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
Composite polymer electrolytes based on polyethylene oxide(PEO) were prepared by using LiClO4 as doping salt and silane-modified SiO2 as filler. SiO2 was formed in-situ in (PEO)8LiClO4 matrix by the hydrolysis and con...Composite polymer electrolytes based on polyethylene oxide(PEO) were prepared by using LiClO4 as doping salt and silane-modified SiO2 as filler. SiO2 was formed in-situ in (PEO)8LiClO4 matrix by the hydrolysis and condensation reaction of Si(OC4H9)4. The crystallinity,morphology and ionic conductivity of composite polymer electrolyte films were examined by differential scanning calorimetry,scanning electron microscopy,atom force microscopy and alternating current impedance spectroscopy,respectively. Compared with the crystallinity of the unmodified SiO2 as inert filler,that of composite polymer electrolytes is decreased. The results show that silane-modified SiO2 particles are uniformly dispersed in (PEO)8LiClO4 composite polymer electrolyte film and the addition of silane-modified SiO2 increases the ionic conductivity of the (PEO)8LiClO4 more noticeably. When the mass fraction of SiO2 is about 10%,the conductivity of (PEO)8LiClO4-modified SiO2 attains a maximum value of 4.8×10-5 S·cm-1.展开更多
(PEO)8LiClO4-SiO2 composite polymer electrolytes(CPEs)were prepared by in-situ reaction,in which ethyl-orthosilicate(TEOS)was catalyzed by HCl and NH3.H2O,respectively.The ionic conductivity,the contact angle and the ...(PEO)8LiClO4-SiO2 composite polymer electrolytes(CPEs)were prepared by in-situ reaction,in which ethyl-orthosilicate(TEOS)was catalyzed by HCl and NH3.H2O,respectively.The ionic conductivity,the contact angle and the morphology of inorganic particles in the CPEs were investigated by AC impedance spectra,contact angle method and TEM.The conductivities of acid-catalyzed CPE and alkali-catalyzed CPE are 2.2×10-5and 1.1×10-5S/cm respectively at 30℃.The results imply that the catalyst plays an important role in the structure of in-situ preparation of SiO2,and influences the surface energy and conductivity of CPE films directly.Meanwhile,the ionic conductivity is related to the surface energy.展开更多
PEO-LiClO4-TiO2 composite polymer electrolyte films were prepared. TiO2 was formed directly in matrix by hydrolysis and condensation reaction of tetrabutyl titanate. The crystallinity, morphology and ionic conductivit...PEO-LiClO4-TiO2 composite polymer electrolyte films were prepared. TiO2 was formed directly in matrix by hydrolysis and condensation reaction of tetrabutyl titanate. The crystallinity, morphology and ionic conductivity of composite polymer electrolyte films were examined by differential scanning calorimetry, scanning electron microscopy, atom force microscopy and alternating current impedance spectroscopy, respectively. The glass transition temperature and the crystallinity of composite polymer electrolytes are decreased compared with those of PEO-LiClO4 polymer electrolyte film. The results show that TiO2 particles are uniformly dispersed in PEO-LiClO4-5%TiO2 composite polymer electrolyte film. The maximal conductivity of 5.5×10、5 Scm at 20 ℃ of PEO-LiClO4-TiO2 film is obtained at 5% mass fraction of TiO2.展开更多
One of the majorissuesli mitingtheintroduction of polymer electrolyte membranefuel cells(PEMFCs) is thelowtemperature ofoperation which makes platinum-based anode catalysts susceptible to poisoning by the trace amount...One of the majorissuesli mitingtheintroduction of polymer electrolyte membranefuel cells(PEMFCs) is thelowtemperature ofoperation which makes platinum-based anode catalysts susceptible to poisoning by the trace amount of CO,inevitably present in reformedfuel.In order to alleviate the problemof COpoisoning andi mprove the power density of the cell,operating at temperature above 100 ℃ispreferred.Nafion-type perfluorosulfonated polymers have been typically used for PEMFC.However,the conductivity of Nafion-typepolymers is not high enoughto be usedfor fuel cell operations at higher temperature(>90 ℃) and atmospheric pressure because they dehy-drate under these condition.An additional problem which faces the introduction of PEMFCtechnology is that of supplying or storing hydrogen for cell operation,especially for vehicular applications.Consequently the use of alternative fuels such as methanol and ethanol is of interest,especially if thiscan be used directlyinthe fuel cell,without reformationto hydrogen.Ali mitation of the direct use of alcohol is thelower activity of oxida-tionin comparison to hydrogen,which means that power densities are considerably lower.Hence to i mprove activity and power outputhigher temperatures of operation are preferable.To achieve this goal,requires a newpolymer electrolyte membrane which exhibits stabilityand high conductivityin the absence of liquid water.Experi mental data on a polybenzi midazole based PEMFC were presented.Asi mple steady-stateisothermal model of the fuel cell is alsoused to aidin fuel cell performance opti misation.The governing equations involve the coupling of kinetic,ohmic and mass transport.Thispaper also considers the advances madeinthe performance of direct methanol and solid polymer electrolyte fuel cells and considers theirli mi-tations in relation to the source and type of fuels to be used.展开更多
