Mineralising legal system in situ has machine-Inorganic multilayer compound proton exchange membrane preparation methodTechnical field
The invention belongs to proton exchange membrane field, it is related to a kind of mineralising legal system in situ and has machine-Inorganic multilayer composite protonThe preparation method of exchange membrane carries out commercial sulfonic acid base ionomer Surface modification of proton exchange membrane in situ after poly-dopamine is modifiedThe organic-inorganic composite proton exchange membrane that mineralising is prepared, by swelling ratio, water absorption rate and electro-chemical test, compound matterProton exchange has both the characteristic of high high-temp water-preserving rate and high-quality electron conductivity and low swelling ratio when having 80 DEG C or more.
Background technique
Fuel cell is a kind of device that the chemical energy being stored in fuel is directly converted to electric energy by chemically reacting.According to the difference of polymer dielectric film, polymer electrolyte fuel cells are divided into pem fuel fuel cell, direct firstAlcohol fuel battery and anion-exchange membrane fuel cells.Proton Exchange Membrane Fuel Cells is the maximum one kind of current development scale,Have many advantages, such as that starting is fast, specific power is high, stable, there is very wide application in terms of electric car and portable powerProspect.
Proton exchange membrane is one of key component of Proton Exchange Membrane Fuel Cells, it is necessary to it is high, high to have proton conductivityGood chemistry is low with the permeability of mechanical stability, reaction gas under temperature, load that be conducive to catalyst and lowerThe market price the features such as.
Perfluorosulfonic acid proton exchange film due to its high proton conductivity, chemistry-mechanical stability and by extensive concern.The Nafion series perfluorosulfonic acid proton exchange film developed by DuPont Corporation, realizes commercialization earliest.Nafion seriesMolecular structure be to there is hydrophilic sulfonic acid group to constitute by the main chain of polytetrafluoroethylene (PTFE) and suspended side chain.Nafion membrane low temperature is highProton conductivity with higher under wet；But when temperature is higher than 80 DEG C, excessively it is swollen since film absorbs water, causes the mechanical performance of filmIt is deteriorated, fuel battery service life is made to shorten.
In order to improve the thermal stability of film, the market price is reduced, poly- aryl quasi polymer has also carried out extensive research, such as poly-Sulfone (PSf), polyether-ether-ketone (PEEK), polybenzimidazoles (PBI), polyimides (PI) etc..This quasi polymer is contained due to main chainAromatic group and have high glass transition temperature, high mechanical performance and thermal stability.But this quasi polymer itself is notContaining leading Protic Group, it is necessary to pass through sulfonated or phosphorylation, make it that could be used as proton exchange membrane with acid groups.Therefore,The proton conductivity of the proton exchange membrane of this quasi polymer preparation depends on sulfonation degree, and sulfonation degree is higher, the proton conductivity of filmAlso higher；But swelling ratio of the film under hot and humid environment will increase, and be unfavorable for proton exchange membrane in the long-time of fuel cellWork.
In order to promote the proton conductivity of sulphonic substrate proton exchange, it is necessary to promote sulfonation degree and to inhibit sulfonation degreeThe swelling of higher sulfonic polymeric object film, there are two types of thinkings at present.One is use for reference Nafion membrane to improve mechanical stabilityInorganic filler (e.g., SiO is added in method2,TiO2,SnO2And ZrO2And carbon nanotube, graphene etc.), this method preparationHybrid organic-inorganic film is conducive to improve conductivity and hot and humid environment lower film of the Nafion membrane under high temperature low humidityMechanical stability, but have when filler is added to when hybrid organic-inorganic film is constructed in sulfonated polysulfone base to proton conductivity promotionLimit, and film becomes highly brittle, is unfavorable for the preparation of membrane electrode.It is another kind of, be realized using multilayered structure is constructed sulfonation degree compared withThe proton conductivity of high sulfonic polymeric object film, while inhibiting its swelling under hot and humid environment.Ceramics-polymer-" sandwich " structure of ceramics can inhibit the swelling of polymer film due to the good thermal stability of inorganic matter significantly.ButIonomer surface Direct precipitation inorganic layer can reduce proton exchange on the one hand since inorganic layer is not involved in the transmission of protonThe proton conductivity of film；On the other hand, due to the inorganic matter of deposition and the weak interaction of ionomer membrane interface, occurringDuring be swollen-going swelling, interfacial separation can occur because of the different of swelling ratio, increase the interface impedance of composite membrane, to dropLow proton conductivity.
