CN102945972A - Preparation method of composite proton exchange membrane for all vanadium redox flow battery - Google Patents
Preparation method of composite proton exchange membrane for all vanadium redox flow battery Download PDFInfo
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Abstract
The invention discloses a preparation method of a composite proton exchange membrane for an all vanadium redox flow battery and belongs to the technology of proton exchange membranes. The composite proton exchange membrane mainly comprises sulfonated poly(ether ether ketone) and additives. The preparation method comprises the following steps that poly(ether ether ketone) is added into concentrated sulfuric acid and undergoes a sulfonation reaction with stirring for a certain time; the reaction solution is poured into ice water so that the sulfonation reaction is stopped and sulfonated poly(ether ether ketone) precipitates are separated out; the sulfonated poly(ether ether ketone) precipitates are treated to form purified sulfonated poly(ether ether ketone); the purified sulfonated poly(ether ether ketone) and the additives are dissolved in an organic solvent according to a certain ratio so that a membrane preparation solution is obtained; the membrane preparation solution is poured into a mold and is processed into a membrane by curtain coating; and the membrane is processed into the composite proton exchange membrane. The composite proton exchange membrane has the advantages of good proton conductivity, chemical stability, vanadium resistance and good mechanical properties and is an excellent proton exchange membrane for an all vanadium redox flow battery. The preparation method has simple processes, a low cost and good environmental benefits, can be industrialized easily and can be widely used in the field of all vanadium redox flow batteries.
Description
Technical field
The present invention relates to the vanadium redox battery field, specifically a kind of preparation method who is applicable to vanadium redox battery usefulness composite proton exchange membrane material.
Background technology
Vanadium redox battery (VRB) is a kind of new and effective electrochemical energy storage system that grew up from 1984.The vanadium ion electrolyte of different redox states circulates under the promotion of pump, and discharge provides electric energy at the proton exchange membrane place.This system has lot of advantages,, greatly electric current harmless deep discharge, long service life, easy to operate and safeguard adjustable such as capacity and power can be widely used in the fields such as the energy storage of " peak load shifting ", solar energy and wind power generation of network system and power station energy storage.
Proton exchange membrane is one of critical material of restriction VRB development.At present, the polytetrafluoroethylene cation-exchange membrane (Nafion film series) produced of the du pont company advantages such as conductance is high because having, chemistry and electrochemical stability are good are widely adopted.But its high vanadium ion permeability and expensive price have restricted the commercialization process of VRB.Therefore, develop a kind of VRB cheap and easy to get and excellent performance and with proton exchange membrane very great meaning is arranged.
Polyether-ether-ketone (PEEK) is a kind of functional material of function admirable.Researchers find, the product sulfonated polyether-ether-ketone (SPEEK) that PEEK obtains after sulfonation has higher proton conductivity, good chemical stability and mechanical strength.In recent years, researchers find after the optimization processes such as doped and compounded by the SPEEK film is carried out, the performances such as its alcohol-rejecting ability, conductance, chemical stability, mechanical strength can meet or exceed the Nafion film, are expected to replace expensive Nafion film and are widely used in fuel cell field.Because the barrier film of fuel cell and the barrier film of VRB have common part in function, have recent years part Study person begin one's study the utilization of SPEEK film in VRB (such as Qing T. L., etal., J. Membr. Sci. 2008,325,553-558; Li Liangqiong etc. chemical journal. 2009,67 (24): 2785-2790; Jia, C., etal., J. Power Sources 2010,195,4380-4383; Mai, Z., etal., J. Power Sources 2011,196,482-487; Lu Hui etc. chemical research and application. 2011,23 (6): 689-695; Liu Jianguo etc. CN101931070A, 2009).Research is found, the modification of SPEEK film process, and the performances such as its resistance vanadium performance, conductance, chemical stability, mechanical strength can meet or exceed the Nafion film, are expected to replace expensive Nafion film and are widely used in the VRB field.Therefore, develop a kind of preparation and method of modifying of suitable SPEEK film extremely important.
Summary of the invention
The object of the invention is to provide a kind of vanadium redox battery cheap and easy to get and excellent performance preparation method of compound proton exchange membrane.
