CN107240705A - A kind of middle temperature melting proton conductor dielectric film and its production and use - Google Patents
A kind of middle temperature melting proton conductor dielectric film and its production and use Download PDFInfo
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- CN107240705A CN107240705A CN201710326839.8A CN201710326839A CN107240705A CN 107240705 A CN107240705 A CN 107240705A CN 201710326839 A CN201710326839 A CN 201710326839A CN 107240705 A CN107240705 A CN 107240705A
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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
- H01M8/14—Fuel cells with fused electrolytes
- H01M8/144—Fuel cells with fused electrolytes characterised by the electrolyte material
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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
- H01M8/02—Details
- H01M8/0289—Means for holding the electrolyte
- H01M8/0295—Matrices for immobilising electrolyte melts
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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
- H01M2300/00—Electrolytes
- H01M2300/0017—Non-aqueous electrolytes
- H01M2300/0025—Organic electrolyte
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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
Abstract
The invention provides middle temperature melting proton conductor dielectric film of one kind and its production and use.The middle temperature melting proton conductor dielectric film includes matrix and oxysalt, and the oxysalt is loaded into matrix；Described matrix is inorganic oxide/heat-resistant polymer composite support matrix.Prepared melting proton conductor dielectric 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 can reduce the cost of dielectric film and fuel cell simultaneously, be 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
The present invention relates to a kind of electrolyte of electrochemical technology field and preparation method thereof, and in particular to be a kind of
The purposes of middle temperature melting proton conductor dielectric film and preparation method thereof and the dielectric film in intermediate temperature fuel cell.
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 melting proton conductor dielectric film and its production and use.Middle temperature melts proton
Conductor dielectric film is suitable for being operated in warm area in 100-400 DEG C, and branch support group is used as using the flexible polymer of high mechanical properties
Body, loads the molten state oxysalt with high proton conductive capability, and can be prepared using traditional curtain coating coating method ultra-thin
(10-100 μm) support substrate.Polybenzimidazoles (PBI) has good mechanical strength, chemistry steady with fluoropolymer (such as PVDF)
Qualitative and heat endurance, the present invention is used as polymer support matrix.Containing with proton conducting ability in support substrate
The loading capacity of oxygen hydrochlorate is the key parameter for determining dielectric film proton conducting ability, to obtain high proton conductive capability, it is desirable to
It is as far as possible to load oxysalt more.The present invention, adulterate inorganic oxide particles in polymer support matrix, forms inorganic oxide
Thing/polymer composite support matrix.On the one hand, by forming the space of connection between particle, loose structure is obtained, is contained with improving
The useful load of oxygen acid melt body；On the other hand, adulterated by inorganic oxide, further improve the resistance to heat energy of dielectric film
Power.
The purpose of the present invention is achieved through the following technical solutions：
It is described oxygen-containing the invention provides the middle temperature melting proton conductor dielectric film of one kind, including matrix and oxysalt
Hydrochlorate is loaded into matrix；Described matrix is inorganic oxide/heat-resistant polymer composite support matrix.The oxysalt has
Proton conducting ability.
Preferably, the weight ratio of described matrix and the oxysalt is 1：(0.1~20)；In described matrix, resistance to hot polymerization
The weight ratio of compound and inorganic oxide is 1：(0.01~20).
It is highly preferred that described matrix and the weight of oxysalt ratio are 1：1~5；In described matrix, heat-resistant polymer and nothing
The weight ratio of machine oxide is 1:0.1~0.5.
