CN101375444B - High molocular electrolyte membrane for fuel cell, and membrane-electrode assembly thereby, fuel cell - Google Patents
High molocular electrolyte membrane for fuel cell, and membrane-electrode assembly thereby, fuel cell 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
- H01M8/1018—Polymeric electrolyte materials
- H01M8/102—Polymeric electrolyte materials characterised by the chemical structure of the main chain of the ion-conducting polymer
- H01M8/103—Polymeric electrolyte materials characterised by the chemical structure of the main chain of the ion-conducting polymer having nitrogen, e.g. sulfonated polybenzimidazoles [S-PBI], polybenzimidazoles with phosphoric acid, sulfonated polyamides [S-PA] or sulfonated polyphosphazenes [S-PPh]
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
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- H01M8/1004—Fuel cells with solid electrolytes characterised by membrane-electrode assemblies [MEA]
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- 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
- H01M8/102—Polymeric electrolyte materials characterised by the chemical structure of the main chain of the ion-conducting polymer
- H01M8/1027—Polymeric electrolyte materials characterised by the chemical structure of the main chain of the ion-conducting polymer having carbon, oxygen and other atoms, e.g. sulfonated polyethersulfones [S-PES]
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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
- H01M8/102—Polymeric electrolyte materials characterised by the chemical structure of the main chain of the ion-conducting polymer
- H01M8/1032—Polymeric electrolyte materials characterised by the chemical structure of the main chain of the ion-conducting polymer having sulfur, e.g. sulfonated-polyethersulfones [S-PES]
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- 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
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
- H01M8/1018—Polymeric electrolyte materials
- H01M8/1041—Polymer electrolyte composites, mixtures or blends
- H01M8/1046—Mixtures of at least one polymer and at least one additive
- H01M8/1048—Ion-conducting additives, e.g. ion-conducting particles, heteropolyacids, metal phosphate or polybenzimidazole with phosphoric acid
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- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
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Abstract
Disclosed is a polymer electrolyte membrane for a fuel cell that has a high ionic conductivity even at a high temperature without humidification. The polymer electrolyte membrane comprises a film composed of a polyimide copolymer containing phenylbenzimidazole, and an acid impregnated within the polyimide copolymer film. Disclosed is another polymer electrolyte membrane for a fuel cell that has good chemical resistance and improved physical properties when compared to those of the previous polymer electrolyte membrane.
Description
Technical field
The present invention relates to be used for the polymer dielectric film of fuel cell, the fuel cell that uses the membrane-electrode assembly of this dielectric film and comprise this sub-assembly.More specifically, the present invention relates to be used for the polymer dielectric film of fuel cell, this polymer dielectric film at high temperature stably shows the high proton conductivity, it is moistening promptly applicable to fuel cell system to make that it at high temperature need not, and has the good chemical-resistant and the physical property of improvement; Use the membrane-electrode assembly of this dielectric film; And the fuel cell that comprises this sub-assembly.
Background technology
Ion exchange polymer film has been widely used for various application, separates such as diffusion dialysis, electrodialysis and vapor permeates.Recent focus has been devoted to develop the polymer electrolyte fuel cells that uses cation exchange polymer.
Fuel cell is to be converted to the energy conversion system of electric energy effectively with being stored in chemical energy in the fuel.In fuel cell, close to produce electric energy as the hydrogen of gas storage and as the methyl alcohol and the oxidation of liquid or gas storage.Especially, Proton Exchange Membrane Fuel Cells (PEMFC) is the clean energy resource that can substitute fossil fuel, and has high power density and high energy conversion efficiency.
Be known as electrolytical proton-conducting polymer membranes in the fuel cell usually based on the copolymer of perfluorinated sulfonic acid and tetrafluoroethene.Fuel cell is made of following elements: polymer dielectric film, electrode, be used to isolator that constitutes in heap etc.
Usually, negative electrode and anode are connected to polymer dielectric film to make membrane-electrode assembly by distinct methods.In order to make the surface area maximization of platinum catalyst, make two electrodes by the platinum grain of absorption nano-scale on the surface of material with carbon element (for example carbon black).Material with carbon element is in usually and has hundreds of square metres of every gram (m
2/ g) the powder type of effective surface area, platinum grain is as the catalyst of oxidation/reduction reaction.