First, constructing poly-dopamine (PDA) coating using bionics principle in film surface, playing the role of adhesive.ByContain a large amount of-OH ,-NH in PDA3, the groups such as-NH-, on the one hand can be formed with film surface formed hydrogen bond, firmly gatherOn the other hand film surface-OH meeting and Zr are exposed in film surface4+Chelation occurs, Zr can be induced4+Mineralising in situ,And ZrO2It may also participate in the conduction of proton after absorption proton.Second, preparation has porous film surface.Because of not only pore structure" defect " of itself can form Embedded inorganic layer in porous film surface, increase combination between layers；And it is porousSurface have biggish specific surface area, the later period can be reduced when preparing membrane electrode (MEA) interface between diaphragm and electrode resistanceIt is anti-.Currently, the preparation method of perforated membrane has: phase point partition method, pulling method, method of electrostatic spinning etc., wherein phase separation method is to prepareThe most common method of perforated membrane.Phase separation method includes: thermally induced phase separation, phase separation method, solvent volatilization cause phase againPartition method.And non-solvent cause phase separation method it is relatively easy, and operating condition more easy-regulating and be widely used.
Summary of the invention
Technical problems to be solved
In order to avoid the shortcomings of the prior art, the present invention proposes that a kind of mineralising legal system in situ has machine-Inorganic multilayerThe preparation method of compound proton exchange membrane solves current commercial proton exchange membrane matrix caused by 80 DEG C of dehydrations present onConductivity rapid drawdown and the larger problem of swelling ratio.
Technical solution
It is a kind of original position mineralising legal system have machine-Inorganic multilayer compound proton exchange membrane preparation method, it is characterised in that stepIt is rapid as follows:
Step 1 deposits poly-dopamine on Ionomer base film: Ionomer base film is placed in DOPAIn amine aqueous solution, the reaction time be 3~for 24 hours, obtain poly-dopamine deposition proton exchange membrane matrix, with a thickness of 0.1~1 μm；
The aqueous dopamine solution is: Dopamine hydrochloride being mixed with Tris-HCl buffer solution, in which: Dopamine hydrochlorideConcentration is 2mg/ml, and the concentration of Tris-HCl buffer solution is 10mmol/L, pH=8.5；
The concentration of the Ionomer base film is 0.15~0.5g/mL；
Organic-inorganic composite proton exchange membrane is prepared in step 2, mineralising in situ:
The proton exchange membrane matrix that poly-dopamine deposits is put into Zr (SO4)2Mineralising in situ is carried out in acid solution, at 25 DEG CAt~50 DEG C, reaction 1h~for 24 hours；ZrO is generated in poly-dopamine coating surface original position mineralising2Ceramic layer, then in deionized waterIt impregnates for 24 hours, drying at room temperature obtains mineralising ZrO in situ2The sulfonated polysulfone compound proton exchange membrane of the poly-dopamine modification of layer；
Zr (the SO4)2The concentration of solution is 1~20mmol/L；
Zr (the SO4)2Acid solution be: by Zr (SO4)2·4H2It is molten that O is dissolved in the dilute hydrochloric acid that concentration is 10~0.1mol/LLiquid.
The Ionomer base film is porous or smooth base film.
The aperture size of the perforated membrane is 0.8~2 μm, and porosity is 30%~50%, with a thickness of 80~100 μm.
The preparation of the porous ion type polymeric matrix film: casting solution is made in Ionomer and solvent, in glassThe solution film with a thickness of 100~400 μm is made in glass plate, is dipped in coagulating bath after 20~50 minutes, taking-up is loaded with porousPerforated membrane is separated with glass plate, film is washed with deionized three times, is dried to obtain with a thickness of 50~200 μm by the glass plate of filmPerforated membrane proton exchange membrane；The proportion of the Ionomer and solvent is so that sulfonation degree is 40~60%.
The preparation of the smooth Ionomer base film: casting solution, degasification is made in Ionomer and solventAfter bubble transfer merging polytetrafluoroethylene (PTFE) culture dish in, in a vacuum drying oven, heating so that solvent is volatilized, obtain afterwards for 24 hours with a thickness of50~200 μm of homogeneous smooth Ionomer base film；The proportion of the Ionomer and solvent is so that sulfonation degreeIt is 40~60%.
The Ionomer is one or both of sulfonated polysulfone, perfluorinated sulfonic resin, sulfonated polyether-ether-ketoneMore than.
The solvent is N,N-dimethylformamide or DMAC N,N' dimethyl acetamide.
