CN107331883B - Intermediate-temperature proton exchange membrane and preparation method thereof - Google Patents
Intermediate-temperature proton exchange membrane and preparation method thereof Download PDFInfo
- Publication number
- CN107331883B CN107331883B CN201710326667.4A CN201710326667A CN107331883B CN 107331883 B CN107331883 B CN 107331883B CN 201710326667 A CN201710326667 A CN 201710326667A CN 107331883 B CN107331883 B CN 107331883B
- Authority
- CN
- China
- Prior art keywords
- temperature
- proton exchange
- exchange membrane
- heat
- medium
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
Classifications
-
- 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
-
- 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
-
- 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
Landscapes
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Sustainable Development (AREA)
- Sustainable Energy (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Fuel Cell (AREA)
Abstract
The invention provides a medium-temperature proton exchange membrane and a preparation method thereof; the medium-temperature proton exchange membrane comprises a heat-resistant polymer matrix and oxysalt, wherein the oxysalt is loaded in the heat-resistant polymer matrix. The prepared medium-temperature proton exchange membrane not only has high proton conductivity and good thermal stability, but also has excellent mechanical properties. It is suitable for working in the temperature range of 100-400 ℃ and the operating temperature is lower than that of the molten carbonate electrolyte, so that the flexible polymer with high mechanical strength can be used as a supporting matrix for loading the molten oxysalt. The molten proton conductor electrolyte membrane disclosed by the invention is simple and convenient in preparation process and suitable for industrial production; meanwhile, the cheap raw materials of the electrolyte membrane are beneficial to reducing the cost of the electrolyte membrane and the fuel cell, and the electrolyte membrane is expected to be widely applied to the field of medium-temperature fuel cells and the related field needing the medium-temperature proton conduction electrolyte membrane.
Description
Technical Field
The invention relates to an electrolyte in the technical field of electrochemistry and a preparation method thereof, in particular to a medium-temperature proton exchange membrane and a preparation method thereof.
Background
A fuel cell is a power generation device that directly converts chemical energy in fuel into electrical energy through an electrochemical reaction. Of the various fuel cells, medium temperature fuel cells (operating at 100 ℃ C. and 400 ℃ C.) exhibit attractive advantages. Compared with a low-temperature fuel cell, the medium-temperature fuel cell has enhanced CO tolerance, higher catalytic efficiency, electrode dynamics and the like; compared with a high-temperature fuel cell, the material used by the medium-temperature fuel cell has wider choice, so that the material cost can be reduced.
To maintain the electrolyte in a Molten state, Fuel Cell operating temperatures higher than 550 ℃ (650 ℃ for standard operating temperatures) are required0.52Na0.48)2CO3、(Li0.62K0.38)2CO3) It is required to be loaded in a porous ceramic support. While to maintain its good mechanical strength, MCFCs possess very thick electrolytes (0.5-1.5 mm), causing an increase in the ohmic power loss of the electrolyte. On the other hand, the operating temperature of 550-650 ℃ limits the material selection range so that flexible polymers cannot be usedAs the support, only a ceramic material which is resistant to temperature but brittle and easily broken can be used.
Disclosure of Invention
The invention provides a medium-temperature proton exchange membrane and a preparation method thereof. The medium-temperature proton exchange membrane is suitable for working in a medium-temperature region of 100-400 ℃, adopts flexible polymer with high mechanical strength as a supporting substrate, loads molten oxysalt with high proton conductivity, and can prepare an ultrathin (10-100 mu m) supporting substrate by adopting a traditional tape-casting coating method. Polybenzimidazole (PBI) has good mechanical strength, chemical stability, and thermal stability with fluoropolymers such as PVDF, which are used as polymer support matrices in the present invention.
The purpose of the invention is realized by the following technical scheme:
the invention provides a medium-temperature proton exchange membrane which comprises a heat-resistant polymer matrix and oxysalt, wherein the oxysalt is loaded in the heat-resistant polymer matrix. The oxoacid salt has proton-conducting ability.
Preferably, the weight ratio of the heat resistant polymer matrix to the salt of an oxyacid is 1: (0.1-5).
