CN102181069B - Preparation method of amphoteric ion exchange membrane - Google Patents
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Abstract
The invention discloses a preparation method of an amphoteric ion exchange membrane and relates to a preparation method of an amphoteric ion exchange membrane for an all-vanadium redox flow battery. According to the scheme, the preparation method comprises the following steps of: performing irradiation grafting on polymer powder poly(vinylidene fluoride); transforming the irradiation-grafted polymer powder into a membrane material; and sulfonating the membrane material, hydrolyzing, introducing a sulfonate radical group with a cationic exchange function, putting the membrane material into a hydrochloric acid aqueous solution for undergoing a protonation reaction and introducing basic nitril with an anion exchange function to obtain the amphoteric ion exchange membrane. In the method, commercial poly(vinylidene fluoride) resin with low price is taken as a raw material, so that the membrane making cost can be lowered; a C-F bond has large bond energy, so that the membrane can keep high chemical stability in a strong acid and high oxidizing electrochemical environment; and meanwhile, the problem of non-uniform distribution of grafted chains of the conventional heterogeneous irradiation-grafted membrane in the vertical direction of the membrane is solved.
Description
Technical field
The present invention relates to electrochemistry and high molecular functional technology field of membrane materials, be specifically related to a kind of preparation method who is used for the amphoteric ion exchange membrane of all-vanadium flow battery.
Background technology
All-vanadium flow battery (VRFB) is a kind of with the energy storage system of different valence state vanadium ion as the cell reaction active substance, has the energy storage efficiency height, has extended cycle life, advantage such as safe and reliable, low cost, in extensive energy storage, good prospects for application is being arranged.Ion exchange membrane material is the Core Feature assembly of VRFB, and it mainly act as electrolytic solution and the proton conducting of separating positive and negative polarities.In order to improve the VRFB energy efficiency and to prolong its cycle life, ion-exchange membrane should be able to effectively hinder the vanadium ion infiltration, and has performances such as proton conductivity height, chemicalstability are good.
The general status of just present commercialization ion-exchange membrane does not also have a kind of ion-exchange membrane can satisfy above-mentioned requirements fully.Because the strongly-acid and the VO of VRFB electrolytic solution
2 +Strong oxidizing property, a lot of ion-exchange membranees can be degraded being used for VRFB, can not satisfy request for utilization; Though the Nafion that E.I.Du Pont Company produces series barrier film stability better, specific conductivity is performed poor aspect ion selectivity also than higher, and the crossed contamination phenomenon is serious, and costs an arm and a leg, and can not satisfy the needs of extensive energy storage.In order to address the above problem, the various countries investigator has carried out a large amount of work.M.Styllas-Kazacos is soaked in Daramic in Vinylstyrene (DVB) solution; It is crosslinked in Sodium persulfate, to add thermal initiation DVB then, with the vitriol oil composite package is carried out the cationic exchange membrane (J.Membr.Sci.1995 (107): 35-45) that sulfonation obtains stable performance at last.Xi etc. have prepared Nafion/SiO
2Composite package (J.Power Souces.2007,166:531-536).This composite package has shown loading capacity and the specific conductivity close with the Nafion film, is then obtaining tangible improvement aspect the vanadium ion rate of permeation, but this film cost is than higher, incompatibility scale operation.Therefore, exploitation has the IX film system of special construction and new film-forming process, and is significant to the commercialized development that advances all-vanadium flow battery.
Summary of the invention
The purpose of this invention is to provide a kind of low cost, be fit to large-scale industrial production and be applicable to the preparation method of the amphoteric ion exchange membrane of all-vanadium flow battery.
The amphoteric ion exchange membrane that is used for all-vanadium flow battery, its chemical structure is suc as formula shown in the I
(formula I)
In the formula (I), R
1, R
2, R
3Can be H, F, any in the alkyl; Polymer is the pvdf (PVDF) with different molecular weight and MWD.
