential factor obeys the Arrhenius Law quite well with the activation energy of 0.23 eV,and the decay constant is averaged to be 2.62%.While the closed porosity causes ionic conductivity to decrease linearly.The slope and intercept of this linear pattern also obey the Arrhenius Law and the activation energies are 0.24 and 0.27 eV,respectively.Moreover,the total porosity is linearly dependent on the open porosity,and different sintering conditions will lead to different linear patterns with different slopes and intercepts.展开更多
In this work the diffusion coefficients of Na+, K+, Ca2+, NO3- and Cl- ions were estimated in terms of measuring apparent direct current (DC) conductivities of latosol, red soil and yellow-brown earth containing, resp...In this work the diffusion coefficients of Na+, K+, Ca2+, NO3- and Cl- ions were estimated in terms of measuring apparent direct current (DC) conductivities of latosol, red soil and yellow-brown earth containing, respectively, NaNO3, KCI, and CaCl2 of different concentrations (0.005, 0.05, 0.10, and 0.15 mol / L) in the case of moisture contents ranging from wet to water saturation. The results showed that when bulk density, moisture content, and electrolyte concentration were constant, the diffusion coefficients of cations were in the order Na+> K+> Ca2+ except for Na+ and K+ in latosol, while the order for anions was NO3- > Cl-. The diffusion coefficients (Di) of cations and anions were linearly proportional to volumetric moisture content (θ) as electrolyte concentration and bulk density were unchanged. When moisture content and bulk density were constant, the diffusion coefficients of cations decreased, to varying extents, with the increase of electrolyte concentration, and the decrement in different soils followed the order yellow-brown earth > red soil > latosol, but the decrement order of different cations was Na+> K+ > Ca2+.展开更多
Cel-xSmxO2 (x=0, 0.1, 0.2 and 0.3) and Sm-doped ceria+(2%-8%)Al2O3 were synthesized through sol-gel process followed by low temperature combustion. The synthesis, structure, densification, conductivity and therma...Cel-xSmxO2 (x=0, 0.1, 0.2 and 0.3) and Sm-doped ceria+(2%-8%)Al2O3 were synthesized through sol-gel process followed by low temperature combustion. The synthesis, structure, densification, conductivity and thermal expansion were studied, and the structure and phase were confirmed by XRD. Dense ceramics were obtained through sintering the pellets at 1300 ℃. 2% and 4% Al2O3 were added into Ce0.8Sm0.2O2 to promote the densification at 1250 ℃. The surface morphology of the sintered pellets was analyzed using SEM. A two-probe AC impedance spectroscopy was used to study the total ionic conductivity.展开更多
The conductivities of LiBr, LiCl, and LiNO 3 in methanol, ethanol, 1-propanol, and 2-propanol (with electrolyte concentrations <0.08 mol·L-1 ) were determined at 298.15 K, 313.15 K, and 323.15 K at atmosphere ...The conductivities of LiBr, LiCl, and LiNO 3 in methanol, ethanol, 1-propanol, and 2-propanol (with electrolyte concentrations <0.08 mol·L-1 ) were determined at 298.15 K, 313.15 K, and 323.15 K at atmosphere pressure separately by using a conductivity meter. The conductivity data were correlated with Foss-Chen-Justice (FCJ) equation and the limiting molar conductivities were obtained. The mean ionic activity coefficients of the salts in the organic solvents were calculated according to the Debye-Hückel limiting law and Onsager-Falkenhangen equations. The calculated results were compared with those activity coefficients in literature.展开更多