The solvent is that water, tetrahydrofuran, dichloro are added in N,N-dimethylformamide or DMAC N,N' dimethyl acetamideThe mixed solvent of methane or toluene.
The coagulation bath composition is one or more of toluene, tetrahydrofuran, methylene chloride.
The glass plate uses acetone treatment.
Beneficial effect
A kind of mineralising legal system in situ proposed by the present invention has machine-Inorganic multilayer compound proton exchange membrane preparation method,For the problem that commercial proton exchange membrane matrix conductivity rapid drawdown and swelling ratio caused by 80 DEG C of dehydrations present on is larger,Respectively with the polyether-ether-ketone of different sulfonation degrees, polysulfones and perfluorinated sulfonic resin (Nafion) are polymer matrix body Model, designA kind of method that organic-inorganic composite proton exchange membrane is prepared by mineralising method in situ.Wherein, polymeric matrix can pass throughIt pours or phase separation method is prepared into smooth or porous base film, it is then, poly- more in film surface deposition using air at room temperature oxidizing processBar amine (PDA) coating；Finally, the base film for depositing poly-dopamine is put into Zr (SO4)2In solution, mineralising in situ is carried out, is passed throughThe ZrO with interlayer structure is made in time, temperature and the pH size for regulating and controlling deposition2- PDA modifies Organic-inorganic composite protonExchange membrane.Compound proton exchange membrane prepared by the present invention has both high high-temp water-preserving rate and high proton conductance when having 80 DEG C or moreThe characteristic of rate and low swelling ratio, and low energy consumption for preparation method, it is high-efficient, it is easy to be mass produced.
The present invention has had the following advantages compared with current material and technology:
1) it is conducted using the proton with higher of compound proton exchange membrane made of preparation method proposed by the inventionRate；
2) prepared by the method compound proton exchange membrane is significantly reduced in high temperature (80 DEG C or more) swelling ratio, and is retainedRate is improved；
3) prepared by the method compound proton exchange membrane has porous coarse structure, is easy to the attachment of catalyst,Reduce the interface impedance between membrane electrode septation and electrode；
4) preparation method of the present invention is simple, can carry out post-processing modification to existing commercialization film, is conducive to extensiveCommercially produce.
Detailed description of the invention
Fig. 1 be embodiment 1 prepare porous sulfonated polysulfone membrane surface electromicroscopic photograph (a be front；B is section；C is anti-Face)；
Fig. 2 is that (a be positive for the electromicroscopic photograph of the porous sulfonated polysulfone membrane that embodiment 1 prepares poly-dopamine deposition；B is anti-Face)；
Fig. 3 is that (a be positive for the electromicroscopic photograph of the porous sulfonated polysulfone composite membrane of PDA- that embodiment 1 prepares zirconium oxide cladding；B is reverse side)；
Specific embodiment
Now in conjunction with embodiment, attached drawing, the invention will be further described:
The present invention is mainly designed from such as lower angle: one, having invented the skill of a kind of general in-situ deposition mineralized layerArt, the technology (the porous sulfonation prepared by phase separation method wide to the chemical composition of base film and the scope of application of microstructureThe plate membrane of polysulfones, Nafion and polyether-ether-ketone or the sulfonated polysulfone poured, Nafion and polyether-ether-ketone).Mine in situThe Organic inorganic film for changing preparation is provided with the effect for inhibiting swelling and report water conservation, and the preparation of porous matrix also makes suchOrganic inorganic film has in flow battery a possibility that as ion selective membrane application；Two, due to middle layerIt introduces, so that the organic-inorganic composite proton exchange membrane, has good interface performance, prevent the Direct precipitation because of ceramic layerAnd decline proton conductivity.This composite construction can not only play the role of inhibiting swelling, but also hydrophilic due to PDAProperty, the water retention property of proton exchange membrane can be improved.In addition, the structure between layers of Fine design, can prevent layerIt falls off.
Above-mentioned purpose of the invention, which adopts the following technical scheme that, to be resolved:
(1) preparation of perforated membrane and smooth film matrix
1. the preparation of perforated membrane Ionomer base film
The N,N-dimethylformamide for configuring a certain amount of sulfonated polysulfone, perfluorinated sulfonic resin or sulfonated polyether-ether-ketone mixesLiquid.The glass plate that acetone treatment is crossed is taken, casting solution is made on self-control knifing machine with a thickness of 100~400 μm on a glassSolution film, be dipped in coagulating bath mutually separated rapidly.In coagulation bath after 20~50 minutes, taking-up is loaded with perforated membraneGlass plate, and perforated membrane is separated with glass plate, film is washed with deionized three times, after dry, perforated membrane IonomerAbout 50~200 μm of matrix film thickness.