The structure of membrane-electrode assembly and performance are most important factors in the polymer electrolyte fuel cells technology.Fuel cell generates electricity based on following principle.As react shown in 1, the hydrogen of the gas that acts as a fuel is fed to anode, and the platinum catalyst that is adsorbed in anode is also oxidized to produce proton and electronics.
2H
2→4H
++4e
- (1)
The electronics that produces flows and the arrival negative electrode along external circuit.Proton passes polymer dielectric film and is delivered to negative electrode.As react shown in 2 and 3, the electronics that the oxygen molecule reception is delivered to negative electrode is to be reduced to oxonium ion, and the reaction of proton and oxonium ion is to generate water and generating then.
O
2+4e
-→2O
2- (2)
2O
2-+4H
+→2H
2O (3)
The polymer dielectric film that is used for fuel cell is an electrical insulator, but conduct is with proton (H during battery operation
+) be delivered to the medium of negative electrode from anode.Polymer dielectric film also has the effect of isolating fuel gas or liquid and oxidant gas.Therefore, the amberplex that is used for fuel cell must have good mechanical performance, high electrochemical stability and have low ohmic loss under high current density.
The exploitation that is used for the polymer dielectric film of fuel cell in the sixties in 20th century is early stage, the hydrocarbyl polymers film has been carried out a large amount of research.Since E.I.Du Pont de Nemours, since Inc. developed fluoridized sulfonic acid (Nafion) in nineteen sixty-eight, it had been mainly used in mount type fuel cell and portable fuel battery.
Use the problem of the fuel cell of Nafion type polymer dielectric film to be: electrode catalyst 80 ℃ or more during the cold operation under the low temperature CO poison, and pass (crossover) of methyl alcohol takes place in direct methanol fuel cell (DMFC), and this makes fuel cell performance deterioration and become the main cause of its lifetime.At present just carrying out a large amount of research to address these problems.
In addition, fluorinated polymer electrolyte film such as Nafion has thermal instability under 90 ℃ or higher temperature, is difficult to the problem of synthetic and material expensive.In these cases, developing the sulfonated hydrocarbon base polymer electrolyte at present, this is because the thermal stability of the film that improves and the cost of reduction.
Yet, because sulfonated hydrocarbon base polymer electrolyte film is the system that proton conductive can take place in the presence of moisture, so the dehydration phenomenon of film inside generation causes the quick reduction of proton conductivity during the hot operation under 100 ℃ or the higher temperature.
Recent fuel cell system need be used to have high generating efficiency and be suitable for the polymer dielectric film of hot operation with the fuel cell of the used heat that is used to oneself front yard fuel cell.
The durability of fuel cell is vital for the commercialization of fuel cell.That is, the characteristic of battery must not can because of the long-play deterioration.Therefore, need exploitation to be used to have the polymer dielectric film of the fuel cell that improves durability.
Summary of the invention
Technical problem
An object of the present invention is to provide the polymer dielectric film that is used for fuel cell, this fuel cell is owing to can stably show proton conductivity to the improving tolerance of issuable free radical during fuel cell operation, wherein polymer dielectric film uses the new polymers structure that has stable proton conductivity under 150 ℃ or higher high temperature to form, at high temperature need not moisteningly can show battery behavior, and have good chemical-resistant and fabulous physical property.
Treat to be not limited to above-mentioned purpose of the present invention by the purpose that the present invention realizes.By following description, other purpose that those skilled in the art will not mention above will being expressly understood.
Technical scheme
According to first embodiment of the present invention that is used to realize above-mentioned purpose, be provided for the polymer dielectric film of fuel cell, comprising:
By the film that the polyimide copolymer that comprises phenyl benzimidazole part constitutes, described polyimide copolymer is represented by formula 1:
(wherein B is the group that is derived from the divalent organic group of two aminophenyl benzimidazoles and selects free style 2 expressions:
Each of A and P all is to be derived from the quadrivalent organic radical group of acid dianhydride and to be selected from following group:
D is derived from the divalent organic group of aromatic diamine and is selected from following group:
M and n satisfy relation: 0.5≤m/ (m+n)≤1.0 and 0≤n/ (m+n)≤0.5); With the acid that is immersed in the polyimide copolymer membrane.