The preparing method's of amphoteric ion exchange membrane provided by the invention technical scheme is following:
Scheme 1: a kind of preparation method of amphoteric ion exchange membrane, it is characterized in that, comprise the steps:
1) polymer powder is carried out irradiation grafting, two kinds of methods is arranged:
A) polymer powder, reaction monomers, solvent are joined in the irradiation tube logical nitrogen (N
2) the back sealing, use then
60Co gamma-radiation or electron beam at room temperature carry out the mutual radiation graft reaction, and absorption dose is 5-100kGy;
B) method of employing pre-irradiation grafting, concrete steps are the environment that earlier polymer powder placed aerobic or anaerobic, use
60Co gamma-radiation or electron beam irradiation doses (5-100kGy), and, then the powder behind the irradiation is mixed stirring reaction 1-6h under specified temp (40-80 ℃) with monomer solution in low temperature (20 ℃) preservation down;
After reaction finished, the powder behind the taking-up irradiation grafting was cleaned homopolymer and the intact monomer of unreacted with toluene;
Wherein, polymer powder is pvdf (PVDF); Monomer I is one or more in vinylbenzene, αJia Jibenyixi and the trifluorostyrene; Monomer II is a dimethylaminoethyl methacrylate; Reaction solvent is an acetone, a kind of in Virahol and the methylene dichloride or more than one;
2) above-mentioned irradiation grafting post polymerization powder is changed into mould material, two kinds of methods is arranged:
A) solution phase inversion process; With the heated and stirred dissolving in organic solvent of the polymer powder after the grafting; Obtain certain density polymkeric substance film-casting liquid, be injected into subsequently on the sheet glass of smooth cleaning, with the thickness of scraper control liquid film at the 20-100 micron; Place baking oven 50-100 ℃ of oven dry film forming, clean with deionized water at last;
B) pressure sintering directly places thermocompressor with the polymer powder after the grafting, 185-190 ℃ with 8-10MPa under, hot pressing 20-30min obtains macromolecule member material;
3) above-mentioned mould material is carried out sulfonation, hydrolysis; Introducing has the sulfonate group of cationic exchange function, then, this mould material is put into aqueous hydrochloric acid carry out protonation reaction; Introducing has uncle's amino of anionresin function, obtains amphoteric ion exchange membrane.
Scheme 2: as a kind of preferred realization of scheme 1; It is characterized in that; After step 1) finished, the graft polymerization powder of purifying and inorganics blend, performing step 2 then); Be prepared into the organic/inorganic cluster ion exchange membrane like this, can further improve the character such as physical strength, specific conductivity of ion-exchange membrane.
Scheme 3: a kind of preferred realization as scheme 2 is characterized in that said inorganics is one or more in silicon-dioxide, titanium oxide, ZIRCONIUM DIOXIDE 99.5, phospho-wolframic acid and the phospho-molybdic acid.
Scheme 4: a kind of preferred realization as scheme 1, it is characterized in that, after step 3), further, self-assembly in the amphoteric ion exchange membrane immersion polyelectrolyte solution that makes is prepared into bilayer or multilayer ion-exchange membrane.
Scheme 5: a kind of preferred realization as scheme 4 is characterized in that said polyelectrolyte solution is one or more in Nafion solution, Lewatit solution, quaternary ammoniated polystyrene solution and the quaternary ammoniated polyaryletherketone solution.
Scheme 6: a kind of preferred realization as scheme 1 is characterized in that the molecular weight of said pvdf is from 100000-630000.
Scheme 7: a kind of preferred realization as scheme 1, it is characterized in that monomer I and the monomer II volumetric molar concentration in solution is 0.1mol/L-2mol/L in the said step 1), the molar mass proportioning of the two is 1: 1-1: 5.
Scheme 8: a kind of preferred realization as scheme 1 is characterized in that said step 2) step a) in, the concentration of polymkeric substance film-casting liquid is 0.1g/mL-0.3g/mL; Organic solvent is a kind of in N-Methyl pyrrolidone, N, N,N-DIMETHYLACETAMIDE and the DMSO 99.8MIN. or more than one.
Scheme 9: as a kind of preferred realization of scheme 1; It is characterized in that; Sulfonation in the said step 3), hydrolytic process are: immerse sulfonation 12h in the chlorsulfonic acid dichloromethane solution that volumetric molar concentration is 0.02-0.1mol/L to mould material, put it into hydrolysis 12h in the zero(ppm) water subsequently.