To achieve these goals, the present invention adopts following technical scheme:
A kind of vanadium redox battery preparation method of compound proton exchange membrane comprises the steps and process conditions:
(1) by weight, it is in 95～98% the concentrated sulfuric acid that 1 part of dry polyether-ether-ketone of processing is added 10～60 parts of weight percent concentration, behind 25～65 ℃ of water bath with thermostatic control reaction 3～10h, reactant liquor poured into stop sulfonation in the frozen water, separate out the sulfonated polyether-ether-ketone precipitation, decompress filter, wash sediment with water to neutral, shift dry 6～24h in sediment to the 100 ℃ drying box, obtain sulfonated polyether-ether-ketone, then place desiccator for subsequent use.
(2) sulfonated polyether-ether-ketone that obtains in the step (1) is added in the high boiling solvent, add thermal agitation 1～5h to fully dissolving at 60～120 ℃, be mixed with mass fraction and be 5～30% solution.
(3) add additive in the gained solution in step (2), its addition is 0～200% of sulfonated polyether-ether-ketone quality, then adds thermal agitation 1～5h to complete dispersing and dissolving at 60～120 ℃, obtains preparation liquid.
(4) preparation liquid that is made in the step (3) is poured in the clean flat plate mold, at 30～80 ℃ of drying 4～48h, obtained wet film.Again with wet film at 50～150 ℃ of drying 1～24h, obtain dry film.
(5) dry film in the step (4) is cooled to room temperature after, soak with deionized water and to take off film, cut off the corner, under the room temperature with the H of film at 1～5M
2SO
4Behind middle immersion 24～72h, take out with washed with de-ionized water for several times, at last film is immersed in the deionized water to be measured.
(6) the described high boiling solvent of step (2) is DMF, DMA, dimethyl sulfoxide (DMSO) or 1-METHYLPYRROLIDONE.
(7) the described additive of step (3) is one or more in organic substance such as Polyetherimide, polyimides, polyether sulfone, polyvinylpyrrolidone, polyvinyl alcohol etc., one or more in inorganic matter such as titanium dioxide, silicon dioxide, basic zirconium phosphate, aluminium oxide, zinc oxide, the molecular sieve etc.
(8) in the step (1), when reactant liquor added frozen water, controlling its adding speed was 50～500mL/min.
(9) in the step (3), described preparation liquid filters purifying with glass sand hourglass before pouring mould into.
(10) in the step (3), the proportion of described preparation liquid is 0.1～5g/mL.
Preparation method of the present invention adds various organic-inorganic additives in sulfonated polyether-ether-ketone solution, adopt casting filming therapy, has prepared various SPEEK composite membranes.In the situation that substantially do not affect proton conductivity, the method effectively raises resistance vanadium performance, chemical stability and the mechanical performance of SPEEK film, has increased its useful life in VRB.The SPEEK composite membrane thickness that adopts the present invention to obtain is 80～180 μ m, and appearance transparent is fine and close, and is smooth even.
The present invention has the following advantages:
(1) compares the sulfonation of PEEK among the present invention with the preparation method of existing SPEEK
Time shorten is to 10h, and method is simpler, and cost is cheaper.
(2) compare with the preparation method of existing SPEEK, by adding various organic-inorganic additives, improved Film conductivity energy, resistance vanadium performance and mechanical performance among the present invention.
(3) compare with the Nafion117 film, the SPEEK film price of the present invention's preparation is cheaper, and proton conductivity is higher, and the vanadium transmitance is lower, and mechanical performance is better.
Embodiment
Below in conjunction with specific embodiment enforcement of the present invention is described further:
Embodiment 1:
Step and the process conditions of the present embodiment are as follows:
(1) take by weighing 5g PEEK, add fast and contain in the 250mL round-bottomed flask of the 100mL concentrated sulfuric acid, mechanical agitation is after PEEK dissolves fully, in 35 ℃ of water bath with thermostatic control reaction 8h.Reaction is poured reactant mixture in the frozen water into fast immediately and is stirred after finishing, and forms white precipitate.After precipitation was complete, decompress filter washed sediment with water to neutral, shifts dry 10h in sediment to the 100 ℃ drying box, obtains sulfonated polyether-ether-ketone, then is placed in the desiccator for subsequent use.
(2) take by weighing the SPEEK0.6g that obtains in the step (1) and add among an amount of DMAc, add thermal agitation 2h to fully dissolving at 100 ℃, be mixed with mass fraction and be 10% solution.
