CN107331883A - A kind of middle temperature proton exchange film and preparation method thereof - Google Patents
A kind of middle temperature proton exchange film and preparation method thereof Download PDFInfo
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- CN107331883A CN107331883A CN201710326667.4A CN201710326667A CN107331883A CN 107331883 A CN107331883 A CN 107331883A CN 201710326667 A CN201710326667 A CN 201710326667A CN 107331883 A CN107331883 A CN 107331883A
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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
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- 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
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- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
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Abstract
The invention provides a kind of middle temperature proton exchange film and preparation method thereof；The middle temperature proton exchange film includes heat-resistant polymer matrix and oxysalt, and the oxysalt is loaded into heat-resistant polymer matrix.Prepared middle temperature proton exchange film not only has high proton conductivity, good heat endurance, and with outstanding mechanical performance.It is suitable for being operated in 100 400 DEG C of warm areas, and running temperature is less than fused carbonate electrolyte, thus, it is possible to the flexible polymer using high mechanical properties as support substrate, loads molten state oxysalt.Melting proton conductor dielectric film disclosed by the invention, preparation technology is easy, is adapted to industrialized production；Its cheap raw material helps to reduce the cost of dielectric film and fuel cell simultaneously, is expected to be used widely in intermediate temperature fuel cell field and the related field for needing middle temperature proton-conductive electrolyte membrane.
Description
Technical field
It is specifically a kind of middle temperature matter the present invention relates to a kind of electrolyte of electrochemical technology field and preparation method thereof
Proton exchange and preparation method thereof.
Background technology
Fuel cell is the TRT that the chemical energy in fuel is converted into electric energy by electrochemical reaction.Each
Plant in fuel cell, intermediate temperature fuel cell (running temperature is at 100-400 DEG C) illustrates attracting advantage.Compared to low temperature
Fuel cell, intermediate temperature fuel cell possesses enhanced CO tolerances, higher catalytic efficiency and electrode kinetics etc.；Compared to height
Temp fuel battery, the choice of intermediate temperature fuel cell material therefor is wider, thus can reduce material cost.
The core of fuel cell is electrolyte, and it determines the operating temperature of fuel cell.So far, in various fuel cells
In, molten carbonate fuel cell (Molten Carbonate Fuel Cell, MCFC) is uniquely to use molten state electrolyte
Fuel cell.In order to keep the electrolyte to be molten state, it is desirable to higher than 550 DEG C (standard work temperature of temperature of fuel cell
Degree is 650 DEG C).Compared to other fuel cells, MCFC sharpest edges are to use molten state electrolyte, easily realize that gas is close
Seal and the interface contact resistance of electrode and electrolyte can be reduced.Also, because of its molten state, fused carbonate electrolyte is (for example
(Li0.52Na0.48)2CO3、(Li0.62K0.38)2CO3) need to be loaded into a porous ceramic support.And in order to maintain its good
Mechanical strength, MCFC possesses very thick electrolyte (0.5-1.5mm), causes the increase of electrolyte Ohmic power loss.The opposing party
Face, 550-650 DEG C of operation temperature limits material selection range, so that it cannot use the polymer of flexibility as support
Body, and heatproof can only be used but fragility and the ceramic material that easily splits.
The content of the invention
The present invention provides a kind of middle temperature proton exchange film and preparation method thereof.Middle temperature proton exchange film is suitable for being operated in
Warm area in 100-400 DEG C, using the flexible polymer of high mechanical properties as support substrate, loading has high proton conductive capability
Molten state oxysalt, and ultra-thin (10-100 μm) support substrate can be prepared using traditional curtain coating coating method.Polyphenyl is simultaneously
Imidazoles (PBI) has good mechanical strength, chemical stability and heat endurance, the present invention with fluoropolymer (such as PVDF)
It is used as polymer support matrix.
