CN105070933A - Composite proton-exchange membrane for fuel cell and preparation method of composite proton-exchange membrane - Google Patents
Composite proton-exchange membrane for fuel cell and preparation method of composite proton-exchange membrane Download PDFInfo
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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
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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
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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
- H01M8/1039—Polymeric electrolyte materials halogenated, e.g. sulfonated polyvinylidene fluorides
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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
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Abstract
The invention belongs to the technical field of high polymer materials, and particularly discloses a composite proton-exchange membrane for a fuel cell and a preparation method of the composite proton-exchange membrane. According to the composite proton-exchange membrane disclosed by the invention, the composite membrane which contains a phosphoric acid derivative SiPOH and perfluorosulfonated resin and takes a porous polymer membrane as a carrier is prepared by blending phosphoric acid derivative SiPOH gel and a perfluorosulfonated resin solution and enhancing the mixture with the porous polymer membrane, wherein the thickness of the membrane can be controlled between 20 microns and 30 microns. Compared with the traditional Nafion(R) membrane and other perfluorosulfonate membranes, the composite proton-exchange membrane disclosed by the invention has good mechanical strength; the proton conductivity is not obviously lowered; the optimum working temperature of a monocell and the performance of the monocell are obviously improved; and the composite proton-exchange membrane can be used as a proton-exchange membrane which can work in the environment with medium-high temperature and low humidity.
Description
Technical field
The invention belongs to technical field of polymer materials, be specifically related to a kind of composite proton exchange membrane for fuel cell and preparation method thereof.
Background technology
Proton Exchange Membrane Fuel Cells (PEMFC) is a kind of device chemical energy being converted into electric energy, it has that energy conversion efficiency is high, energy density is large and the advantage such as clean environment firendly, simultaneously also due to its electrolyte be solid proton exchange membrane, without electrolyte loss, can started quickly at low temperature, without discharge, generate the plurality of advantages such as water is easily got rid of, specific power and specific energy are high, be used to electric automobile, electric bicycle, bus, stand-by power supply, boats and ships and underwater vehicle, notebook computer etc. at present.
Proton exchange membrane (PEM) is one of core material of PEMFC, rises and intercepts the important function such as fuel and oxidant, proton conducting, attachment eelctro-catalyst, is one of main determining factor determining PEMFC military service performance.Desirable proton exchange membrane material must have good barrier property to fuel gas and oxygen or air, there is higher proton conductivity, superior mechanical performance, sufficiently long useful life, reasonable prices etc. (Han Shuaiyuan, Yue Baohua, Yan Liuming. based on the progress [J] of the high temperature proton exchange film of phosphonate group. Acta PhySico-Chimica Sinica, 2014,30 (1): 8-21.).The most ripe, most popular proton exchange membrane is perfluorinated sulfonic acid class proton exchange membrane at present, its Typical Representative comprises the Nafion film of E.I.Du Pont Company, it is developed by Dupont (DuPond) company and produced, and other commercial perfluoro sulfonic acid membranes are as the Aquivion film etc. of the Aciplex film of the Dow film of DowChemical company of the U.S., Japanese AsahiChemical company, the Flemion film of Japanese AsalliGlass company and Italian SolvaySolexis company.Although perfluoro sulfonic acid membrane has high proton conductivity and good chemical stability, also have that cost is high, water holding capacity is poor, swelling ratio and a problem such as fuel permeability is high.And the Proton Exchange Membrane Fuel Cells run under the high temperature conditions is expected to overcome the low and adaptive capacity to environment difference of low-temperature fuel cell radiating efficiency and waits technology barrier, the proton exchange membrane thus under high temperature and low humidity conditions in exploitation with excellent proton conductivity of phosphoric acid is the difficult problem during current PEMFC studies.