Lithium-sulfur(Li-S)batteries have attracted enormous interest due to their super-high theoretical energy density(2600 W·h/kg)in recent years.However,issues such as lithium dendrites and the shuttle effect severe...Lithium-sulfur(Li-S)batteries have attracted enormous interest due to their super-high theoretical energy density(2600 W·h/kg)in recent years.However,issues such as lithium dendrites and the shuttle effect severely hampered the large-scale application of Li-S batteries.Herein,a novel bifunctional gel polymer electrolyte,poly(N,Ndiallyl-N,N-dimethylammonium bis(trifluoromethylsulfonylimide))-P(VDF-HFP)(PDDA-TFSI-P(VDF-HFP),PTP),was prepared by anion exchange reaction to tackle the above problems.Benefited from the interaction between TFSI-and quaternary ammonium ion in PTP,a higher lithium-ion transference number was obtained,which could availably protect Li metal anodes.Meanwhile,due to the adsorption interactions between PDDA-TFSI and polysulfides(LiPSs),the shuttle effect of Li-S batteries could be alleviated effectively.Consequently,the Li symmetric batteries assembled with PTP cycled more than 1000 h and lithium metal anodes were protected effectively.Li-S batteries assembled with this polymer electrolyte show a discharge specific capacity of 813 mA·h/g after 200 cycles and 467 mA·h/g at 3 C,exhibiting excellent cycling stability and C-rates performance.展开更多
Poly（vinylidene fluoride-co-hexafluoropropylene） （PVDF-HFP） based composite polymer electrolyte （CPE） modified with CeO2, La2O3 and Y2O3 nano-rare earth oxides was prepared by phase inversion technique. Physical...Poly（vinylidene fluoride-co-hexafluoropropylene） （PVDF-HFP） based composite polymer electrolyte （CPE） modified with CeO2, La2O3 and Y2O3 nano-rare earth oxides was prepared by phase inversion technique. Physical and chemical properties of the modified CPEs were studied by SEM, TG-DSC and electrochemical methods. The results show that the CPE modified with 10% La2O3 （mass fraction） has the best practical applicability, which indicates that the thermal and electrochemical stability can reach over 400 ℃ and 4.5 V, respectively, and temperature dependence of ionic conductivity follows Vogel-Tamman-Fulcher （VTF） relationship and ionic conductivity at room temperature is up to 3.3 mS/cm. The interfacial resistance Ri reaches a stable value about 557 Ω after 6 d storage.展开更多
A polymer electrolyte based on poly(vinylidene) fluoride-hexafluoropropylene was prepared by evaporating the solvent of dimethyl formamide, and non-woven fabric was used to reinforce the mechanical strength of polymer...A polymer electrolyte based on poly(vinylidene) fluoride-hexafluoropropylene was prepared by evaporating the solvent of dimethyl formamide, and non-woven fabric was used to reinforce the mechanical strength of polymer electrolyte and maintain a good interfacial property between the polymer electrolyte and electrodes. Polymer lithium batteries were assembled by using LiCoO2 as cathode material and lithium foil as anode material. Scanning electron microscopy, alternating current impedance, linear sweep voltammetry and charge-discharge tests were used to study the properties of polymer membrane and polymer Li-ion batteries. The results show that the technics of preparing polymer electrolyte by directly evaporating solvent is simple. The polymer membrane has rich micro-porous structure on both sides and exhibits 280% uptake of electrolyte solution. The electrochemical stability window of this polymer electrolyte is about 5.5 V, and its ionic conductivity at room temperature reaches 0.151 S/m. The polymer lithium battery displays an initial discharge capacity of 138 mA·h/g and discharge plateau of about 3.9 V at 0.2 current rate. After 30 cycles, its loss of discharge capacity is only 2%. When the battery discharges at 0.5 current rate, the voltage plateau is still 3.7 V. The discharge capacities of 0.5 and 1.0 current rates are 96% and 93% of that of 0.1 current rate, respectively.展开更多
A practical method of estimation for the internal-resistance of polymer electrolyte membrane fuel cell (PEMFC) stack was adopted based on radial basis function (RBF) neural networks. In the training process, k-means c...A practical method of estimation for the internal-resistance of polymer electrolyte membrane fuel cell (PEMFC) stack was adopted based on radial basis function (RBF) neural networks. In the training process, k-means clustering algorithm was applied to select the network centers of the input training data. Furthermore, an equivalent electrical-circuit model with this internal-resistance was developed for investigation on the stack. Finally using the neural networks model of the equivalent resistance in the PEMFC stack, the simulation results of the estimation of equivalent internal-resistance of PEMFC were presented. The results show that this electrical PEMFC model is effective and is suitable for the study of control scheme, fault detection and the engineering analysis of electrical circuits.展开更多
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.
