CN101807703B - Intermediate-temperature proton exchange film of organic polysiloxane phosphonic acid group and preparation method thereof - Google Patents
Intermediate-temperature proton exchange film of organic polysiloxane phosphonic acid group and preparation method thereof Download PDFInfo
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Abstract
The invention relates to an intermediate-temperature proton exchange film of an organic polysiloxane phosphonic acid group and a preparation method thereof. The intermediate-temperature proton exchange film of the organic polysiloxane phosphonic acid group is characterized by being prepared by gamma-(2,3-epoxy propoxycaine) propyl trimethoxy silane, 2-(3,4-epoxy cyclohexyl) ethyltrimethoxy silane and phosphonic acid group alkoxy silane via a sol-gel process, and the molar ratio of the raw materials of the gamma-(2,3-epoxy propoxycaine) propyl trimethoxy silane, the 2-(3,4-epoxy cyclohexyl) ethyltrimethoxy silane and the phosphonic acid group alkoxy silane is 1:1:1.5 to 1:0.3:0.2. The intermediate-temperature proton exchange film has higher proton conductivity at intermediate temperature and low humidity, even can conduct the proton under the condition without water, and has good flexibility, high mechanical strength and long service life in an intermediate-temperature fuel cell.
Description
Technical field
The invention belongs to the fuel cell technology field, relate to temperature proton exchange film and preparation method thereof in a kind of used in proton exchange membrane fuel cell.
Background technology
Proton Exchange Membrane Fuel Cells (PEMFC) will become the energy generator of close concern to each other with human daily life owing to have advantage such as efficient, environmental protection, all be the emphasis that people study at a few years from now on and even in a very long time.PEM (PEM) has very big influence as one of key component of PEMFC to the PEMFC performance.
PEMFC generally adopts Pt or Pt alloy to make catalyst at present, adopts perfluorinated sulfonic acid ionic membrane (PFSI) to make exchange membrane.When perfluorinated sulfonic acid ionic membrane (PFSI) was 80 ℃ of left and right sides in working temperature, performance was comparatively excellent, but in this temperature range, the Pt catalyst is more to CO absorption, made the Pt catalyst poisoning, thereby reduced the performance of battery significantly.One of effective ways that solve CO poisoning problem are to improve more than the working temperature to 100 ℃ of battery, yet, on the one hand; Under the working temperature more than 100 ℃, the PFSI film can be that the humidity reduction is dried up because of a large amount of volatilizations of moisture, makes its conductivity sharply descend; Thereby cause the PEMFC performance to become very poor, simultaneously, it is prone to degraded long-term use of the working temperature more than 100 ℃; On the other hand, the PFSI film is too expensive, and this has also greatly hindered extensive popularization and the application of PEMFC.In order to address the above problem, make PEMFC really become safe and reliable " popular " product, people are devoted to temperature (100 ℃～200 ℃) excellent performance and cheap PEM in the development.
At present, the research of centering temperature proton exchange film both at home and abroad is very active, and approach is varied, wherein adopts heteropoly acid such as phosphotungstic acid (PWA), silico-tungstic acid (STA) or basic zirconium phosphate [Zr (HPO
4)
2.H
2O] etc. be a main research focus as the middle temperature proton exchange film of non-water proton conduction unit; Phosphoric acid is the electrolyte of phosphoric acid fuel cell; Very high proton conductive ability is arranged itself, and also have good self-ionization performance, can under non-water condition, conduct electricity; Thereby caused people's great attention, like phosphate-doped polybenzimidazoles (PBI) PEM.Although should under the lower situation of highly doped amount, higher temperature and relative humidity, can keep good conductivity by middle temperature proton exchange film; But because phosphoric acid is difficult to form chemical bond with the macromolecule fertile material; Thereby doping is limited, and in use can lose with current, influences the long-term behaviour of fuel cell; And when high volume; The mechanical strength of this PEM also can descend, and therefore, how non-water proton conduction unit being anchored on the macromolecule matrix should be temperature proton exchange film research focus in this type.
