CN105140545A - Preparation technology of composite proton exchange membrane - Google Patents
Preparation technology of composite proton exchange membrane Download PDFInfo
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- CN105140545A CN105140545A CN201510481139.7A CN201510481139A CN105140545A CN 105140545 A CN105140545 A CN 105140545A CN 201510481139 A CN201510481139 A CN 201510481139A CN 105140545 A CN105140545 A CN 105140545A
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- China
- Prior art keywords
- exchange membrane
- proton conductor
- proton exchange
- proton
- organic polymer
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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
- H01M8/1069—Polymeric electrolyte materials characterised by the manufacturing processes
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
Abstract
The invention relates to a preparation technology of a composite proton exchange membrane. With polyvinylidene fluoride (PVDF) as an organic polymer base, a composite proton conductor is added to prepare a composite proton exchange membrane through a hot-pressing technology; and the composite proton conductor is prepared from solid cesium hydrogen sulfate CsHSO4 and mesoporous alumina Al2O3 powder through a wet ball-milling method. A monocell assembled by the composite membrane prepared by the method has cell performance at 145 DEG C, and can be applied to a high-temperature proton exchange membrane fuel cell.
Description
Technical field
The invention belongs to Proton Exchange Membrane Fuel Cells technical field, relate to a kind of preparation method of compound proton exchange membrane.
Background technology
Fuel cell is a kind of Blast Furnace Top Gas Recovery Turbine Unit (TRT) chemical energy in fuel being converted into electric energy, and it does not limit by Carnot cycle, has higher conversion ratio, and high with its energy density, the advantages such as low stain become the power source of future ideality.Wherein the remarkable advantage such as Proton Exchange Membrane Fuel Cells (ProtonExchangeMembranesFuelCell, PEMFC), energy saving standard efficient with it is applied to the fields such as power station, portable power source and automobile widely.According to the difference of working temperature, Proton Exchange Membrane Fuel Cells can be divided into low temperature PEMFC (< 100 DEG C) and high temperature PEMFC (100 DEG C-200 DEG C).At present, the low temperature PEMFC commercialization being representative with perfluorinated sulfonic acid PEMFC, but perfluorinated sulfonic acid PEMFC is using water as the medium of its proton conducting, because the disappearance of moisture causes conductivity sharply to reduce after working temperature is more than 80 DEG C, reduce battery operated performance, when temperature continues to raise, PEMFC decomposes thereupon, loses battery operated performance.Secondly work in this temperature range, catalyst is easily poisoned by impurity contained in the fuel such as CO.Therefore develop high temperature PEMFC to widen battery operating temperature scope there is larger Research Significance.
The core of PEMFC is proton exchange membrane (ProtonExchangeMembrane, PEM), PEM serves transmission proton as solid electrolyte, separate the multiple action of fuel and oxidant, also to ensure that from outside electronics and gas can not pass through with holding structure under normal operation circumstances constant, so the serviceability temperature of membrane material generally determines the final working temperature of battery.At present, perfluoro sulfonic acid membrane (Nafion film) can be divided into according to the difference of membrane material, nonfluorinated film, solid sorrel and organic/inorganic composite film etc.Wherein organic/inorganic composite film is the one general designation of the PEM of inorganic constituents and organic polymeric composition, be that substrate doping inorganic solid proton conductor is composited with organic polymer, farthest make use of inorganic matter and organic polymer advantage separately, there is larger utilization prospect.Research for PEM is not only selection, and the technique of preparation PEM is also the important directions of a research.The preparation method of compound proton exchange membrane has blending method, sol-gal process, situ aggregation method, modification and Insertion method etc.Due to the imperfection that some prepare composite membrane technique, make the uniformity of organic polymer and inorganic component dispersion not high, thus have impact on the Structure and Properties of composite membrane.
Summary of the invention
One of content, the present invention relates to the hot pressing method for preparing of a kind of compound PEM applied in high temperature PEMFC.The quality of PEM performance, first relevant with the macroscopic scale between the own performance of organic polymer and inorganic solid proton conductor, material, secondly with the microstructure of membrane material, the dispersiveness of such as organic granular and inorganic particle, particle size, the thickness of film, the porosity on film surface etc. are relevant.This inventive method comprises: (a) provides a kind of preparation of inorganic compounding proton conductor.B organic polymer and inorganic compounding proton conductor evenly effectively mix by ().C () provides more excellent Stock allotment right between one group of organic polymer and inorganic compounding proton conductor.D () makes composite membrane by pressure sintering.E () provides corresponding hot-press method and parameter.During hot pressing film forming, the raw-material mix proportion of composite membrane, hot pressing temperature, the difference of time and pressure, all have a great impact the surface structure of the film be pressed into and performance, suitable mix proportion and hot pressing condition parameter can eliminate the shrinkage of film forming, crackle, the defect such as uneven.