The purpose of the present invention is achieved through the following technical solutions：
It is described oxygen-containing the invention provides a kind of middle temperature proton exchange film, including heat-resistant polymer matrix and oxysalt
Hydrochlorate is loaded into heat-resistant polymer matrix.The oxysalt has proton conducting ability.
Preferably, the weight ratio of the heat-resistant polymer matrix and oxysalt is 1：(0.1~5).
It is highly preferred that the weight ratio of the heat-resistant polymer matrix and oxysalt is 1：0.35~5.
Preferably, the heat-resistant polymer is one or more kinds of groups in heat-resisting hydrocarbon polymer, fluoropolymer
Close；
The oxysalt is MHXO4、MH2X’O4、MH5(X’O4)2In one or more combinations, wherein M be Cs,
Rb, K or NH4 +, X is S or Se, X ' and it is P or As.
Preferably, the heat-resisting hydrocarbon polymer is polybenzimidazoles (PBI)；The fluoropolymer is Kynoar
(PVDF)。
Preferably, the oxysalt is perphosphate MH5(PO4)2；More preferably peroxophosphoric acid hydrogen caesium (CsH5(PO4)2)。
The invention provides a kind of preparation method of described middle temperature proton exchange film, comprise the following steps：
S1, heat-resistant polymer is dissolved in solvent, obtains solution A；
S2, the solution A is poured cast from a substrate, dry solidify afterwards film forming C；
S3, the film C cleaned with water, film D is obtained after drying；
S4, described film D is soaked in the oxysalt of melting, the oxyacid of film remained on surface is fallen in immersion post processing
Salt, obtains the middle temperature proton exchange film.
Preferably, in step S1, the solvent is dimethylformamide (DMF), dimethyl acetamide (DMAc), N- methyl
One or more in pyrrolidones (NMP), dimethyl sulfoxide (DMSO) (DMSO), acetone, ethanol, methyl acetone, methyl second acetone.More
Preferred solvent is dimethyl acetamide (DMAc).
Preferably, in step S2, the substrate is glass substrate.
Preferably, in step S1, the solution temperature is that dissolution time is 5-15h less than 10-50 DEG C of solvent boiling point.Institute
State solution temperature too high, solvent evaporation；Solution temperature is too low, causes heat-resistant polymer dissolution time long.The dissolution time
Too short, heat-resistant polymer can not fully dissolve；Dissolution time is long, the volatilization of more multi-solvent, causes to waste, and lose time.
Preferably, in step S4, the film D is soaked in the oxysalt of melting, and soaking temperature is higher than oxysalt
5-20 DEG C of melting temperature, soak time is 1-24h.The too low oxysalt of temperature can not fully melt；The too high behaviour of temperature
Make inconvenience, and waste the energy.The soak time is too short, and the oxysalt of melting can not be sufficiently submerged in heat-resistant polymer；Leaching
The bubble time is oversize, loses time and the energy.
The invention provides fuel cell prepared by a kind of middle temperature proton exchange film.
Compared with prior art, the present invention has following beneficial effect：
Fused carbonate electrolyte works in 550~650 DEG C of warm areas, it is necessary to using heatproof but fragility and the ceramics that easily split
Support substrate.With this contrast, the middle temperature proton exchange film that the present invention is provided is suitable for being operated in 100~400 DEG C of warm areas, operation temperature
Degree is lower, it is thus possible to be used as support substrate using high mechanical properties and with flexible heat-resistant polymer.
The invention provides a kind of low production cost, technique is simple, strong operability preparation method.It is of the invention prepared
Middle temperature proton exchange film be expected to need the conduction of middle temperature proton in the correlation such as intermediate temperature fuel cell and electrolytic cell, super capacitor
It is used widely in the electrochemical appliance of dielectric film.
Brief description of the drawings
By reading the detailed description made with reference to the following drawings to non-limiting example, further feature of the invention,
Objects and advantages will become more apparent upon：
Fig. 1 is the stereoscan photograph of middle temperature proton exchange film prepared by embodiment 1；
Fig. 2 is the proton conductivity and the graph of a relation of temperature of middle temperature proton exchange film prepared by embodiment 1；
Fig. 3 is the output performance curve of the intermediate temperature fuel cell assembled using the middle temperature melting proton conductor of embodiment 1.