Polyimide copolymer has the number-average molecular weight (Mn) of 10000～500000g/mol.
In formula 1, the mol ratio of A and P is 1: 1 substantially, and total mol% of A and P is 100%, and total mol% of B and D is 100%.
If desired, the mol ratio of A and P can be changed into 1: 0.9～0.9: 1, with the molecular-weight adjusting of polymer to optimal level.In this case, total mol% of A and P or B and D can need not to be 100%.
In formula 1, A can be identical dianhydride or different dianhydrides with P.If different dianhydrides is as A and P in the formula 1, then to be different from m can be 1: 99 with the ratio of n and the mol ratio of A and P to the mol ratio of B and D, is preferably 30: 70.
At this moment, B can exist with the amount of 10～100mol%, and D can exist with the amount of 0～90mol%.Preferably, B can exist with the amount of 50～100mol%, and D can exist with the amount of 0～50mol%.More preferably, B can exist with the amount of 60～95mol%, and D can exist with the amount of 5～40mol%.
The representative example of polyimide polymer that can be used for the polyimide copolymer of preparation formula 1 comprises following polymer:
Provide these polymer to understand the present invention but not the intention restriction is used for the structure of polyimide polymer of the present invention with auxiliary.
Polyimide polymer is used to form the polymer dielectric film of fuel cell, below will be described.
Use polyimide polymer to be formed for the polymer dielectric film of fuel cell according to following method.At first, make polymer film.According to polymerization and film manufacturing method, can adopt two kinds of methods to make polymer film to use polyimide polymer.
According to first method, following manufacturing thickness is the film of 10～500 μ m: the preparation polyamic acid is as polyimide precursor, the solution of curtain coating polyamic acid to be obtaining wet film, by being heated to 200 ℃ or highlyer make the wet film dehydration forming imide ring, and the film of dry described heating.
According to second method, following manufacturing film: use acetate dianhydride and pyridine to carry out chemical imidization reaction with solution state, use base catalyst (for example isoquinolin) carries out polymerisation in solution (it also is possible using the polymerisation in solution of acidic catalyst in basic solvent) or carry out imidization reaction based on the azeotropism that uses solvent (for example toluene) in basic solvent (for example N-N-methyl-2-2-pyrrolidone N-) in acid flux material (for example metacresol), the precipitation reaction product is to obtain solid polymer, with dissolution of solid polymer in organic solvent, the described solution of curtain coating, and do not carry out imidization reaction with the plain mode evaporating solvent.
Yet the final polyimides product of polymerization need be dissolved in the organic solvent in second method.Therefore, have only when using certain monomers such as alicyclic acid dianhydride, just use second method.
For proton conductive (being hydrogen ion conductivity) being given the polymer film of making by one of described method, need with acid such as phosphoric acid (H
3PO
4) flood described polymer film.
In the present invention, working concentration is 85% phosphate-doped polymer film.Other strong acid is such as sulfuric acid (H
2SO
4) and acid such as the ethyl phosphonic acid of modifying can be used for giving polymer film with proton conductive.
With the acid dip polymer film to finish the formation of the proton conductive polymer dielectric film that is used for fuel cell.
According to second embodiment of the present invention, be provided for the polymer dielectric film of fuel cell, comprising:
The polyimide copolymer membrane that constitutes by polyimide copolymer that comprises the phenyl benzimidazole and crosslinking agent, described crosslinking agent have the epoxy radicals of being selected from, two key, triple bond and an amido one or more plant crosslinkable reactive group, polyimide copolymer is by formula 6 expressions:
(wherein B is the group that is derived from the divalent organic group of two aminophenyl benzimidazoles and selects free style 8 expressions:
Each is A and P the quadrivalent organic radical group that is derived from acid dianhydride and is selected from following group:
D is derived from the divalent organic group of aromatic diamine and is selected from following group:
Crosslinking agent is selected from following compound:
(wherein R can be selected from alicyclic ring, aromatics and heteroaromatic moiety, and epoxy compounds has two or more reactive functional groups, and R1 can be selected from aromatics and heteroaromatic moiety, and amines has three or more functional groups); And
Be immersed in the acid in the polyimide copolymer membrane.
Compare with those polymer dielectric films, have the good chemical-resistant and the physical property of improvement according to the polymer dielectric film of second embodiment of the invention according to first embodiment of the invention.