Scheme 10: a kind of preferred realization as scheme 1 is characterized in that the aqueous hydrochloric acid concentration in the said step 3) is 1mol/L.
Advantage of the present invention and useful effect are:
1. the present invention is through the radiation grafting polymerization, on the polymer base material of no ion exchanging function, has introduced the macromolecular grafted chain that contains negatively charged ion and cation exchange group with the form of covalent linkage.Because the Donna repelling effect, the vanadium ion of high valence state has received the repulsion of positive charge group, and its ability that sees through amphoteric ion exchange membrane has obtained inhibition, and the sulfonic acid group on the grafted chain can guarantee the wetting ability of film and the conduction of proton again simultaneously.
The present invention be with cheap commercialization polyvinylidene fluoride resin as starting material, can reduce on the one hand the cost of system film; On the other hand,, make this film under the electrochemical environment of strong acid strong oxidizing property, can keep good chemical-resistant stability, be fit to commercial applications because the bond energy of C-F key is bigger.
3. the present invention can regulate and control the performances such as ion capacity, proton conduction and the infiltration of obstruction vanadium ion of ion-exchange membrane easily through the processing parameter that changes irradiation absorption dose, monomer concentration and proportioning and system film.
4. the present invention is first at polymer powder grafting functional property monomer, and the laggard one-step functional of solution inversion of phases or hot pressing film forming obtains amphoteric ion exchange membrane.Than the ion-exchange membrane that directly graft modification is prepared on the commercialization film, the grafted chain that the ion-exchange membrane of novel process preparation has solved traditional irradiation grafting film is in the vertical direction of film problem pockety.
Description of drawings
Fig. 1 is the operational path of embodiment 1 preparation amphoteric ion exchange membrane.
Fig. 2 is the resistance vanadium ion penetrating quality figure of amphoteric ion exchange membrane under the different percentage of grafting.
Fig. 3 is the section SEM-EDX picture (distribution of curve representation sulphur (S) element above the film section) of amphoteric ion exchange membrane.
Wherein the GY among Fig. 2 and Fig. 3 representes percentage of grafting.
Embodiment
Illustrate the present invention with embodiment below, but these embodiment should not be interpreted as limitation of the present invention.
With molecular weight is in the dichloromethane solution of 430000 pvdf (PVDF) the powder vinylbenzene (St) and the dimethylaminoethyl methacrylate (DMAEMA) that are immersed in 1mol/L, uses then
60The Co gamma-radiation at room temperature carries out irradiation, and absorption dose is 35kGy, and wherein the molar mass ratio of vinylbenzene (St) and dimethylaminoethyl methacrylate (DMAEMA) is 1: 5.After irradiation finishes, for use with oven dry behind the intact monomer of toluene flush away homopolymer and unreacted.
Powder after the 2g grafting is dissolved in the solvent dimethylformamide of 100mL.This solution heated and stirred in 50 ℃ of water-baths is even, obtain transparent viscous soln.This viscous soln is cast on the sheet glass of smooth cleaning and 60 ℃ of oven dry film forming down, and in deionized water, cleans.Subsequently, react 12h in the chlorsulfonic acid dichloromethane solution with this film immersion 0.2mol/L, introduce sulfonic acid group with cationic exchange function.At last, film is immersed protonation reaction 12h in the aqueous hydrochloric acid of 1mol/L, obtain amphoteric ion exchange membrane.
Specific embodiment 2
With molecular weight is in the dichloromethane solution of 430000 the pvdf powder vinylbenzene and the dimethylaminoethyl acrylate methyl ammonia ethyl ester that are immersed in 1mol/L, uses then
60The Co gamma-radiation at room temperature carries out irradiation, and absorption dose is 35kGy, and wherein the molar mass ratio of vinylbenzene and dimethylaminoethyl acrylate methyl ammonia ethyl ester is 1: 5.After irradiation finishes, for use with oven dry behind the intact monomer of toluene flush away homopolymer and unreacted.