文摘Composite polymer electrolytes based on polyethylene oxide(PEO) were prepared by using LiClO4 as doping salt and silane-modified SiO2 as filler. SiO2 was formed in-situ in (PEO)8LiClO4 matrix by the hydrolysis and condensation reaction of Si(OC4H9)4. The crystallinity,morphology and ionic conductivity of composite polymer electrolyte films were examined by differential scanning calorimetry,scanning electron microscopy,atom force microscopy and alternating current impedance spectroscopy,respectively. Compared with the crystallinity of the unmodified SiO2 as inert filler,that of composite polymer electrolytes is decreased. The results show that silane-modified SiO2 particles are uniformly dispersed in (PEO)8LiClO4 composite polymer electrolyte film and the addition of silane-modified SiO2 increases the ionic conductivity of the (PEO)8LiClO4 more noticeably. When the mass fraction of SiO2 is about 10%,the conductivity of (PEO)8LiClO4-modified SiO2 attains a maximum value of 4.8×10-5 S·cm-1.
文摘(PEO)8LiClO4-SiO2 composite polymer electrolytes(CPEs)were prepared by in-situ reaction,in which ethyl-orthosilicate(TEOS)was catalyzed by HCl and NH3.H2O,respectively.The ionic conductivity,the contact angle and the morphology of inorganic particles in the CPEs were investigated by AC impedance spectra,contact angle method and TEM.The conductivities of acid-catalyzed CPE and alkali-catalyzed CPE are 2.2×10-5and 1.1×10-5S/cm respectively at 30℃.The results imply that the catalyst plays an important role in the structure of in-situ preparation of SiO2,and influences the surface energy and conductivity of CPE films directly.Meanwhile,the ionic conductivity is related to the surface energy.
文摘PEO-LiClO4-TiO2 composite polymer electrolyte films were prepared. TiO2 was formed directly in matrix by hydrolysis and condensation reaction of tetrabutyl titanate. The crystallinity, morphology and ionic conductivity of composite polymer electrolyte films were examined by differential scanning calorimetry, scanning electron microscopy, atom force microscopy and alternating current impedance spectroscopy, respectively. The glass transition temperature and the crystallinity of composite polymer electrolytes are decreased compared with those of PEO-LiClO4 polymer electrolyte film. The results show that TiO2 particles are uniformly dispersed in PEO-LiClO4-5%TiO2 composite polymer electrolyte film. The maximal conductivity of 5.5×10、5 Scm at 20 ℃ of PEO-LiClO4-TiO2 film is obtained at 5% mass fraction of TiO2.
文摘One of the majorissuesli mitingtheintroduction of polymer electrolyte membranefuel cells(PEMFCs) is thelowtemperature ofoperation which makes platinum-based anode catalysts susceptible to poisoning by the trace amount of CO,inevitably present in reformedfuel.In order to alleviate the problemof COpoisoning andi mprove the power density of the cell,operating at temperature above 100 ℃ispreferred.Nafion-type perfluorosulfonated polymers have been typically used for PEMFC.However,the conductivity of Nafion-typepolymers is not high enoughto be usedfor fuel cell operations at higher temperature(>90 ℃) and atmospheric pressure because they dehy-drate under these condition.An additional problem which faces the introduction of PEMFCtechnology is that of supplying or storing hydrogen for cell operation,especially for vehicular applications.Consequently the use of alternative fuels such as methanol and ethanol is of interest,especially if thiscan be used directlyinthe fuel cell,without reformationto hydrogen.Ali mitation of the direct use of alcohol is thelower activity of oxida-tionin comparison to hydrogen,which means that power densities are considerably lower.Hence to i mprove activity and power outputhigher temperatures of operation are preferable.To achieve this goal,requires a newpolymer electrolyte membrane which exhibits stabilityand high conductivityin the absence of liquid water.Experi mental data on a polybenzi midazole based PEMFC were presented.Asi mple steady-stateisothermal model of the fuel cell is alsoused to aidin fuel cell performance opti misation.The governing equations involve the coupling of kinetic,ohmic and mass transport.Thispaper also considers the advances madeinthe performance of direct methanol and solid polymer electrolyte fuel cells and considers theirli mi-tations in relation to the source and type of fuels to be used.