Preferably, the inorganic oxide has in 10~2000m2Specific surface area in/g range, i.e. inorganic oxide
Specific surface area be 10~2000m2/g。
Preferably, the heat-resistant polymer is one or more kinds of combinations in heat-resisting hydrocarbon polymer, fluoropolymer；
Contain in the inorganic oxide selected from least one of Ti, Zr, Si and Al element；
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)；The inorganic oxide is SiO2。
Preferably, the oxysalt is perphosphate MH5(PO4)2；More preferably peroxophosphoric acid hydrogen caesium (CsH5(PO4)2)。
The invention provides the preparation method that a kind of middle temperature melts proton conductor dielectric film, comprise the following steps：
S1, heat-resistant polymer is dissolved in solvent, obtains organic polymer soln A；
S2, by particulate inorganic oxide B and heat-resistant polymer solution A mixing and ball milling, obtain slurry C；
S3, the slurry C is poured cast from a substrate, dry solidify afterwards film forming D；
S4, the film D cleaned with water, film E is obtained after drying；
S5, described film E 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 melting proton conductor dielectric 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 S3, 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 S5, the film E is soaked in the oxysalt of melting, and the soaking temperature is higher than oxygen-containing
5-20 DEG C of the melting temperature of hydrochlorate, soak time is 1-24h.The too low oxysalt of temperature can not fully melt, temperature mistake
Height operation inconvenience, and waste the energy.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.
Present invention also offers fuel cell prepared by a kind of middle temperature melting proton conductor dielectric film.
The present invention has the oxysalt of high proton conductive capability based on molten state, with the polymer containing inorganic oxide
As support substrate, by the way that support substrate is impregnated in the molten mass of oxysalt, forms oxysalt and be loaded into branch support group
The structure of body, has prepared middle temperature melting proton conductor dielectric 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 melting proton conductor dielectric film that the present invention is provided is suitable for being operated in 100~400 DEG C
Warm area, running temperature 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 melting proton conductor dielectric film be expected to intermediate temperature fuel cell and electrolytic cell, super capacitor etc. correlation need in
It is used widely in the electrochemical appliance of warm proton-conductive electrolyte membrane.
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 base film (SiO prepared by embodiment 32/ PBI) and matrix in load CsH5(PO4)2Middle temperature melting
The optical photograph of proton conductor dielectric film；
Fig. 2 (a) is the stereoscan photograph of the base film in embodiment 3；
Fig. 2 (b) is the stereoscan photograph that middle temperature prepared by embodiment 3 melts proton conductor dielectric film；
Fig. 3 is that the mechanical performance (stress-strain) of middle temperature melting proton conductor dielectric film prepared by embodiment 1,2,3 is bent
Line；
Fig. 4 is proton conductivity and the pass of temperature of middle temperature melting proton conductor dielectric film prepared by embodiment 1,2,3
System's figure；
Fig. 5 is the output of the intermediate temperature fuel cell assembled using the middle temperature melting proton conductor dielectric film of embodiment 3
Can curve.
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
In the present embodiment, constituting heat-resistant polymer (polybenzimidazoles) and the inorganic oxide of matrix, (specific surface area is
343m2/ g SiO2Particle) weight ratio be 1：0.11.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：By SiO2Particle is mixed with polybenzimidazoles (PBI) (5wt%) solution A, and ball grinding stirring 24h obtains slurry
B；
Step 3：Slurry B cast is coated on glass substrate, heating makes solvent volatilize, so that grout curing film forming C；
Step 4：Cleaned for the film C after solidifying in step 3 with water, base film D is obtained after drying；
Step 5：Base film D 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 melting proton conductor dielectric film is finally given.
Embodiment 2
In the present embodiment, constituting heat-resistant polymer (polybenzimidazoles) and the inorganic oxide of matrix, (specific surface area is
343m2/ g SiO2Particle) weight ratio be 1：0.25.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：By SiO2Particle is mixed with polybenzimidazoles (PBI) (5wt%) solution A, and ball grinding stirring 24h obtains slurry
B；
Step 3：Slurry B cast is coated on glass substrate, heating makes solvent volatilize, so that grout curing film forming C；
Step 4：Cleaned for the film C after solidifying in step 3 with water, base film D is obtained after drying；
Step 5：Base film D 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 melting proton conductor dielectric film is finally given.
Embodiment 3
In the present embodiment, constituting heat-resistant polymer (polybenzimidazoles) and the inorganic oxide of matrix, (specific surface area is
343m2/ g SiO2Particle) weight ratio be 1：0.43.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：By SiO2Particle is mixed with polybenzimidazoles (5wt%) solution A, and ball grinding stirring 24h obtains slurry B；
Step 3：Slurry B cast is coated on glass substrate, heating makes solvent volatilize, so that grout curing film forming C；
Step 4：Cleaned for the film C after solidifying in step 3 with water, base film D is obtained after drying；
Step 5：Base film D 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 melting proton conductor dielectric film is finally given.