Number with the functional group that comprises in the crosslinking agent of epoxide-reactive groups is 2～4.The content of this crosslinking agent is 1～40wt% in the polyimide compositions, based on the solids content of polymer.
Number with the functional group that comprises in the crosslinking agent of amine reactive group is 3 or 4.The content of this crosslinking agent is 1～40wt% in the polyimide compositions, based on the solids content of polymer.
Between polymerization period, use with the terminal monomer of acetenyl aniline introducing polymer and with the amount of 2～20mol%.
Between polymerization period, maleic anhydride is introduced the terminal monomer of polymer and used with the amount of 2～20mol%.
Preparation by the polyimides of formula 6 expression and with above-mentioned first embodiment in identical mode be processed into film.In second embodiment, improve the chemistry and the physical property of polyimides by reactant cross-linker being joined polyimides.The representative example of polyimides and the representative example of crosslinking agent are as follows:
Provide described polyimides and crosslinking agent to understand the present invention but not the structure of intention restriction polyimides and crosslinking agent with auxiliary.
Polyimides and crosslinking agent are used to form the polymer dielectric film of fuel cell, below will be described.
Use polyimide polymer to be formed for the polymer dielectric film of fuel cell according to following method.At first, make polymer film.Can adopt any extensively known method to make polymer film to use polyimide polymer.In second embodiment, adopt the method for describing in the first embodiment.
According to the kind of the crosslinking agent that uses, the adding method of crosslinking agent mainly is divided into following two kinds of methods.
According to first method, after polymerization is finished, add epoxy or three amine crosslinkers and need not to participate in the preparation of polymer with the form of additive.At this moment, quantitative epoxy or three amine crosslinkers are joined in the reaction solution.Based on the weight of final polymer product, the amount of the epoxy of adding or three amine crosslinkers is 1%～40%, and is preferred 3%～30%, more preferably 5～20%.
According to second method, during polymer manufacture, add the crosslinking agent of terminal amine or terminal acid anhydride.Under the situation of the crosslinking agent (for example acetenyl aniline) that adds terminal amine, add acid dianhydride with the amount of 100mol%, add diamines with the preparation polyimides with the amount of 90mol%～99mol%.At this moment, the crosslinking agent that adds terminal amine with the amount of 2mol%～20mol%.Under the situation of the crosslinking agent of acid anhydride (for example maleic anhydride), with the amount adding diamines of 100mol%, with the amount adding acid dianhydride of 90mol%～99mol%, this adding with the crosslinking agent of terminal amine is opposite endways.At this moment, the crosslinking agent that adds terminal acid anhydride with the amount of 2mol%～20mol%.
On glass plate, apply the polyimide solution that comprises crosslinking agent by curtain coating, and progressively be heated to 300 ℃ or higher to obtain crosslinked polyimide film.
For proton conductive (being hydrogen ion conductivity) being given the polymer film of making by one of described method, need with acid such as phosphoric acid (H
3PO
4) flood described polymer film.
In the present invention, working concentration is 85% phosphate-doped polymer film (polyimide film that promptly comprises crosslinking agent).Other strong acid is such as sulfuric acid (H
2SO
4) and acid such as the ethyl phosphonic acid of modifying can be used for giving polymer film with proton conductive.
With the acid dip polymer film to finish the formation of the proton conductive polymer dielectric film that is used for fuel cell.
Beneficial effect
Even the polymer dielectric film that is used for fuel cell according to embodiments of the present invention need not moistening high phosphate impregnation rate and the high ionic conductivity of also can showing under 150 ℃ or higher high temperature.In addition, this polymer dielectric film provides gratifying characteristic and shows good chemical-resistant and the physical property of improvement.Therefore, even adopt the fuel cell long-time running of described polymer dielectric film also to provide fabulous characteristic such as high stability.
Description of drawings
By detailed description, will more be expressly understood above-mentioned and other purpose, feature and other advantage of the present invention below in conjunction with accompanying drawing.
