CN100565994C - High temperature proton exchange film for fuel cell and preparation method thereof - Google Patents
High temperature proton exchange film for fuel cell and preparation method thereof Download PDFInfo
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- CN100565994C CN100565994C CNB200710203269XA CN200710203269A CN100565994C CN 100565994 C CN100565994 C CN 100565994C CN B200710203269X A CNB200710203269X A CN B200710203269XA CN 200710203269 A CN200710203269 A CN 200710203269A CN 100565994 C CN100565994 C CN 100565994C
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Abstract
The present invention relates to high temperature proton exchange film for fuel cell and preparation method thereof, belong to the fuel cell technology field.The matrix of high temperature proton exchange film provided by the invention is made of the organic polymer of acidifying and the nano inoganic particle that is dispersed in the polymeric matrix, and the inorganic particulate surface is coated with the polymer that proton is had solvability; Wherein, the organic polymer of acidifying is as proton donor, the polymer that the inorganic particulate surface is coated with the ether oxygen groups produces solvation to proton, produce free proton, and the inorganic particulate of acidifying organic polymer and ether oxygen polymer overmold is immiscible, and formed boundary provides easy access for proton transport.This high temperature proton exchange film for fuel cell does not rely on the existence of water and has higher proton conductivity under hot conditions, good alcohol-rejecting ability, mechanical performance, and with low cost, a kind of proton exchange membrane of tool industrial applicibility is provided for fuel cell field.
Description
Technical field
The present invention relates to high temperature proton exchange film for fuel cell and preparation method thereof, belong to the fuel cell technology field.
Background technology
Fuel cell is the device that a kind of chemical energy that will be stored in fuel and the oxidant is converted into electric energy.Be with the difference of conventional batteries:, just have continual electric power output as long as have fuel and oxidant to supply with.Fuel cell produces NO hardly
xAnd SO
xDischarging.And, CO
2Discharge capacity also reduce more than 40% than conventional power generation usage factory.Also have simultaneously and start fast, battery life length, specific power, specific energy advantages of higher, more than these characteristics determined it to have broad application prospects with aspects such as power supply, distributed power source, spacecraft power supply, portable type electronic product and used for vehicle power supplys at stationary power generation system, scene.Research about Proton Exchange Membrane Fuel Cells (PEMFCs) in recent years concentrates on the every field relevant with high temperature PEMFCs.Proton exchange membrane both provided the passage of hydrogen ions travel as electrolyte in fuel cell, played the effect of isolating two electrode reaction gases as barrier film again.Proton exchange membrane (PEMs) is the important component part of PEMFCs, yet the performance of existing PEMs all fails to reach the degree of commercial applications under hot conditions.The Nafion of Du Pont? film has very high proton conductivity, and better chemical stability and mechanical performance are present most widely used proton exchange membrane.Yet, when the operating temperature of fuel cell is higher than 100 ℃, Nafion? the film dehydration has caused the proton exchange membrane conductivity to descend.Nafion in addition? also have some other not enough as: expensive price, higher methanol permeability etc. has limited its application.
Polyethylene glycol (PEG) backbone structure contains the ether oxygen groups.Because the ether oxygen groups has higher electron donation, be electron donor preferably, it is the ligand of preferred metal ion, proton etc., can promote the disassociation of inorganic or organic salt, is a kind of polymer that proton is had higher solvation.But, limited its application because the shortcoming of PEG maximum is to have very high crystallinity.When polyethylene glycol is introduced in the proton exchange membrane, and when under hot conditions, using, can improve the fuel cell performance of using this proton exchange membrane.H.Y.Chang, C.W.Lin.Proton conductingmembranes based on PEG/SiO
2Nanocomposites for direct methanol fuel cells.Journal of Membrane Science 218, (2003) disclosed organic/inorganic composite film PEG/SiO
2Film, when high temperature uses, the segment warm-up movement of polyethylene glycol is accelerated, the high crystalline of polymer is overcome, formation can be for the accurate fluid conductors of proton conduction, thereby can improve the conductivity of this proton exchange membrane, but, the proton donor of this film is a DBSA, has good water-solubility, but does not have the performance of resistance alcohol, when under the environment of water is arranged, using, DBSA is understood water-soluble and is run off gradually, causes the proton concentration in the barrier film to descend, and finally causes the conductivity of barrier film to descend; In addition,, in fuel cell, can't play the supporting role of barrier film, not have the actual application value that high-temperature fuel cell uses because polyethylene glycol mechanics mechanical performance is low.
Therefore, need a kind of ionic exchange film for fuel cell that is suitable under the hot conditions with low cost of exploitation, this proton exchange membrane does not make water play the effect of proton solvent and has better mechanical performance.
Summary of the invention
Technical problem to be solved by this invention provides and does not rely on the existence of water under a kind of hot conditions and proton is had higher solvation, and has a proton exchange membrane of higher proton conductivity, this film has good alcohol-rejecting ability and mechanical performance, and with low cost.
The matrix of proton exchange membrane of the present invention is made of the organic polymer of acidifying and the inorganic particulate that is dispersed in the organic filler, and the proton conduction approach is that the organic polymer of acidifying and coating have proton is had solvation polymer inorganic ion two-phase interface passage.