2. the preparation of smooth Ionomer base film
Configure a certain amount of sulfonated polysulfone, perfluorinated sulfonic resin or sulfonated polyether-ether-ketone solution, after bubble removing, solution transferIt is placed in polytetrafluoroethylene (PTFE) culture dish.In a vacuum drying oven, heating makes solvent volatilize.Obtain Ionomer base afterwards for 24 hoursBody film, about 50~200 μm of thickness.
(2) preparation of poly-dopamine middle layer
Firstly, configuration Tris-HCl pH=8.5 buffer solution；It weighs certain mass Dopamine hydrochloride and is put into Tris-HClBuffer solution is made into aqueous dopamine solution, film prepared by step (1) is put into the above-mentioned solution prepared, when reacting at room temperature severalBetween.The Ionomer base film deposited through poly-dopamine is washed with deionized three times, is placed in a vacuum drying oven for 24 hours.
(3) mineralising method in situ prepares organic-inorganic composite proton exchange membrane
Zr(SO4)2·4H2O, which is dissolved in dilute hydrochloric acid solution, is made into Zr (SO4)2Acid solution.The base film that poly-dopamine is depositedIt is put into above-mentioned solution.It stirs at different temperatures certain time, then generates ZrO in poly-dopamine coating surface original position mineralising2Ceramic layer.This film deionized water is impregnated for 24 hours, obtains organic-inorganic composite proton exchange membrane after dry.
The present invention devises a kind of porous surface topography, promotes the specific surface area and shape characteristic of film surface, is conducive toPolymer film surface constructs micro nano structure.
The present invention prepares porous ion type polymeric matrix film using phase separation method.N, N- dimethyl are used firstFormamide dissolving ion type polymer, the concentration of Ionomer are 0.15~0.5g/mL.Coagulation bath composition is toluene, fourOne or more of hydrogen furans, methylene chloride.
The Ionomer are as follows: sulfonated polysulfone (sulfonation degree is 40%~60%), perfluorinated sulfonic resin, sulfonation are poly-One or more of ether ether ketone (sulfonation degree is 10%~60%).
As a preferred embodiment, solvent may be n,N-dimethylacetamide, or tetrahydrofuran, dichloromethane is addedThe mixed solvent of the volatile substances such as alkane, toluene and N,N-dimethylformamide, DMAC N,N' dimethyl acetamide.
The present invention prepares smooth Ionomer base film using casting method.Casting is made in Ionomer and solventFilm liquid obtains smooth Ionomer base film after dry after bubble removing in transfer merging polytetrafluoroethylene (PTFE) culture dish；It is describedThe sulfonation degree of Ionomer is 40~60%, and the concentration of Ionomer is 0.1~0.5g/mL.
As a preferred embodiment, solvent may be n,N-dimethylacetamide.
Poly-dopamine coating is introduced into the design of the multilayer complex films of proton exchange membrane by the present invention.The present invention uses room temperatureDopamine air oxidation process deposits poly-dopamine coating on porous sulfonated polysulfone surface.Buffer solution is Tris-HCl buffer solution(10mmol/L；PH=8.5), Dopamine hydrochloride concentration is 2mg/ml；Room temperature reaction 3-24 hours.Obtain poly-dopamine depositionIonomer base film.
Preferably, middle layer can also be constructed by levodopa, catechol monomer.
Mineralising method in original position of the present invention prepares inorganic nano layer.Zr(SO4)2·4H2O, which is dissolved in dilute hydrochloric acid solution, to be made intoZr (the SO of 1mmol/L~20mmol/L4)2Solution；It is reacted 1~24 hour at 25~50 DEG C, Organic-inorganic composite matter is madeProton exchange.Dilute hydrochloric acid concentration is in 10mmol/L~0.1mol/L.