Fig. 1 is the cross-sectional view that schematically shows the membrane-electrode assembly (MEA) that uses polymer dielectric film manufacturing of the present invention;
Fig. 2 is the exploded perspective view that schematically shows the fuel cell that comprises membrane-electrode assembly of the present invention;
Fig. 3 is the figure that shows the I-V characteristic of the fuel cell that uses the polymer dielectric film manufacturing that forms in embodiments of the invention 3, does not have moistening the evaluation under 150 ℃;
Fig. 4 is the figure that shows the I-V characteristic of the fuel cell that uses the polymer dielectric film manufacturing that forms in embodiments of the invention 9, does not have moistening the assessment under 150 ℃; With
Fig. 5 is the figure that shows the result of the test fuel battery long-time running stability of using the polymer dielectric film manufacturing that forms in embodiments of the invention 9.
Optimal mode
Fig. 1 is the cross-sectional view that schematically shows the membrane-electrode assembly (MEA) that uses polymer dielectric film manufacturing of the present invention.
With reference to figure 1, membrane-electrode assembly 10 of the present invention comprises polymer dielectric film 100, is coated in two lip-deep catalyst layers 110 and 110 ' and be arranged on gas diffusion layers 120 and 120 ' on each catalyst layer outer surface of polymer dielectric film 100 by deposition.
Gas diffusion layers (GDL) 120 and 120 ' is arranged on the outer surface of each catalyst layer 110 and 110 '.
Gas diffusion layers 120 and 120 ' be used for from the outside to catalyst layer fully hydrogen supply and oxygen with the formation of the three phase boundary of cocatalyst layer, dielectric film and gas.Preferred carbon paper or the carbon cloth of using forms gas diffusion layers.
Membrane-electrode assembly 10 of the present invention also can comprise the microporous layers (MPL) 121 and 121 ' that is separately positioned between catalyst layer 110 and the gas diffusion layers 120 and between catalyst layer 110 ' and the gas diffusion layers 120 '.Form microporous layers 121 and 121 ' diffusion with auxiliary hydrogen and oxygen.
Fig. 2 is the exploded perspective view that schematically shows the fuel cell that comprises membrane-electrode assembly.
With reference to figure 2, fuel cell 1 of the present invention comprises membrane-electrode assembly 10 and the bipolar plates 20 that is arranged on these membrane-electrode assembly two sides.
Embodiment
Below, will illustrate in greater detail structure of the present invention and effect with reference to following specific embodiment and Comparative Examples.Yet these embodiment are used to provide further understanding of the present invention and are not intended to limit the scope of the invention by any way.
Embodiment
1. explanation is according to the embodiment of the effect of the polymer dielectric film of first embodiment of the invention
＜embodiment 1 〉
In the four-hole boiling flask of being furnished with blender, thermostat, nitrogen injected system and condenser, will be as a mole 6 of diamines, 4 '-diaminourea-2-Phenylbenzimidazole (formula 12) is dissolved in the N-N-methyl-2-2-pyrrolidone N-(NMP, Junsei Chemical), makes nitrogen pass through described flask simultaneously.
1 mole of pyromellitic dianhydride (PMDA, Cat.No.B0040, Tokyo ChemicalIndustry) is added in the described solution.This mixture of vigorous stirring.Solids content in this mixture is 15wt%.When keeping temperature to be lower than 25 ℃, made mixture reaction 24 hours, with preparation polyamic acid solution (PAA-1).
＜embodiment 2 〉
Except using 0.5 mole 4,4 ' diaminodiphenyl ether (Cat.No.00088, Tokyo ChemicalIndustry) and 0.5 mole 6,4 '-diaminourea-2-Phenylbenzimidazole is as outside the diamines, with embodiment 1 in identical mode prepare polyamic acid solution (PAA-2).
＜embodiment 3 〉
Except using 0.3 mole 4,4 '-diaminodiphenyl ether, 0.7 mole 6, outside 4 '-diaminourea-2-Phenylbenzimidazole and the 1 mole of pyromellitic dianhydride (PMDA), with embodiment 1 in identical mode prepare polyamic acid solution (PAA-3).
＜embodiment 4 〉
Except using 0.3 mole 4,4 '-diaminodiphenyl ether, 0.7 mole 6,4 '-diaminourea-2-Phenylbenzimidazole and 1 mole 1,4,5, outside the 8-naphthalenetetracarbacidic acidic dianhydride (Cat.No.N0369, Tokyo ChemicalIndustry), with embodiment 1 in identical mode prepare polyamic acid solution (PAA-4).
