CN1790792A - Fuel cell composite proton membrane and its preparing method - Google Patents
Fuel cell composite proton membrane and its preparing method Download PDFInfo
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- CN1790792A CN1790792A CNA200410098797XA CN200410098797A CN1790792A CN 1790792 A CN1790792 A CN 1790792A CN A200410098797X A CNA200410098797X A CN A200410098797XA CN 200410098797 A CN200410098797 A CN 200410098797A CN 1790792 A CN1790792 A CN 1790792A
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Abstract
The invention provides a composite proton membrane for fuel cell, which comprises: the all-fluorosulfuric polymer proton membrane coated the outside of the following membrane, and the non-all-fluorosulfuric solid polymer proton membrane with proton exchange capacity larger than 0.8 milli-equivalent per gram. This invention has low cost, high proton conductivity, can prevent elution of the membrane from cell. It also provides the opposite preparation method.
Description
Technical field
The present invention relates to have the organic composite material of proton conductive performance, can be used as the solid electrolyte in the electrochemistry, particularly fuel cell proton film.Specifically, the present invention relates to a kind of fuel cell composite proton membrane and preparation method thereof.
Background technology
The proton film is a key member of fuel cell, also is the member that accounts for the cost maximum.Fuel cell proton film mainly is the perfluorinated sulfonic acid polymer film at present, as Nafion series (USPatent No.3,282,875 of DuPont company; US Patent No.4,330,645).Because perfluoro sulfonic acid membrane price height, its application is restricted.In order to reduce the cost of fuel cell, people are researching and developing cheap proton film always.For example, sulfonation polytrifluorostyrene film (US Patent No.5,422,411); Sulfonation PAEK (sulfonated polyarylether ketones, SPEK) (Eu.Patent574891 A2, WO 9629360 A1); Sulfonation polyaryl ether ether ketone (sulfonated polyetherether ketone, SPEEK) (DE 19754305 A1); Sulfonation gathers aralkyl ethers sulfone (sulfonatedpoly arylene ether sulfone, SPSU) (JP 09245818 A2, JP 2001261833A2, WO 9726284 A1, GB2090843 A); Acid doping polyphenylene imidazoles (acid dopedpolybenzimidazole, PBI) (EP 0967674, and WO 0118894) etc.
Desirable fuel cell proton film should have ionic conductivity height, stable, the high and cheap characteristic of mechanical strength of chemical property concurrently.But up to the present, there is not a kind of proton film can satisfy above performance requirement fully as yet.
Sulfonation polyaryl ether ether ketone, sulfonation PAEK (SPEEK, SPEK) and sulfonation poly arylene ether sulfone (SPSU) material are because cheapness and chemical property are stable, obtained in recent years paying close attention to widely, but the molecule of these materials contains many polar groups, after sulfonation degree is brought up to a certain degree, its swelling in water enlarges markedly, even water-soluble fully, wash-out is gone out from battery.For example, the chemical constitution unit of the poly-aralkyl ethers sulfone (SPSU) of sulfonation is as follows:
Can see that from this structural formula SPSU contains-SO
2-(sulfone) and-O-(ether) group, they have extremely strong hydrophily, but conductivity is had no contribution, thereby utilize these materials to be difficult to synthetic high conductivity film.
In order to reduce water-swellable, adopt molecule crosslinked way usually, but molecule crosslinked be to finish by the bonding action of sulfonic acid group, can cause the reduction of conductivity.Studies show that at present the conductivity of synthetic SPSU only has 0.01S/cm, than low order of magnitude of conductivity of the perfluorinated sulfonic acid type solid polymer Nafion-115 of DuPont company.
Therefore, how keeping the proton film when having high conductivity, can not separated by water-soluble again, is a key issue of new fuel cell proton film research.
Summary of the invention
The object of the present invention is to provide a kind of good fuel cell composite proton membrane, this film is composited by two kinds of different materials, and whole proton film is not only cheap, and has ionic conductivity height, water-fast characteristic concurrently.