This work provides a method to explore the transport property of the electrolyte aqueous solutions with one or two ionic liquids, especially focus on their electrical conductivity. The conductivities were measured for...This work provides a method to explore the transport property of the electrolyte aqueous solutions with one or two ionic liquids, especially focus on their electrical conductivity. The conductivities were measured for the ternary systems Na Cl–[C6mim][Cl](1-hexyl-3-methylimidazolium chloride)–H2O, [C6mim][BF4]–[C6mim][Cl]–H2O,Na NO3–[C6mim][BF4](1-hexyl-3-methylimidazolium tetrafluoroborate)–H2O, and [C4mim][BF4](1-butyl-3-methylimidazolium tetrafluoroborate)–[C6mim][BF4]–H2O, and their binary subsystems NaN O3–H2O, NaC l–H2O,[C6mim][BF4]–H2O, [C6mim][Cl]–H2O, and [C4mim][BF4]–H2O, respectively. The conductivities of the ternary systems were also determined using generalized Young's rule and semi-ideal solution theory in terms of the data of their binary solutions. The comparison showed that the two simple equations provide good predictions for conductivity of mixed electrolyte solutions and the mixed ionic liquid solutions based on the conductivity of their binary subsystems.展开更多
A series of Cr^(3+)-substituted Na_(1+x)Ti_(2−x)Cr_(x)P_(3)O_(12)(x=0.1,0.2,0.3,0.4,0.5,molar fraction)solid electrolytes were prepared by the solid-phase reaction method.The effects of Cr^(3+)ions on the phase compos...A series of Cr^(3+)-substituted Na_(1+x)Ti_(2−x)Cr_(x)P_(3)O_(12)(x=0.1,0.2,0.3,0.4,0.5,molar fraction)solid electrolytes were prepared by the solid-phase reaction method.The effects of Cr^(3+)ions on the phase composition,microstructure,and electrochemical ion conductivity of Na-based conductors were studied using X-ray powder diffraction,field emission scanning electron microscopy,and AC impedance measurement.The results show that the main crystal phase of NaTi_(2)(PO_(4))_(3) is formed in the solid electrolytes.The substitution of Ti4+sites by 15 at.%Cr^(3+)ions contributes to the enhancement of electrical conductivity,which is attributed to the combined effect of suppressing the formation of impurity phases,broadening ion channels,and improving the bonding degree of grains.Na_(1.3)Ti_(1.7)Cr_(0.3)P_(3)O_(12) electrolyte can obtain the best ionic conductivity of 6.13×10^(−6)S/cm at room temperature,which is 8 times that of the undoped NaTi_(2)(PO_(4))_(3) electrolyte.展开更多
The development of high-performance solid polymer electrolytes is crucial for producing all-solid-state lithium metal batteries with high safety and high energy density.However,the low ionic conductivity of solid poly...The development of high-performance solid polymer electrolytes is crucial for producing all-solid-state lithium metal batteries with high safety and high energy density.However,the low ionic conductivity of solid polymer electrolytes and their unstable electrolyte/electrode interfaces have hindered their widespread utilization.To address these critical challenges,a strong Lewis acid(aluminum fluoride(AIF_(3)))with dual functionality is introduced into poly(ethylene oxide)(PEO)-based polymer electrolyte.The AlF;facilitates the dissociation of lithium salt,increasing the iontransfer efficiency due to the Lewis acid-base interaction;further the in-situ formation of lithium fluoride-rich interfacial layer is promoted,which suppresses the uneven lithium deposition and continuous undesired reactions between the Li metal and PEO matrix.Benefiting from our rational design,the symmetric Li/Li battery with the modified electrolyte exhibits much longer cycling stability(over 3600 h)than that of the pure PEO/lithium bis(trifluoromethanesulfonyl)imide(LiTFSI)electrolyte(550 h).Furthermore,the all-solid-state LiFeP04 full cell with the composite electrolyte displays a much higher Coulombic efficiency(98.4%after 150 cycles)than that of the electrolyte without the AlF;additive(63.3%after 150 cycles)at a large voltage window of 2.4-4.2 V,demonstrating the improved interface and cycling stability of solid polymer lithium metal batteries.展开更多
As a critical component of alkaline fuel cells, anion exchange membranes determine the energy efficiency, output power density and the long term stability. Recently, the anion exchange membranes with gemini-cation sid...As a critical component of alkaline fuel cells, anion exchange membranes determine the energy efficiency, output power density and the long term stability. Recently, the anion exchange membranes with gemini-cation side chains exhibit superior ion conductivity due to their good nanophase separation. However, the costly and complicated synthesis limits their scaling up and commercialization. To address this problem, a convenient synthetic procedure under mild conditions is well developed. A tertiary amine precursor is introduced onto the polymer by the nucleophilic substitution reaction to avoid the conventional chloro/bromo-methylation. Followed by a simple Menshutkin reaction with 6- bromo-N,N,N-trimethylhexan-1-am inium bromide, the polym er electrolytes are obtained in a high yield. The resulting anion exchange membranes with high conductivity, good fuel cell performance and restricted swelling suggest the potential for the application in fuel cell devices.展开更多