＜embodiment 5 〉
Except using 1 mole 6,4 '-diaminourea-2-Phenylbenzimidazole and 1 mole 1,4,5, outside the 8-naphthalenetetracarbacidic acidic dianhydride, with embodiment 1 in identical mode prepare polyamic acid solution (PAA-5).
＜embodiment 6 〉
Except using 0.3 mole 4,4 '-diaminodiphenyl ether, 0.7 mole 6,4 '-diaminourea-2-Phenylbenzimidazole and 1 mole 3,3 ', 4, outside 4 '-benzophenone tetracarboxylic acid dianhydride (Cat.No.N0369, TokyoChemical Industry), with embodiment 1 in identical mode prepare polyamic acid solution (PAA-6).
＜embodiment 7 〉
Except using 1 mole 6,4 '-diaminourea-2-Phenylbenzimidazole and 1 mole 3,3 ', 4, outside 4 '-benzophenone tetracarboxylic acid dianhydride, with embodiment 1 in identical mode prepare polyamic acid solution (PAA-7).
Use every kind of polyamic acid solution manufacturing polyimide polymer film of preparation among the embodiment 1～7.Estimate the characteristic of polyimide polymer film and the character that this polyimide polymer film is used phosphate impregnation.The result is as shown in table 1.
Table 1
| Polymer | Film forms | Build (μ m) | Dipping back thickness (μ m) | ? aImpregnation rate (%) |
| Embodiment 1 | O | 28 | 70 | ?455 |
| Embodiment 2 | O | 31 | 49 | ?300 |
| Embodiment 3 | O | 32 | 43 | ?280 |
| Embodiment 4 | O | 35 | 61 | ?260 |
| Embodiment 5 | O | 32 | 65 | ?410 |
| Embodiment 6 | O | 36 | 48 | ?240 |
| Embodiment 7 | O | 29 | 51 | ?325 |
Annotate:
a=(the film weight-dry film weight behind the dipping) * 100
Can find out that by the data shown in the table 1 polyimide polymer film has high phosphate impregnation rate.
Use the polymer dielectric film that forms among the embodiment 3 to make fuel cell.Under 150 ℃, there is not to estimate the I-V characteristic of described fuel cell moisteningly.The results are shown in Fig. 3.
The result of Fig. 3 shows: the fuel cell that uses the polymer dielectric film manufacturing that forms among the embodiment 3 is at 0～0.3A/cm
2Current range in demonstrate magnitude of voltage up to 600mV.
2. explanation is according to the embodiment of the effect of the polymer dielectric film of second embodiment of the invention
＜embodiment 8 〉
With with embodiment 1 in identical mode prepare polyimides, then to wherein being added in N-N-methyl-2-2-pyrrolidone N-(NMP, the solution of the triglycidyl isocyanurate of the 15wt% Junsei Chemical) (socyanuric acid triglycidyl ester) (Cat.No.I0428, Tokyo ChemicalIndustry).At this moment, based on the solids content of polymer, use triglycidyl isocyanurate with the amount of 20wt%.Used mechanical agitator vigorous stirring mixture 6 hours, with preparation homogeneous polymer solution.
＜embodiment 9 〉
With with embodiment 1 in identical mode prepare polyimides, then to wherein being added in N-N-methyl-2-2-pyrrolidone N-(NMP, the solution of the triglycidyl isocyanurate of the 15wt% Junsei Chemical) (Cat.No.I0428, Tokyo Chemical Industry).At this moment, based on the solids content of polymer, use triglycidyl isocyanurate with the amount of 5wt%.Use mechanical agitator vigorous stirring mixture 6 hours with preparation homogeneous polymer solution.
＜embodiment 10 〉
With with embodiment 1 in identical mode prepare polyimides, then to wherein being added in N-N-methyl-2-2-pyrrolidone N-(NMP, the solution of the melamine monomer of the 15wt% Junsei Chemical) (Cat.No.T0337, Tokyo Chemical Industry).At this moment, based on the solids content of polymer, use triglycidyl isocyanurate with the amount of 10wt%.Used mechanical agitator vigorous stirring mixture 6 hours, with preparation homogeneous polymer solution.