Embodiment
With reference to specific embodiment, the present invention is described in detail.Following examples will be helpful to the technology of this area
Personnel further understand the present invention, but the invention is not limited in any way.It should be pointed out that to the ordinary skill of this area
For personnel, without departing from the inventive concept of the premise, some changes and improvements can also be made.These belong to the present invention
Protection domain.
Embodiment 1
It is polybenzimidazoles (PBI) as the heat-resistant polymer of matrix in the present embodiment.Specifically include following steps：
Step 1：Polybenzimidazoles (PBI) is dissolved in 120 DEG C of dimethyl acetamide (DMAc), is incubated and passes through at 120 DEG C
The strong stirring for spending lasting 10 hours obtains polybenzimidazoles (PBI) (5wt%) solution A；
Step 2：Solution A cast is coated on glass substrate, solidify afterwards film forming B is dried；
Step 3：Cleaned for the film B after solidifying in step 3 with water, base film C is obtained after drying；
Step 4：Base film C after solidifying in step 4 is impregnated into 160 DEG C of melting peroxophosphoric acid hydrogen caesium (CsH5(PO4)2)
In, 24h is incubated, middle temperature proton exchange film is finally given.
Embodiment 2
It is polybenzimidazoles (PBI) as the heat-resistant polymer of matrix in the present embodiment.Specifically include following steps：
Step 1：Polybenzimidazoles (PBI) is dissolved in 120 DEG C of dimethylformamide (DMF), is incubated and passes through at 120 DEG C
The strong stirring for continuing 10 hours obtains polybenzimidazoles (PBI) (5wt%) solution A；
Step 2：Solution A cast is coated on glass substrate, solidify afterwards film forming B is dried；
Step 3：Cleaned for the film B after solidifying in step 3 with water, base film C is obtained after drying；
Step 4：Base film C after solidifying in step 4 is impregnated into 160 DEG C of melting peroxophosphoric acid hydrogen caesium (CsH5(PO4)2)
In, 1h is incubated, middle temperature proton exchange film is finally given.
Embodiment 3
It is polybenzimidazoles (PBI) as the heat-resistant polymer of matrix in the present embodiment.Specifically include following steps：
Step 1：Polybenzimidazoles (PBI) is dissolved in 120 DEG C of dimethyl sulfoxide (DMSO) (DMSO), is incubated and passes through at 120 DEG C
The strong stirring for continuing 10 hours obtains polybenzimidazoles (PBI) (5wt%) solution A；
Step 2：Solution A cast is coated on glass substrate, solidify afterwards film forming B is dried；
Step 3：Cleaned for the film B after solidifying in step 3 with water, base film C is obtained after drying；
Step 4：Base film C after solidifying in step 4 is impregnated into 160 DEG C of melting peroxophosphoric acid hydrogen caesium (CsH5(PO4)2)
In, 150h is incubated, middle temperature proton exchange film is finally given.
Embodiment 4
It is Kynoar (PVDF) as the heat-resistant polymer of matrix in the present embodiment.Specifically include following steps：
Step 1：Kynoar (PVDF) is dissolved in 120 DEG C of dimethyl acetamide (DMAc), is incubated and passes through at 120 DEG C
The strong stirring for spending lasting 10 hours obtains Kynoar (PVDF) (15wt%) solution A；
Step 2：Solution A cast is coated on glass substrate, solidify afterwards film forming B is dried；
Step 3：Cleaned for the film B after solidifying in step 3 with water, base film C is obtained after drying；
Step 4：Base film C after solidifying in step 4 is impregnated into 160 DEG C of melting peroxophosphoric acid hydrogen caesium (CsH5(PO4)2)
In, 24h is incubated, middle temperature proton exchange film is finally given.