As one of the most promising next-generation energy storage devices,the lithium-metal battery has been extensively investigated.However,safety issues and undesired lithium dendrite growth hinder its development.The ap...As one of the most promising next-generation energy storage devices,the lithium-metal battery has been extensively investigated.However,safety issues and undesired lithium dendrite growth hinder its development.The application of solid-state electrolytes has attracted increasing attention as they can solve safety issues and show great potential to inhibit the growth of lithium dendrites.Polyethylene oxide(PEO)-based electrolytes are very promising due to their enhanced safety and excellent flexibility.However,they suffer from low ionic conductivity at room temperature and cannot effectively inhibit lithium dendrites at high temperatures due to the intrinsic semicrystalline properties and poor mechanical strength.In this work,a novel coral-like Li_(6.25)Al_(0.25)La_(3)Zr_(2)O_(12)(C-LALZO)is synthesized to serve as an active ceramic filler in PEO.The PEO with LALZO coral(PLC)exhibits increased ionic conductivity and mechanical strength,which leads to uniform deposition/stripping of lithium metal.The Li symmetric cells with PLC do not cause a short circuit after cycling for 1500 h at 60℃.The assembled LiFePO_(4)/PLC/Li batteries display excellent cycling stability at both 60 and 50℃.This work reveals that the electrochemical properties of the composite electrolyte can be effectively improved by tuning the microstructure of the filler,such as the C-LALZO architecture.展开更多
With the proliferation of energy storage and power applications, electric vehicles particularly, solid-state batteries are considered as one of the most promising strategies to address the ever-increasing safety conce...With the proliferation of energy storage and power applications, electric vehicles particularly, solid-state batteries are considered as one of the most promising strategies to address the ever-increasing safety concern and high energy demand of power devices. Here, we demonstrate the Al4B2O9 nanorods-modified poly(ethylene oxide) (PEO)-based solid polymer electrolyte (ASPE) with high ionic conductivity, wide electrochemical window, decent mechanical property and nonflammable performance. Specifically, because of the longer-range ordered Li+ transfer channels conducted by the interaction between Al4B2O9 nanorods and PEO, the optimal ASPE (ASPE-1) shows excellent ionic conductivity of 4.35×10^−1 and 3.1×10^−1 S cm^−1 at 30 and 60℃, respectively. It also has good electrochemical stability at 60℃ with a decomposition voltage of 5.1 V. Besides, the assembled LiFePO4//Li cells show good cycling performance, delivering 155 mA h g−1 after 300 cycles at 1 C under 60℃, and present excellent low temperature adaptability, retaining over 125 mA h g^−1 after 90 cycles at 0.2 C under 30℃. These results verify that the addition of Al4B2O9 nanorods can effectively promote the integrated performance of solid polymer electrolyte.展开更多