＜embodiment 11 〉
Except using 0.95 mole 6,4 '-diaminourea-2-Phenylbenzimidazole and 0.1 mole of 4-acetenyl aniline (Cat.No.E0505, Tokyo Chemical Industry) outside, with with embodiment 1 in identical mode prepare polyamic acid solution, and with embodiment 1 in identical mode prepare polyimides.
＜embodiment 12 〉
Except using 0.95 mole of pyromellitic dianhydride (PMDA, Cat.No.B0040, TokyoChemical Industry) and 0.1 mole of maleic anhydride (Cat.No.M0005, Tokyo ChemicalIndustry) outside, with with embodiment 1 in identical mode prepare polyamic acid solution, and with embodiment 1 in identical mode prepare polyimides.
Every kind of polyamic acid solution that use prepares in embodiment 8 is made crosslinked polyimide film.Test the chemical-resistant of crosslinked polyimide film.The results are shown in table 2.
Table 2
| Polymer | Film forms | The weight (g) of Fenton test cephacoria | The weight (g) of Fenton test caudacoria | Weight conservation rate (%) |
| Embodiment 8 | O | 0.0534 | 0.0502 | 94 |
| Embodiment 9 | O | 0.0475 | 0.0437 | 92 |
| Embodiment 10 | O | 0.0544 | 0.0473 | 87 |
| Embodiment 11 | O | 0.0716 | 0.0558 | 78 |
| Embodiment 12 | O | 0.0561 | 0.0465 | 83 |
| Embodiment 1 | O | 0.0423 | Crisp | Can't measure |
By Fenton test the carrying out test of chemical-resistant.Particularly, with the FeSO of 20ppm
4Be dissolved in the solution that is used for the Fenton test in the hydrogenperoxide steam generator with preparation.Each polyimide film is joined in the solution in the container.The solution that uses oscillator in 80 ℃ water-bath, to vibrate to be soaked with polyimide film 6 hours.Thereafter, film is taken out from solution, water cleans, and under 60 ℃ in vacuum drying oven dry 3 hours, and weigh.
By the result of table 2 obviously as seen, the film that does not comprise the embodiment 1 of crosslinking agent is highly brittle and shows the big loss in weight after the Fenton test.That is, can't measure the weight conservation rate of film.
On the contrary, after the Fenton test, also show high relatively weight conservation rate even comprise the film of the embodiment 8～12 of crosslinking agent.Especially, the weight retention rate very high (94%) of the film of making among the embodiment 8.
Use the polymer dielectric film that forms among the embodiment 9 to make fuel cell.Under 150 ℃, there is not to estimate the I-V characteristic of described fuel cell moisteningly.The results are shown in Fig. 4.
The result of Fig. 4 shows: the fuel cell that uses the polymer dielectric film manufacturing that forms among the embodiment 9 is at 0.3A/cm
2Current density under show magnitude of voltage up to 670mV.
Use the polymer dielectric film that forms among the embodiment 9 to make the test fuel battery.Estimate the long-time running stability of this test fuel battery.The results are shown in Fig. 5.
Though do not show among Fig. 5, but the persistence (＜300 hours) that the fuel cell performance that is to use among the embodiment 1 the film manufacturing that does not comprise crosslinking agent of preparation is gone on business, and use the film that comprises crosslinking agent of preparation is made among the embodiment 1 fuel cell with 0.2A/cm
2The condition of current density long-time running under show the persistence (〉=3500 hours) of remarkable improvement.
Claims (12)
1. polymer dielectric film that is used for fuel cell comprises:
The film that the polyimide copolymer of being represented by through type 1 constitutes:
Wherein each of A and P all is selected from the quadrivalent organic radical group that is derived from acid dianhydride,
B selects the group of free style 2 expressions:
D be selected from the divalent organic group that is derived from aromatic diamine and
M and n satisfy relation: 0.5≤m/ (m+n)≤1.0 and 0≤n/ (m+n)≤0.5; And
Be immersed in the acid in the described polyimide copolymer membrane.
2. polymer dielectric film according to claim 1, wherein each of A and P all is selected from following group:
3. polymer dielectric film according to claim 1, wherein A is identical dianhydride with P and has 1: 1 mol ratio.
4. polymer dielectric film according to claim 1, wherein A is different dianhydrides with P and has 1: 1 mol ratio.