Described proton donor is the polymer of acidifying.Because the polymer of acidifying has the proton that can dissociate, both as the matrix of proton exchange membrane, the while was as proton donor; Described proton channel has the solvability segment by the coating of inorganic particulate surface to proton and bears, rising along with temperature, the activity of segment increases, but limit with the inorganic nano-particle that is dispersed in the organic polymer mutually owing to be subjected to the organic polymer of acidifying, liquid freely phase can not be formed, a kind of continuous phase that is similar to liquid can only be formed.The continuous phase that is similar to liquid is fixed by the organic polymer of acidifying and the inorganic nano-particle that is dispersed in the organic polymer, be called accurate liquid phase, this accurate liquid phase has been eliminated the high crystalline of original polymer, as the solvent of proton, provides the passage of proton transport for proton exchange membrane.
Wherein said inorganic nano-particle is nano level SiO
2, TiO
2, ZrO
2Or Al
2O
3Described have a polymer that proton is had solvability, is selected from polymer such as polymer (such as polyethylene glycol PEG) with ether-oxygen bond repetitive or poly-pyrazoles, polyimidazole, polybenzimidazoles; The polymer with proton conduction performance that covering amount coats in inorganic nano-particle accounts for the mass percent of inorganic nano-particle and polymer total amount, between 20%-50%.
The organic polymer of described acidifying is meant reaction such as polyacrylonitrile, polyacrylamide, Kynoar, polyvinyl alcohol, polyimides and metaphosphoric acid, phosphorous acid, pyrophosphoric acid, orthophosphoric acid, sulfuric acid, pyrosulfuric acid or boric acid and gets.
The organic polymer of acidifying in the finished film, surface coat that to have the percentage ranges of the shared film gross mass of inorganic nano-particle that proton is had a polymer of solvability be respectively 32.0%～66.1% and 33.9%～68.0%.Preferred range 55-60% and 40-45%, optimum: 57.9% and 42.1%.
The preferred scheme of proton exchange membrane of the present invention is, by the PVA and the surperficial nanometer SiO that is coated with the PEG of silane coupler end-blocking of acidifying
2Colloid emulsion mixes the back film forming, forms through Overheating Treatment.
Polyvinyl alcohol (PVA) is a kind of common polymer, and it has good alcohol-resistant performance, preferably film forming, thermal stability and mechanical performance.Particularly owing to exist on the PVA segment and a large amount of be available for crosslinked and reflecting point other chemical reaction, for the improvement of its performance provides may.
Proton exchange membrane section microstructure schematic diagram is seen Fig. 1, A-inorganic nano component wherein, and B-has the polymer rich phase of ether-oxygen bond repetitive, the polymer rich phase of C-strong acidization.Wherein, continuous B has formed proton channel in polymeric matrix.
Polymer with ether-oxygen bond repetitive is silane coupler end-blocking PEG, and its structural formula is:
The silane coupler that is used for end-blocking be can with one or several of the polymer reaction that contains active hydrogen bond.Comprise gamma-aminopropyl-triethoxy-silane (KH-550), γ-An Bingjisanjiayangjiguiwan, N-aminoethyl-γ-An Bingjisanjiayangjiguiwan, anilinomethyl triethoxysilane, γ-urea propyl-triethoxysilicane, N-(β-aminoethyl)-γ-aminopropyl methyl dimethoxysilane, γ-aminopropyl methyldiethoxysilane, vinyltriethoxysilane, vinyltrimethoxy silane, the vinyl methyldiethoxysilane, the vinyl methyl dimethoxysilane, vinyl three ('beta '-methoxy ethyoxyl) silane, γ-glycidyl ether oxygen base propyl trimethoxy silicane, vinyl three ('beta '-methoxy ethyoxyl) silane, 3-isocyanic acid propyl-triethoxysilicane, 2-(3, the 4-epoxycyclohexyl) ethyl trimethoxy silane, 2-(3, the 4-epoxycyclohexyl) ethyl triethoxysilane, γ-glycidyl ether oxygen base propyl trimethoxy silicane, γ-glycidyl ether oxygen base propyl group methyl dimethoxysilane, γ-glycidyl ether oxygen base propyl group methyldiethoxysilane, γ-glycidyl ether oxygen base propyl-triethoxysilicane etc.
The preparation method of proton exchange membrane of the present invention may further comprise the steps:
In the process of the polymer solution for preparing acidifying, will react as being added to be dissolved with in aqueous acid or the organic solvent by the polymer of acidifying.The polymer of the acidifying that obtains is precipitated in poor solvent with after removing unreacted acid, be dissolved in the polymer solution that has finally obtained acidifying in the certain amount of solvent.According to different reaction requirements, the concentration difference of the polymer solution of the acidifying that finally obtains, its solid matter content is 10% to 15%.
Coat in the process of solution on preparation surface, will use the polymer that proton is had a solvability that has of silane coupler end-blocking to mix mutually as the surface coating with tetraethoxysilane and have the presoma that proton is had the polymer inorganic nano particle of solvability with the polymer inorganic nano particle that proton is had solvability.Wherein having of silane coupler end-blocking has the polymer of solvability and the molar ratio of tetraethoxysilane is controlled between 1: 10 to 10: 1 to proton.By having of well-mixed silane coupler end-blocking had the polymer of solvability and the presoma of tetraethoxysilane is hydrolyzed and polycondensation reaction to proton, obtained the solution that surperficial coating has the polymer inorganic nano particle of proton conduction performance.According to the process of different hydrolysis and polycondensation, the surface that obtains coats has the concentration difference of solution that proton is had the polymer inorganic nano particle of solvability, and the scope of its solid matter content is 5% to 20%.