Hydrogel systems promote the development of flexible energy storage devices because of their inherent mechanical elasticity and ionic conductivity.However,achieving stable energy storage capacity under violent mechani...Hydrogel systems promote the development of flexible energy storage devices because of their inherent mechanical elasticity and ionic conductivity.However,achieving stable energy storage capacity under violent mechanical deformation is still a challenge for hydrogel devices.In this work,an all-in-one integrated supercapacitor(AISC)was assembled using in situ deposited polyaniline/graphene oxide nanocomposites for both sides of the incorporated ionic hydrogel electrolyte.The assembly process of the AISC was greatly simplified,and the displacement and separation of the multilayer structured hydrogel complex were avoided during mechanical deformation.The hydrogel electrolyte with ionic additives exhibited strong adhesion and flexibility,and high ionic conductivity,thereby ensuring the excellent specific capacitance and rate performance of the AISC.The specific capacitances of the AISC were 222.8 mF cm^(−2) at the current density of 0.2 mA cm^(−2) and 151.7 mF cm^(−2) at 3.2 mA cm^(−2).The capacitance retention rate was 68.1%.The energy density of a piece of the device reached 44.6μW h cm^(−2) at a power density of 120.0μW cm^(−2).Moreover,reliable and reproducible energy storage was acquired under bending,compression,and stretching deformations.The AISC was also easily assembled in series to power a light-emitting diode(LED)light.This work provides a facile approach to the construction of flexible supercapacitors for the development of energy storage devices in flexible electronics.展开更多
基金supported by the National Natural Science Foundation of China(No.21421063,No.21473166,No.21573211,No.21633007,No.21790350,No.21803067,No.91950207)the Chinese Academy of Sciences(QYZDB-SSW-SLH018)+3 种基金the Anhui Initiative in Quantum Information Technologies(AHY090200)the USTC-NSRL Joint Funds(UN2018LHJJ)the Anhui Provincial Natural Science Foundation(2108085QB63)Numerical Theoretical simulations were done in the Supercomputing Center of USTC.
文摘In the current aera of rapid development in the field of electric vehicles and electrochemical energy storage,solid-state battery technology is attracting much research and attention.Solid-state electrolytes,as the key component of next-generation battery technology,are favored for their high safety,high energy density,and long life.However,finding high-performance solid-state electrolytes is the primary challenge for solid-state battery applications.Focusing on inorganic solid-state electrolytes,this work highlights the need for ideal solid-state electrolytes to have low electronic conductivity,good thermal stability,and structural and phase stability.Traditional experimental and theoretical computational methods suffer from inefficiency,thus machine learning methods become a novel path to intelligently predict material properties by analyzing a large number of inorganic structural properties and characteristics.Through the gradient descent-based XGBoost algorithm,we successfully predicted the energy band structure and stability of the materials,and screened out only 194 ideal solid-state electrolyte structures from more than 6000 structures that satisfy the requirements of low electronic conductivity and stability simultaneously,which greatly accelerated the development of solid-state batteries.
基金funded by the National Natural Science Foundation of China(Nos.51672310,51272288,51972344)。
文摘Li_(1.5)Ga_(0.5)Ti_(1.5)PO_(4))_(3)(LGTP)is recognized as a promising solid electrolyte material for lithium ions.In this work,LGTP solid electrolyte materials were prepared under different process conditions to explore the effects of sintering temperature and holding time on relative density,phase composition,microstructure,bulk conductivity,and total conductivity.In the impedance test under frequency of 1-10^(6) Hz,the bulk conductivity of the samples increased with increasing sintering temperature,and the total conductivity first increased and then decreased.SEM results showed that the average grain size in the ceramics was controlled by the sintering temperature,which increased from(0.54±0.01)μm to(1.21±0.01)μm when the temperature changed from 750 to 950°C.The relative density of the ceramics increased and then decreased with increasing temperature as the porosity increased.The holding time had little effect on the grain size growth or sample density,but an extended holding time resulted in crack generation that served to reduce the conductivity of the solid electrolyte.