At present; The research of a small amount of R&D institution temperature proton exchange film in carrying out as macromolecule matrix of the Japan and the U.S. with hybrid inorganic-organic materials; The main chain of this hybrid inorganic-organic materials is a stable skeleton of alternately being made up of silicon atom and oxygen atom, and side chain is the silicon atom and the formation that link to each other such as organic group such as methyl, phenyl or vinyl through main chain.Because this specific molecule structure and composition; It not only has the excellent properties such as high-low temperature resistant, weather-resistant, anti-ozone, electric insulation, anti-combustion, the corrosion of nontoxic nothing and physiology inertia of inorganic matter silicon dioxide; And have high-molecular organic material and be prone to machining characteristics; Can process the product that can satisfy various uses according to demands of different, thus with it as parent, add again non-water proton conduction unit prepare in temperature proton exchange film be one and well select.This type PEM is mostly with tetraethoxysilane (TEOS) and γ-(2; 3-epoxy third oxygen) propyl trimethoxy silicane (GPTMS) is as presoma; Ethanol is as solvent, and adds various non-water proton conduction unit such as phosphoric acid etc., prepares through sol-gel technology.Its PEM for preparing has false polyethylene glycol network configuration; The passage of proton transfer can be provided for non-water proton conduction unit; But because the general proton conduction unit phosphoric acid that adopts is difficult to form chemical bond with the hybrid inorganic-organic fertile material; Therefore under middle temperature low humidity, there are shortcomings such as conductivity is not high, mechanical strength difference in temperature proton exchange film in this.
Summary of the invention
The object of the present invention is to provide a kind of temperature proton exchange film in the excellent organopolysiloxane phosphonate group of higher proton conductivity and mechanical property that under middle gentle low humidity, all has.
Another object of the present invention is to provide the preparation method of temperature proton exchange film in a kind of organopolysiloxane phosphonate group.
For solving the technical problem that the present invention proposes; The technical scheme that the present invention adopted is: temperature proton exchange film in a kind of organopolysiloxane phosphonate group; It is characterized in that it is by γ-(2; 3-epoxy third oxygen) propyl trimethoxy silicane (GPTMS), 2-(3, the 4-epoxycyclohexyl) ethyl trimethoxy silane (EHTMS) and phosphonate group alkoxy silane (PATOS) are prepared from through sol-gel technology, said each raw material γ-(2; 3-epoxy third oxygen) propyl trimethoxy silicane: 2-(3, the 4-epoxycyclohexyl) ethyl trimethoxy silane: the mol ratio of phosphonate group alkoxy silane is 1: 1: 1.5～1: 0.3: 0.2.
Press such scheme, described phosphonate group alkoxy silane is a kind of in phosphonic acids ethyl trimethoxy silane, phosphonic acids phenethyl trimethoxy silane, phosphonic acids trifluoroethyl trimethoxy silane, phosphonic acids isopropyl trimethoxy silane, phosphonic acids ethyl triethoxysilane, phosphonic acids phenethyl triethoxysilane, phosphonic acids trifluoroethyl triethoxysilane, the phosphonic acids isopropyl triethoxysilane.
Press such scheme, the preparation method of described phosphonate group alkoxy silane may further comprise the steps:
1) according to hydrogen-containing siloxane: alkenyl phosphonic acid: acetylacetone,2,4-pentanedione platinum: the mol ratio of solvent=(1.5～2.5): (1.5～2.5): (1.5 * 10
-3～2.5 * 10
-3): raw material is prepared in (10～20);
2) under nitrogen protection, in the reactor that electromagnetic mixing apparatus and previously baked drying are housed, add hydrogen-containing siloxane, acetylacetone,2,4-pentanedione platinum, in ultraviolet light irradiation down, stirred simultaneously 10～20 minutes then;
3) alkenyl phosphonic acid is used solvent solution-forming, under nitrogen protection and room-temperature water bath cooling, it is added drop-wise in the reactor, continue reaction 1.0～1.5 hours then;
4) in step (3) reacted solution, add active carbon, remove by filter catalyst acetylacetone,2,4-pentanedione platinum, rotation is steamed and is desolventized then, obtains faint yellow transparent thick liquid;
5) vacuumize obtains phosphonate group alkoxy silane product.