Embodiment 1
The preparation of (1) 50% sulfonated polysulfone porous ion type polymeric matrix film
The sulfonation degree for configuring 0.3g/mL is the N,N-dimethylformamide homogeneous phase solution of 50% sulfonated polysulfone.It takes at acetoneThe solution film with a thickness of 200 μm is made on self-control knifing machine on a glass, rapidly by it in casting solution by the glass plate managedIt immerses in 20 DEG C of coagulating bath (toluene solution) and is mutually separated.In coagulation bath after twenty minutes, the glass for being loaded with perforated membrane is taken outPlate, and perforated membrane is separated with glass plate, film is washed with deionized three times, after dry, about 100 μm of obtained film thickness；
(2) preparation of poly-dopamine middle layer
Tris-HCl pH=8.5 buffer solution is configured, 50mg Dopamine hydrochloride is weighed and is put into 50mL Tris-HCl bufferingSolution is made into aqueous dopamine solution (2mg/mL), and film prepared by step (1) is put into the above-mentioned solution prepared, reacts at room temperature5h.The Ionomer base film that poly-dopamine deposits is washed with deionized three times, is placed in a vacuum drying oven for 24 hours；
(3) mineralising method in situ prepares organic-inorganic composite proton exchange membrane
Zr(SO4)2·4H2O is dissolved in the ZrSO that 4mmol/L is made into 0.1mol/L HCl solution4Solution.By poly-dopamineThe base film of deposition is put into solution.Mineralising 12h at room temperature generates ZrO in poly-dopamine coating surface original position mineralising2It is inorganicLayer.This film is impregnated to the organic-inorganic composite proton exchange membrane for obtaining mineralising method preparation in situ after dry for 24 hours with deionized water.
Before test, film is placed in deionized water and impregnates 30min.The conductance of film is measured by two electrode AC impedance methodsRate, conductivity are calculated with formula once:
σ: conductivity (S/cm)
The distance between l: two electrodes (cm)
R: resistance
S: the sectional area (cm of film2)
The water absorption rate at various temperatures and swelling ratio test method of film are as follows: firstly, film is placed in a vacuum drying oven dryIt is dry for 24 hours, weigh (W1) and length (L1)；Later, film is placed in 90 DEG C of deionized waters and impregnates 30min, measure the quality of film later(W2) and length (L2).The calculation formula of water absorption rate and swelling ratio are as follows:
Water absorption rate:
Swelling ratio:
Table 1 be case study on implementation 1 prepare the swelling ratio of sulfoxidation zirconium organic-inorganic compound proton exchange membrane, water absorption rate withAnd the comparison diagram of conductivity and pure sulfonated polysulfone perforated membrane, it can be seen that have both high high-temp water-preserving when temperature is at 80 DEG C or moreThe characteristic of rate and high-quality electron conductivity and low swelling ratio.
Embodiment 2
The preparation of the smooth Ionomer base film of (1) 50% sulfonated polysulfone
The sulfonation degree for configuring 0.15g/mL is the N,N-dimethylformamide homogeneous phase solution of 50% sulfonated polysulfone.Bubble removingAfterwards, in solution transfer merging polytetrafluoroethylene (PTFE) culture dish.In a vacuum drying oven, heating makes solvent volatilize.It obtains afterwards for 24 hours homogeneousProton exchange membrane, about 100 μm of thickness.
(2) preparation of poly-dopamine middle layer
Tris-HCl pH=8.5 buffer solution is configured, 25mg Dopamine hydrochloride is weighed and is put into 50mL Tris-HCl bufferingSolution is made into aqueous dopamine solution (2mg/mL), and film prepared by step (1) is put into the above-mentioned solution prepared, reacts at room temperature5h.The smooth Ionomer base film that poly-dopamine deposits is washed with deionized three times, is placed in a vacuum drying oven24h；
(3) mineralising method in situ prepares organic-inorganic composite proton exchange membrane
Zr(SO4)2·4H2O is dissolved in the Zr (SO that 4mmol/L is made into 40mmol/L HCl solution4)2Solution.By poly- DOPAThe base film of amine deposition is put into solution.Mineralising 5h at 50 °C is generated in poly-dopamine coating surface original position mineralisingZrO2Inorganic layer after deionized water washing three times, this film deionized water is impregnated for 24 hours, obtains mineralising legal system in situ after dryStandby organic-inorganic composite proton exchange membrane.