基金The National Basic Research Program of China (973 Program) (No.2007CB936300)the Natural Science Foundation of Jiangsu Province (No.BK2009293)
文摘Ce0.8Sm0.2O1.9-δ-La0.9Sr0.1Ga0.8Mg0.2O3-δ(SDC-LSGM)is prepared by the glycine-nitrate process(GNP).SDC-LSGM composite electrolyte samples with different weight ratios are prepared by the co-combustion method so as to obtain homogeneous nano-sized precursor powders. The X-ray diffraction (XRD) and the scan electron microscope (SEM) are used to investigate the phases and microstructures. The measurements and analyses of oxygen ionic conductivity of SDC-LSGM are carried out through the four-terminal direct current (DC) method and the electrochemical impendence spectroscopy, respectively. The optimum weight ratio of SDC-LSGM is 8∶2, of which the ionic conductivity is 0.113 S/cm at 800℃ and the conductivity activation energy is 0.620 eV. The impendence spectra shows that the grain boundary resistance becomes the main barrier for the ionic conductivity of electrolyte at lower temperatures. The appropriate introduction of LSGM to the electrolyte SDC can not only decrease the electronic conductivity but also improve the conditions of the grain and grain boundary, which is advantageous to cause an increase in oxygen ionic conductivity.
文摘Through orthogonal experiment, a new type of LiClO4-LiNO3-LiBr eutectic salt with optimum mole ratio of n(LiClO4)∶n(LiNO3)∶n(LiBr)=1.6∶3.8∶1.0 was prepared. The poly(lithium acrylate-acrylonitrile)/LiClO4-LiNO3-LiBr solid polymer electrolytes were prepared with poly(lithium acrylate-acrylonitrile) and (LiClO4-LiNO3-LiBr) eutectic salts. The effect of LiClO4-LiNO3-LiBr eutectic salts content on the conductivity of solid polymer electrolytes was studied by alternating current impedance method, and the structures of eutectic salts and solid polymer electrolytes were characterized by differential thermal analysis, infrared spectroscopy and X-ray diffractometry. The results show that the room temperature conductivity of LiClO4-LiNO3-LiBr eutectic salts reaches (3.11×10-4 S·cm-1.) The poly(lithium acrylate-acrylonitrile)/LiClO4-LiNO3-LiBr solid polymer electrolytes possess the highest room temperature conductivity at 70% LiClO4-LiNO3-LiBr eutectic salts content, and exhibit lower glass transition temperature of 75 ℃ compared with that of poly(lithium acrylate-acrylonitrile) of 105 ℃. A complex may be formed in the solid polymer electrolytes from the differential thermal analysis and infrared spectroscopy analysis. X-ray diffraction results show that the poly(lithium acrylate-acrylonitrile) can suppress the crystallization of eutectic salts in this system.
基金supported by the Innovation and Entrepreneurship Project of Hunan Province,China(No.2019GK5053)Program of Huxiang Young Talents,China(No.2019RS2002)+1 种基金the Natural Science Foundation for Distinguished Young Scholars of Hunan Province,China(No.2020JJ2047)the Fundamental Research Funds for the Central Universities of Central South University,China。
文摘Ionic conductivity is one of the crucial parameters for inorganic solid-state electrolytes.To explore the relationship between porosity and ionic conductivity,a series of Li_(6.4)Ga_(0.2)La_(3)Zr_(2)O_(12) garnet type solid-state electrolytes with different porosities were prepared via solid-state reaction.Based on the quantified data,an empirical decay relationship was summarized and discussed by means of mathematical model and dimensional analysis method.It suggests that open porosity causes ionic conductivity to decrease exponentially.The pre-exponential factor obeys the Arrhenius Law quite well with the activation energy of 0.23 eV,and the decay constant is averaged to be 2.62%.While the closed porosity causes ionic conductivity to decrease linearly.The slope and intercept of this linear pattern also obey the Arrhenius Law and the activation energies are 0.24 and 0.27 eV,respectively.Moreover,the total porosity is linearly dependent on the open porosity,and different sintering conditions will lead to different linear patterns with different slopes and intercepts.
文摘In this work the diffusion coefficients of Na+, K+, Ca2+, NO3- and Cl- ions were estimated in terms of measuring apparent direct current (DC) conductivities of latosol, red soil and yellow-brown earth containing, respectively, NaNO3, KCI, and CaCl2 of different concentrations (0.005, 0.05, 0.10, and 0.15 mol / L) in the case of moisture contents ranging from wet to water saturation. The results showed that when bulk density, moisture content, and electrolyte concentration were constant, the diffusion coefficients of cations were in the order Na+> K+> Ca2+ except for Na+ and K+ in latosol, while the order for anions was NO3- > Cl-. The diffusion coefficients (Di) of cations and anions were linearly proportional to volumetric moisture content (θ) as electrolyte concentration and bulk density were unchanged. When moisture content and bulk density were constant, the diffusion coefficients of cations decreased, to varying extents, with the increase of electrolyte concentration, and the decrement in different soils followed the order yellow-brown earth > red soil > latosol, but the decrement order of different cations was Na+> K+ > Ca2+.