Embodiment 5
It is polybenzimidazoles (PBI) as the heat-resistant polymer of matrix in the present embodiment.Specifically include following steps：
Step 1：Polybenzimidazoles (PBI) is dissolved in 120 DEG C of dimethyl acetamide (DMAc), is incubated and passes through at 120 DEG C
The strong stirring for spending lasting 10 hours obtains polybenzimidazoles (PBI) (5wt%) solution A；
Step 2：Solution A cast is coated on glass substrate, solidify afterwards film forming B is dried；
Step 3：Cleaned for the film B after solidifying in step 3 with water, base film C is obtained after drying；
Step 4：Base film C after solidifying in step 4 is impregnated into 160 DEG C of melting peroxophosphoric acid hydrogen potassium (KH5(PO4)2)
In, 24h is incubated, middle temperature proton exchange film is finally given.
Embodiment 6
It is polybenzimidazoles (PBI) as the heat-resistant polymer of matrix in the present embodiment.Specifically include following steps：
Step 1：Polybenzimidazoles (PBI) is dissolved in 120 DEG C of dimethyl acetamide (DMAc), is incubated and passes through at 120 DEG C
The strong stirring for spending lasting 10 hours obtains polybenzimidazoles (PBI) (5wt%) solution A；
Step 2：Solution A cast is coated on glass substrate, solidify afterwards film forming B is dried；
Step 3：Cleaned for the film B after solidifying in step 3 with water, base film C is obtained after drying；
Step 4：Base film C after solidifying in step 4 is impregnated into 160 DEG C of melting peroxophosphoric acid hydrogen rubidium (RbH5(PO4)2)
In, 24h is incubated, middle temperature proton exchange film is finally given.
Embodiment 7
It is polybenzimidazoles (PBI) as the heat-resistant polymer of matrix in the present embodiment.Specifically include following steps：
Step 1：Polybenzimidazoles (PBI) is dissolved in 120 DEG C of dimethyl acetamide (DMAc), is incubated and passes through at 120 DEG C
The strong stirring for spending lasting 10 hours obtains polybenzimidazoles (PBI) (5wt%) solution A；
Step 2：Solution A cast is coated on glass substrate, solidify afterwards film forming B is dried；
Step 3：Cleaned for the film B after solidifying in step 3 with water, base film C is obtained after drying；
Step 4：Base film C after solidifying in step 4 is impregnated into 160 DEG C of melting KH5(AsO4)2In, 24h is incubated, most
Prepared middle temperature proton exchange film is obtained eventually.
Embodiment 8
It is polybenzimidazoles (PBI) as the heat-resistant polymer of matrix in the present embodiment.Specifically include following steps：
Step 1：Polybenzimidazoles (PBI) is dissolved in 120 DEG C of dimethyl acetamide (DMAc), is incubated and passes through at 120 DEG C
The strong stirring for spending lasting 10 hours obtains polybenzimidazoles (PBI) (5wt%) solution A；
Step 2：Solution A cast is coated on glass substrate, solidify afterwards film forming B is dried；
Step 3：Cleaned for the film B after solidifying in step 3 with water, base film C is obtained after drying；
Step 4：Base film C after solidifying in step 4 is impregnated into 160 DEG C of melting CsH2PO4In, 24h is incubated, finally
Obtain middle temperature proton exchange film.
Embodiment 9
It is polybenzimidazoles (PBI) as the heat-resistant polymer of matrix in the present embodiment.Specifically include following steps：
Step 1：Polybenzimidazoles (PBI) is dissolved in 120 DEG C of dimethyl acetamide (DMAc), is incubated and passes through at 120 DEG C
The strong stirring for spending lasting 10 hours obtains polybenzimidazoles (PBI) (5wt%) solution A；
Step 2：Solution A cast is coated on glass substrate, solidify afterwards film forming B is dried；
Step 3：Cleaned for the film B after solidifying in step 3 with water, base film C is obtained after drying；
Step 4：Base film C after solidifying in step 4 is impregnated into 160 DEG C of melting NH4H2PO4In, 24h is incubated, finally
Obtain middle temperature proton exchange film.