The polymer solution of the acidifying that prepared and the surface that has prepared coated have the solution that proton is had a polymer inorganic nano particle of solvability and mix with different part by weight, variable concentrations according to two kinds of mixed liquors, the solid matter content difference of the mixed liquor that obtains, the scope of its solid matter content is 9.5% to 20%.The mixed liquor that obtains is coated on the clean inertia base material, after the air dry, peels off; Obtain proton exchange membrane of the present invention through after the high-temperature heat treatment.
Polymer and the surperficial nanometer SiO that is coated with the PEG of silane coupler end-blocking with acidifying
2The high temperature proton exchange film that the colloid emulsion cross-linking reaction forms is an example, adopts the following steps preparation:
(1) preparation of the polymer solution of acidifying:
Can be used for the polymer of acidifying such as polyacrylonitrile, polyacrylamide, Kynoar, polyvinyl alcohol, polyimides etc. joins and contains aqueous acid or organic solvent, stirred 1-5 hour at 60 ℃-150 ℃, form the solution of transparent homogeneous, organic solvent extraction separates, be dissolved in the acidifying polymer solution that obtains in a certain amount of water or the organic solvent after the drying again, its solid matter content is between 10% to 15%.
(2) has the preparation of inorganic particulate colloid emulsion of the polymer overmold of ether-oxygen bond repetitive: the building-up process reference literature (H.Y.Chang of the PEG of silane coupler end-blocking, C.W.Lin.Proton conducting membranesbased on PEG/SiO2 nanocomposites for direct methanol fuel cells.Journal ofMembrane Science 218, (2003), method 295-306), the PEG of one or more silane coupler end-blockings is mixed the mixture that obtains as the inorganic nano-particle precursor with tetraethoxysilane, by hydrolysis and polycondensation method, prepare the PEG clad nano inorganic particulate colloid emulsion of silane coupler end-blocking, the scope of its solid matter content is between 5% to 20%.
(3) preparation of high temperature proton exchange film:
The colloid emulsion that obtains in the polymer solution of step (1) gained acidifying and the step (2) is mixed, and the solid matter content of gained mixed solution is controlled between 9.5%～20%, and the solution that obtains is coated on the clean inertia base material, and drying is peeled off; Place vacuum drying oven, obtain the final sample film after heat treatment 1-12 hour at 80 ℃-120 ℃.
The organic polymer that preferred scheme is described acidifying is the PVA of acidifying; Polymer overmold inorganic particulate with ether-oxygen bond repetitive is the PEG clad nano SiO of silane coupler end-blocking
2Its preparation method may further comprise the steps:
(1) preparation of the polymer solution of acidifying:
The polymer poly vinyl alcohol that needs acidifying is joined concentration in the aqueous solution that contains metaphosphoric acid, phosphorous acid, pyrophosphoric acid, orthophosphoric acid, sulfuric acid, pyrosulfuric acid or boric acid between the 0.1M to 10M, stirred 1-5 hour at 60 ℃-150 ℃, form the polymer solution of the acidifying of transparent homogeneous, the solid matter content of the acidifying polymer solution that obtains is 10% to 15%.
The consumption of acid is controlled according to the concentration that adds acid in the reactant liquor, and the concentration of acid is big more in the reactant liquor, and the concentration of the acid in the final proton exchange membrane is big more.Can obtain the concentration of best use acid by the means such as conductivity of testing the proton exchange membrane that in the solution of the acid of variable concentrations, is synthesized in this experiment.
(2) PEG/SiO
2The preparation of colloid emulsion: with the mixture of the PEG of one or more silane coupler end-blockings and tetraethoxysilane (TEOS) precursor as inorganic nano-particle, through processes such as hydrolysis, polycondensations, wherein oil-water ratio is controlled between 1: 1 to 1: 15 in the process of hydrolysis and polycondensation, finally prepares the PEG clad nano SiO of solid matter content at 5% to 20% silane coupler end-blocking
2Colloid emulsion; Covering amount accounts for SiO with the PEG of silane coupler end-blocking
2With the mass percent meter of the PEG sum of silane coupler end-blocking, between 20%-50%.
The detection of covering amount can be carried out by the following method: have the polymer emulsion that proton is had solvability a---PEG/SiO with what the inorganic nano-particle of preparation coated
2Colloid emulsion is sedimentation in supercentrifuge, repeatedly with deionized water rinsing to remove attached to inorganic nano-particle sub-surface polymers grafted not, the solid matter that obtains is dried to constant weight and weighs in 100 ℃ of vacuum drying ovens.In crucible, calcination is to constant weight and weigh in 700 ℃ of muffle furnaces with the solid transfer of bone dry.Weightlessness according to solid before and after the calcination is calculated the mass percent that inorganic nano-particle coats PEG.
(3) preparation of high temperature proton exchange film:
The colloid emulsion that obtains in the polymer solution of step (1) gained acidifying and the step (2) is mixed, and the scope of the solid matter content of gained mixed solution is coated in the solution that obtains on the clean inertia base material 9.5%～20%, and drying is peeled off; Place vacuum drying oven, obtain the final sample film after heat treatment 1-12 hour at 80 ℃-120 ℃.