The compound proton exchange membrane be successfully prepared loads after a membrane electrode assembly (MembraneElectrodeAssembly, MEA) makes monocell, and monocell being loaded model is in 5620-F fuel battery performance test macro, temperature 145 DEG C, and anode O
2, negative electrode H
2, test under test condition.
Accompanying drawing explanation
Fig. 1: the monocell polarization curve of embodiment 1
Fig. 2: the monocell polarization curve of embodiment 2
Fig. 3: the monocell polarization curve of embodiment 3
Fig. 4: the picture of the film of embodiment 3
Fig. 5: the monocell polarization curve of embodiment 4
Describe in detail
A kind of compound PEM of following preparation: inorganic compounding proton conductor and organic polymer are hot pressed into film after Homogeneous phase mixing.
In the selection of inorganic compounding proton conductor, select mesoporous material (the such as Al that moisture absorption is stronger
2o
3, ZrO
2, TiO
2deng) and there is solid-acid material (the such as CsHSO of solid electrolyte effect
4, CsH
2pO
4, K
3h (SO
4)
2deng) be mixed and made into composite proton conductor.Moisture absorption oxide is due to its special loose structure, and adsorbed water molecule shows higher proton conductivity, and solid acid has superproton and changes performance under middle high temperature, thus makes it under middle high temperature, have higher proton conductivity; Secondly above-mentioned moisture absorption oxide is sulfonated because of the acid material of high proton electrical conductance, keep using the OH group of inorganic particle surfaces acidity as proton carrier film from moisturising, thus there is better proton conductive.In organic polymer selection, the high polymer that namely high polymer gathers mutually and crosslinking degree is high that general selection mass fraction is larger, to weaken the hydrolysis of high polymer, next has higher machinery and structural strength, thus it is minimum (as Kynoar PVDF to make PEM be out of shape under tension, polypropylene is fine, or polyimides etc.).Such as:, the PVDF that chemical stability good high with mechanical strength in embodiment 1 for organic polymer substrate with at high temperature there is the solid acid CsHSO that superproton changes ability
4as proton conductor composite membrane-forming.Embodiment 2 is by the proton conductor CsHSO in embodiment 1
4with mesoporous material Al
2o
3make inorganic compounding proton conductor by wet ball mill method, then with organic polymer hot pressing composite membrane-forming.And the performance of composite membrane in the scale effect of inorganic constituents and organic polymer in composite membrane, inorganic solid proton conductor ratio is larger theoretically, the proton conductivity of film is stronger (contrast of embodiment 2 and embodiment 3), but due to proton conductor occupy ratio excessive time, composite membrane fragility after hot pressing is comparatively large, cannot be used in PEMFC.By organizing test, obtain in the method for hot pressing film forming that inorganic compounding proton conductor volume content should between 20%-80% more.
Composite proton conductor obtains by methods such as such as fusion method, polishing, dry ball-milling method, wet ball mill methods, recombination process mesopore caves in and causes the pore-size of sample and volume can diminish along with the process of grinding, material property can be caused to decline, cosolvent in wet ball mill method reduces the mechanical strength that ball milling produces, less to the destruction of sample, therefore select wet ball mill method to be preparation method.Preparation condition is: equimolar CsHSO
4powder and meso-porous alumina Al
2o
3powder, 5ml ethanol, setting speed is 200rpm, ball milling 2h.
After organic polymer and the mixing of inorganic compounding proton conductor, make composite membrane by hot pressing.Wherein the temperature of hot pressing should between organic polymer and inorganic compounding proton conductor fusing point, pressure is be the bigger the better in the scope that substrate can bear, because the composite membrane more flat smooth that pressure is made more greatly, film thickness is also (contrast of embodiment 3 and embodiment 4) thinning along with the increase of pressure, and the press mold time is drawn by test of many times.Finally obtaining best hot pressing condition is: temperature is 175 DEG C, and pressure is 0.4MPa, and the time is 5min.