For reaching above-mentioned purpose, the invention provides a kind of fuel cell composite proton membrane, combine by perfluorinated sulfonic acid polymer proton film and non-perfluorinated sulfonic acid type solid polymer proton film, and perfluorinated sulfonic acid polymer proton film is coated on the skin of solid polymer proton film, and the proton exchange ability of described solid polymer proton film is greater than 0.8 mM equivalent/gram.Promptly, the skin of composite proton membrane of the present invention is a perfluorinated sulfonic acid polymer proton film, internal layer is the high but water-soluble big non-perfluorinated sulfonic acid type solid polymer proton film of proton conductivity, in actual applications, generally require the proton exchange ability of the solid polymer proton film of internal layer can be at 0.8～3.3 mM equivalent/gram.
Adopt fuel cell composite proton membrane of the present invention, can effectively solve the stable contradiction of proton film between high conductivity and low aqueous solubility of present cheapness and chemical property.The solid polymer proton film in intermediate layer has the characteristic that cheapness, chemical property are stable, proton conductivity is high; Outer field perfluorinated sulfonic acid polymer proton film water swelling ratio is low, and some polymer macromolecules can not pass, the composite membrane that is combined to form not only can have high conductance, and can effectively stop the big proton film of water in intermediate layer dissolubility in fuel cell, to be washed out by water-soluble separating, therefore this novel proton film that is composited by two kinds of materials in use can reach and have the high and water-fast purpose of ionic conductivity concurrently.
During composite proton membrane of the present invention is formed, the outer higher perfluorinated sulfonic acid polymer film of present known price, for example the Nafion series of DuPont company (for example Nafion1100) used.This outer membrane not only plays the effect of proton conductive, and plays the not eluted effect of high conductivity proton film of protection intermediate course.Outer membrane is thin more, and the cost of composite membrane is low more, but considers that from making angle the thickness of outer perfluorinated sulfonic acid polymer proton film is advisable with 10～25 microns.
In the composite proton membrane of the present invention internal layer be cheap, chemical property stable, conductance is high but water-soluble big polymer proton membrane material, preferably by containing aromatic rings and ether (O-) and/or ketone group
As/or sulfuryl
The polymer sulfonation obtain.For example, these polymer can be selected from poly-aralkyl ethers sulfone, poly arylene ether sulfone, PAEK and polyether-ether-ketone, and its structural formula is as follows:
n＝15～400
n＝20～500
n＝25～800
n＝20～500
According to specific embodiments of the present invention, can make these materials have high conductivity by the method that promotes sulfonation degree, intermediate layer as fuel cell composite proton membrane of the present invention, and, because the present invention has used the low perfluoro sulfonic acid membrane of water swelling ratio (Nafion film) as the skin that coats the intermediate layer, and polymer macromolecules such as SPEEK, SPEK and SPSU all can not pass the Nafion film, can effectively solve above-mentioned polymer sulfonation degree and improve the water-soluble problem of back proton film.
Composite membrane of the present invention can be identical with the fuel cell proton film that generally uses at present on thickness, the thickness of outer perfluorinated sulfonic acid polymer proton film (Nafion film) is preferably 10～25 microns, and the thickness of described internal layer solid polymer proton film is preferably 30～170 microns.
Simultaneously, the present invention also provides the preparation method of described fuel cell composite proton membrane, mainly comprises the both sides that described perfluorinated sulfonic acid polymer proton mould are attached to solid polymer proton film, with the synthetic process that obtains fuel cell composite proton membrane of the present invention.
For satisfying the requirement of conductance, the internal layer solid polymer membrane of composite membrane provided by the invention is the product after the degree of depth sulfonation, the present invention can directly use satisfactory polymer to make composite membrane, also can carry out sulfonation to this polymer voluntarily and handle, and described sulfonation processing can be adopted known sulfonating reaction process.Preferably, the preparation method of fuel cell composite proton membrane provided by the present invention mainly may further comprise the steps:
(1) carries out sulfonating reaction, synthesize described proton conductivity height but water-soluble big solid polymer proton film by the way that promotes sulfonation degree;
(2) with solid polymer proton film casting film forming, the thickness of this film is preferably 50～120 μ m greatly about 30～170 μ m;
(3) casting perfluorinated sulfonic acid polymer proton film (Nafion film), about 10～25 μ m of thickness;
(4) perfluorinated sulfonic acid polymer proton mould is attached to the both sides of described solid polymer proton film, just syntheticly obtains fuel cell composite proton membrane of the present invention.