Embodiment 4
In the present embodiment, constituting heat-resistant polymer (polybenzimidazoles) and the inorganic oxide of matrix, (specific surface area is
343m2/ g SiO2Particle) weight ratio be 1：0.01.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 substrate, heating makes solvent volatilize, so that grout curing film forming B；
Step 3：Cleaned for the film B after solidifying in step 2 with water, base film C is obtained after drying；
Step 3：Base film C in step 3 is impregnated into 160 DEG C of melting peroxophosphoric acid hydrogen caesium (CsH5(PO4)2) in, insulation
24h, finally gives middle temperature melting proton conductor dielectric film.
Embodiment 5
In the present embodiment, constituting heat-resistant polymer (polybenzimidazoles) and the inorganic oxide of matrix, (specific surface area is
343m2/ g SiO2Particle) weight ratio be 1：20.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：By SiO2Particle is mixed with polybenzimidazoles (5wt%) solution A, and ball grinding stirring 24h obtains slurry B；
Step 3：Slurry B cast is coated on glass substrate, heating makes solvent volatilize, so that grout curing film forming C；
Step 4：Cleaned for the film C after solidifying in step 3 with water, base film D is obtained after drying；
Step 5：Base film D 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 melting proton conductor dielectric film is finally given.
Embodiment 6
In the present embodiment, constituting heat-resistant polymer (polybenzimidazoles) and the inorganic oxide of matrix, (specific surface area is
20m2/ g SiO2Particle) weight ratio be 1：0.43.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：By SiO2Particle is mixed with polybenzimidazoles (PBI) (5wt%) solution A, and ball grinding stirring 24h obtains slurry
B；
Step 3：Slurry B cast is coated on substrate, heating makes solvent volatilize, so that grout curing film forming C；
Step 4：Cleaned for the film C after solidifying in step 3 with water, base film D is obtained after drying；
Step 5：Base film D after to 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 melting proton conductor dielectric film is finally given.
Embodiment 7
In the present embodiment, constituting heat-resistant polymer (polybenzimidazoles) and the inorganic oxide of matrix, (specific surface area is
2000m2/ g SiO2Particle) weight ratio be 1：0.43.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：By SiO2Particle is mixed with polybenzimidazoles (PBI) (5wt%) solution A, and ball grinding stirring 24h obtains slurry
B；
Step 3：Slurry B cast is coated on substrate, heating makes solvent volatilize, so that grout curing film forming C；
Step 4：Cleaned for the film C after solidifying in step 3 with water, base film D is obtained after drying；
Step 5：Base film D 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 melting proton conductor dielectric film is finally given.
Embodiment 8
In the present embodiment, constituting heat-resistant polymer (polybenzimidazoles) and the inorganic oxide of matrix, (specific surface area is
100m2/ g ZrO2Particle) weight ratio be 1：0.43.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：By ZrO2Particle is mixed with polybenzimidazoles (5wt%) solution A, and ball grinding stirring 24h obtains slurry B；
Step 3：Slurry B cast is coated on glass substrate, heating makes solvent volatilize, so that grout curing film forming C；
Step 4：Cleaned for the film C after solidifying in step 3 with water, base film D is obtained after drying；
Step 5：Base film D 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 melting proton conductor dielectric film is finally given.
Embodiment 9
In the present embodiment, constituting heat-resistant polymer (polybenzimidazoles) and the inorganic oxide of matrix, (specific surface area is
100m2/ g TiO2Particle) weight ratio be 1：0.43.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：By TiO2Particle is mixed with polybenzimidazoles (5wt%) solution A, and ball grinding stirring 24h obtains slurry B；
Step 3：Slurry B cast is coated on glass substrate, heating makes solvent volatilize, so that grout curing film forming C；
Step 4：Cleaned for the film C after solidifying in step 3 with water, base film D is obtained after drying；
Step 5：Base film D 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 melting proton conductor dielectric film is finally given.