基金Project(21935006)supported by the National Natural Science Foundation of China。
文摘Lithium-sulfur(Li-S)batteries have attracted enormous interest due to their super-high theoretical energy density(2600 W·h/kg)in recent years.However,issues such as lithium dendrites and the shuttle effect severely hampered the large-scale application of Li-S batteries.Herein,a novel bifunctional gel polymer electrolyte,poly(N,Ndiallyl-N,N-dimethylammonium bis(trifluoromethylsulfonylimide))-P(VDF-HFP)(PDDA-TFSI-P(VDF-HFP),PTP),was prepared by anion exchange reaction to tackle the above problems.Benefited from the interaction between TFSI-and quaternary ammonium ion in PTP,a higher lithium-ion transference number was obtained,which could availably protect Li metal anodes.Meanwhile,due to the adsorption interactions between PDDA-TFSI and polysulfides(LiPSs),the shuttle effect of Li-S batteries could be alleviated effectively.Consequently,the Li symmetric batteries assembled with PTP cycled more than 1000 h and lithium metal anodes were protected effectively.Li-S batteries assembled with this polymer electrolyte show a discharge specific capacity of 813 mA·h/g after 200 cycles and 467 mA·h/g at 3 C,exhibiting excellent cycling stability and C-rates performance.
基金Project(2011FJ1005)supported by the Major Provincial Science and Technology Program of Hunan Province,ChinaProject(2010qzzd0101)supported by the Central College on the 2010 Operational Costs of Basic Research Program,China
文摘Poly（vinylidene fluoride-co-hexafluoropropylene） （PVDF-HFP） based composite polymer electrolyte （CPE） modified with CeO2, La2O3 and Y2O3 nano-rare earth oxides was prepared by phase inversion technique. Physical and chemical properties of the modified CPEs were studied by SEM, TG-DSC and electrochemical methods. The results show that the CPE modified with 10% La2O3 （mass fraction） has the best practical applicability, which indicates that the thermal and electrochemical stability can reach over 400 ℃ and 4.5 V, respectively, and temperature dependence of ionic conductivity follows Vogel-Tamman-Fulcher （VTF） relationship and ionic conductivity at room temperature is up to 3.3 mS/cm. The interfacial resistance Ri reaches a stable value about 557 Ω after 6 d storage.
基金Project (2003AA32X010) supported by the National High Technology Research and Development Program of China
文摘A polymer electrolyte based on poly(vinylidene) fluoride-hexafluoropropylene was prepared by evaporating the solvent of dimethyl formamide, and non-woven fabric was used to reinforce the mechanical strength of polymer electrolyte and maintain a good interfacial property between the polymer electrolyte and electrodes. Polymer lithium batteries were assembled by using LiCoO2 as cathode material and lithium foil as anode material. Scanning electron microscopy, alternating current impedance, linear sweep voltammetry and charge-discharge tests were used to study the properties of polymer membrane and polymer Li-ion batteries. The results show that the technics of preparing polymer electrolyte by directly evaporating solvent is simple. The polymer membrane has rich micro-porous structure on both sides and exhibits 280% uptake of electrolyte solution. The electrochemical stability window of this polymer electrolyte is about 5.5 V, and its ionic conductivity at room temperature reaches 0.151 S/m. The polymer lithium battery displays an initial discharge capacity of 138 mA·h/g and discharge plateau of about 3.9 V at 0.2 current rate. After 30 cycles, its loss of discharge capacity is only 2%. When the battery discharges at 0.5 current rate, the voltage plateau is still 3.7 V. The discharge capacities of 0.5 and 1.0 current rates are 96% and 93% of that of 0.1 current rate, respectively.
基金Project (2003AA517020) supported by the National High-Tech Research and Development Program of China
文摘A practical method of estimation for the internal-resistance of polymer electrolyte membrane fuel cell (PEMFC) stack was adopted based on radial basis function (RBF) neural networks. In the training process, k-means clustering algorithm was applied to select the network centers of the input training data. Furthermore, an equivalent electrical-circuit model with this internal-resistance was developed for investigation on the stack. Finally using the neural networks model of the equivalent resistance in the PEMFC stack, the simulation results of the estimation of equivalent internal-resistance of PEMFC were presented. The results show that this electrical PEMFC model is effective and is suitable for the study of control scheme, fault detection and the engineering analysis of electrical circuits.