In document, perfluorinated sulfonic resin proton exchange membrane (as Nafion film) and some organic and inorganic materials mainly carry out blendedly preparing composite membrane with the method improving its high-temperature working performance by modification perfluorinated sulfonic resin proton exchange membrane, and these inorganic matters comprise SiO
2, TiO
2deng, if China Patent Publication No. is the preparation method that CN103972562A discloses a kind of high temperature proton exchange film for fuel cell.The method is that Nafion barrier film is carried out preliminary treatment, then immerses in water and mixed alkoxide solution, continues to add tetraethoxysilane and mixed alkoxide solution in mixed solution, in Nafion membrane surface generation sol gel reaction, and preparation Nafion-SiO
2high temperature proton exchange film.The high temperature proton exchange film for fuel cell made by this preparation method can more than 100 DEG C environmental work.China Patent Publication No. is that CN104779407A discloses double-deck proton exchange membrane of a kind of nitrogenous polyphosphonic acid based polysiloxane/Nafion and preparation method thereof.Nitrogenous polyphosphonic acid based polysiloxane solution is coated on pretreated Nafion film by the method, then 12h is placed at 30 ~ 50 DEG C of constant temperature, subsequently respectively 100 DEG C, 120 DEG C with 150 DEG C at heat treatment 2h, this double-deck proton exchange membrane has higher proton conductivity and low methanol permeability under the high temperature conditions, also has good pliability and mechanical strength.China Patent Publication No. is that CN104733739A discloses a kind of inorganic/organic composite proton exchange membrane and preparation method thereof, and the method is by sol-gel process, is introduced by perfluorinated sulfonic acid polymer and is fixed on SiO
2in skeleton, obtain the proton conducting glass containing perfluorinated sulfonic acid polymer, then by itself and low cost sulfonation polycyclic aromatic hydrocarbon polymer compound, obtain inorganic/organic composite proton exchange membrane thus, perfluorinated sulfonic acid polymer proton exchange membrane (as Nafion film) is compared, this composite membrane not only overall cost reduces, and has again high proton conductivity and good durability simultaneously.These methods are be main solution based on the water retention property improving PEM substantially.
Meanwhile, use enhancing by polymer perfluorosulfonic acid proton exchange film, not only can strengthen the mechanical strength of film, reduce the swellability of film, improve the dimensional stability of film, resistance and reduction material cost that ultra-thin proton exchange membrane reduces film can also be prepared.At most for being the polytetrafluoroethylene (PTFE) of porous as the polymer of the enhancement layer preparing composite membrane.Porous PTFE not only can give the good mechanical strength of composite membrane and dimensional stability, to avoid because proton exchange membrane material water suction is excessively swelling, the Catalytic Layer that causes and film are peeled off, and can also regulate proton conductivity and gas or methanol permeability by the porosity of change basilar memebrane and aperture.
The present invention is by a kind of phosphoric acid derivatives SiPOH gel of brand-new synthesis and perfluorinated sulfonic resin (Nafion) compound, recycling apertured polymeric film strengthens composite membrane, and preparing with apertured polymeric film is the composite membrane containing phosphoric acid derivatives SiPOH and perfluorinated sulfonic resin of carrier.
Summary of the invention
In order to overcome ionic exchange film for fuel cell, particularly perfluoro sulfonic acid membrane is to the shortcoming of ambient humidity high dependency, promote its working temperature and mechanical strength, the invention provides composite proton exchange membrane for fuel cell of a kind of excellent performance and preparation method thereof.
Composite proton exchange membrane for fuel cell provided by the invention, by phosphoric acid derivatives SiPOH gel and perfluorinated sulfonic resin (as Nafion) solution blending, recycling polymer porous film strengthens, and what prepare take polymer porous film as the composite membrane containing phosphoric acid derivatives SiPOH and perfluorinated sulfonic resin of carrier.This kind of composite membrane not only has good dimensional stability and higher mechanical strength, there is desirable proton conductivity and excellent monocell performance simultaneously, the Nafion series membranes that the working temperature of its best is purer is significantly improved, can as a kind of proton exchange membrane used under middle high temperature, low humidity conditions.
Composite proton exchange membrane for fuel cell provided by the invention, be made up of phosphoric acid derivatives (i.e. SiPOH gel), perfluorinated sulfonic resin (as Nafion) and the polymer porous film three for strengthening, its proportion of composing is as follows:
SiPOH gel 30 ~ 80wt%
Perfluor sulfoacid resin solution 15 ~ 50wt%
Polymer porous film 5 ~ 30wt%;
Three's summation is 100wt%.