Embodiment 10
In the present embodiment, constituting heat-resistant polymer (polybenzimidazoles) and the inorganic oxide of matrix, (specific surface area is
100m2/ g Al2O3Particle) weight ratio be 1：0.43.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：By Al2O3Particle is mixed with polybenzimidazoles (5wt%) solution A, and ball grinding stirring 24h obtains slurry B；
Step 3：Slurry B cast is coated on glass substrate, heating makes solvent volatilize, so that grout curing film forming C；
Step 4：Cleaned for the film C after solidifying in step 3 with water, base film D is obtained after drying；
Step 5：Base film D 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 melting proton conductor dielectric film is finally given.
Embodiment 11
In the present embodiment, constituting heat-resistant polymer (Kynoar) and the inorganic oxide of matrix, (specific surface area is
343m2/ g SiO2Particle) weight ratio be 1：0.43.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：By SiO2Particle is mixed with Kynoar (PVDF) solution A, and ball grinding stirring 24h obtains slurry B；
Step 3：Slurry B cast is coated on glass substrate, heating makes solvent volatilize, so that grout curing film forming C；
Step 4：Cleaned for the film C after solidifying in step 3 with water, base film D is obtained after drying；
Step 5：Base film D 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 melting proton conductor dielectric film is finally given.
Embodiment 12
In the present embodiment, constituting heat-resistant polymer (polybenzimidazoles) and the inorganic oxide of matrix, (specific surface area is
343m2/ g SiO2Particle) weight ratio be 1：0.43.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：By SiO2Particle is mixed with polybenzimidazoles (5wt%) solution A, and ball grinding stirring 24h obtains slurry B；
Step 3：Slurry B cast is coated on glass substrate, heating makes solvent volatilize, so that grout curing film forming C；
Step 4：Cleaned for the film C after solidifying in step 3 with water, base film D is obtained after drying；
Step 5：Base film D after solidifying in step 4 is impregnated into 150 DEG C of melting peroxophosphoric acid hydrogen potassium (KH5(PO4)2)
In, 24h is incubated, middle temperature melting proton conductor dielectric film is finally given.
Embodiment 13
In the present embodiment, constituting heat-resistant polymer (polybenzimidazoles) and the inorganic oxide of matrix, (specific surface area is
343m2/ g SiO2Particle) weight ratio be 1：0.43.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：By SiO2Particle is mixed with polybenzimidazoles (5wt%) solution A, and ball grinding stirring 24h obtains slurry B；
Step 3：Slurry B cast is coated on glass substrate, heating makes solvent volatilize, so that grout curing film forming C；
Step 4：Cleaned for the film C after solidifying in step 3 with water, base film D is obtained after drying；
Step 5：Base film D after solidifying in step 4 is impregnated into 150 DEG C of melting peroxophosphoric acid hydrogen rubidium (RbH5(PO4)2)
In, 24h is incubated, middle temperature melting proton conductor dielectric film is finally given.
Embodiment 14
In the present embodiment, constituting heat-resistant polymer (polybenzimidazoles) and the inorganic oxide of matrix, (specific surface area is
343m2/ g SiO2Particle) weight ratio be 1：0.43.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：By SiO2Particle is mixed with polybenzimidazoles (5wt%) solution A, and ball grinding stirring 24h obtains slurry B；
Step 3：Slurry B cast is coated on glass substrate, heating makes solvent volatilize, so that grout curing film forming C；
Step 4：Cleaned for the film C after solidifying in step 3 with water, film D is obtained after drying；
Step 5：Film D after solidifying in step 4 is impregnated into 180 DEG C of melting KH5(AsO4)2In, 24h is incubated, it is final to obtain
Proton conductor dielectric film is melted to prepared middle temperature.
Embodiment 15
In the present embodiment, constituting heat-resistant polymer (polybenzimidazoles) and the inorganic oxide of matrix, (specific surface area is
343m2/ g SiO2Particle) weight ratio be 1：0.43.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：By SiO2Particle is mixed with polybenzimidazoles (5wt%) solution A, and ball grinding stirring 24h obtains slurry B；
Step 3：Slurry B cast is coated on glass substrate, heating makes solvent volatilize, so that grout curing film forming C；
Step 4：Cleaned for the film C after solidifying in step 3 with water, base film D is obtained after drying；
Step 5：Base film D after solidifying in step 4 is impregnated into 400 DEG C of melting CsH2PO4In, 24h is incubated, finally
Obtain middle temperature melting proton conductor dielectric film.
