CN109065926A - Mineralising legal system in situ has machine-Inorganic multilayer compound proton exchange membrane preparation method - Google Patents
Mineralising legal system in situ has machine-Inorganic multilayer compound proton exchange membrane preparation method Download PDFInfo
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- CN109065926A CN109065926A CN201810882641.2A CN201810882641A CN109065926A CN 109065926 A CN109065926 A CN 109065926A CN 201810882641 A CN201810882641 A CN 201810882641A CN 109065926 A CN109065926 A CN 109065926A
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
- H01M8/1018—Polymeric electrolyte materials
- H01M8/1067—Polymeric electrolyte materials characterised by their physical properties, e.g. porosity, ionic conductivity or thickness
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
- H01M8/1018—Polymeric electrolyte materials
- H01M8/1041—Polymer electrolyte composites, mixtures or blends
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
- H01M8/1018—Polymeric electrolyte materials
- H01M8/1069—Polymeric electrolyte materials characterised by the manufacturing processes
- H01M8/1081—Polymeric electrolyte materials characterised by the manufacturing processes starting from solutions, dispersions or slurries exclusively of polymers
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Abstract
The present invention relates to a kind of mineralising legal systems in situ to have machine-Inorganic multilayer compound proton exchange membrane preparation method, polymeric matrix can be by pouring or phase separation method is prepared into smooth or porous base film, then, using air at room temperature oxidizing process, poly-dopamine (PDA) coating is deposited in film surface；Finally, the base film for depositing poly-dopamine is put into Zr (SO4)2In solution, mineralising in situ is carried out, the ZrO with interlayer structure is made by the time of regulation deposition, temperature and pH size2- PDA modifies organic-inorganic composite proton exchange membrane.Compound proton exchange membrane prepared by the present invention 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, and low energy consumption for preparation method, high-efficient, is easy to be mass produced.
Description
Technical 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 proton
The preparation method of exchange membrane carries out commercial sulfonic acid base ionomer Surface modification of proton exchange membrane in situ after poly-dopamine is modified
The organic-inorganic composite proton exchange membrane that mineralising is prepared, by swelling ratio, water absorption rate and electro-chemical test, compound matter
Proton 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 first
Alcohol 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 power
Prospect.
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 conductivity
Good chemistry is low with the permeability of mechanical stability, reaction gas under temperature, load that be conducive to catalyst and lower
The 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 series
Molecular 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 high
Proton 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 film
It 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 chain
Aromatic group and have high glass transition temperature, high mechanical performance and thermal stability.But this quasi polymer itself is not
Containing 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 film
Also 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 cell
Work.
In order to promote the proton conductivity of sulphonic substrate proton exchange, it is necessary to promote sulfonation degree and to inhibit sulfonation degree
The 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 stability
Inorganic filler (e.g., SiO is added in method2,TiO2,SnO2And ZrO2And carbon nanotube, graphene etc.), this method preparation
Hybrid organic-inorganic film is conducive to improve conductivity and hot and humid environment lower film of the Nafion membrane under high temperature low humidity
Mechanical stability, but have when filler is added to when hybrid organic-inorganic film is constructed in sulfonated polysulfone base to proton conductivity promotion
Limit, 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 with
The 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.But
Ionomer surface Direct precipitation inorganic layer can reduce proton exchange on the one hand since inorganic layer is not involved in the transmission of proton
The proton conductivity of film；On the other hand, due to the inorganic matter of deposition and the weak interaction of ionomer membrane interface, occurring
During be swollen-going swelling, interfacial separation can occur because of the different of swelling ratio, increase the interface impedance of composite membrane, to drop
Low proton conductivity.
First, constructing poly-dopamine (PDA) coating using bionics principle in film surface, playing the role of adhesive.By
Contain 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 gather
On 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 porous
Surface have biggish specific surface area, the later period can be reduced when preparing membrane electrode (MEA) interface between diaphragm and electrode resistance
It 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 prepare
The most common method of perforated membrane.Phase separation method includes: thermally induced phase separation, phase separation method, solvent volatilization cause phase again
Partition 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 multilayer
The preparation method of compound proton exchange membrane solves current commercial proton exchange membrane matrix caused by 80 DEG C of dehydrations present on
Conductivity 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 step
It is rapid as follows:
Step 1 deposits poly-dopamine on Ionomer base film: Ionomer base film is placed in DOPA
In 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 hydrochloride
Concentration 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 C
At~50 DEG C, reaction 1h~for 24 hours；ZrO is generated in poly-dopamine coating surface original position mineralising2Ceramic layer, then in deionized water
It 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/L
Liquid.
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 glass
The 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 porous
Perforated 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 film
Perforated 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 solvent
After 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 of
50~200 μm of homogeneous smooth Ionomer base film；The proportion of the Ionomer and solvent is so that sulfonation degree
It is 40~60%.