The preparation method of above-mentioned compound proton exchange membrane provided by the invention, concrete steps are as follows:
(1) by SiPOH gel and appropriate perfluor sulfoacid resin solution blended, magnetic agitation 20 ~ 24h, then more than ultrasonic disperse 4h (being generally 4h-6h) in ultrasonic pond, again by vacuumizing the bubble getting rid of mixed solution, prepare finely dispersed SiPOH/ perfluorinated sulfonic resin (DMF) mixed solution;
(2) polymer porous film is evenly laid in framed in, then being cast in equably by the mixed solution in step (1) is covered with in the instrument bezel of perforated membrane, 60 ~ 70 DEG C of insulations more than 12h (being generally 12h-15h), solvent evaporated obtains even, the intimate transparent film of a thickness;
(3) by above-mentioned film at H
2o
2insulation 50-70 minute (being generally 1h) that (be generally 35-40 DEG C) at 40 DEG C is being less than in solution, again film is put into and be no more than the dry 5 ~ 8h of 60 DEG C of (being generally 50-60 DEG C) drying boxes, to remove the moisture of composite film surface, namely obtain required compound proton exchange membrane.
Compound proton exchange membrane prepared by the present invention is evenly close to transparent film, and its thickness is 20 ~ 30 μm, and hot strength is higher than 30MPa.
In the present invention, described phosphoric acid derivatives SiPOH gel, it is the white slurry that a kind of viscosity is very large, this slurry dissolves in suitable deionized water, can obtain a kind of intimate transparent gel after placing a period of time, it is insoluble to the organic solvents such as dimethyl formamide (DMF), ethanol, methyl-sulfoxide (DMSO) and chloroform.It is obtained by following preparation process:
(1) by anhydrous phosphoric acid (>99.0%) and anhydrous silicon tetrachloride (>99.9999%) under the sustainable protection of nitrogen atmosphere, react at initial temperature 40 ~ 50 DEG C, then be slowly warming up to 95-105 DEG C (generally at about 100 DEG C), insulation 3h ~ 4h, until HCl gas is all drained;
(2) be slowly warming up to 250 ~ 270 DEG C, then under 260-270 DEG C (being generally 270 DEG C), be incubated 1 ~ 2h;
(3) product more than the high speed centrifugation 20min will generated, removing supernatant liquor, can obtain SiPOH gel.
In the present invention, described perfluor sulfoacid resin solution is obtained by following preparation process:
(1) a kind of commercial perfluorinated sulfonic resin is chosen, as Nafion;
(2) H on sulfonic acid group is all changed into Na by perfluorinated sulfonic resin NaOH solution; Use H again
2sO
4na atom on sulfonic acid group is all converted into H atom by solution;
(3) perfluorinated sulfonic resin after transition is dissolved in DMF solution in autoclave, prepares the DMF solution that concentration is the perfluorinated sulfonic resin of the clear of 0.02 ~ 0.03g/mL.
In the present invention, described perfluorinated sulfonic resin, it is the polymer that main chain or side chain are all made up of carbon-fluorine bond, wherein, sulfonic acid group is with by side chain, as the Aquivion resin etc. of the Dow perfluorinated sulfonic resin of the Nafion of DuPond, DowChemical, the Aciplex resin of AsahiChemical, the Flemion resin of AsalliGlass and SolvaySolexis, but be not limited only to this.
In the present invention, described polymer porous film, its aperture size is micron order or nanoscale, hole is uniformly distributed, and there is stronger mechanical strength, can use as the enhancing matrix of perfluorinated sulfonic resin, as polytetrafluoroethylporous porous membrane (PTFE), polyvinylidene fluoride porous film (PVDF) and polyethylene porous membrane, but be not limited only to this.