Powder after the 2g grafting is directly placed thermocompressor, and under 190 ℃ of conditions with 8MPa, hot pressing 30min obtains macromolecule member material.Subsequently, react 12h in the chlorsulfonic acid dichloromethane solution with this film immersion 0.2mol/L, introduce sulfonic acid group with cationic exchange function.At last, film is immersed protonation reaction 12h in the aqueous hydrochloric acid of 1mol/L, obtain amphoteric ion exchange membrane.
With molecular weight be 430000 pvdf powder in air, use
60The Co gamma-radiation at room temperature carries out irradiation, and absorption dose is 15kGy, and places-20 ℃ to preserve down.Powder behind the irradiation is mixed with the 1mol/L monomer solution, and at 60 ℃ of stirred in water bath reaction 6h, wherein the molar mass ratio of vinylbenzene and dimethylaminoethyl acrylate methyl ammonia ethyl ester is 1: 5.After reaction finishes, dry for use behind the monomer that finishes with toluene flush away homopolymer and unreacted.
Powder after the 2g grafting is dissolved in the solvent dimethylformamide of 100mL, and adds the silicon dioxide granule of 0.2g in addition.This mixing solutions heated and stirred in 50 ℃ of water-baths is even.This viscosity mixing solutions is cast on the sheet glass of smooth cleaning and 60 ℃ of oven dry film forming down, and in deionized water, cleans.Subsequently, react 12h in the chlorsulfonic acid dichloromethane solution with this film immersion 0.2mol/L, introduce sulfonic acid group with cationic exchange function.At last, film is immersed protonation reaction 12h in the aqueous hydrochloric acid of 1mol/L, obtain amphoteric ion exchange membrane.
Specific embodiment 4
Use with embodiment 1 identical method and prepare amphoteric ion exchange membrane, with 24h in the Nafion solution of film immersion 5%, obtain compound amphoteric ion exchange membrane after the oven dry subsequently.
Specific embodiment 5
Use the method identical with embodiment 1, different is that absorption dose is 20kGy in the irradiation grafting reaction.
Specific embodiment 6
Use the method identical with embodiment 1, different is the electron beam irradiation that adopts rumbatron to produce.
Specific embodiment 7
Use the method identical with embodiment 3, different is that the inorganics that adds is the titanium oxide of 0.2g.
Specific embodiment 8
Use the method identical with embodiment 1, different is that monomeric concentration is 2mol/L in the irradiation grafting reaction.
Specific embodiment 9
Use the method identical with embodiment 1, the mole proportioning of different is in irradiation grafting reaction vinylbenzene and dimethylaminoethyl methacrylate is 1: 3.
Specific embodiment 10
Use the method identical with embodiment 1, different is is the polymer powder after the organic solvent dissolution grafting with the N-Methyl pyrrolidone.
Specific embodiment 11
Use the method identical with embodiment 1, the concentration of different the is graft polymerization powder the is dissolved in film-casting liquid that organic solvent obtains is 0.1g/mL.
Specific embodiment 12
Use the method identical with embodiment 1, the concentration of different the is graft polymerization powder the is dissolved in film-casting liquid that organic solvent obtains is 0.15g/mL.
Specific embodiment 13
Use the method identical with embodiment 2, different is graft polymerization powder is hot-forming to be under 180 ℃ of conditions with 10MPa, to carry out.
Specific embodiment 14
Use the method identical with embodiment 1, the concentration of different is chlorsulfonic acid dichloromethane solution in the sulfonation reaction is 0.4mol/L.
Specific embodiment 15
Use the method identical with embodiment 1, the monomer of reaction that different is is αJia Jibenyixi and dimethylaminoethyl methacrylate.
Specific embodiment 16
Use the method identical with embodiment 1, the monomer of reaction that different is is trifluorostyrene and dimethylaminoethyl methacrylate.
Specific embodiment 17
Use the method identical with embodiment 1, the molecular weight of different is pvdf is 630000.
Specific embodiment 18
Use the method identical with embodiment 1, the molecular weight of different is pvdf is 103000.