The Ionomer is one or both of sulfonated polysulfone, perfluorinated sulfonic resin, sulfonated polyether-ether-ketone
More 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 acetamide
The 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, design
A kind of method that organic-inorganic composite proton exchange membrane is prepared by mineralising method in situ.Wherein, polymeric matrix can pass through
It 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 process
Bar 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 through
The ZrO with interlayer structure is made in time, temperature and the pH size for regulating and controlling deposition2- PDA modifies Organic-inorganic composite proton
Exchange 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 more
The 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 invention
Rate；
2) prepared by the method compound proton exchange membrane is significantly reduced in high temperature (80 DEG C or more) swelling ratio, and is retained
Rate 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 extensive
Commercially 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 layer
Art, the technology (the porous sulfonation prepared by phase separation method wide to the chemical composition of base film and the scope of application of microstructure
The plate membrane of polysulfones, Nafion and polyether-ether-ketone or the sulfonated polysulfone poured, Nafion and polyether-ether-ketone).Mine in situ
The 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 such
Organic inorganic film has in flow battery a possibility that as ion selective membrane application；Two, due to middle layer
It introduces, so that the organic-inorganic composite proton exchange membrane, has good interface performance, prevent the Direct precipitation because of ceramic layer
And decline proton conductivity.This composite construction can not only play the role of inhibiting swelling, but also hydrophilic due to PDA
Property, the water retention property of proton exchange membrane can be improved.In addition, the structure between layers of Fine design, can prevent layer
It 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 mixes
Liquid.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 glass
Solution film, be dipped in coagulating bath mutually separated rapidly.In coagulation bath after 20~50 minutes, taking-up is loaded with perforated membrane
Glass plate, and perforated membrane is separated with glass plate, film is washed with deionized three times, after dry, perforated membrane Ionomer
About 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 transfer
It is placed in polytetrafluoroethylene (PTFE) culture dish.In a vacuum drying oven, heating makes solvent volatilize.Obtain Ionomer base afterwards for 24 hours
Body 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-HCl
Buffer 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 several
Between.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 deposited
It is put into above-mentioned solution.It stirs at different temperatures certain time, then generates ZrO in poly-dopamine coating surface original position mineralising2
Ceramic 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 to
Polymer 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 first
Formamide dissolving ion type polymer, the concentration of Ionomer are 0.15~0.5g/mL.Coagulation bath composition is toluene, four
One 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 added
The 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 solvent
Film liquid obtains smooth Ionomer base film after dry after bubble removing in transfer merging polytetrafluoroethylene (PTFE) culture dish；It is described
The 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 temperature
Dopamine 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 deposition
Ionomer 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 into
Zr (the SO of 1mmol/L~20mmol/L4)2Solution；It is reacted 1~24 hour at 25~50 DEG C, Organic-inorganic composite matter is made
Proton 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 acetone
The 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 managed
It 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 out
Plate, 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 buffering
Solution 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 temperature
5h.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-dopamine
The base film of deposition is put into solution.Mineralising 12h at room temperature generates ZrO in poly-dopamine coating surface original position mineralising2It is inorganic
Layer.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 methods
Rate, 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 dry
It 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 with
And 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 more
The 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 removing
Afterwards, in solution transfer merging polytetrafluoroethylene (PTFE) culture dish.In a vacuum drying oven, heating makes solvent volatilize.It obtains afterwards for 24 hours homogeneous
Proton 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 buffering
Solution 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 temperature
5h.The smooth Ionomer base film that poly-dopamine deposits is washed with deionized three times, is placed in a vacuum drying oven
24h；
(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- DOPA
The base film of amine deposition is put into solution.Mineralising 5h at 50 °C is generated in poly-dopamine coating surface original position mineralising
ZrO2Inorganic layer after deionized water washing three times, this film deionized water is impregnated for 24 hours, obtains mineralising legal system in situ after dry
Standby 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 plate
On 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 rapidly
Benzole 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 plate
Separation, 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 buffering
Solution 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 temperature
5h.The porous ion type polymeric matrix film that poly-dopamine deposits is washed with deionized three times, is placed in a vacuum drying oven
24h；
(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- DOPA
The base film of amine deposition is put into solution.Mineralising 1h at 50 °C is generated in poly-dopamine coating surface original position mineralising
ZrO2Inorganic layer.After deionized water washing three times, this film deionized water is impregnated for 24 hours, obtains mineralising legal system in situ after dry
Standby 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 merging
In polytetrafluoroethylene (PTFE) culture dish.In a vacuum drying oven, heating makes solvent volatilize.Obtain homogeneous proton exchange membrane afterwards for 24 hours, it is thick
About 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 buffering
Solution 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 temperature
5h.The smooth Ionomer base film that poly-dopamine deposits is washed with deionized three times, is placed in a vacuum drying oven
24h；
(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- DOPA
The base film of amine deposition is put into solution.Mineralising 5h at 50 °C is generated in poly-dopamine coating surface original position mineralising
ZrO2Inorganic layer after deionized water washing three times, this film deionized water is impregnated for 24 hours, obtains mineralising legal system in situ after dry
Standby 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 acetone
The 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 managed
It 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 out
Plate, 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 buffering
Solution 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 temperature
5h.The sulfonated polysulfone porous ion type polymeric matrix film that poly-dopamine deposits is washed with deionized three times, vacuum is placed in
In 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-dopamine
The base film of deposition is put into solution.Mineralising 12h at room temperature generates ZrO in poly-dopamine coating surface original position mineralising2It is inorganic
Layer.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.