The present invention, compared with existing perfluorosulfonic acid proton exchange film, has the following advantages:
The synthesis technique of 1.SiPOH is simple, manufacturing cycle system is short, cost is lower, SiPOH adds the consumption that can reduce perfluorinated sulfonic resin, the cost of proton exchange membrane is declined to a great extent, and the minimizing of perfluorinated sulfonic resin consumption simultaneously also makes the environmental pollution produced because producing perfluorinated sulfonic resin reduce;
2.SiPOH/ perfluorinated sulfonic resin/polymer porous film compound proton exchange membrane has higher mechanical strength and toughness, makes it have stable physical property and longer service life;
3.SiPOH/ perfluorinated sulfonic resin/polymer porous film compound proton exchange membrane is compared with perfluorinated sulfonic resin proton exchange membrane, its proton conductivity is decay not, and the working temperature of its best and the performance of monocell have had obvious lifting, can as a kind of proton exchange membrane used under middle high temperature, low-humidity environment.
Accompanying drawing explanation
Fig. 1 is that SiPOH content (accounting for the summation of SiPOH and Nafion quality) is respectively the pure Nafion double teeming film of 0%(), the proton conductivity variation with temperature figure of SiPOH/Nafion/PTFE compound proton exchange membrane of 30% and 50%.
Fig. 2 is for using the monocell photo made by the self-control proton exchange membrane described in Fig. 1.
Fig. 3 to be SiPOH content be 30% the monocell performance curve that records on fuel battery test system (850e, ScribnerAssociates, Inc, USA) of SiPOH/Nafion/PTFE compound proton exchange membrane, relative humidity is 100%.
Fig. 4 to be SiPOH content be 50% the monocell performance curve that records on fuel battery test system (850e, ScribnerAssociates, Inc, USA) of SiPOH/Nafion/PTFE compound proton exchange membrane, relative humidity is 100%.
Fig. 5 to be SiPOH content be 30% the monocell performance curve that records on fuel battery test system (Greenlight20) of SiPOH/Nafion/PTFE compound proton exchange membrane, relative humidity is 50%.
Fig. 6 to be SiPOH content be 30% the monocell performance curve that records on fuel battery test system (Greenlight20) of SiPOH/Nafion/PTFE compound proton exchange membrane, relative humidity is 100%.
Fig. 7 to be SiPOH content be 50% the monocell performance curve that records on fuel battery test system (Greenlight20) of SiPOH/Nafion/PTFE compound proton exchange membrane, relative humidity is respectively 50% and 100%.
Embodiment
For a better understanding of the present invention, content of the present invention is set forth further below in conjunction with example.
Raw materials used as follows:
Anhydrous silicon tetrachloride (SiCl
4>=99.9999%), lark prestige Science and Technology Ltd.;
Crystalline (H
3pO
4>=99.0%), EnergyChemistry
DMF (DMF, 99.8%), Chemical Reagent Co., Ltd., Sinopharm Group;
Perfluorinated sulfonic resin Nafion, du pont company;
The specific embodiment of the present invention is as follows:
The first step: the derivative (SiPOH) of chemical synthesis synthesis phosphoric acid
First anhydrous phosphoric acid is joined in the there-necked flask of 100mL; continue to pass into nitrogen protection; there-necked flask is put into oil bath pan heat; temperature is raised to 40 DEG C to be then incubated; and lasting magnetic agitation stirs, after anhydrous phosphoric acid dissolves completely, silicon tetrachloride is dropwise instilled in anhydrous phosphoric acid; after dripping off, oil bath pan temperature is risen to 100 DEG C gradually, and keep 100 DEG C constant until not regeneration HCl gas.Then change oil bath pan into electric heating cover, be warming up to 270 DEG C gradually, be incubated 1h after reaching 270 DEG C, obtained white slurry is carried out high speed centrifugation, removing supernatant liquor, namely obtains SiPOH.
Second step: prepare SiPOH/Nafion/PTFE composite film with casting method
The SiPOH first step prepared mixes with Nafion (DMF) solution of different quality respectively, through the magnetic agitation of certain hour, ultrasonic disperse and eliminating bubble, SiPOH and Nafion (DMF) solution is mixed.Again by the solution casting mixed in the instrument bezel being covered with one deck polytetrafluoroethylporous porous membrane (PTFE), at 70 DEG C, be incubated 12h, surface solvent evaporate to dryness can be obtained the different SiPOH/Nafion/PTFE composite film of a series of SiPOH content.