Embodiment 10
It is polybenzimidazoles (PBI) as the heat-resistant polymer of matrix in the present embodiment.Specifically include following steps：
Step 1：Polybenzimidazoles (PBI) is dissolved in 120 DEG C of dimethyl acetamide (DMAc), is incubated and passes through at 120 DEG C
The strong stirring for spending lasting 10 hours obtains polybenzimidazoles (PBI) (5wt%) solution A；
Step 2：Solution A cast is coated on glass substrate, solidify afterwards film forming B is dried；
Step 3：Cleaned for the film B after solidifying in step 3 with water, base film C is obtained after drying；
Step 4：Base film C after solidifying in step 4 is impregnated into 160 DEG C of melting RbH2PO4In, 24h is incubated, finally
Obtain middle temperature proton exchange film.
Embodiment 11
It is polybenzimidazoles (PBI) as the heat-resistant polymer of matrix in the present embodiment.Specifically include following steps：
Step 1：Polybenzimidazoles (PBI) is dissolved in 120 DEG C of dimethyl acetamide (DMAc), is incubated and passes through at 120 DEG C
The strong stirring for spending lasting 10 hours obtains polybenzimidazoles (PBI) (5wt%) solution A；
Step 2：Solution A cast is coated on glass substrate, solidify afterwards film forming B is dried；
Step 3：Cleaned for the film B after solidifying in step 3 with water, base film C is obtained after drying；
Step 4：Base film C after solidifying in step 4 is impregnated into 160 DEG C of melting KH2PO4In, 24h is incubated, it is final to obtain
To middle temperature proton exchange film.
Embodiment 12
It is polybenzimidazoles (PBI) as the heat-resistant polymer of matrix in the present embodiment.Specifically include following steps：
Step 1：Polybenzimidazoles (PBI) is dissolved in 120 DEG C of dimethyl acetamide (DMAc), is incubated and passes through at 120 DEG C
The strong stirring for spending lasting 10 hours obtains polybenzimidazoles (PBI) (5wt%) solution A；
Step 2：Solution A cast is coated on glass substrate, solidify afterwards film forming B is dried；
Step 3：Cleaned for the film B after solidifying in step 3 with water, base film C is obtained after drying；
Step 4：Base film C after solidifying in step 4 is impregnated into 160 DEG C of melting CsHSO4In, 24h is incubated, finally
Obtain middle temperature proton exchange film.
Embodiment 13
It is polybenzimidazoles (PBI) as the heat-resistant polymer of matrix in the present embodiment.Specifically include following steps：
Step 1：Polybenzimidazoles (PBI) is dissolved in 120 DEG C of dimethyl acetamide (DMAc), is incubated and passes through at 120 DEG C
The strong stirring for spending lasting 10 hours obtains polybenzimidazoles (PBI) (5wt%) solution A；
Step 2：Solution A cast is coated on glass substrate, solidify afterwards film forming B is dried；
Step 3：Cleaned for the film B after solidifying in step 3 with water, base film C is obtained after drying；
Step 4：Base film C after solidifying in step 4 is impregnated into 160 DEG C of melting KHSO4In, 24h is incubated, it is final to obtain
To middle temperature proton exchange film.
Embodiment 14
It is polybenzimidazoles (PBI) as the heat-resistant polymer of matrix in the present embodiment.Specifically include following steps：
Step 1：Polybenzimidazoles (PBI) is dissolved in 150 DEG C of dimethyl acetamide (DMAc), is incubated and passes through at 150 DEG C
The strong stirring for spending lasting 5 hours obtains polybenzimidazoles (PBI) (5wt%) solution A；
Step 2：Solution A cast is coated on glass substrate, solidify afterwards film forming B is dried；
Step 3：Cleaned for the film B after solidifying in step 3 with water, base film C is obtained after drying；
Step 4：Base film C after solidifying in step 4 is impregnated into 160 DEG C of melting RbHSO4In, 24h is incubated, finally
Obtain middle temperature proton exchange film.