Embodiment 16
In the present embodiment, constituting heat-resistant polymer (polybenzimidazoles) and the inorganic oxide of matrix, (specific surface area is
343m2/ g SiO2Particle) weight ratio be 1：0.43.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：By SiO2Particle is mixed with polybenzimidazoles (5wt%) solution A, and ball grinding stirring 24h obtains slurry B；
Step 3：Slurry B cast is coated on glass substrate, heating makes solvent volatilize, so that grout curing film forming C；
Step 4：Cleaned for the film C after solidifying in step 3 with water, base film D is obtained after drying；
Step 5：Base film D after solidifying in step 4 is impregnated into 200 DEG C of melting NH4H2PO4In, 24h is incubated, finally
Obtain middle temperature melting proton conductor dielectric film.
Embodiment 17
In the present embodiment, constituting heat-resistant polymer (polybenzimidazoles) and the inorganic oxide of matrix, (specific surface area is
343m2/ g SiO2Particle) weight ratio be 1：0.43.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：By SiO2Particle is mixed with polybenzimidazoles (5wt%) solution A, and ball grinding stirring 24h obtains slurry B；
Step 3：Slurry B cast is coated on glass substrate, heating makes solvent volatilize, so that grout curing film forming C；
Step 4：Cleaned for the film C after solidifying in step 3 with water, base film D is obtained after drying；
Step 5：Base film D after solidifying in step 4 is impregnated into 310 DEG C of melting RbH2PO4In, 24h is incubated, finally
Obtain middle temperature melting proton conductor dielectric film.
Embodiment 18
In the present embodiment, constituting heat-resistant polymer (polybenzimidazoles) and the inorganic oxide of matrix, (specific surface area is
343m2/ g SiO2Particle) weight ratio be 1：0.43.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：By SiO2Particle is mixed with polybenzimidazoles (5wt%) solution A, and ball grinding stirring 24h obtains slurry B；
Step 3：Slurry B cast is coated on glass substrate, heating makes solvent volatilize, so that grout curing film forming C；
Step 4：Cleaned for the film C after solidifying in step 3 with water, base film D is obtained after drying；
Step 5：Base film D after solidifying in step 4 is impregnated into 270 DEG C of melting KH2PO4In, 24h is incubated, it is final to obtain
Proton conductor dielectric film is melted to middle temperature.
Embodiment 19
In the present embodiment, constituting heat-resistant polymer (polybenzimidazoles) and the inorganic oxide of matrix, (specific surface area is
343m2/ g SiO2Particle) weight ratio be 1：0.43.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：By SiO2Particle is mixed with polybenzimidazoles (5wt%) solution A, and ball grinding stirring 24h obtains slurry B；
Step 3：Slurry B cast is coated on glass substrate, heating makes solvent volatilize, so that grout curing film forming C；
Step 4：Cleaned for the film C after solidifying in step 3 with water, base film D is obtained after drying；
Step 5：Base film D after solidifying in step 4 is impregnated into 250 DEG C of melting CsHSO4In, 24h is incubated, finally
Obtain middle temperature melting proton conductor dielectric film.
Embodiment 20
In the present embodiment, constituting heat-resistant polymer (polybenzimidazoles) and the inorganic oxide of matrix, (specific surface area is
343m2/ g SiO2Particle) weight ratio be 1：0.43.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：By SiO2Particle is mixed with polybenzimidazoles (5wt%) solution A, and ball grinding stirring 24h obtains slurry B；
Step 3：Slurry B cast is coated on glass substrate, heating makes solvent volatilize, so that grout curing film forming C；
Step 4：Cleaned for the film C after solidifying in step 3 with water, base film D is obtained after drying；
Step 5：Base film D after solidifying in step 4 is impregnated into 210 DEG C of melting KHSO4In, 24h is incubated, it is final to obtain
Proton conductor dielectric film is melted to middle temperature.