5. polymer dielectric film according to claim 1, wherein D is selected from following group:
6. polymer dielectric film that is used for fuel cell comprises:
The polymer film that the polyimide copolymer of being represented by through type 6 constitutes:
Wherein each of A and P all is selected from the following quadrivalent organic radical group that is derived from acid dianhydride:
B selects the group of free style 8 expressions:
D is selected from the following divalent organic group that is derived from aromatic diamine:
Be selected from the product of the crosslinking agent of following compound:
Wherein R is selected from alicyclic ring, aromatics and heteroaromatic moiety, and epoxy compounds has two or more reactive functional groups, and R1 is selected from aromatics and heteroaromatic moiety, and amines has three or more functional groups; And
Be immersed in the acid in the described polyimide copolymer membrane.
7. polymer dielectric film according to claim 6, the described crosslinking agent that wherein has an epoxide-reactive groups have two to four functional groups and exist based on the solids content of the described polyimides amount with 1～40wt%.
8. polymer dielectric film according to claim 6, the described crosslinking agent that wherein has an amine reactive group have three or four functional groups and exist based on the solids content of the described polyimides amount with 1～40wt%.
9. polymer dielectric film according to claim 6 is wherein introduced acetenyl aniline the terminal monomer of described polyimides and is used with the amount of 2～20mol% between the polymerization period of described polyimides.
10. polymer dielectric film according to claim 6 is wherein introduced maleic anhydride the terminal monomer of described polyimides and is used with the amount of 2～20mol% between the polymerization period of described polyimides.
11. a membrane-electrode assembly comprises:
According to any described polymer dielectric film in the claim 1～10,
By deposition be coated in described polymer dielectric film two lip-deep catalyst layers and
Be arranged on the gas diffusion layers on described each catalyst layer outer surface.
12. a fuel cell comprises:
Membrane-electrode assembly according to claim 11 and
Be arranged in the bipolar plates on the described membrane-electrode assembly two sides.
Applications Claiming Priority (7)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1020060015710A KR100654244B1 (en) | 2006-02-17 | 2006-02-17 | High molocular electrolyte membrane for fuel cell, and membrane-electrode assembly thereby, fuel cell |
| KR1020060015710 | 2006-02-17 | ||
| KR10-2006-0015710 | 2006-02-17 | ||
| JP2006300390 | 2006-11-06 | ||
| JP2006-300390 | 2006-11-06 | ||
| JP2006300390A JP5079306B2 (en) | 2006-11-06 | 2006-11-06 | Polymer electrolyte membrane for fuel cell, membrane-electrode assembly, and fuel cell |
| PCT/KR2006/005902 WO2007094561A1 (en) | 2006-02-17 | 2006-12-29 | High molocular electrolyte membrane for fuel cell, and membrane-electrode assembly thereby, fuel cell |
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| CN101375444B true CN101375444B (en) | 2011-01-26 |
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| JP5079306B2 (en) | 2006-11-06 | 2012-11-21 | チェイル インダストリーズ インコーポレイテッド | Polymer electrolyte membrane for fuel cell, membrane-electrode assembly, and fuel cell |
| CN111073283B (en) * | 2019-11-28 | 2022-05-31 | 李南文 | Cross-linked polyimide film, optical film and preparation method thereof |
| CN111073282B (en) * | 2019-11-28 | 2022-05-31 | 李南文 | Solvent-resistant colorless transparent cross-linked polyimide film and preparation method thereof |
| TWI774321B (en) * | 2021-04-15 | 2022-08-11 | 李長榮化學工業股份有限公司 | Polyamic acid, polyimide, and element formed therefrom |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6586561B1 (en) * | 1999-02-18 | 2003-07-01 | Case Western Reserve University | Rigid rod ion conducting copolymers |
| CN1490345A (en) * | 2002-07-06 | 2004-04-21 | 三星Sdi株式会社 | Proton conductive polymer and producing method thereof, membrane therewith and fuel cell with the membrane |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6586561B1 (en) * | 1999-02-18 | 2003-07-01 | Case Western Reserve University | Rigid rod ion conducting copolymers |
| CN1490345A (en) * | 2002-07-06 | 2004-04-21 | 三星Sdi株式会社 | Proton conductive polymer and producing method thereof, membrane therewith and fuel cell with the membrane |
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