3rd step: the SiPOH/Nafion/PTFE composite film of preparation is carried out post-processed
Film in film frame in second step is peeled slowly from film frame, if comparatively tight bonding with instrument bezel of film, suitable deionized water can be dripped between film and instrument bezel, after soaking a period of time, take proton exchange membrane off again.The proton exchange membrane taken off is put into H
2o
2stir 6h at normal temperatures in solution, except the impurity on striping surface, then dry with the water of filter paper by Surface modification of proton exchange membrane.By the film after drying at 270 DEG C of hot pressing 3min, then at room temperature cold pressing 3min, makes film surface can be smooth.
4th: the monocell making SiPOH/Nafion/PTFE composite film
The carbon paper scribbling Pt/C catalyst is sticked in 3rd step hot pressing and upper and lower two surfaces of SiPOH/Nafion/PTFE composite film after colding pressing, and then the compound result of this sandwich-like is placed on hot press, hot pressing 5min at 270 DEG C, cold pressing 5min more at normal temperatures, after taking-up, edge, two sides sticks the insulating tape of polyimides, has namely been made into the monocell of SiPOH/Nafion/PTFE composite film.
Embodiment 1
The present embodiment relates to the compound method of the DMF solution of a kind of Nafion, and its preparation method is as follows:
The acidifying of step 1:Nafion resin.Get 10gNafion NR40 resin to join in 250mL single port flask, then add 30mL distilled water, 15gNaOH solid, 10mLDMSO successively, then at 80 DEG C, be incubated 5h, in whole process, adopt magnetic agitation always.
The alkalization of step 2:Nafion resin.By the Nafion resin filter after acidifying out, wash repeatedly with deionized water until its pH is in neutral.Then Nafion resin is joined in 250mL single port flask, then add 50mL distilled water, 10mL concentrated hydrochloric acid successively, at 80 DEG C, be incubated 2h, by the Nafion resin filter after alkalization out, wash repeatedly with deionized water until its pH is in neutral.The moisture on Nafion resin surface is dried, stand-by.
The dissolving of step 3:Nafion resin.Getting 3g joins in the beaker of the polytetrafluoroethylene of 100mL according to the Nafion resin after step 1 and step 2 make the transition, add DMF solution and the magnetic stir bar of 80mL, again this polytetrafluoroethylene beaker is put in autoclave, tighten lid, be heated to 200 DEG C by sand-bath and be incubated 5h.
The filtration of step 4:Nafion solution and purification.The DMF solution of the Nafion solution after dissolving is carried out condensing reflux 6h at 160 DEG C under nitrogen protection, refilters 2 times, get the DMF solution that supernatant liquor is pure transparent Nafion solution.
The mensuration of step 5:Nafion solution concentration.This solution getting three parts of 1mL, in the middle of the clean glass plate that three have weighed up quality, is incubated 10h, solvent evaporated, then takes the quality of glass plate, determined the concentration of Nafion solution by the mean value of both differences at 100 DEG C.
Embodiment 2
Get 0.35g concentration be the DMF solution of the Nafion of 0.02531g/mL in 100mL single port flask, then add 0.25gSiPOH, magnetic agitation 12h, then at the ultrasonic 3h in ultrasonic pond, then take out 1h to remove the bubble in mixed solution with water pump.Cutting out lower area is again the polytetrafluoroethylporous porous membrane of 12cm × 12cm.Bottom the glass plate of 10cm × 10cm, drip upper several above-mentioned mixed solutions, tiled on a glass by the polytetrafluoroethylporous porous membrane under cutting out, ensureing that perforated membrane is smooth does not have fold.Then the mixed solution of Nafion and SiPOH is added drop-wise in instrument bezel.Put in baking oven by this instrument bezel and be incubated 12h at 70 DEG C, the proton exchange membrane that the solvent on evaporate to dryness surface can obtain similar transparent is for subsequent use.