Specifically, the present invention also provides and has carried out sulfonating reaction but the method for water-soluble big solid polymer proton film high with synthetic described proton conductivity.Mainly comprise step:
Solid polymer proton membrane material is dissolved in the solvent, adds the sulfonating agent reaction, meet the requirements of cessation reaction after the sulfonation degree, reclaim sulfonated product then.
The poly-aralkyl ethers sulfone of sulfonation, sulfonation poly arylene ether sulfone (SPSU), sulfonation PAEK (SPEK) and sulfonated polyether-ether-ketone (SPEEK) that the solid polymer proton membrane material that ion-exchange capacity described in the present invention is big, proton conductivity is high is preferably above-mentioned, when carrying out sulfonating reaction, the sulfonating agent of use preferably is selected from trimethyl silane chlorosulfonic acid (ClSO
3Si (CH
3)
3), the group of chlorosulfonic acid, sulfuric acid, sulfur trioxide etc.
Consider from the sulfonation effect and to the influence of polymer, preferably use the trimethyl silane chlorosulfonic acid to be sulfonating agent, it is 0～50 ℃ that reaction temperature preferably is controlled at, the mol ratio of polymer (for example poly arylene ether sulfone (or ketone)) monomer and sulfonating agent is preferably 1: 0.5～and 3.5, when reaction finishes (the proton exchange ability reaches requirement), can adopt conventional method, with the low mass molecule alcohol cessation reaction.Then, carry out sulfonated product and reclaim, under about 50～150 ℃ temperature, normal pressure or vacuum evaporation remove the materials such as (for example halogenated hydrocarbons or other common solvent), low mass molecule alcohol, silicon-containing compound and micromolecule sulfuric ester that desolvate, and obtain degree of depth sulfonated polymers.
Afterwards, the sulfonated products (for example sulfonation poly arylene ether sulfone (or ketone)) that obtains is cast as the film of desired thickness.This film promptly is the solid polymer proton film that is suitable as the intermediate layer of fuel cell MULTILAYER COMPOSITE proton film of the present invention, and its conductance can reach 0.06～0.2S/cm.
Cast the perfluorinated sulfonic acid polymer film (Nafion film) of 10～15 μ m then.
At last the Nafion mould is attached to the both sides of sulfonated products proton film, just syntheticly obtains MULTILAYER COMPOSITE fuel cell proton film of the present invention.
In the above-mentioned composite membrane, because intermediate layer sulfonated polymer molecule is big and carry and Nafion film like charges, they can not pass the Nafion film and dissolve in the water.The consumption of Nafion in whole proton film be less than 30Wt%, but it is suitable to contain the performance and the Nafion-115 (DuPont company) of battery of MULTILAYER COMPOSITE proton film of the present invention, stable chemical performance, and material cost is lower than Nafion-115.So composite membrane of the present invention is a kind of fuel cell composite proton membrane with applications well prospect.
Description of drawings
Fig. 1 is that the solid polymer proton film of specific embodiments of the invention and Nafion-115 are at 80 ℃ and 120 ℃ of following conductivity test curves.
Fig. 2 is the battery performance and the time relation curve chart of the fuel cell MULTILAYER COMPOSITE proton film of specific embodiments of the invention.
Fig. 3 shows the battery performance test result of the fuel cell composite proton membrane of specific embodiments of the invention under the various operating conditions.
Embodiment
Below in conjunction with the beneficial effect that the drawings and specific embodiments are introduced realization of the present invention in detail and had, understand novelty essence of the present invention place better to help the reader, but do not constitute qualification the scope of the present invention.
Embodiment one, sulfonation example 1
One, preparation method
Get the poly-aralkyl ethers sulfone (PSU) of 10 grams, be dissolved into 100 milliliter 1, in the 2-dichloroethanes, under 25 ℃, stir in the nitrogen atmosphere, dissolve fully up to PSU.