Embodiment 21
In the present embodiment, constituting heat-resistant polymer (polybenzimidazoles) and the inorganic oxide of matrix, (specific surface area is
343m2/ g SiO2Particle) weight ratio be 1：0.43.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：By SiO2Particle is mixed with polybenzimidazoles (5wt%) solution A, and ball grinding stirring 24h obtains slurry B；
Step 3：Slurry B cast is coated on glass substrate, heating makes solvent volatilize, so that grout curing film forming C；
Step 4：Cleaned for the film C after solidifying in step 3 with water, base film D is obtained after drying；
Step 5：Base film D after solidifying in step 4 is impregnated into 220 DEG C of melting RbHSO4In, 24h is incubated, finally
Obtain middle temperature melting proton conductor dielectric film.
Embodiment performance test
The weight change immersed by heat-resistant polymer before and after oxysalt melt, determines oxysalt in heat-resistant polymer
Useful load.The cross-sectional picture of prepared sample is obtained using JSM-7800F field emission scanning electron microscopes.Use
DMA8000 dynamic mechanical analyzers carry out measuring mechanical property to prepared sample, and the size of test sample is 3mm × 30mm
(width x length)；Test condition is at room temperature, draw speed is 0.3N/min.Proton conductivity is tested：Surveyed using conductive silver glue
Two parallel and equal length electrodes are prepared on test agent respectively, proton is tested with impedance spectrometer (SI-1260, Solartron)
Electrical conductivity, 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,
Tested.Proton conductivity test temperature is within the scope of 100-400 DEG C.Monocell performance test：It is public using SGL Group
The S10CC model platinum carrying capacity of department is 0.5mg cm-2Carbon paper, prepare active area for 5cm2Membrane electrode, by hydrogen and oxygen
Each lead into the cathode and anode of monocell, the gas flow of hydrogen and oxygen is 60cm3min-1, and by adding 0.12ml
min–1Water, to hydrogen humidify, fuel battery performance test temperature is within the scope of 100-400 DEG C.
Fig. 1 shows, PBI and SiO2(the SiO of particle composition2/ PBI) base film present grey, opaque outward appearance.In base
CsH is loaded in body film5(PO4)2Afterwards, the middle temperature melting proton conductor dielectric film of acquisition has lurid outward appearance.All films
All it is flexible.
Fig. 2 (a) shows that the base film in embodiment 3 is by PBI mesh skeletons and the SiO being embedded in skeleton2Particle group
Into.Fig. 2 (b) shows that middle temperature melting proton conductor dielectric film prepared by embodiment 3 has 40 μ m thicks, and CsH5(PO4)2Filling
Into in base film.
As seen from Figure 3, the tensile strength for the middle temperature melting proton conductor dielectric film that prepared by embodiment 1,2,3 is high
In 34MPa, extensibility shows good mechanical performance more than 1.3%.
As seen from Figure 4, the characteristics of middle temperature melting proton conductor dielectric film that prepared by embodiment 1,2,3 has common,
Its proton conductivity is all raised and improved with temperature.Specifically, in 100-140 DEG C of warm area, proton conductivity with temperature progressively
Improve, its value is about 10–5–10–3S cm–1, because CsH5(PO4)2Fusing point at 150 DEG C or so, in this temperature range,
CsH5(PO4)2Still in solid-state, proton conductivity is 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)2In melting
State, is lifted with temperature, and proton conductivity is slowly improved；More than 250 DEG C, because of CsH5(PO4)2Dehydration so that proton concentration subtracts
It is small, cause proton conductivity to have small reduction.Oxide particle has facilitation to proton conductivity, and one is by oxide
Grain accumulation, forms space, is convenient to CsH5(PO4)2Molten mass fills matrix, will be seen that from Fig. 3 and the data of table 1, containing aerobic
Compound particle is more, the CsH in matrix5(PO4)2Loading it is bigger, proton conductivity is higher；Two be oxide particle with
CsH5(PO4)2Between form contact interface, cause CsH5(PO4)2Interface disorder phase formation, further lift Proton conducting
Rate.
Middle temperature melting proton conductor dielectric film based on embodiment 3 is assembled with the monocell of fuel cell, test temperature
For 200 DEG C, its open-circuit voltage (OCV) reaches 1.08V, also, as shown in figure 5, in 100mA cm-2Constant output current density
Under, keep regulated output voltage within continuous 150 hours, show good fuel cell output.