Embodiment performance test
The cross-sectional picture of prepared sample is obtained using JSM-7800F field emission scanning electron microscopes.Use DMA
8000 dynamic mechanical analyzers carry out measuring mechanical property to prepared sample, the size of test sample for 3mm × 30mm (it is wide ×
It is long)；Test condition is at room temperature, draw speed is 0.3N/min.Proton conductivity is tested：Using conductive silver glue in test sample
It is upper to prepare two parallel and equal length electrodes respectively, proton conductivity is tested with impedance spectrometer (SI-1260, Solartron),
Test alternating voltage is 20mv.Sample is put into baking oven, and is passed through in an oven under the conditions of 80 DEG C of saturated steams, is surveyed
Examination.Proton conductivity test temperature is within the scope of 100-400 DEG C.Monocell performance test：Use SGL Group companies
S10CC model platinum carrying capacity is 0.5mg cm-2Carbon paper, prepare active area for 5cm2Membrane electrode, hydrogen and oxygen are distinguished
It is passed through the cathode and anode of monocell, the gas flow of hydrogen and oxygen is 60cm3min-1, and by adding 0.12ml min–1
Water, to hydrogen humidify, fuel battery performance test temperature is within the scope of 100-400 DEG C.
CsH is loaded in matrix prepared by embodiment 15(PO4)2Middle temperature proton exchange film, as shown in Figure 1.In prepared
Temperature proton exchange film possesses good pliability and mechanical performance.
As seen from Figure 2, the proton conductivity of middle temperature proton exchange film prepared by embodiment 1 is all raised and carried with temperature
It is high.Specifically, in 100-140 DEG C of warm area, proton conductivity is stepped up with temperature, and its value is about 10–5–10–3S cm–1, this
It is because CsH5(PO4)2Fusing point at 150 DEG C or so, in this temperature range, CsH5(PO4)2Still in solid-state, proton conductivity
In reduced levels；In 140-160 DEG C of warm area, CsH5(PO4)2Melt, cause proton conductivity quickly to improve, reach 10–3–10–2S cm–1；In 160-250 DEG C of warm area, CsH5(PO4)2Molten state is in, is lifted with temperature, proton conductivity is slowly carried
It is high；More than 250 DEG C, because of CsH5(PO4)2Dehydration so that proton concentration reduce, cause proton conductivity to have small reduction.
Middle temperature proton exchange film based on embodiment 1 is assembled with the monocell of fuel cell, and test temperature is 200 DEG C, such as
Shown in Fig. 3, its open-circuit voltage (OCV) reaches 1.02V, shows good fuel cell output.
The component ratio of middle temperature proton exchange film prepared by each embodiment and performance and assembled using the electrolyte
The performance of fuel cell, as shown in table 1.
Table 1
In summary, the middle temperature proton exchange film that prepared by the present invention not only has high proton conductivity, good heat steady
It is qualitative, and with outstanding mechanical performance.It is suitable for being operated in 100-400 DEG C of warm area, and running temperature is less than melting carbonic acid
Salt electrolyte, thus, it is possible to the flexible polymer using high mechanical properties as support substrate, loads molten state oxysalt.This
The melting proton conductor dielectric film of disclosure of the invention, preparation technology is easy, is adapted to industrialized production；While its cheap raw material
Help to reduce the cost of dielectric film and fuel cell, be expected in intermediate temperature fuel cell field and the related middle temperature of needs
It is used widely in the field of proton-conductive electrolyte membrane.
The specific embodiment of the present invention is described above.It is to be appreciated that the invention is not limited in above-mentioned
Particular implementation, those skilled in the art can make a variety of changes or change within the scope of the claims, this not shadow
Ring the substantive content of the present invention.In the case where not conflicting, feature in embodiments herein and embodiment can any phase
Mutually combination.