文摘Cel-xSmxO2 (x=0, 0.1, 0.2 and 0.3) and Sm-doped ceria+(2%-8%)Al2O3 were synthesized through sol-gel process followed by low temperature combustion. The synthesis, structure, densification, conductivity and thermal expansion were studied, and the structure and phase were confirmed by XRD. Dense ceramics were obtained through sintering the pellets at 1300 ℃. 2% and 4% Al2O3 were added into Ce0.8Sm0.2O2 to promote the densification at 1250 ℃. The surface morphology of the sintered pellets was analyzed using SEM. A two-probe AC impedance spectroscopy was used to study the total ionic conductivity.
文摘The conductivities of LiBr, LiCl, and LiNO 3 in methanol, ethanol, 1-propanol, and 2-propanol (with electrolyte concentrations <0.08 mol·L-1 ) were determined at 298.15 K, 313.15 K, and 323.15 K at atmosphere pressure separately by using a conductivity meter. The conductivity data were correlated with Foss-Chen-Justice (FCJ) equation and the limiting molar conductivities were obtained. The mean ionic activity coefficients of the salts in the organic solvents were calculated according to the Debye-Hückel limiting law and Onsager-Falkenhangen equations. The calculated results were compared with those activity coefficients in literature.
基金Supported by the National Natural Science Foundation of China(51066004)the Scientific Research Project of Higher Education Institutions of Inner Mongolia(NJZY14172)the Innovation Fund of Inner Mongolia Science and Technology(2011NCL060)
文摘This work provides a method to explore the transport property of the electrolyte aqueous solutions with one or two ionic liquids, especially focus on their electrical conductivity. The conductivities were measured for the ternary systems Na Cl–[C6mim][Cl](1-hexyl-3-methylimidazolium chloride)–H2O, [C6mim][BF4]–[C6mim][Cl]–H2O,Na NO3–[C6mim][BF4](1-hexyl-3-methylimidazolium tetrafluoroborate)–H2O, and [C4mim][BF4](1-butyl-3-methylimidazolium tetrafluoroborate)–[C6mim][BF4]–H2O, and their binary subsystems NaN O3–H2O, NaC l–H2O,[C6mim][BF4]–H2O, [C6mim][Cl]–H2O, and [C4mim][BF4]–H2O, respectively. The conductivities of the ternary systems were also determined using generalized Young's rule and semi-ideal solution theory in terms of the data of their binary solutions. The comparison showed that the two simple equations provide good predictions for conductivity of mixed electrolyte solutions and the mixed ionic liquid solutions based on the conductivity of their binary subsystems.
基金supported by the National Natural Science Foundation of China(No.51972344)the Natural Science Foundation of Hunan Province,China(No.2018JJ3646).
文摘A series of Cr^(3+)-substituted Na_(1+x)Ti_(2−x)Cr_(x)P_(3)O_(12)(x=0.1,0.2,0.3,0.4,0.5,molar fraction)solid electrolytes were prepared by the solid-phase reaction method.The effects of Cr^(3+)ions on the phase composition,microstructure,and electrochemical ion conductivity of Na-based conductors were studied using X-ray powder diffraction,field emission scanning electron microscopy,and AC impedance measurement.The results show that the main crystal phase of NaTi_(2)(PO_(4))_(3) is formed in the solid electrolytes.The substitution of Ti4+sites by 15 at.%Cr^(3+)ions contributes to the enhancement of electrical conductivity,which is attributed to the combined effect of suppressing the formation of impurity phases,broadening ion channels,and improving the bonding degree of grains.Na_(1.3)Ti_(1.7)Cr_(0.3)P_(3)O_(12) electrolyte can obtain the best ionic conductivity of 6.13×10^(−6)S/cm at room temperature,which is 8 times that of the undoped NaTi_(2)(PO_(4))_(3) electrolyte.