Embodiment 1
To get etc. molar concentration be 98% the concentrated sulfuric acid and purity be 99
+cesium sulfate (the Cs of %
2sO
4), after getting the 400ml distilled water diluting concentrated sulfuric acid, by Cs
2sO
4add in the sulfuric acid solution diluted, stir after making it fully react and solution is put into baking oven, 80 DEG C of constant temperature 24h, dry and obtain solid acid cesium hydrogen sulfate CsHSO
4powder.Then PVDF and the CsHSO that model is FR906 is got
4volume ratio is 60: 40 mixing, powder grinds 30min in agate mortar, take the 4mm common glass sheet central authorities that the ground powder of 0.5g is placed in a slice 10cm × 10cm, cover after a same sheets gently flattens, being placed on model is in the fuel cell precise instrument of JYFC-M, parameters: the time is 5min, temperature is 175 DEG C, and pressure is 0.4MPa.Be hot pressed into the PVDF-CsHSO that thickness is 0.06mm
4compound proton exchange membrane.After the compound proton exchange membrane assembling MEA be successfully prepared makes monocell, monocell being loaded model is in 5620-F fuel battery performance test macro, temperature 145 DEG C, and anode O
2, negative electrode H
2test condition under test.
Fig. 1 shows the polarization curve of the made monocell of the present embodiment, meet above in described PEM solid acid as proton conductor, show and at high temperature there is battery performance.
Embodiment 2
Get equimolar CsHSO
4powder (obtaining with embodiment 1 method) and meso-porous alumina Al
2o
3powder (patent No.: ZL200810061848.X), puts into ball grinder, adds 5ml ethanol, is that in the planetary type ball-milling instrument of QM-3SP04, setting speed is 200rpm, ball milling 2h, obtains inorganic compounding proton conductor powder in model.Getting PVDF and inorganic compounding proton conductor volume ratio is to mix at 60: 40, grind 30min in agate mortar after, take the 4mm common glass sheet central authorities that the ground powder of 0.5g is placed in a slice 10cm × 10cm, cover after a same sheets gently flattens, being placed on model is in the fuel cell precise instrument of JYFC-M, parameters: the time is 5min, temperature is 175 DEG C, and pressure is 0.4MPa.Be hot pressed into the PVDF-CsHSO that thickness is 0.08mm
4/ Al
2o
3compound proton exchange membrane.By the method that embodiment 1 is identical, film is assembled into monocell to test.
Fig. 2 shows the polarization curve of the made monocell of the present embodiment, compare with the polarization curve of Fig. 1, the known intermediary hole material of PEM as mentioned before and solid acid are combined into inorganic compounding proton conductor, show and have better high-temperature battery performance than simple Bronsted acid proton conductor.
Embodiment 3
Solid acid CsHSO is obtained with embodiment 2 same procedure
4with mesoporous Al
2o
3inorganic compounding proton conductor powder.Getting PVDF and inorganic compounding proton conductor volume ratio is to mix at 40: 60, grind 30min in agate mortar after, take after the ground powder of 0.5g is placed in the 4mm common glass sheet central authorities of a slice 10cm × 10cm, cover after a same sheets gently flattens, being placed on model is in the fuel cell precise instrument of JYFC-M, parameters: the time is 5min, temperature is 175 DEG C, and pressure is 0.4MPa.Be hot pressed into the PVDF-CsHSO that thickness is 0.08mm
4/ Al
2o
3compound proton exchange membrane, Fig. 4 is the picture of the present embodiment institute masking.By the method that embodiment 1 is identical, film is assembled into monocell to test.
Fig. 3 shows the polarization curve of the made monocell of the present embodiment, compares with the polarization curve in Fig. 2, as mentioned before known, and along with the increase of inorganic compounding proton conductor ratio in PEM, the proton conductivity of phosphoric acid of composite membrane improves.
Embodiment 4
Solid acid CsHSO is obtained with embodiment 2 same procedure
4with mesoporous Al
2o
3inorganic compounding proton conductor powder.Getting PVDF and inorganic compounding proton conductor volume ratio is to mix at 40: 60, grind 30min in agate mortar after, take after the ground powder of 0.5g is placed in the 4mm common glass sheet central authorities of a slice 10cm × 10cm, cover after a same sheets gently flattens, being placed on model is in the fuel cell precise instrument of JYFC-M, parameters: the time is 5min, temperature is 175 DEG C, and pressure is 0.2MPa.Be hot pressed into the PVDF-CsHSO that thickness is 0.1mm
4/ Al
2o
3compound proton exchange membrane.Contrast with embodiment 2 and 3, the reduction of hot compression parameters pressure have impact on the evenness of composite membrane, and film thickness is also thickening.By the method that embodiment 1 is identical, film is assembled into monocell to test.