Embodiment 3
The preparation of (1) 50% sulfonated polyether-ether-ketone porous ion type polymeric matrix film
Configure the homogeneous phase solution of the 50% sulfonation degree SPEEK of 0.3g/mL.The glass plate that acetone treatment is crossed is taken, in glass plateOn by casting solution self-control knifing machine on the solution film with a thickness of 200 μm is made, be dipped in (first in 20 DEG C of coagulating bath rapidlyBenzole soln) mutually separated.In coagulation bath after twenty minutes, it takes out and is loaded with the glass plate of perforated membrane, and by perforated membrane and glass plateSeparation, is washed with deionized film three times, after dry, about 100 μm of obtained film thickness；
(2) preparation of poly-dopamine middle layer
Tris-HCl pH=8.5 buffer solution is configured, 25mg Dopamine hydrochloride is weighed and is put into 50mL Tris-HCl bufferingSolution is made into aqueous dopamine solution (2mg/mL), and film prepared by step (1) is put into the above-mentioned solution prepared, reacts at room temperature5h.The porous ion type polymeric matrix film that poly-dopamine deposits is washed with deionized three times, is placed in a vacuum drying oven24h；
(3) mineralising method in situ prepares organic-inorganic composite proton exchange membrane
Zr(SO4)2·4H2O is dissolved in the Zr (SO that 4mmol/L is made into 0.1mol/L HCl solution4)2Solution.By poly- DOPAThe base film of amine deposition is put into solution.Mineralising 1h at 50 °C is generated in poly-dopamine coating surface original position mineralisingZrO2Inorganic layer.After deionized water washing three times, this film deionized water is impregnated for 24 hours, obtains mineralising legal system in situ after dryStandby organic-inorganic composite proton exchange membrane.
Embodiment 4
(1) preparation of the smooth Ionomer base film of perfluorinated sulfonic resin (Nafion)
Configure the N,N-dimethylformamide homogeneous phase solution of the Nafion of 0.15g/mL.After bubble removing, solution transfer mergingIn polytetrafluoroethylene (PTFE) culture dish.In a vacuum drying oven, heating makes solvent volatilize.Obtain homogeneous proton exchange membrane afterwards for 24 hours, it is thickAbout 100 μm of degree.
(2) preparation of poly-dopamine middle layer
Tris-HCl pH=8.5 buffer solution is configured, 25mg Dopamine hydrochloride is weighed and is put into 50mL Tris-HCl bufferingSolution is made into aqueous dopamine solution (2mg/mL), and film prepared by step (1) is put into the above-mentioned solution prepared, reacts at room temperature5h.The smooth Ionomer base film that poly-dopamine deposits is washed with deionized three times, is placed in a vacuum drying oven24h；
(3) mineralising method in situ prepares organic-inorganic composite proton exchange membrane
Zr(SO4)2·4H2O is dissolved in the Zr (SO that 4mmol/L is made into 40mmol/L HCl solution4)2Solution.By poly- DOPAThe base film of amine deposition is put into solution.Mineralising 5h at 50 °C is generated in poly-dopamine coating surface original position mineralisingZrO2Inorganic layer after deionized water washing three times, this film deionized water is impregnated for 24 hours, obtains mineralising legal system in situ after dryStandby organic-inorganic composite proton exchange membrane.
Embodiment 5
The preparation of (1) 60% sulfonated polysulfone porous ion type polymeric matrix film
The sulfonation degree for configuring 0.3g/mL is the N,N-dimethylformamide homogeneous phase solution of 60% sulfonated polysulfone.It takes at acetoneThe solution film with a thickness of 200 μm is made on self-control knifing machine on a glass, rapidly by it in casting solution by the glass plate managedIt immerses in 20 DEG C of coagulating bath (toluene solution) and is mutually separated.In coagulation bath after twenty minutes, the glass for being loaded with perforated membrane is taken outPlate, and perforated membrane is separated with glass plate, film is washed with deionized three times, after dry, about 100 μm of obtained film thickness；
(2) preparation of poly-dopamine middle layer
Tris-HCl pH=8.5 buffer solution is configured, 50mg Dopamine hydrochloride is weighed and is put into 50mL Tris-HCl bufferingSolution is made into aqueous dopamine solution (2mg/mL), and film prepared by step (1) is put into the above-mentioned solution prepared, reacts at room temperature5h.The sulfonated polysulfone porous ion type polymeric matrix film that poly-dopamine deposits is washed with deionized three times, vacuum is placed inIn drying box for 24 hours；
(3) mineralising method in situ prepares organic-inorganic composite proton exchange membrane
Zr(SO4)2·4H2O is dissolved in the ZrSO that 4mmol/L is made into 0.1mol/L HCl solution4Solution.By poly-dopamineThe base film of deposition is put into solution.Mineralising 12h at room temperature generates ZrO in poly-dopamine coating surface original position mineralising2It is inorganicLayer.This film is impregnated to the organic-inorganic composite proton exchange membrane for obtaining mineralising method preparation in situ after dry for 24 hours with deionized water.