The composition of middle temperature proton exchange film prepared by each embodiment and performance and the fuel assembled using the electrolyte
The performance of battery, as shown in table 1.
Table 1
In summary, what prepared by the present invention, which melts proton conductor dielectric film, not only has high proton conductivity, good
Heat endurance, and with outstanding mechanical performance.Compared to being operated in 550-650 DEG C of warm area and need to use brittle ceramic
The fused carbonate electrolyte of support substrate, middle temperature melting proton conductor dielectric film is suitable for being operated in 100-400 DEG C of warm area,
Running temperature is less than fused carbonate electrolyte, thus, it is possible to the flexible polymer using high mechanical properties as support substrate,
Load molten state oxysalt.Melting proton conductor dielectric film disclosed by the invention, preparation technology is easy, is adapted to industry metaplasia
Production；Its cheap raw material helps to reduce the cost of dielectric film and fuel cell simultaneously, is expected in intermediate temperature fuel cell
Field and the related field for needing middle temperature proton-conductive electrolyte membrane are used widely.
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 melting proton conductor dielectric film, it is characterised in that including matrix and oxysalt, the oxysalt
It is loaded into matrix；Described matrix is inorganic oxide/heat-resistant polymer composite support matrix.
2. middle temperature melting proton conductor dielectric film according to claim 1, it is characterised in that described matrix contains with described
The weight ratio of oxygen hydrochlorate is 1：(0.1~20)；In described matrix, the weight ratio of heat-resistant polymer and inorganic oxide is 1：
(0.01~20).
3. middle temperature melting proton conductor dielectric film according to claim 1 or 2, it is characterised in that the inorganic oxide
Thing has in 10~2000m2Specific surface area in/g range.
4. middle temperature melting proton conductor dielectric film according to claim 1 or 2, it is characterised in that the resistance to thermal polymerization
Thing is one or more kinds of combinations in heat-resisting hydrocarbon polymer, fluoropolymer；
Contain in the inorganic oxide selected from least one of Ti, Zr, Si and Al element；
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.
5. middle temperature melting proton conductor dielectric film according to claim 4, it is characterised in that the heat-resisting hydrocarbon polymerization
Thing is polybenzimidazoles；The fluoropolymer is Kynoar；The inorganic oxide is SiO2。
6. middle temperature melting proton conductor dielectric film according to claim 4, it is characterised in that the oxysalt was
Phosphate.
7. a kind of middle temperature according to claim 1 melts the preparation method of proton conductor dielectric film, it is characterised in that bag
Include following steps：
S1, heat-resistant polymer is dissolved in solvent, obtains organic polymer soln A；
S2, by particulate inorganic oxide B and heat-resistant polymer solution A mixing and ball milling, obtain slurry C；
S3, the slurry C is poured cast from a substrate, dry solidify afterwards film forming D；
S4, the film D cleaned with water, film E is obtained after drying；
S5, described film E 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 melting proton conductor dielectric film.
8. middle temperature according to claim 7 melts the preparation method of proton conductor dielectric film, it is characterised in that step S1
In, the solution temperature is that dissolution time is 5-15h less than 10-50 DEG C of solvent boiling point.
9. middle temperature according to claim 7 melts the preparation method of proton conductor dielectric film, it is characterised in that step S5
In, the film E is soaked in the oxysalt of melting, and 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 melting proton conductor dielectric film based on described in claim any one of 1-6.
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| CN109755656A (en) * | 2019-01-14 | 2019-05-14 | 西北工业大学 | Novel " self-excitation live-in " lithium ion secondary reserve cell of one kind and preparation method thereof |
| 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 |
| 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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| US20050233202A1 (en) * | 2004-04-20 | 2005-10-20 | Fay Matthew M | Thermoplastic-imbibed diffusion media to help eliminate MEA edge failure |
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| CN109755656A (en) * | 2019-01-14 | 2019-05-14 | 西北工业大学 | Novel " self-excitation live-in " lithium ion secondary reserve cell of one kind and preparation method thereof |
| 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 |
| 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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