基金supported by the research fund of Shenzhen Science and Technology Innovation Committee(SGDX20201103093600003)the University of Macao,Macao SAR(MYRG2018-00079-IAPME and MYRG2019-00115-IAPME)+2 种基金the Science and Technology Development Fund,Macao SAR(0092/2019/A2,0059/2018/A2,and 009/2017/AMJ)the National Thousand Young Talent planthe National Natural Science Foundation of China(21875040&21905051)。
文摘The development of high-performance solid polymer electrolytes is crucial for producing all-solid-state lithium metal batteries with high safety and high energy density.However,the low ionic conductivity of solid polymer electrolytes and their unstable electrolyte/electrode interfaces have hindered their widespread utilization.To address these critical challenges,a strong Lewis acid(aluminum fluoride(AIF_(3)))with dual functionality is introduced into poly(ethylene oxide)(PEO)-based polymer electrolyte.The AlF;facilitates the dissociation of lithium salt,increasing the iontransfer efficiency due to the Lewis acid-base interaction;further the in-situ formation of lithium fluoride-rich interfacial layer is promoted,which suppresses the uneven lithium deposition and continuous undesired reactions between the Li metal and PEO matrix.Benefiting from our rational design,the symmetric Li/Li battery with the modified electrolyte exhibits much longer cycling stability(over 3600 h)than that of the pure PEO/lithium bis(trifluoromethanesulfonyl)imide(LiTFSI)electrolyte(550 h).Furthermore,the all-solid-state LiFeP04 full cell with the composite electrolyte displays a much higher Coulombic efficiency(98.4%after 150 cycles)than that of the electrolyte without the AlF;additive(63.3%after 150 cycles)at a large voltage window of 2.4-4.2 V,demonstrating the improved interface and cycling stability of solid polymer lithium metal batteries.
基金supported by the National Natural Science Foundation of China (21720102003, 91534203 and 21522607)the Fundamental Research Funds for the Central Universities (WK2060190072 and WK2340000066)
文摘As a critical component of alkaline fuel cells, anion exchange membranes determine the energy efficiency, output power density and the long term stability. Recently, the anion exchange membranes with gemini-cation side chains exhibit superior ion conductivity due to their good nanophase separation. However, the costly and complicated synthesis limits their scaling up and commercialization. To address this problem, a convenient synthetic procedure under mild conditions is well developed. A tertiary amine precursor is introduced onto the polymer by the nucleophilic substitution reaction to avoid the conventional chloro/bromo-methylation. Followed by a simple Menshutkin reaction with 6- bromo-N,N,N-trimethylhexan-1-am inium bromide, the polym er electrolytes are obtained in a high yield. The resulting anion exchange membranes with high conductivity, good fuel cell performance and restricted swelling suggest the potential for the application in fuel cell devices.
基金supported by the School Research Startup Expenses of Harbin Institute of Technology(Shenzhen)(DD29100027)the National Natural Science Foundation of China(52002094)+2 种基金China Postdoctoral Science Foundation(2019M661276)Guangdong Basic and AppliedBasic Research Foundation(2019A1515110756)the High-level Talents Discipline Construction Fund of Shandong University(31370089963078)。
文摘As one of the most promising next-generation energy storage devices,the lithium-metal battery has been extensively investigated.However,safety issues and undesired lithium dendrite growth hinder its development.The application of solid-state electrolytes has attracted increasing attention as they can solve safety issues and show great potential to inhibit the growth of lithium dendrites.Polyethylene oxide(PEO)-based electrolytes are very promising due to their enhanced safety and excellent flexibility.However,they suffer from low ionic conductivity at room temperature and cannot effectively inhibit lithium dendrites at high temperatures due to the intrinsic semicrystalline properties and poor mechanical strength.In this work,a novel coral-like Li_(6.25)Al_(0.25)La_(3)Zr_(2)O_(12)(C-LALZO)is synthesized to serve as an active ceramic filler in PEO.The PEO with LALZO coral(PLC)exhibits increased ionic conductivity and mechanical strength,which leads to uniform deposition/stripping of lithium metal.The Li symmetric cells with PLC do not cause a short circuit after cycling for 1500 h at 60℃.The assembled LiFePO_(4)/PLC/Li batteries display excellent cycling stability at both 60 and 50℃.This work reveals that the electrochemical properties of the composite electrolyte can be effectively improved by tuning the microstructure of the filler,such as the C-LALZO architecture.