Press such scheme, described hydrogen-containing siloxane is triethoxy hydrogen silane or trimethoxy hydrogen silane.
Press such scheme, the granularity of described acetylacetone,2,4-pentanedione platinum grain is less than 20 μ m.
Press such scheme, described alkenyl phosphonic acid is any in trifluoro vinyl phosphonate, styryl phosphonic acids, vinyl phosphonate, the isopropylene phosphonic acid.
Press such scheme, described solvent is any in absolute ethyl alcohol, absolute methanol, isopropyl alcohol, the toluene.
The preparation method of temperature proton exchange film is characterized in that it comprises the steps: in above-mentioned a kind of organopolysiloxane phosphonate group
1) preparation of colloidal sol: according to each raw material γ-(2; 3-epoxy third oxygen) propyl trimethoxy silicane: 2-(3, the 4-epoxycyclohexyl) ethyl trimethoxy silane: the mol ratio of phosphonate group alkoxy silane is to choose raw material in 1: 1: 1.5～1: 0.3: 0.2, adds in the reactor; Add and γ-(2 then; 3-epoxy third oxygen) the propyl trimethoxy silicane mol ratio is 6.0～7.0 methyl alcohol, and adding is 4.0～5.0 deionized water with γ-(2,3-epoxy third oxygen) propyl trimethoxy silicane mol ratio again; Stirring at room 12～24 hours must be stablized limpid colloidal sol;
2) preparation of gel mould: the colloidal sol that step 1) obtains is poured in the polytetrafluoroethylene mould; Cover aluminium foil; The dealcoholysis 12～24 hours of promptly dewatering is handled in 65～70 ℃ of gelations, when sol solution becomes thickness, removes aluminium foil again; Continue gelation 40～60 minutes, obtain not having the gel mould of macroscopic cracking;
The gel mould vacuumize of the no macroscopic cracking that 3) drying: with step 2) obtains obtains temperature proton exchange film in the organopolysiloxane phosphonate group.
The present invention adopts the phosphonate group alkoxy silane as the proton conduction unit, when sol-gel, can form chemical bond with the organopolysiloxane network, has strengthened the proton conductivity of temperature proton exchange film under middle gentle low humidity in this; Adopt the presoma of γ-(2,3-epoxy third oxygen) propyl trimethoxy silicane (GPTMS),, the passage of proton transfer can be provided for non-water proton conduction unit because of having false polyethylene glycol network configuration behind the GPTMS hydrolytic polymerization as sol-gel; Adopt 2-(3, the 4-epoxycyclohexyl) ethyl trimethoxy silane (EHTMS) to make presoma, can make synthetic PEM have longer organic chain, thereby improve the pliability of this PEM widely.
The present invention and existing foreign method relatively have following advantage:
1) temperature proton exchange film in the organopolysiloxane phosphonate group of this method preparation has higher proton conductivity under middle gentle low humidity, even still can proton conducting under anhydrous condition.
2) the temperature proton exchange film pliability is good in the organopolysiloxane phosphonate group of this method preparation, mechanical strength is high, the long service life in intermediate temperature fuel cell.
3) adopt temperature proton exchange film fuel battery assembled in the organopolysiloxane phosphonate group of this method preparation, working temperature is high, can reduce CO greatly to the poisoning of catalyst, and improves activity of such catalysts, thereby improves the power output of fuel cell.
Description of drawings
Fig. 1 is the structure diagram of temperature proton exchange film in a kind of organopolysiloxane phosphonate group of the present invention's preparation.