Claims (10)
1. a kind of original position mineralising legal system has machine-Inorganic multilayer compound proton exchange membrane preparation method, it is characterised in that step
It is as follows:
Step 1 deposits poly-dopamine on Ionomer base film: Ionomer base film is placed in DOPA aqueous amine
In 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 hydrochloride concentration
For 2mg/ml, 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, 25 DEG C~50
At DEG C, reaction 1h~for 24 hours；ZrO is generated in poly-dopamine coating surface original position mineralising2Then ceramic layer is impregnated in deionized water
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)2·4H2O is dissolved in the dilute hydrochloric acid solution that concentration is 10~0.1mol/L.
2. mineralising legal system in situ has machine-Inorganic multilayer compound proton exchange membrane preparation method according to claim 1,
Be characterized in that: the Ionomer base film is porous or smooth base film.
3. original position mineralising legal system according to claim 1 or claim 2 has machine-Inorganic multilayer compound proton exchange membrane preparation side
Method, it is characterised in that: the aperture size of the perforated membrane is 0.8~2 μm, and porosity is 30%~50%, with a thickness of 80~100
μm。
4. original position mineralising legal system according to claim 1 or claim 2 has machine-Inorganic multilayer compound proton exchange membrane preparation side
Method, it is characterised in that: the preparation of the porous ion type polymeric matrix film: casting film is made in Ionomer and solvent
The solution film with a thickness of 100~400 μm is made in liquid on a glass, is dipped in coagulating bath after 20~50 minutes, takes out and carries
There is the glass plate of perforated membrane, perforated membrane is separated with glass plate, film is washed with deionized three times, be dried to obtain with a thickness of 50~
200 μm of perforated membrane proton exchange membrane；The proportion of the Ionomer and solvent is so that sulfonation degree is 40~60%.
5. original position mineralising legal system according to claim 1 or claim 2 has machine-Inorganic multilayer compound proton exchange membrane preparation side
Method, it is characterised in that: the preparation of the smooth Ionomer base film: casting film is made in Ionomer and solvent
Liquid, after bubble removing in transfer merging polytetrafluoroethylene (PTFE) culture dish, in a vacuum drying oven, heating makes solvent volatilize, and obtains afterwards for 24 hours
With a thickness of 50~200 μm of homogeneous smooth Ionomer base film；The proportion of the Ionomer and solvent so that
Sulfonation degree is 40~60%.
6. the according to claim 1 or 2 or 4 or 5 mineralising legal systems in situ have machine-Inorganic multilayer compound proton exchange membrane system
Preparation Method, it is characterised in that: the Ionomer is sulfonated polysulfone, in perfluorinated sulfonic resin, sulfonated polyether-ether-ketone
It is one or more kinds of.
7. original position mineralising legal system according to claim 4 or 5 has machine-Inorganic multilayer compound proton exchange membrane preparation side
Method, it is characterised in that: the solvent is n,N-Dimethylformamide or n,N-dimethylacetamide.
8. original position mineralising legal system according to claim 4 or 5 has machine-Inorganic multilayer compound proton exchange membrane preparation side
Method, it is characterised in that: the solvent is that water, tetrahydro furan are added in n,N-Dimethylformamide or n,N-dimethylacetamide
It mutters, the mixed solvent of methylene chloride or toluene.
9. mineralising legal system in situ has machine-Inorganic multilayer compound proton exchange membrane preparation method according to claim 4,
Be characterized in that: the coagulation bath composition is one or more of toluene, tetrahydrofuran, methylene chloride.
10. mineralising legal system in situ has machine-Inorganic multilayer compound proton exchange membrane preparation method according to claim 1,
It is characterized by: the glass plate uses acetone treatment.
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| CN112652795A (en) * | 2020-12-14 | 2021-04-13 | 南京大学 | Composite proton exchange membrane of fuel cell and preparation method thereof |
| CN113314748A (en) * | 2021-05-31 | 2021-08-27 | 安徽中能元隽氢能科技股份有限公司 | Preparation method of enhanced proton exchange membrane based on surface modified polymer framework |
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