基金financially supported by the National Natural Science Foundation of China (51804344)the Huxiang Youth Talent Support Program (2019RS2002)+2 种基金the Innovation and Entrepreneurship Project of Hunan Province,China (2018GK5026)the Innovation-Driven Project of Central South University (2020CX027)Guangdong Yang Fan Plan for Postdoctor Program
文摘With the proliferation of energy storage and power applications, electric vehicles particularly, solid-state batteries are considered as one of the most promising strategies to address the ever-increasing safety concern and high energy demand of power devices. Here, we demonstrate the Al4B2O9 nanorods-modified poly(ethylene oxide) (PEO)-based solid polymer electrolyte (ASPE) with high ionic conductivity, wide electrochemical window, decent mechanical property and nonflammable performance. Specifically, because of the longer-range ordered Li+ transfer channels conducted by the interaction between Al4B2O9 nanorods and PEO, the optimal ASPE (ASPE-1) shows excellent ionic conductivity of 4.35×10^−1 and 3.1×10^−1 S cm^−1 at 30 and 60℃, respectively. It also has good electrochemical stability at 60℃ with a decomposition voltage of 5.1 V. Besides, the assembled LiFePO4//Li cells show good cycling performance, delivering 155 mA h g−1 after 300 cycles at 1 C under 60℃, and present excellent low temperature adaptability, retaining over 125 mA h g^−1 after 90 cycles at 0.2 C under 30℃. These results verify that the addition of Al4B2O9 nanorods can effectively promote the integrated performance of solid polymer electrolyte.
基金supported by the Natural Science Foundation of Shandong Province(ZR2020KB018)the Natural Science Foundation of Jiangsu Province(BK20190688)+2 种基金the Six Talent Peak Innovation Team in Jiangsu Province(TD-SWYY-009)the"Taishan Scholars"Construction Special Fund of Shandong Provincethe Industrial Alliance Fund of Shandong Provincial Key Laboratory(SDKL2016038)。
文摘Hydrogel systems promote the development of flexible energy storage devices because of their inherent mechanical elasticity and ionic conductivity.However,achieving stable energy storage capacity under violent mechanical deformation is still a challenge for hydrogel devices.In this work,an all-in-one integrated supercapacitor(AISC)was assembled using in situ deposited polyaniline/graphene oxide nanocomposites for both sides of the incorporated ionic hydrogel electrolyte.The assembly process of the AISC was greatly simplified,and the displacement and separation of the multilayer structured hydrogel complex were avoided during mechanical deformation.The hydrogel electrolyte with ionic additives exhibited strong adhesion and flexibility,and high ionic conductivity,thereby ensuring the excellent specific capacitance and rate performance of the AISC.The specific capacitances of the AISC were 222.8 mF cm^(−2) at the current density of 0.2 mA cm^(−2) and 151.7 mF cm^(−2) at 3.2 mA cm^(−2).The capacitance retention rate was 68.1%.The energy density of a piece of the device reached 44.6μW h cm^(−2) at a power density of 120.0μW cm^(−2).Moreover,reliable and reproducible energy storage was acquired under bending,compression,and stretching deformations.The AISC was also easily assembled in series to power a light-emitting diode(LED)light.This work provides a facile approach to the construction of flexible supercapacitors for the development of energy storage devices in flexible electronics.