Embodiment
In order to understand the present invention better, further illustrate content of the present invention below in conjunction with embodiment, but content of the present invention not only is confined to following embodiment.
It is pure that the γ that is adopted in the following example-(2,3-epoxy third oxygen) propyl trimethoxy silicane (GPTMS), 2-(3, the 4-epoxycyclohexyl) ethyl trimethoxy silane (EHTMS) and methyl alcohol are analysis, and purity is greater than 98% (wt%).
The preparation method of the phosphonic acids ethyl trimethoxy silane that is adopted is: according to the trimethoxy hydrogen siloxane: vinyl phosphonate: acetylacetone,2,4-pentanedione platinum: the mol ratio of methyl alcohol is 1.5: 1.5: 1.5 * 10
-3: 20 take by weighing raw material.Under nitrogen protection, in the there-necked flask of the previously baked drying that electromagnetic agitation is housed, add trimethoxy hydrogen silane, the acetylacetone,2,4-pentanedione platinum of accurately metering, in ultraviolet light irradiation down, stirred simultaneously 10 minutes; Vinyl phosphonate is used the methyl alcohol wiring solution-forming, under nitrogen protection and room-temperature water bath cooling, it is added drop-wise in the reactor, continue reaction 1.0 hours then; Add active carbon, stirred 10 minutes, remove by filter catalyst acetylacetone,2,4-pentanedione platinum, rotation is steamed and is desolventized then, obtains faint yellow transparent thick liquid; 130 ℃ of vacuumize obtained in 1.0 hours.
Preparation method with reference to above-mentioned phosphonic acids ethyl trimethoxy silane; Choose raw material according to each proportion of raw materials in the following table 1, experiment 1～7 can prepare phosphonic acids phenethyl triethoxysilane, phosphonic acids trifluoroethyl triethoxysilane, phosphonic acids isopropyl triethoxysilane, phosphonic acids ethyl triethoxy hydrogen siloxane, phosphonic acids phenethyl trimethoxy silane, phosphonic acids trifluoroethyl trimethoxy silane, phosphonic acids isopropyl trimethoxy silane respectively with subsequent use.
Table 1
| The experiment number | Proportion of raw materials |
| Experiment 1 | Triethoxy hydrogen silane: styryl phosphonic acids: acetylacetone,2,4-pentanedione platinum: the mol ratio of methyl alcohol=1.5: 1.5: 1.5 * 10 -3∶20 |
| Experiment 2 | Triethoxy hydrogen silane: trifluoro vinyl phosphonate: acetylacetone,2,4-pentanedione platinum: the mol ratio of methyl alcohol=1.5: 1.5: 1.5 * 10 -3∶20 |
| Experiment 3 | Triethoxy hydrogen silane: isopropylene phosphonic acid: acetylacetone,2,4-pentanedione platinum: the mol ratio of methyl alcohol=1.5: 1.5: 1.5 * 10 -3∶20 |
| Experiment 4 | Triethoxy hydrogen siloxane: vinyl phosphonate: acetylacetone,2,4-pentanedione platinum: methyl alcohol mol ratio=1.5: 1.5: 1.5 * 10 -3∶20 |
| Experiment 5 | Trimethoxy hydrogen silane: styryl phosphonic acids: acetylacetone,2,4-pentanedione platinum: methyl alcohol mol ratio=1.5: 1.5: 1.5 * 10 -3∶20 |
| Experiment 6 | Trimethoxy hydrogen siloxane: trifluoro vinyl phosphonate: acetylacetone,2,4-pentanedione platinum: methyl alcohol mol ratio=1.5: 1.5: 1.5 * 10 -3∶20 |
| Experiment 7 | Trimethoxy hydrogen silane: isopropylene phosphonic acid: acetylacetone,2,4-pentanedione platinum: methyl alcohol mol ratio=1.5: 1.5: 1.5 * 10 -3∶20 |
Embodiment 1
Preparation method's concrete steps of temperature proton exchange film are following in the organopolysiloxane phosphonate group:
1) preparation of colloidal sol: according to each raw material γ-(2,3-epoxy third oxygen) propyl trimethoxy silicane: 2-(3, the 4-epoxycyclohexyl) ethyl trimethoxy silane: the mol ratio of phosphonic acids ethyl trimethoxy silane is 1.0: 1.0: 1.5; Choose raw material; Add in the reactor, adding and GPTMS mol ratio are 7.0 methyl alcohol then, and adding and GPTMS mol ratio are 5.0 deionized water again; Stirring at room 24 hours must be stablized limpid colloidal sol;
2) preparation of gel mould: the sol solution that step 1) obtains is poured in the polytetrafluoroethylene mould; Cover aluminium foil, put into baking oven then, in 65～70 ℃ of gelations dealcoholysis 12 hours of promptly dewatering; When sol solution becomes thickness; Remove aluminium foil again, continue gelation 45 minutes, obtain not having the gel mould of macroscopic cracking;
130 ℃ of vacuumizes of the gel mould of the no macroscopic cracking that 3) drying: with step 2) obtains 1～2 hour get temperature proton exchange film in the organopolysiloxane phosphonate group.
The structure diagram of temperature proton exchange film is seen Fig. 1 in the organopolysiloxane phosphonate group.Its basic physical property test result is listed in table 2.
Embodiment 2
Preparation method's concrete steps of temperature proton exchange film are following in the organopolysiloxane phosphonate group:
1) preparation of colloidal sol: according to each raw material γ-(2,3-epoxy third oxygen) propyl trimethoxy silicane: 2-(3, the 4-epoxycyclohexyl) ethyl trimethoxy silane: the mol ratio of phosphonic acids phenethyl triethoxysilane is 1.0: 0.5: 0.7; Choose raw material; Add in the reactor, adding and GPTMS mol ratio are 6.0 methyl alcohol then, and adding and GPTMS mol ratio are 4.0 deionized water again; Stirring at room 18 hours must be stablized limpid colloidal sol;
2) preparation of gel mould: the sol solution that step 1) obtains is poured in the polytetrafluoroethylene mould; Cover aluminium foil, put into baking oven then, 65～70 ℃ of gelations (dehydration dealcoholysis) 24 hours; When sol solution becomes thickness; Remove aluminium foil again, continue gelation 50 minutes, obtain not having the gel mould of macroscopic cracking;
130 ℃ of vacuumizes of the gel mould of the no macroscopic cracking that 3) drying: with step 2) obtains 1～2 hour get temperature proton exchange film in the organopolysiloxane phosphonate group.
Its basic physical property test result is listed in table 2.
Embodiment 3
Preparation method's concrete steps of temperature proton exchange film are following in the organopolysiloxane phosphonate group:
1) preparation of colloidal sol: according to each raw material γ-(2,3-epoxy third oxygen) propyl trimethoxy silicane: 2-(3, the 4-epoxycyclohexyl) ethyl trimethoxy silane: the mol ratio of phosphonic acids trifluoroethyl triethoxysilane is 1.0: 1.0: 0.6; Choose raw material; Add in the reactor, adding and GPTMS mol ratio are 7.0 methyl alcohol then, and adding and GPTMS mol ratio are 5.0 deionized water again; Stirring at room 24 hours must be stablized limpid colloidal sol;
2) preparation of gel mould: the sol solution that step 1) obtains is poured in the polytetrafluoroethylene mould; Cover aluminium foil, put into baking oven then, 65～70 ℃ of gelations (dehydration dealcoholysis) 12 hours; When sol solution becomes thickness; Remove aluminium foil again, continue gelation 60 minutes, obtain not having the gel mould of macroscopic cracking;
150 ℃ of vacuumizes of the gel mould of the no macroscopic cracking that 3) drying: with step 2) obtains 1～2 hour get temperature proton exchange film in the organopolysiloxane phosphonate group.