Claims (10)
1. a kind of middle temperature proton exchange film, it is characterised in that including heat-resistant polymer matrix and oxysalt, the oxysalt
It is loaded into heat-resistant polymer matrix.
2. middle temperature proton exchange film according to claim 1, it is characterised in that the heat-resistant polymer matrix and oxyacid
The weight ratio of salt is 1：(0.1~5).
3. middle temperature proton exchange film according to claim 1 or 2, it is characterised in that the heat-resistant polymer is heat-resisting carbon
One or more kinds of combinations in hydrogen polymer, fluoropolymer；
The oxysalt is MHXO4、MH2X’O4、MH5(X’O4)2In one or more combinations, wherein M be Cs, Rb, K or
NH4 +, X is S or Se, X ' and it is P or As.
4. middle temperature proton exchange film according to claim 3, it is characterised in that the heat-resisting hydrocarbon polymer be polyphenyl simultaneously
Imidazoles；The fluoropolymer is Kynoar.
5. middle temperature proton exchange film according to claim 3, it is characterised in that the oxysalt is perphosphate.
6. a kind of preparation method of middle temperature proton exchange film according to claim 1, it is characterised in that including following step
Suddenly：
S1, heat-resistant polymer is dissolved in solvent, obtains solution A；
S2, the solution A is poured cast from a substrate, dry solidify afterwards film forming C；
S3, the film C cleaned with water, film D is obtained after drying；
S4, described film D is soaked in the oxysalt of melting, the oxysalt of film remained on surface is fallen in immersion post processing, obtains
To the middle temperature proton exchange film.
7. the preparation method of middle temperature proton exchange film according to claim 6, it is characterised in that in step S1, described molten
Agent is dimethylformamide, dimethyl acetamide, 1-METHYLPYRROLIDONE, dimethyl sulfoxide (DMSO), acetone, ethanol, methyl acetone, first
One or more in base second acetone.
8. the preparation method of middle temperature proton exchange film according to claim 6, it is characterised in that in step S1, described molten
Solve temperature and be less than 10-50 DEG C of solvent boiling point, dissolution time is 5-15h.
9. the preparation method of middle temperature proton exchange film according to claim 6, it is characterised in that in step S4, the film D
It is soaked in the oxysalt of melting, the soaking temperature is 5-20 DEG C of the melting temperature higher than oxysalt, soak time is
1-24h。
10. fuel cell prepared by a kind of middle temperature proton exchange film based on described in claim any one of 1-5.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113437338A (en) * | 2021-06-30 | 2021-09-24 | 上海交通大学 | Fuel cell membrane electrode and preparation method thereof |
| CN113471494A (en) * | 2021-06-30 | 2021-10-01 | 上海交通大学 | Membrane electrode based on molten proton conductor electrolyte membrane and preparation method thereof |
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| CN101320817A (en) * | 2008-07-11 | 2008-12-10 | 山东东岳神舟新材料有限公司 | Fibre reinforced multi-layer fluorine-contained cross-linking doping ionic membrane and preparation method thereof |
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| CN103554537A (en) * | 2013-10-30 | 2014-02-05 | 中国计量学院 | Membrane and preparation method thereof |
| CN105990591A (en) * | 2015-02-06 | 2016-10-05 | 上海交通大学 | Flexible composite electrolyte membrane and preparation method thereof |
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| CN113437338A (en) * | 2021-06-30 | 2021-09-24 | 上海交通大学 | Fuel cell membrane electrode and preparation method thereof |
| CN113471494A (en) * | 2021-06-30 | 2021-10-01 | 上海交通大学 | Membrane electrode based on molten proton conductor electrolyte membrane and preparation method thereof |
| CN113437338B (en) * | 2021-06-30 | 2022-12-09 | 上海交通大学 | Fuel cell membrane electrode and preparation method thereof |
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