(3) preparation liquid that is made in the step (2) is poured in the clean flat plate mold,
80 ℃ of dry 10h obtain wet film.Again with wet film at 120 ℃ of dry 8h, obtain dry film.
(4) dry film in the step (3) is cooled to room temperature after, soak with deionized water and to take off film, cut off the corner, under the room temperature with the H of film at 1M
2SO
4Behind the middle immersion 24h, take out with washed with de-ionized water for several times, at last film is immersed in the deionized water to be measured.
The composite membrane thickness that the present embodiment obtains is 120 μ m, and appearance transparent is fine and close, and is smooth even.The composite membrane conductance that records under the room temperature is 0.11S/cm, and the vanadium transmitance is 7.5 * 10
-7Cm
2/ min.
Embodiment 2:
Step and the process conditions of the present embodiment are as follows:
(1) take by weighing 5g PEEK, add fast and contain in the 250mL round-bottomed flask of the 100mL concentrated sulfuric acid, mechanical agitation is after PEEK dissolves fully, in 50 ℃ of water bath with thermostatic control reaction 7h.Reaction is poured reactant mixture in the frozen water into fast immediately and is stirred after finishing, and forms white precipitate.After precipitation was complete, decompress filter washed sediment with water to neutral, shifts dry 10h in sediment to the 100 ℃ drying box, obtains sulfonated polyether-ether-ketone, then is placed in the desiccator for subsequent use.
(2) take by weighing the SPEEK 0.6g that obtains in the step (1) and add among an amount of DMAc, add thermal agitation 2h to fully dissolving at 100 ℃, be mixed with mass fraction and be 10% solution.
(3) add Polyetherimide (PEI) in the gained solution in step (2), its addition is 5% of sulfonated polyether-ether-ketone quality, then adds thermal agitation 2h to complete dispersing and dissolving at 60～120 ℃, obtains preparation liquid.
(4) preparation liquid that is made in the step (3) is poured in the clean flat plate mold, at 80 ℃ of dry 10h, obtained wet film.Again with wet film at 120 ℃ of dry 8h, obtain dry film.
(5) dry film in the step (4) is cooled to room temperature after, soak with deionized water and to take off film, cut off the corner, under the room temperature with the H of film at 1M
2SO
4Behind the middle immersion 24h, take out with washed with de-ionized water for several times, at last film is immersed in the deionized water to be measured.
The composite membrane thickness that the present embodiment obtains is 150 μ m, and appearance transparent is fine and close, and is smooth even.The composite membrane conductance that records under the room temperature is 0.12S/cm, and the vanadium transmitance is 1.0 * 10
-6Cm
2/ min.
Embodiment 3:
Step and the process conditions of the present embodiment are as follows:
(1) take by weighing 5g PEEK, add fast and contain in the 250mL round-bottomed flask of the 100mL concentrated sulfuric acid, mechanical agitation is after PEEK dissolves fully, in 55 ℃ of water bath with thermostatic control reaction 6h.Reaction is poured reactant mixture in the frozen water into fast immediately and is stirred after finishing, and forms white precipitate.After precipitation was complete, decompress filter washed sediment with water to neutral, shifts dry 10h in sediment to the 100 ℃ drying box, obtains sulfonated polyether-ether-ketone, then is placed in the desiccator for subsequent use.
(2) take by weighing the SPEEK 0.6g that obtains in the step (1) and add among an amount of DMAc, add thermal agitation 2h to fully dissolving at 100 ℃, be mixed with mass fraction and be 10% solution.
(3) add polyether sulfone (PES) in the gained solution in step (2), its addition is 30% of sulfonated polyether-ether-ketone quality, then adds thermal agitation 2h to complete dispersing and dissolving at 60～120 ℃, obtains preparation liquid.
(4) preparation liquid that is made in the step (3) is poured in the clean flat plate mold, at 80 ℃ of dry 10h, obtained wet film.Again with wet film at 120 ℃ of dry 8h, obtain dry film.
(5) dry film in the step (4) is cooled to room temperature after, soak with deionized water and to take off film, cut off the corner, under the room temperature with the H of film at 1M
2SO
4Behind the middle immersion 24h, take out with washed with de-ionized water for several times, at last film is immersed in the deionized water to be measured.
The composite membrane thickness that the present embodiment obtains is 170 μ m, and appearance transparent is fine and close, and is smooth even.The composite membrane conductance that records under the room temperature is 0.106S/cm, and the vanadium transmitance is 1.1 * 10
-6Cm
2/ min.