Its basic physical property test result is listed in table 2.
Embodiment 4
Preparation method's concrete steps of temperature proton exchange film are following in the organopolysiloxane phosphonate group:
1) preparation of colloidal sol: according to each raw material γ-(2,3-epoxy third oxygen) propyl trimethoxy silicane: 2-(3, the 4-epoxycyclohexyl) ethyl trimethoxy silane: the mol ratio of phosphonic acids isopropyl triethoxysilane is 1.0: 0.3: 0.2; Choose raw material; Add in the reactor, adding and GPTMS mol ratio are 6.0 methyl alcohol then, and adding and GPTMS mol ratio are 4.0 deionized water again; Stirring at room 12 hours must be stablized limpid colloidal sol;
2) preparation of gel mould: the sol solution that step 1) obtains is poured in the polytetrafluoroethylene mould; Cover aluminium foil, put into baking oven then, 65～70 ℃ of gelations (dehydration dealcoholysis) 18 hours; When sol solution becomes thickness; Remove aluminium foil again, continue gelation 40 minutes, obtain not having the gel mould of macroscopic cracking;
140 ℃ of vacuumizes of the gel mould of the no macroscopic cracking that 3) drying: with step 2) obtains 1～2 hour get temperature proton exchange film in the organopolysiloxane phosphonate group.
Its basic physical property test result is listed in table 2.
Embodiment 5～8
| Embodiment | Proportion of raw materials |
| Embodiment 5 | γ-(2,3-epoxy third oxygen) propyl trimethoxy silicane: 2-(3, the 4-epoxycyclohexyl) ethyl trimethoxy silane: the mol ratio of phosphonic acids ethyl triethoxysilane=1.0: 1.0: 1.5 |
| Embodiment 6 | γ-(2,3-epoxy third oxygen) propyl trimethoxy silicane: 2-(3, the 4-epoxycyclohexyl) ethyl trimethoxy silane: the mol ratio of phosphonic acids phenethyl trimethoxy silane=1.0: 1.0: 1.5 |
| Embodiment 7 | γ-(2,3-epoxy third oxygen) propyl trimethoxy silicane: 2-(3, the 4-epoxycyclohexyl) ethyl trimethoxy silane: the mol ratio of phosphonic acids trifluoroethyl trimethoxy silane=1.0: 1.0: 1.5 |
| Embodiment 8 | γ-(2,3-epoxy third oxygen) propyl trimethoxy silicane: 2-(3, the 4-epoxycyclohexyl) ethyl trimethoxy silane: the mol ratio of phosphonic acids isopropyl trimethoxy silane=1.0: 1.0: 1.5 |
By each proportion of raw materials in the last table, with reference to the experimental technique among the embodiment 1, embodiment 5～8 can prepare temperature proton exchange film in the organopolysiloxane phosphonate group respectively.
The The performance test results of temperature proton exchange film in the organopolysiloxane phosphonate group of table 2 different experiments method preparation
Annotate: conductivity of temperature proton exchange film is 0.027S/cm under 130 ℃ and 37% relative humidity in this type of of bibliographical information at present.
Table 2 has been explained: in the organopolysiloxane phosphonate group of the present invention preparation temperature proton exchange film under middle temperature (130 ℃) and low humidity (25% relative humidity), all have higher proton conductivity (>=0.06S/cm) and mechanical property excellence (hot strength >=23.1MPa).