Under 25 ℃, add 5.0 milliliters of trimethyl silane chlorosulfonic acids in the nitrogen atmosphere in above-mentioned solution, stirring reaction 36 hours adds 10 ml methanol, cessation reaction in reaction system.
Methyl alcohol and dichloroethanes are reclaimed in 50～80 ℃ of evaporations under normal pressure, then product are heated up, and evaporate down at 130 ℃ and remove silicon-containing compound and micromolecule sulfuric ester.Obtain the poly-aralkyl ethers sulfone product of 11.8 gram sulfonation (numbering SPSU-1).
Two, Performance Detection
Making sample with S4200 type ESEM (Hitachi, Ltd's production) can spectrogram, does not detect the existence of silicon, illustrates that siliceous residual compounds removes from product fully.
The ion-exchange capacity that records SPSU-1 with titration is 1.68 mMs equivalent/gram, and is more much higher than the ion-exchange capacity (0.91 mM equivalent/gram, measured value) of the Nafion-115 of Dupont company.
The conductivity of measuring the conductivity obtain SPSU-1 and the Nafion-115 of Dupont company with reactance method quite (seeing also shown in Figure 1) under higher relative humidity, the sulfonation that is higher than bibliographical information far away gathers the conductivity (F.Lufrano of aralkyl ethers sulfone; G.Squardrito; A.Patti; E.Passalacqua, " Sulfonated polysulfone as promising membranes forpolymer electrolyte fuel cells " J.of Applied Polymer Science, 2000, Vol.77,1250-1257).
Embodiment two, sulfonation example 2
One, preparation method
The poly-aralkyl ethers sulfone (PSU) of 20 grams is dissolved in 220 milliliter of 1,2 dichloroethanes, under 25 ℃, stirs in nitrogen (or other inert gases) atmosphere, dissolve fully up to PSU.
Under 25 ℃, in above-mentioned solution, add 20.0 milliliters of trimethyl silane chlorosulfonic acids, stirring reaction 36 hours in nitrogen (or other inert gases) atmosphere.
Add 40 ml methanol, cessation reaction in the above-mentioned reaction system.
Evaporation is removed methyl alcohol and with its recovery, then product is removed silicon-containing compound and micromolecule sulfuric ester 120 ℃ of following vacuum evaporation under normal pressure.Obtain the poly-aralkyl ethers sulfone product of 25.0 gram sulfonation (numbering SPSU-2).
Two, Performance Detection
Making sample with S4200 type (Hitachi, Ltd's production) ESEM can spectrogram, does not detect the existence of silicon, illustrates that siliceous residual compounds removes from product fully.
The ion-exchange capacity that records SPSU-2 with titration is 2.33 mMs equivalent/gram, is higher than the ion-exchange capacity of SPSU-1, more is higher than the ion-exchange capacity (0.91 mM equivalent/gram, measured value) of the Nafion115 of Dupan company.
Obtain the conductivity under higher relative humidity high (see also shown in Figure 1) of the conductivity of SPSU-2 with reactance method mensuration, be higher than the conductivity of the poly-aralkyl ethers sulfone of reporting in the existing document of sulfonation far away than the Nafion-115 of Dupont company.
Embodiment three, sulfonation example 3
20 gram polyaryl ether ether ketone (PEEK) are dissolved in 1 liter 96～98% the sulfuric acid, and at room temperature stirring reaction is about 200 hours.
Above-mentioned reactant mixture is slowly added in the deionization frozen water, separate out sulfonation polyaryl ether ether ketone flocky precipitate.
Above-mentioned flocky precipitate is extremely approximately neutral with the washing of deionization frozen water; At room temperature obtain 18 gram sulfonation polyaryl ether ether ketone behind the airing.
The ion-exchange capacity that records above-mentioned sulfonation polyaryl ether ether ketone with titration is 2.3 mMs equivalent/gram; Measure with reactance method that to obtain it be 0.08S/cm in the conductivity under 80 ℃ and 95% humidity.
The casting of embodiment four, proton film
Get the SPSU-1 that 0.32 gram embodiment one prepares, add the 25ml isopropyl alcohol.Put into the smooth glass casting film device in bottom after the stirring and dissolving, and 80 ℃ of following evaporating solvents 6 hours, be warming up to then 130 ℃ aging 30 minutes, solvent is evaporated fully.Obtain 77 micron thickness, 32 square centimeters SPSU film.