Fig. 5 shows the polarization curve of the made monocell of the present embodiment, compares with the monocell polarization curve in Fig. 3, known with above described in, along with the increase of hot compression parameters pressure, the proton conductivity of phosphoric acid of composite membrane improves.
Claims (7)
1. a preparation method for compound proton exchange membrane, is characterized in that: take organic polymer as substrate, according to certain volume than after interpolation inorganic compounding proton conductor, is prepared into organic-inorganic composite proton exchange membrane by pressure sintering.
2. according to the selection of organic polymer described in claim 1, it is characterized in that: described organic polymer gathers for vinylidene, the fine or polyimides of polypropylene.
3. according to the selection of inorganic compounding proton conductor described in claim 1, it is characterized in that: the mesoporous material Al that moisture absorption is stronger
2o
3, ZrO
2or TiO
2with the solid-acid material CsHSO with solid electrolyte effect
4, CsH
2pO
4or K
3h (SO
4)
2compound.
4. according to the preparation method of claim 1 and inorganic compounding proton conductor according to claim 3, it is characterized in that: obtain with wet ball mill method.
5. according to the preparation condition of wet ball mill method according to claim 4, it is characterized in that: equimolar CsHSO
4powder and meso-porous alumina Al
2o
3powder, 5ml ethanol, setting speed is 200rpm, ball milling 2h.
6., according to the volume ratio of organic polymer described in claim 1 and inorganic compounding proton conductor, it is characterized in that: inorganic compounding proton conductor volume content should between 20%-80%.
7. prepare organic-inorganic composite proton exchange membrane according to pressure sintering described in claim 1, it is characterized in that best hot compression parameters is: temperature is 175 DEG C, pressure is 0.4MPa, and the time is 5min.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108039498A (en) * | 2017-12-26 | 2018-05-15 | 成都新柯力化工科技有限公司 | A kind of method of modifying of polyphenylacetylene modification fuel battery proton exchange film |
| CN111613820A (en) * | 2020-05-08 | 2020-09-01 | 深圳氢时代新能源科技有限公司 | Composite proton exchange membrane, preparation method thereof and fuel cell |
| CN112111757A (en) * | 2020-09-15 | 2020-12-22 | 中国科学院大连化学物理研究所 | Composite membrane for high-temperature water electrolysis and preparation method and application thereof |
| CN113839074A (en) * | 2021-09-24 | 2021-12-24 | 上海交通大学 | Preparation method of solid acid proton conduction membrane |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108039498A (en) * | 2017-12-26 | 2018-05-15 | 成都新柯力化工科技有限公司 | A kind of method of modifying of polyphenylacetylene modification fuel battery proton exchange film |
| CN108039498B (en) * | 2017-12-26 | 2020-08-07 | 成都新柯力化工科技有限公司 | Modification method for fuel cell proton exchange membrane modified by polyphenylacetylene |
| CN111613820A (en) * | 2020-05-08 | 2020-09-01 | 深圳氢时代新能源科技有限公司 | Composite proton exchange membrane, preparation method thereof and fuel cell |
| CN111613820B (en) * | 2020-05-08 | 2021-03-12 | 深圳氢时代新能源科技有限公司 | Composite proton exchange membrane, preparation method thereof and fuel cell |
| CN112111757A (en) * | 2020-09-15 | 2020-12-22 | 中国科学院大连化学物理研究所 | Composite membrane for high-temperature water electrolysis and preparation method and application thereof |
| CN112111757B (en) * | 2020-09-15 | 2022-05-10 | 中国科学院大连化学物理研究所 | Composite membrane for high-temperature water electrolysis and preparation method and application thereof |
| CN113839074A (en) * | 2021-09-24 | 2021-12-24 | 上海交通大学 | Preparation method of solid acid proton conduction membrane |
| CN113839074B (en) * | 2021-09-24 | 2023-10-20 | 上海交通大学 | Preparation method of solid acid proton conducting membrane |
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