The present invention and existing method relatively have following advantage:
(1) utilizes proton exchange composite membrane that preparation method proposed by the invention obtains to constitute, and have nano level phase separation structure between the component by two or more component.
(2) polymer of acidifying owing to have the proton that can dissociate, can be used as the proton donor of proton exchange membrane simultaneously both as the basis material of proton exchange membrane in the component.
(3) polymer with ether-oxygen bond repetitive in the component has stronger solvation to proton, its solvent as proton is dispersed in the polymeric matrix of acidifying, because containing the polymer of the polymer of ether oxygen groups and acidifying, the two is immiscible, the two phase structure that is produced, its boundary provides convenient way for proton conduction.
(4) polymer with ether-oxygen bond repetitive in the component is in proton exchange membrane, along with the rising of temperature, the activity of segment increases, but owing to be subjected to the restriction of other components, liquid freely phase can not be formed, a kind of continuous phase that is similar to liquid can only be formed.This accurate liquid can produce solvation to the proton of acidifying polymer, but produces free migration to proton, reaches the purpose of proton conductive.
(5) this proton exchange membrane has higher proton conductivity owing to having the existence that does not rely on water, can be applied under the condition of bone dry, do not need special humidity conditioner and pressure control device when therefore, using the fuel cell of this proton exchange membrane under hot conditions, to use yet.
Therefore, the proton exchange membrane that adopts preparation method provided by the present invention to obtain is the raising on the fuel cell electrode kinetics, the simplification of hydrothermal treatment consists system, the raising of the electrode anthracemia upper limit, the minimizing of catalyst amount, the comprehensive utilization of used heat etc. provides guarantee, helps promoting the business-like development of high-temperature fuel cell.
Description of drawings
Fig. 1 is a proton exchange membrane section microstructure schematic diagram of the present invention.
The implication of number in the figure: A-inorganic nano component, B-has the polymer rich phase of ether-oxygen bond repetitive, the polymer rich phase of C-strong acidization.Wherein, the proton channel that in polymeric matrix, formed of continuous B.
Fig. 2 is a proton exchange membrane section SEM scintigram of the present invention.
Embodiment
The title of proton exchange membrane is with three letter representations in following examples, and initial is represented acid, and polymer represented in medial, and last letter is represented inorganic nano-particle, such as: SFS represents sulfuric acid, Kynoar, SiO
2PFS represents phosphoric acid, Kynoar, SiO
2PGS represents phosphoric acid, polyvinyl alcohol, SiO
2IGS represents polybenzimidazoles, polyethylene glycol, SiO
2
The preparation (SFS) of embodiment 1 proton exchange membrane of the present invention
Take by weighing 30 gram Kynoar and join 300ml and be dissolved with in the oxolane of sulfuric acid, sulfuric acid concentration is 3M, and constantly stirs, and is warming up to 70 ℃ and kept 3 hours.It is standby to treat after polymer dissolves fully solution to be naturally cooled to room temperature.1.25 moles vinyltrimethoxy silanes are joined in the mixture of 1 mole of poly glycol monomethyl ether (molecular weight is 750) and 1.5 gram catalyst (ammonium persulfate), reaction temperature remains on 60 ℃, and the poly glycol monomethyl ether that has prepared the silane coupler end-blocking in reaction after 80 hours is standby.With the mixture of the poly glycol monomethyl ether of end-blocking and tetraethoxysilane (mol ratio is 1: 1) as nanometer SiO
2Presoma mix after, join in the 300ml deionized water, regulating pH value with watery hydrochloric acid is 6, constant speed stirring hydrolysis was adjusted to 8 with weak aqua ammonia with the pH value after 3 hours, polycondensation 3 hours, it is standby to obtain solid matter content and be 8% reactant liquor.With the product solution behind Sulfated Kynoar solution and the hydrolytie polycondensation with mass ratio be mix at 1: 1 after, be poured on the clean glass plate dry 24 hours at ambient temperature.The film that obtains is stripped down from glass plate, and 80 ℃ of dryings obtain the final sample film after crosslinked 5 hours in vacuum drying oven.
The preparation (PFS) of embodiment 2 proton exchange membrane of the present invention
Take by weighing 30 gram Kynoar and join 250ml and be dissolved with in the oxolane of phosphoric acid, phosphoric acid concentration is 2M, and constantly stirs, and is warming up to 70 ℃ and kept 3 hours.It is standby to treat after polymer dissolves fully solution to be naturally cooled to room temperature.1.25 moles vinyl methyl dimethoxysilanes are joined in the mixture of 1 mole of poly glycol monomethyl ether (molecular weight is 750) and 1.5 gram catalyst (ammonium persulfate), it is standby that reaction temperature remains on 60 ℃ of poly glycol monomethyl ethers that prepared the silane coupler end-blocking after reacting 80 hours.After the poly glycol monomethyl ether of end-blocking and tetraethoxysilane (mol ratio is 3: 7) mixed as the presoma of nano silicon, join in the 200ml deionized water, regulating pH with watery hydrochloric acid is 5, constant speed stirs hydrolysis and with weak aqua ammonia pH is adjusted to 9 after 3 hours, polycondensation 3 hours, the reactant liquor that obtains is standby.After the Kynoar solution of phosphorylation and the product solution behind the hydrolytie polycondensation mixed with part by weight at 1: 1, be poured on the clean glass plate dry 24 hours at ambient temperature.The film of drying is stripped down from glass plate, and 90 ℃ of dryings obtain the final sample film after crosslinked 5 hours in vacuum drying oven.