Embodiment 3
Get 0.25g concentration be the DMF solution of the Nafion of 0.02531g/mL in 100mL single port flask, then add 0.15gSiPOH, magnetic agitation 12h, then at the ultrasonic 3h in ultrasonic pond, then take out 1h to remove the bubble in mixed solution with water pump.Cutting out lower area is again the polytetrafluoroethylporous porous membrane of 12cm × 12cm.Drip upper several above-mentioned mixed solutions bottom the glass plate of present 10cm × 10cm, tiled on a glass by the polytetrafluoroethylporous porous membrane under cutting out, ensureing that perforated membrane is smooth does not have fold.Then the mixed solution of Nafion and SiPOH is added drop-wise in instrument bezel.Put in baking oven by this instrument bezel and be incubated 12h at 70 DEG C, the proton exchange membrane that the solvent on evaporate to dryness surface can obtain similar transparent is for subsequent use.
Embodiment 4
The present embodiment relates to a kind of preparation method of monocell of proton exchange membrane, and its preparation method is as follows:
The preparation of step 1:Pt/C catalyst solution.Get the Pt/C powder of 12.5mg, add the ethanolic solution of the Nafion of 107.14mg5%, 5mL isopropyl alcohol more successively, solution A is designated as after mixing, get the Pt/C powder of 30mg again, add the ethanolic solution of the Nafion of 257.14mg5%, 5mL isopropyl alcohol more successively, after mixing, be designated as solution B.
Step 2: the preparation being loaded with catalyst C paper.Get the C paper of two 5cm × 5cm, dip in solution A in step 1 and solution B respectively at the two sides writing brush of C paper, by the two sides being coated in C paper of dissolution homogeneity, dry in atmosphere.
Step 3: the C paper the being loaded with Pt/C catalyst proton exchange membrane two sides prepared being put above-mentioned preparation, then hot pressing 3min at 270 DEG C, at room temperature cold pressing 5min.Then the insulating tape of polyimides is sticked at the edge of two sides C paper.Be made into monocell as shown in Figure 2.
Claims (6)
1. a composite proton exchange membrane for fuel cell, it is characterized in that, be by phosphoric acid derivatives SiPOH gel and perfluor sulfoacid resin solution blended, recycling polymer porous film strengthens, and what prepare take polymer porous film as the composite membrane containing phosphoric acid derivatives SiPOH and perfluorinated sulfonic resin of carrier; Its proportion of composing is as follows:
SiPOH gel 30 ~ 80wt%
Perfluor sulfoacid resin solution 15 ~ 50wt%
Polymer porous film 5 ~ 30wt%.
2. the preparation method of composite proton exchange membrane for fuel cell according to claim 1, is characterized in that, concrete steps are:
(1) by SiPOH gel and appropriate perfluor sulfoacid resin solution blended, magnetic agitation 20 ~ 24h, then more than ultrasonic disperse 4h in ultrasonic pond, again by vacuumizing the bubble got rid of in mixed solution, prepare finely dispersed SiPOH/ perfluorinated sulfonic resin (DMF) mixed solution;
(2) polymer porous film is evenly laid in glass framed in, then the mixed solution in step (1) is cast in equably the glass being covered with perforated membrane framed in, at 60 ~ 70 DEG C, be incubated more than 12h, namely solvent evaporated obtains even, the intimate transparent film of a thickness;
(3) by above-mentioned film at H
2o
2be incubated 50-70 minute being less than at 40 DEG C in solution, then film is put into be no more than the dry 5 ~ 8h of 60 DEG C of drying boxes, to remove the moisture of composite film surface, namely obtain required compound proton exchange membrane.
3. preparation method according to claim 2, it is characterized in that, described phosphoric acid derivatives SiPOH gel, it is the white slurry that a kind of viscosity is very large, this slurry dissolves in deionized water, can obtain a kind of intimate transparent gel after placing a period of time, it is insoluble to dimethyl formamide, ethanol, methyl-sulfoxide and chloroform, and it is obtained by following preparation process:
(1) by anhydrous phosphoric acid and anhydrous silicon tetrachloride under the sustainable protection of nitrogen atmosphere, react at initial temperature 40 ~ 50 DEG C, be then slowly warming up to 95-105 DEG C, insulation 3 ~ 4h, until HCl gas is all drained;
(2) be slowly warming up to 250 ~ 270 DEG C, then at 260-280 DEG C, be incubated 1 ~ 2h;
(3) product more than the high speed centrifugation 20min will generated, removing supernatant liquor, can obtain SiPOH gel.