Some important performance parameters of table 1 embodiment 1-3 composite membrane and Nafion117 film.
| Proton exchange membrane | Conductance/S/cm | Vanadium transmitance/cm 2/min | Hot strength/MPa |
| Nafion117 | 0.102 | 2.9×10 -6 | 15.4 |
| SPEEK | 0.110 | 0.75×10 -6 | 27.8 |
| SPEEK/PEI | 0.118 | 1.0×10 -6 | 29.7 |
| SPEEK/PES | 0.106 | 1.1×10 -6 | 32.7 |
Table 1 be according to document " chemical research and application. 2011,23 (6): 689-695 " the data that obtain of method of testing.Data Comparison can be found out by experiment, and the composite membrane of the inventive method preparation has than the better performance of Nafion117 film.
Embodiment result shows, take PEEK as raw material, by optimizing synthesis condition, prepares the SPEEK polymer, then this polymer and additive is mixed to get preparation liquid with certain proportion, and the recycling the tape casting prepares the SPEEK composite membrane.The composite membrane of the present invention's preparation has good resistance vanadium performance, proton-conducting, swellability, chemical stability and mechanical performance.Preparation method of the present invention is simple, and is with low cost, and environmental friendliness is easy to industrialization, can be widely used in the all-vanadium flow battery field.
Claims (5)
1. a vanadium redox battery is characterized in that comprising the steps and process conditions with the preparation method of compound proton exchange membrane:
(1) by weight, it is in 95～98% the concentrated sulfuric acid that 1 part of dry polyether-ether-ketone of processing is added 10～60 parts of weight percent concentration, behind 25～65 ℃ of water bath with thermostatic control reaction 3～10h, reactant liquor poured into stop sulfonation in the frozen water, separate out the sulfonated polyether-ether-ketone precipitation, decompress filter, wash sediment with water to neutral, shift dry 6～24h in sediment to the 100 ℃ drying box, obtain sulfonated polyether-ether-ketone, then be placed in the desiccator for subsequent use;
(2) sulfonated polyether-ether-ketone that obtains in the step (1) is added in the high boiling solvent, add thermal agitation 1～5h to fully dissolving at 60～120 ℃, be mixed with mass fraction and be 5～30% solution;
(3) add additive in the gained solution in step (2), its addition is 0～200% of sulfonated polyether-ether-ketone quality, then adds thermal agitation 1～5h to complete dispersing and dissolving at 60～120 ℃, obtains preparation liquid;
(4) preparation liquid that is made in the step (3) is poured in the clean flat plate mold, at 30～80 ℃ of drying 4～48h, is obtained wet film, again with wet film at 50～150 ℃ of drying 1～24h, obtain dry film;
(5) dry film in the step (4) is cooled to room temperature after, soak with deionized water and to take off film, cut off the corner, under the room temperature with the H of film at 1～5 mol/L
2SO
4Behind middle immersion 24～72h, take out with washed with de-ionized water for several times, at last film is immersed in the deionized water to be measured.
2. the preparation method of compound proton exchange membrane according to claim 1 is characterized in that described raw material is polyether-ether-ketone; Described high boiling solvent is a kind of in DMF, DMA, dimethyl sulfoxide (DMSO) or the 1-METHYLPYRROLIDONE; Described additive is one or more in Polyetherimide, polyimides, polyether sulfone, polyvinylpyrrolidone, polyvinyl alcohol, titanium dioxide, silicon dioxide, basic zirconium phosphate, aluminium oxide, zinc oxide, the molecular sieve etc.
3. the preparation method of compound proton exchange membrane according to claim 1 is characterized in that in the described step (1), and when reactant liquor added frozen water, controlling its adding speed was 50～500mL/min.
4. the preparation method of compound proton exchange membrane according to claim 1 is characterized in that in the described step (3), and preparation liquid filters purifying with glass sand hourglass before pouring mould into.
5. the preparation method of compound proton exchange membrane according to claim 1 is characterized in that in the described step (3), the proportion of preparation liquid is 0.1～5g/mL.
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| CN103236553A (en) * | 2013-04-10 | 2013-08-07 | 清华大学深圳研究生院 | A composite ion-exchange membrane and a preparation method thereof, and a redox flow battery |
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