The preparation (SGS) of embodiment 3 proton exchange membrane of the present invention
The polyvinyl alcohol that take by weighing 25 grams join 200ml and are dissolved with in the aqueous solution of sulfuric acid, and sulfuric acid concentration is 3M, and constantly stir, and are warming up to 90 ℃ and kept 3 hours.Treat after polymer dissolves fully solution to be naturally cooled to room temperature, with the polymer in the solution that obtains with the poor solvent acetone precipitation with remove be the acid of reaction after, after the precipitation that obtains is dried to constant weight, be dissolved in that to obtain mass fraction in the deionized water of 300ml be about 10% solution for standby.1.25 moles vinyltrimethoxy silanes are joined in 1 mole of poly glycol monomethyl ether (molecular weight is 750) and a certain amount of mixture of catalysts, and it is standby that reaction temperature remains on 60 ℃ of poly glycol monomethyl ethers that prepared the silane coupler end-blocking after reacting 80 hours.After the poly glycol monomethyl ether of end-blocking and tetraethoxysilane (mol ratio is 1: 1) mixed as the presoma of nano silicon, join in the 200ml deionized water, regulating pH with watery hydrochloric acid is 6, constant speed stirs hydrolysis and with weak aqua ammonia pH is adjusted to 8 after 3 hours, polycondensation 3 hours, the reactant liquor that obtains is standby.After product solution behind Sulfated poly-vinyl alcohol solution and the hydrolytie polycondensation mixed with weight ratio at 2: 3, be poured on the clean glass plate dry 24 hours at ambient temperature.The film of drying is stripped down from glass plate, and 80 ℃ of dryings obtain the final sample film after crosslinked 5 hours in vacuum drying oven.
The preparation (PGS) of embodiment 4 proton exchange membrane of the present invention
Take by weighing 25 gram polyvinyl alcohol and join 300ml and be dissolved with in the deionized water of phosphoric acid, phosphoric acid concentration is 2M, constantly stirs, and is warming up to 90 ℃ and kept 3 hours.Treat after polymer dissolves fully solution to be naturally cooled to room temperature, with the polymer in the solution that obtains with methanol extraction with after removing unreacted phosphoric acid, the precipitation that obtains is dried to constant weight, be dissolved in the deionized water of 250ml standby.2.5 moles vinyl methyl dimethoxysilanes are joined in the mixture of 1 mole of polyethylene glycol (molecular weight is 600) and 1.0 gram ammonium persulfates, it is standby that reaction temperature remains on 70 ℃ of polyethylene glycol that prepared the silane coupler end-blocking after reacting 100 hours.After the polyethylene glycol of end-blocking and tetraethoxysilane (mol ratio is 3: 7) mixed as the presoma of nano silicon, join in the 200ml deionized water, regulating pH with watery hydrochloric acid is 5, constant speed stirs hydrolysis and with weak aqua ammonia pH is adjusted to 9 after 3 hours, polycondensation 3 hours, the reactant liquor solid matter content that obtains are 10% standby.With the poly-vinyl alcohol solution of phosphorylation and the product solution behind the hydrolytie polycondensation with weight ratio be mix at 1: 1 after, be poured on the clean glass plate dry 24 hours at ambient temperature.The film of drying is stripped down from glass plate, and 100 ℃ of dryings obtain the final sample film after crosslinked 5 hours in vacuum drying oven.
The preparation (PGS) of embodiment 5 proton exchange membrane of the present invention
Take by weighing 25 gram polyvinyl alcohol and join 300ml and be dissolved with in the deionized water of phosphoric acid, phosphoric acid concentration is 3M, constantly stirs, and is warming up to 90 ℃ and kept 3 hours.Treat after polymer dissolves fully solution to be naturally cooled to room temperature, with the polymer in the solution that obtains with methanol extraction with after removing unreacted phosphoric acid, the precipitation that obtains is dried to constant weight, be dissolved in the 200ml deionized water standby.2.5 moles 3-isocyanic acid propyl-triethoxysilicanes are joined in 1 mole of polyethylene glycol (molecular weight is 800), and reaction temperature remains on 70 ℃, and the polyethylene glycol that has prepared the silane coupler end-blocking under protection of nitrogen gas after reacting 120 hours is standby.With the polyethylene glycol of end-blocking and tetraethoxysilane (mol ratio is 1: 1) mix as the presoma of nano silicon after, join in the 300ml deionized water, regulating pH with watery hydrochloric acid is 6, constant speed stirs hydrolysis and with weak aqua ammonia pH is adjusted to 9 after 3 hours, polycondensation 3 hours, it is standby to obtain solid matter content and be 8% reactant liquor.With the poly-vinyl alcohol solution of phosphorylation and the product solution behind the hydrolytie polycondensation with weight ratio be mix at 1: 1 after, be poured on the clean glass plate dry 24 hours at ambient temperature.The film of drying is stripped down from glass plate, and 120 ℃ of dryings obtain the final sample film after crosslinked 5 hours in vacuum drying oven.