Claims (3)
1. temperature proton exchange film in the organopolysiloxane phosphonate group, it is characterized in that: it prepares according to following preparation method:
1) preparation of colloidal sol: according to each raw material γ-(2; 3-epoxy third oxygen) propyl trimethoxy silicane: 2-(3, the 4-epoxycyclohexyl) ethyl trimethoxy silane: the mol ratio of phosphonate group alkoxy silane is to choose raw material in 1: 1: 1.5～1: 0.3: 0.2, adds in the reactor; Add and γ-(2 then; 3-epoxy third oxygen) the propyl trimethoxy silicane mol ratio is 6.0～7.0 methyl alcohol, and adding is 4.0～5.0 deionized water with γ-(2,3-epoxy third oxygen) propyl trimethoxy silicane mol ratio again; Stirring at room 12～24 hours must be stablized limpid colloidal sol;
2) preparation of gel mould: the colloidal sol that step 1) obtains is poured in the polytetrafluoroethylene mould, covered aluminium foil, 65～70 ℃ of gelations are handled; When sol solution becomes thickness; Remove aluminium foil again, continue gelation 40～60 minutes, obtain not having the gel mould of macroscopic cracking;
The gel mould vacuumize of the no macroscopic cracking that 3) drying: with step 2) obtains obtains temperature proton exchange film in the organopolysiloxane phosphonate group.
2. temperature proton exchange film in a kind of organopolysiloxane phosphonate group according to claim 1 is characterized in that: described phosphonate group alkoxy silane is any in phosphonic acids ethyl trimethoxy silane, phosphonic acids phenethyl trimethoxy silane, phosphonic acids trifluoroethyl trimethoxy silane, phosphonic acids isopropyl trimethoxy silane, phosphonic acids ethyl triethoxysilane, phosphonic acids phenethyl triethoxysilane, phosphonic acids trifluoroethyl triethoxysilane, the phosphonic acids isopropyl triethoxysilane.
3. the preparation method of temperature proton exchange film is characterized in that it comprises the steps: in a kind of organopolysiloxane phosphonate group as claimed in claim 1
1) preparation of colloidal sol: according to each raw material γ-(2; 3-epoxy third oxygen) propyl trimethoxy silicane: 2-(3, the 4-epoxycyclohexyl) ethyl trimethoxy silane: the mol ratio of phosphonate group alkoxy silane is to choose raw material in 1: 1: 1.5～1: 0.3: 0.2, adds in the reactor; Add and γ-(2 then; 3-epoxy third oxygen) the propyl trimethoxy silicane mol ratio is 6.0～7.0 methyl alcohol, and adding is 4.0～5.0 deionized water with γ-(2,3-epoxy third oxygen) propyl trimethoxy silicane mol ratio again; Stirring at room 12～24 hours must be stablized limpid colloidal sol;
2) preparation of gel mould: the colloidal sol that step 1) obtains is poured in the polytetrafluoroethylene mould, covered aluminium foil, 65～70 ℃ of gelations are handled; When sol solution becomes thickness; Remove aluminium foil again, continue gelation 40～60 minutes, obtain not having the gel mould of macroscopic cracking;
The gel mould vacuumize of the no macroscopic cracking that 3) drying: with step 2) obtains obtains temperature proton exchange film in the organopolysiloxane phosphonate group.
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| CN103408760B (en) * | 2013-08-16 | 2015-09-30 | 武汉理工大学 | A kind of middle temperature proton exchange film material and preparation method thereof and the fuel cell using this material to prepare |
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| CN105098215B (en) * | 2015-08-19 | 2017-05-31 | 武汉理工大学 | A kind of phosphonic acids radical siloxane PEM of hydrolysis-stable and preparation method thereof |
| CN108183249A (en) * | 2017-12-29 | 2018-06-19 | 武汉理工大学 | One kind is modified phosphonic acid base high temperature proton exchange film and preparation method thereof based on acid-base pair |
| CN112980201B (en) * | 2021-02-05 | 2022-08-30 | 珠海冠宇电池股份有限公司 | Phosphonic acid modified graphene oxide cross-linked polybenzimidazole-polysiloxane block copolymer composite material |
| CN114316290B (en) * | 2022-01-17 | 2023-09-26 | 沈金国 | High-efficiency high-temperature-resistant proton conducting material and preparation method thereof |
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