Get Nafion-1100 (DuPon company) emulsion of 1.31 grams 5% (mass percent), add the 10mi isopropyl alcohol.Put into the smooth glass casting film device in bottom after fully stirring, and at 80 ℃ of following evaporating solvents.After treating that solvent evaporation is done, be warmed up to 130 ℃ aging 30 minutes, obtain 10 micron thickness, 32 square centimeters Nafion film.
With the Nafion film of two above-mentioned 10 micron thickness, be hot-pressed onto the both sides of SPSU-1 film, obtain Nafion/SPSU/Nafion MULTILAYER COMPOSITE proton film of the present invention.
Embodiment five, proton membrane fuel battery performance test
Get and carry platinum carbon cloth electrode (available from U.S. E-TEK company), it is 0.4mg/cm that electrode carries the platinum amount
2To carrying on the platinum charcoal cloth electrode, the carrying capacity that is coated with of Nafion-1100 is 1mg/cm with the dip-coating of Nafion-1100 proton conducting material
2, then with electrode at 130 ℃, 200kg/cm
2Membrane-electrode member (MEA) is made in the both sides that are hot-pressed onto composite proton membrane (Nafion/SPSU-1/Nafion) under the condition.The area of electrode is 5cm
2
MEA packed into test in the fuel cell test device, anode leads to hydrogen, logical oxygen of negative electrode or air.Reaction gas elder generation bubbling enters in the bubbling bottle that is filled with water, and enters battery the two poles of the earth then.The humidity of reaction gas is by the adjustment of bubbling bottle, and the temperature of bubbling bottle is higher than 5～8 ℃ on battery, and the humidity of test usefulness (is having liquid water to exist) more than 100% in the battery.By regulating external resistance, measure current-voltage curve.
The battery performance of Nafion/SPSU-1/Nafion composite membrane of the present invention sees also Fig. 2 and shown in Figure 3.Fig. 2 shows the battery performance and the time relation of multilayer complex films of the present invention, thicknesses of layers: 10 μ m/77 μ m/10 μ m, test condition: fuel/oxygen thing: H
2/ O
2, 88 ℃ of anode bubblers, 80 ℃ on battery, 86 ℃ of negative electrode bubblers, stagnation pressure 1 atmospheric pressure.Fig. 3 shows the battery performance Nafion/SPSU-1/Nafion film of composite membrane of the present invention under the various operating conditions, film thickness: 10 μ m/77 μ m/10 μ m, in the test condition " 80 ℃, H
2/ O
2, 1atm " and represent that battery temperature is 80 ℃, the logical respectively humidity of anode and negative electrode is 100% hydrogen and oxygen, stagnation pressure is 1 atmospheric pressure; The rest may be inferred for other conditions.
As can be seen from the figure, battery performance is time to time change not, and the stable chemical performance of MULTILAYER COMPOSITE proton film is described.The voltage of battery reduces with the increase of the density of discharging current.When single battery voltage was 600mv, current density reached 700mA, battery performance good (suitable with the performance of Nafion-115).Reaction pressure is big more, and cell voltage is high more; Under identical total pressure, reaction temperature is high more, because the dividing potential drop step-down of reactant, cell voltage is little.Use air as oxide with oxygen as the oxide ratio, what cell voltage will be high is many.The proton film stops test after working 150 hours under＞100% humidity, unload MEA, tears the carbon cloth electrode, checks and to learn that the proton film still forms by three layers, and SPSU does not have wash-out to go out battery, illustrates that the Nafion film can stop SPSU to dissolve in the water.
Claims (10)
1. fuel cell composite proton membrane, it is characterized in that, combine by perfluorinated sulfonic acid polymer proton film and non-perfluorinated sulfonic acid type solid polymer proton film, and perfluorinated sulfonic acid polymer proton film is coated on the skin of non-perfluorinated sulfonic acid type solid polymer proton film, and the proton exchange ability of described non-perfluorinated sulfonic acid type solid polymer proton film is greater than 0.8 mM equivalent/gram.