The preparation (PGS) of embodiment 6 proton exchange membrane of the present invention
Take by weighing 30 gram polyvinyl alcohol and join 250ml and be dissolved with in the deionized water of phosphoric acid, phosphoric acid concentration is 4M, constantly stirs, and is warming up to 90 ℃ and kept 3 hours.Treat after polymer dissolves fully solution to be naturally cooled to room temperature, with the polymer in the solution that obtains with methanol extraction with after removing unreacted phosphoric acid, the precipitation that obtains is dried to constant weight, be dissolved in the 200ml deionized water standby.2.5 moles vinyl methyl dimethoxysilanes are joined in the mixture of 1 mole of polyethylene glycol (molecular weight is 400) and the 1.5 catalyst ammonium persulfates that restrain, it is standby that reaction temperature remains on 70 ℃ of polyethylene glycol that prepared the silane coupler end-blocking after reacting 100 hours.After the polyethylene glycol of end-blocking and tetraethoxysilane (mol ratio is 1: 1) mixed as the presoma of nano silicon, join in the 300ml deionized water, regulating pH with watery hydrochloric acid is 5, constant speed stirs hydrolysis and with weak aqua ammonia pH is adjusted to 8 after 3 hours, polycondensation 3 hours, it is standby to obtain solid matter content and be 9% reactant liquor.With the poly-vinyl alcohol solution of phosphorylation and the product solution behind the hydrolytie polycondensation with weight ratio be mix at 1: 2 after, be poured on the clean glass plate dry 24 hours at ambient temperature.The film of drying is stripped down from glass plate, and 120 ℃ of dryings obtain the final sample film after crosslinked 5 hours in vacuum drying oven.
The preparation (IGS) of embodiment 7 proton exchange membrane of the present invention
Take by weighing 30 gram polybenzimidazoles and join 300ml and be dissolved with in the dimethylacetylamide of phosphoric acid, phosphoric acid concentration is 4M, constantly stirs, and is warming up to 100 ℃ and kept 3 hours.Treat after polymer dissolves fully solution to be naturally cooled to room temperature, with the polymer in the solution that obtains with acetone precipitation with after removing unreacted phosphoric acid, the precipitation that obtains is dried to constant weight, be dissolved in the 200ml dimethylacetylamide standby again.1.5 moles 3-isocyanic acid propyl-triethoxysilicanes are joined in 1 mole of polyethylene glycol (molecular weight is 400), and it is standby that reaction temperature remains on 70 ℃ of polyethylene glycol that prepared the silane coupler end-blocking after reacting 100 hours.After the polyethylene glycol of end-blocking and a certain amount of tetraethoxysilane (mol ratio is 1: 1) mixed as the presoma of nano silicon, join in the 300ml deionized water, regulating pH with watery hydrochloric acid is 5, constant speed stirs hydrolysis and with weak aqua ammonia pH is adjusted to 8 after 3 hours, polycondensation 3 hours, it is standby to obtain solid matter content and be 8% reactant liquor.With the polybenzimidazoles solution of phosphorylation and the product solution behind the hydrolytie polycondensation with weight ratio be mix at 1: 3 after, be poured on the clean glass plate dry 48 hours at ambient temperature.The film of drying is stripped down from glass plate, and 120 ℃ of dryings obtain the final sample film after crosslinked 5 hours in vacuum drying oven.
The preparation (IGS) of embodiment 8 proton exchange membrane of the present invention
Take by weighing 30 gram polybenzimidazoles and join 400ml and be dissolved with in the dimethylacetylamide of phosphoric acid, phosphoric acid concentration is 5M, constantly stirs, and is warming up to 100 ℃ and kept 3 hours.Treat after polymer dissolves fully solution to be naturally cooled to room temperature, with the polymer in the solution that obtains with acetone precipitation with after removing unreacted phosphoric acid, the precipitation that obtains is dried to constant weight, be dissolved in the 200ml dimethylacetylamide standby again.2 moles 3-isocyanic acid propyl-triethoxysilicanes are joined in 1 mole of poly glycol monomethyl ether (molecular weight is 750), and it is standby that reaction temperature remains on 70 ℃ of poly glycol monomethyl ethers that prepared the silane coupler end-blocking after reacting 80 hours.After the poly glycol monomethyl ether of end-blocking and tetraethoxysilane (mol ratio is 3: 2) mixed as the presoma of nano silicon, join in the 300ml deionized water, it is 5 that watery hydrochloric acid is regulated pH, constant speed stirs hydrolysis and with weak aqua ammonia pH is adjusted to 8 after 3 hours, polycondensation 3 hours, it is standby to obtain solid matter content and be 10% reactant liquor.With the polybenzimidazoles solution of phosphorylation and the product solution behind the hydrolytie polycondensation with weight ratio be mix at 1: 1 after, be poured on the clean glass plate dry 48 hours at ambient temperature.The film of drying is stripped down from glass plate, and 120 ℃ of dryings obtain the final sample film after crosslinked 5 hours in vacuum drying oven.
Structure is identified:
The section SEM photo of the PGS film of embodiment 4 preparations is seen Fig. 2, and the brighter part of color is to contain the more phase of P-PVA.What color was darker is to contain the more phase of PEG, nano level SiO
2Evengranular being dispersed in the polymeric matrix, and by being contained the more encirclement mutually of PEG, contain PEG more with contain more on nanoscale, the existing of P-PVA and be separated.The membrane structure of other embodiment preparation is similar.