4. preparation method according to claim 2, is characterized in that, described perfluor sulfoacid resin solution is obtained by following preparation process:
(1) a kind of commercial perfluorinated sulfonic resin is chosen;
(2) H on sulfonic acid group is all changed into Na by perfluorinated sulfonic resin NaOH solution; Use dense H again
2sO
4na on sulfonic acid group is all converted into H atom;
(3) perfluorinated sulfonic resin after transition is dissolved in DMF solution in autoclave, prepares the DMF solution that concentration is the perfluorinated sulfonic resin of the clear of 0.02 ~ 0.03g/mL.
5. preparation method according to claim 2, it is characterized in that, described perfluorinated sulfonic resin is the polymer that main chain or side chain are all made up of carbon-fluorine bond, wherein, sulfonic acid group is with by side chain, comprise the Nafion of DuPond, the Dow perfluorinated sulfonic resin of DowChemical, the Aciplex resin of AsahiChemical, the Flemion resin of AsalliGlass and the Aquivion resin of SolvaySolexis.
6. preparation method according to claim 2, is characterized in that, described polymer porous film, its aperture size is micron order or nanoscale, hole is uniformly distributed, and has stronger mechanical strength, comprises polytetrafluoroethylporous porous membrane, polyvinylidene fluoride porous film and polyethylene porous membrane.
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Cited By (8)
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| CN106432766A (en) * | 2016-10-09 | 2017-02-22 | 天津大学 | Nafion/orthophosphoric loaded covalent organic framework material composite film, preparation and application |
| CN112349942A (en) * | 2020-10-13 | 2021-02-09 | 南方科技大学 | Proton exchange membrane, preparation method thereof and fuel cell |
| CN112993353A (en) * | 2019-12-14 | 2021-06-18 | 中国科学院大连化学物理研究所 | High-water-retention composite proton exchange membrane and preparation method thereof |
| CN115178731A (en) * | 2022-08-10 | 2022-10-14 | 福州大学 | TiO 2 Application of/MXene photoanode material in photo-generated cathodic protection |
| CN115566238A (en) * | 2022-10-20 | 2023-01-03 | 重庆星际氢源科技有限公司 | Composite proton exchange membrane with high hard water resistance and preparation method and application thereof |
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| CN112993353B (en) * | 2019-12-14 | 2022-07-19 | 中国科学院大连化学物理研究所 | High-water-retention composite proton exchange membrane and preparation method thereof |
| CN112349942A (en) * | 2020-10-13 | 2021-02-09 | 南方科技大学 | Proton exchange membrane, preparation method thereof and fuel cell |
| CN117543039A (en) * | 2022-08-02 | 2024-02-09 | 北京清驰科技有限公司 | Coating liquid for proton exchange membrane and preparation method and application thereof |
| CN115178731A (en) * | 2022-08-10 | 2022-10-14 | 福州大学 | TiO 2 Application of/MXene photoanode material in photo-generated cathodic protection |
| CN115178731B (en) * | 2022-08-10 | 2024-03-12 | 福州大学 | TiO 2 Application of/MXene photo-anode material in photo-generated cathode protection |
| CN115566238A (en) * | 2022-10-20 | 2023-01-03 | 重庆星际氢源科技有限公司 | Composite proton exchange membrane with high hard water resistance and preparation method and application thereof |
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| CN115948012B (en) * | 2022-11-30 | 2023-12-19 | 华电重工股份有限公司 | Fiber reinforced proton exchange membrane for hydrogen production by water electrolysis and preparation method thereof |
| CN115948012A (en) * | 2022-11-30 | 2023-04-11 | 华电重工股份有限公司 | Fiber-reinforced proton exchange membrane for hydrogen production by water electrolysis and preparation method thereof |
| CN117913331A (en) * | 2024-03-14 | 2024-04-19 | 中海储能科技(北京)有限公司 | Proton exchange membrane modification method for iron-chromium flow battery and perfluorinated sulfonic acid composite membrane |
| CN117913331B (en) * | 2024-03-14 | 2024-06-07 | 中海储能科技(北京)有限公司 | Proton exchange membrane modification method for iron-chromium flow battery and perfluorinated sulfonic acid composite membrane |
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