2. the described fuel cell composite proton membrane of claim 1, the proton exchange ability of wherein said non-perfluorinated sulfonic acid type solid polymer proton film is 0.8～3.3 mM equivalent/gram.
3. the described fuel cell composite proton membrane of claim 1, wherein said non-perfluorinated sulfonic acid type solid polymer proton membrane material is obtained by the polymer sulfonation that contains aromatic rings and ether and/or ketone group and/or sulfuryl.
4. the described fuel cell composite proton membrane of claim 3, wherein said non-perfluorinated sulfonic acid type solid polymer proton membrane material are selected from the poly-aralkyl ethers sulfone of sulfonation, sulfonation poly arylene ether sulfone, sulfonation PAEK or sulfonated polyether-ether-ketone.
5. each described fuel cell composite proton membrane of claim 1～4, the thickness of wherein said perfluorinated sulfonic acid polymer proton film is 10～25 microns, the thickness of non-perfluorinated sulfonic acid type solid polymer proton film is 30～170 microns.
6. the preparation method of each described fuel cell composite proton membrane of claim 1～5 comprises that the both sides that perfluorinated sulfonic acid polymer proton mould is attached to non-perfluorinated sulfonic acid type solid polymer proton film are combined into the process of described fuel cell composite proton membrane.
7. the preparation method of the described fuel cell composite proton membrane of claim 6, it also comprises makes the polymer generation sulfonating reaction that contains aromatic rings and ether and/or ketone group and/or sulfuryl, and preparation proton exchange ability is greater than the process of the solid polymer proton film of 0.8 mM equivalent/gram.
8. the preparation method of the described fuel cell composite proton membrane of claim 7, wherein said sulfonating reaction use trimethyl silane chlorosulfonic acid, chlorosulfonic acid, sulfuric acid or sulfur trioxide as sulfonating agent.
9. the preparation method of the described fuel cell composite proton membrane of claim 8, wherein said sulfonating reaction with the trimethyl silane chlorosulfonic acid as sulfonating agent, reaction temperature-5～50 ℃, the mol ratio of polymer monomer and sulfonating agent is 1: 0.5～3.5.
10. the preparation method of the described fuel cell composite proton membrane of claim 9 wherein, after sulfonating reaction is finished, is warmed up to 50～200 ℃ with product, removes silicon-containing compound and micromolecule sulfuric ester.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101210076B (en) * | 2006-12-25 | 2011-05-25 | 同济大学 | Proton exchange film, preparing method and use thereof |
| CN102945972A (en) * | 2012-09-07 | 2013-02-27 | 四川大学 | Preparation method of composite proton exchange membrane for all vanadium redox flow battery |
| CN107994244A (en) * | 2016-10-21 | 2018-05-04 | 中国科学院大连化学物理研究所 | The preparation and film and application of a kind of Multi-layer composite proton exchange membrane |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5795668A (en) * | 1994-11-10 | 1998-08-18 | E. I. Du Pont De Nemours And Company | Fuel cell incorporating a reinforced membrane |
| US5654109A (en) * | 1995-06-30 | 1997-08-05 | The Dow Chemical Company | Composite fuel cell membranes |
| US20030235737A1 (en) * | 2002-06-19 | 2003-12-25 | Yoocharn Jeon | Metal-coated polymer electrolyte and method of manufacturing thereof |
-
2004
- 2004-12-16 CN CNB200410098797XA patent/CN100346513C/en not_active Expired - Fee Related
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101210076B (en) * | 2006-12-25 | 2011-05-25 | 同济大学 | Proton exchange film, preparing method and use thereof |
| CN102945972A (en) * | 2012-09-07 | 2013-02-27 | 四川大学 | Preparation method of composite proton exchange membrane for all vanadium redox flow battery |
| CN107994244A (en) * | 2016-10-21 | 2018-05-04 | 中国科学院大连化学物理研究所 | The preparation and film and application of a kind of Multi-layer composite proton exchange membrane |
| CN107994244B (en) * | 2016-10-21 | 2020-12-01 | 中国科学院大连化学物理研究所 | Preparation of multilayer composite proton exchange membrane, membrane and application |
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