Show that by the Fourier infrared spectrograph detection P-PVA compares with PVA, at 1005cm
-1A new peak has appearred in the place, can be summed up as the vibration peak of P-O-C, has shown at H
3PO
4And esterification taken place between the PVA.In the infrared figure of PGS film, at 1100cm
-1The strong absworption peak of Si-O-Si has appearred in the place, shows SiO in the film
2Existence.
The TG curve shows that the PGS film is beginning decomposition more than 250 ℃, compares 200 ℃ of decomposition with P-PVA to increase.This shows that the PGS film has preferably thermal stability and may be used for high temperature PEMFCs.The improvement of this thermal stability may be owing to P-OH in high-temperature process before, has taken place crosslinked between Si-OH and the C-OH.
Performance test:
Proton conductivity:
The conductivity of proton exchange membrane adopts ac impedance measurement (Solartron 1260 frequency responseanalyzer).It is 0.57cm that sample film is sandwiched in two effective areas
2The Pt electrode between, under different temperatures (from 80 ℃ to 160 ℃), measure.All samples is all completely dried before test.The results are shown in Table 1.
Comparative example: the preparation of P-PVA film
For as a comparison, it is as follows to have prepared P-PVA film its preparation method:
The preparation of P-PVA film:
In 90 ℃ of phosphate aqueous solutions that are dissolved in concentration 5M, constantly stirring reaction is 5 hours, naturally cools to room temperature with the polyvinyl alcohol of 30 grams.Come out to filter with the polymer precipitation of methyl alcohol, be dried to weight to remove unreacted phosphoric acid with acidifying.The polymer that obtains is dissolved in the 500mL deionized water, the solution that obtains is coated on the clean inertia base material, drying is peeled off; 100 ℃ of dryings finally obtain the P-PVA film after crosslinked 8 hours in the vacuum drying oven.
Table 1
The result shows: the conductivity of proton exchange membrane of the present invention and P-PVA film all increases along with the rising of temperature.What wherein, the conductivity of proton exchange membrane of the present invention increased is more obvious.This shows that proton exchange membrane of the present invention has proton donor and proton acceptor simultaneously, and the existence that can not rely on water is moved faster.
Mechanical performance
The sample film that the present invention obtains has the favorable mechanical performance under the condition of bone dry, pliability is better.Sample film is elastic failure in stretching experiment, is not brittle fracture, and its average tensile strength is 24.5-40.2MPa.The result of the hot strength that provides among the embodiment is the mean value of three parallel sample.The results are shown in Table 2.
PEG/SiO
2Itself can't obtain the good film of mechanical strength of self-supporting, therefore can not carry out the hot strength test.
The Mechanics Performance Testing result of table 2 sample film
| Sample film | Hot strength | Elongation at break |
| Embodiment 1 | 40.0MPa | 15.2％ |
| Embodiment 2 | 30.6MPa | 12.8％ |
| Embodiment 3 | 33.0MPa | 14.3％ |
| Embodiment 4 | 40.2MPa | 10.9％ |
| Embodiment 5 | 36.5MPa | 15.9％ |
| Embodiment 6 | 34.7MPa | 14.6％ |
| Embodiment 7 | 25.1MPa | 23.5％ |
| Embodiment 8 | 24.5MPa | 21.3％ |
Claims (7)
1, high temperature proton exchange film for fuel cell, it is characterized in that: the matrix of high temperature proton exchange film is to be made of the organic polymer of acidifying and the inorganic nano-particle that is dispersed in the organic polymer of acidifying, and the inorganic nano-particle sub-surface coats and has the polymer that proton is had solvability or solvation; Wherein, the organic polymer of acidifying is as proton donor, described inorganic nano-particle is surface coated to have polymer that proton is had solvability or a solvation and forms the structure that connects continuously at the polymeric acceptor of acidifying in mutually, and the passage of proton transport is provided for proton exchange membrane;
Wherein said inorganic nano-particle is nano level SiO
2, TiO
2, ZrO
2Or Al
2O
3Described have polymer that proton is had the polymer of solvation to be selected to have the ether-oxygen bond repetitive or poly-pyrazoles, polyimidazole, a polybenzimidazoles; The inorganic nano-particle covering amount is between 20%-50%;
The organic polymer of described acidifying is meant polyacrylonitrile, polyacrylamide, Kynoar, polyvinyl alcohol or polyimides and metaphosphoric acid, phosphorous acid, pyrophosphoric acid, orthophosphoric acid, sulfuric acid, pyrosulfuric acid or acid reaction and gets;
The organic polymer of acidifying in the high temperature proton exchange film, surface coat has that proton is had the mass percent scope of the shared high temperature proton exchange film of inorganic nano-particle of the polymer of solvation is respectively 32.0%～66.1%, 33.9%～68.0%.
2, according to the described high temperature proton exchange film for fuel cell of claim 1, it is characterized in that: described inorganic nano-particle is nanometer SiO
2, the surface coated polymer with ether-oxygen bond repetitive of described inorganic nano-particle is
The polymer of form, wherein n is the natural number more than or equal to 1, R
1And R
2Substituted radical for identical or different, comprise-H ,-OH ,-CH
2OH, ph-OH ,-COOH ,-OCH
3,-OCH
2CH
3,-CO-OCH
3,-CO-OCH
2CH
3,-NH
2,-SH.