Claims (9)
1. a preparation method who is applicable to the amphoteric ion exchange membrane of all-vanadium flow battery is characterized in that, comprises the steps:
1) polymer powder is carried out irradiation grafting, two kinds of methods is arranged:
A) polymer powder, reaction monomers, solvent are joined in the irradiation tube, seal behind the logical nitrogen, use then
60Co gamma-radiation or electron beam at room temperature carry out the mutual radiation graft reaction, and absorption dose is 5-100kGy;
B) method of employing pre-irradiation grafting, concrete steps are the environment that earlier polymer powder placed aerobic or anaerobic, use
60Co gamma-radiation or electron beam irradiation 5-100kGy, and-20 ℃ of preservations down, then the powder behind the irradiation is mixed with monomer solution, at 40-80 ℃ of following stirring reaction 1-6h;
After reaction finished, the powder behind the taking-up irradiation grafting was cleaned homopolymer and the intact monomer of unreacted with toluene;
Wherein, polymer powder is a pvdf; Reaction monomers is the mixture of monomer I and monomer II, and monomer I is one or more in vinylbenzene, αJia Jibenyixi and the trifluorostyrene; Monomer II is a dimethylaminoethyl methacrylate; Reaction solvent is an acetone, a kind of in Virahol and the methylene dichloride or more than one;
2) above-mentioned irradiation grafting post polymerization powder is changed into mould material, two kinds of methods is arranged:
A) solution phase inversion process; With the heated and stirred dissolving in organic solvent of the polymer powder after the grafting; Obtain certain density polymkeric substance film-casting liquid, be injected into subsequently on the sheet glass of smooth cleaning, with the thickness of scraper control liquid film at the 20-100 micron; Place baking oven 50-100 ℃ of oven dry film forming, clean with deionized water at last;
B) pressure sintering directly places thermocompressor with the polymer powder after the grafting, 185-190 ℃ with 8-10MPa under, hot pressing 20-30min obtains macromolecule member material;
3) above-mentioned mould material is carried out sulfonation, hydrolysis; Introducing has the sulfonate group of cationic exchange function, then, this mould material is put into aqueous hydrochloric acid carry out protonation reaction; Introducing has uncle's amino of anionresin function, obtains amphoteric ion exchange membrane.
2. the preparation method of amphoteric ion exchange membrane as claimed in claim 1 is characterized in that, after step 1) finished, the graft polymerization powder of purifying and inorganics blend, performing step 2 then).
3. the preparation method of amphoteric ion exchange membrane as claimed in claim 2 is characterized in that, said inorganics is one or more in silicon-dioxide, titanium oxide, ZIRCONIUM DIOXIDE 99.5, phospho-wolframic acid and the phospho-molybdic acid.
4. the preparation method of amphoteric ion exchange membrane as claimed in claim 1 is characterized in that, after step 3), further, self-assembly in the amphoteric ion exchange membrane immersion polyelectrolyte solution that makes is prepared into bilayer or multilayer ion-exchange membrane.
5. the preparation method of amphoteric ion exchange membrane as claimed in claim 4; It is characterized in that said polyelectrolyte solution is one or more in Nafion solution, Lewatit solution, quaternary ammoniated polystyrene solution and the quaternary ammoniated polyaryletherketone solution.
6. the preparation method of amphoteric ion exchange membrane as claimed in claim 1 is characterized in that, the molecular weight of said pvdf is from 100000-630000.
7. the preparation method of amphoteric ion exchange membrane as claimed in claim 1 is characterized in that, said step 2) step a) in, the concentration of polymkeric substance film-casting liquid is 0.1g/mL-0.3g/mL; Organic solvent is a kind of in N-Methyl pyrrolidone, N, N,N-DIMETHYLACETAMIDE and the DMSO 99.8MIN. or more than one.
8. the preparation method of amphoteric ion exchange membrane as claimed in claim 1; It is characterized in that; Sulfonation in the said step 3), hydrolytic process are: immerse sulfonation 12h in the chlorsulfonic acid dichloromethane solution that volumetric molar concentration is 0.02-0.1mol/L to mould material, put it into hydrolysis 12h in the zero(ppm) water subsequently.
9. the preparation method of amphoteric ion exchange membrane as claimed in claim 1 is characterized in that, the aqueous hydrochloric acid concentration in the said step 3) is 1mol/L.
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