3, high temperature proton exchange film for fuel cell according to claim 2, it is characterized in that: the surface coated polymer with ether-oxygen bond repetitive of inorganic nano-particle is a polyethylene glycol oxide, polyoxygenated third is rare, the ester class or the ether derivative of polyethylene glycol or polyethylene glycol.
4, high temperature proton exchange film for fuel cell according to claim 3 is characterized in that: the organic polymer of described acidifying is the PVA of acidifying; Polymer overmold inorganic nano-particle with ether-oxygen bond repetitive is the PEG clad nano SiO of silane coupler end-blocking
2
5, the method for preparing the described high temperature proton exchange film for fuel cell of claim 3 is characterized in that may further comprise the steps:
(1) preparation of the polymer solution of acidifying:
To need the polymer of acidifying: polyacrylonitrile, polyacrylamide, Kynoar, polyvinyl alcohol or polyimides join in the water or organic solution that contain metaphosphoric acid, phosphorous acid, pyrophosphoric acid, orthophosphoric acid, sulfuric acid, pyrosulfuric acid or boric acid of concentration between 2M～5M, stirred 3 hours at 60 ℃-150 ℃, form the polymer solution of the acidifying of transparent homogeneous, the solid matter content of the polymer solution of this acidifying is 10%～15%;
(2) PEG/SiO
2The preparation of colloid emulsion:,, prepare the PEG clad nano SiO of silane coupler end-blocking through hydrolysis, polycondensation with the mixture of the PEG of one or more silane coupler end-blockings and tetraethoxysilane precursor as inorganic nano-particle
2Colloid emulsion, this colloid emulsion solid matter content is between 8%～10%; Wherein in the process of hydrolysis and polycondensation, oil-water ratio is controlled between 1: 1 to 1: 15;
(3) preparation of high temperature proton exchange film:
Is to mix in 1: 1 or 1: 2 or 1: 3 the colloid emulsion that obtains in the polymer solution of step (1) gained acidifying and the step (2) with weight ratio; The solution that obtains is coated on the clean inertia base material, and drying is peeled off; Place vacuum drying oven, obtain the final sample film after 5 hours 80 ℃ of-120 ℃ of heat treatments.
6, the preparation method of high temperature proton exchange film for fuel cell according to claim 5, it is characterized in that: the polymer solution of the acidifying that step (1) obtains is precipitated out with the poor solvent of polymer or separates with organic solvent extraction, drying is dissolved in the acidifying polymer solution that obtains making with extra care in a certain amount of deionized water or the organic solvent again.
7, the preparation method of high temperature proton exchange film for fuel cell according to claim 5, it is characterized in that: the pH value of step (2) hydrolytic process is controlled between 5 to 6, the pH value of polycondensation process is controlled between 8 to 9, and oil-water ratio is controlled between 1: 1～1: 15 in the whole process.
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| CN102047351B (en) * | 2008-11-21 | 2012-10-31 | 松下电器产业株式会社 | Proton-conducting structure and manufacturing method thereof |
| CN102214828A (en) * | 2010-04-09 | 2011-10-12 | 北京化工大学 | Nanometer particulate matter modified compound proton exchange membrane and preparation method thereof |
| CN104485470B (en) * | 2014-12-16 | 2017-03-08 | 武汉理工大学 | A kind of polysiloxanes polyphosphonic acid doping shitosan high temperature proton exchange film and preparation method thereof |
| CN106356547B (en) * | 2016-09-27 | 2019-07-05 | 中科院大连化学物理研究所张家港产业技术研究院有限公司 | A kind of cross-linking type polybenzimidazoles/silica high temperature proton exchange film and preparation method thereof with high anti-oxidation ability |
| CN110380114B (en) * | 2019-07-24 | 2021-03-23 | 中国科学院过程工程研究所 | Organic-inorganic composite solid electrolyte and preparation method and application thereof |
| CN110783558B (en) * | 2019-11-04 | 2021-04-02 | 苏州大学 | High-performance silicon negative electrode material adaptive to oily binder and preparation method thereof |
| CN113429715B (en) * | 2021-06-28 | 2022-09-02 | 国家电投集团氢能科技发展有限公司 | Phosphorylated polyvinyl alcohol/perfluorinated sulfonic acid resin compound and ion exchange membrane |
| CN114106557B (en) * | 2021-10-25 | 2023-03-28 | 中山大学 | Ultrathin acid-base compound high-temperature proton exchange membrane and preparation method thereof |
| CN117199466B (en) * | 2023-11-07 | 2024-03-12 | 杭州德海艾科能源科技有限公司 | High-conductivity composite membrane for vanadium redox flow battery and preparation method thereof |
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| CN1461070A (en) * | 2003-05-19 | 2003-12-10 | 清华大学 | Method for preparing heat-resisting proton exchange film |
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| CN1461070A (en) * | 2003-05-19 | 2003-12-10 | 清华大学 | Method for preparing heat-resisting proton exchange film |
| CN1648159A (en) * | 2005-01-10 | 2005-08-03 | 北京理工大学 | Quasi-solid polymer water solution system electrolyte film and its preparing method |
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