More preferably, the weight ratio of the heat resistant polymer matrix to the salt of an oxyacid is 1: 0.35 to 5.
Preferably, the heat-resistant polymer is one or more of heat-resistant hydrocarbon polymer and fluorine polymer;
the oxysalt is MHXO4、MH2X’O4、MH5(X’O4)2Wherein M is Cs, Rb, K or NH4 +X is S or Se, and X' is P or As.
Preferably, the heat resistant hydrocarbon polymer is Polybenzimidazole (PBI); the fluoropolymer is polyvinylidene fluoride (PVDF).
Preferably, the oxysalt is a perphosphate salt MH5(PO4)2(ii) a More preferably cesium hydrogen phosphate (CsH)5(PO4)2)。
The invention provides a preparation method of a medium-temperature proton exchange membrane, which comprises the following steps:
s1, dissolving the heat-resistant polymer in a solvent to obtain a solution A;
s2, casting the solution A on a substrate, drying and curing to form a film C;
s3, washing the membrane C with water, and drying to obtain a membrane D;
s4, soaking the membrane D in molten oxysalt, and treating to remove residual oxysalt on the surface of the membrane after soaking to obtain the medium-temperature proton exchange membrane.
Preferably, in step S1, the solvent is one or more selected from Dimethylformamide (DMF), dimethylacetamide (DMAc), N-methylpyrrolidone (NMP), dimethyl sulfoxide (DMSO), acetone, ethanol, methyl acetone, and methyl ethyl acetone. More preferably, the solvent is dimethylacetamide (DMAc).
Preferably, in step S2, the substrate is a glass substrate.
Preferably, in step S1, the dissolving temperature is 10-50 ℃ lower than the boiling point of the solvent, and the dissolving time is 5-15 h. The dissolution temperature is too high, and the solvent is evaporated; the dissolution temperature is too low, resulting in too long dissolution time of the heat-resistant polymer. The dissolution time is too short, the heat-resistant polymer cannot be sufficiently dissolved; the dissolution time is too long, more solvent is volatilized, waste is caused, and time is wasted.
Preferably, in step S4, the film D is soaked in the molten salt of oxyacid, the soaking temperature is 5 to 20 ℃ higher than the melting temperature of the salt of oxyacid, and the soaking time is 1 to 24 hours. Said low temperature oxyacid salt is not sufficiently melted; the operation is inconvenient due to overhigh temperature, and the energy is wasted. The soaking time is too short, and the molten salt of oxyacid cannot be sufficiently immersed in the heat-resistant polymer; the soaking time is too long, which wastes time and energy.
The invention provides a fuel cell prepared from an intermediate-temperature proton exchange membrane.
Compared with the prior art, the invention has the following beneficial effects:
the molten carbonate electrolyte works in a temperature range of 550-650 ℃, and a ceramic supporting matrix which is temperature-resistant, but brittle and easy to crack needs to be used. Compared with the prior art, the medium-temperature proton exchange membrane provided by the invention is suitable for working in a temperature range of 100-400 ℃, and the running temperature is lower, so that a heat-resistant polymer with high mechanical strength and flexibility can be used as a supporting substrate.
The invention provides a preparation method with low production cost, simple process and strong operability. The intermediate-temperature proton exchange membrane prepared by the invention is expected to be widely applied to intermediate-temperature fuel cells, and electrochemical devices such as electrolytic cells, super capacitors and the like which need intermediate-temperature proton conduction electrolyte membranes.
Drawings
Other features, objects and advantages of the invention will become more apparent upon reading of the detailed description of non-limiting embodiments with reference to the following drawings:
FIG. 1 is a scanning electron micrograph of a mesophilic proton exchange membrane prepared in example 1;
FIG. 2 is a graph of proton conductivity versus temperature for the medium temperature proton exchange membrane prepared in example 1;
fig. 3 is a graph of the output performance of an intermediate-temperature fuel cell assembled using the intermediate-temperature molten proton conductor of example 1.
Detailed Description
The present invention will be described in detail with reference to specific examples. The following examples will assist those skilled in the art in further understanding the invention, but are not intended to limit the invention in any way. It should be noted that it would be obvious to those skilled in the art that various changes and modifications can be made without departing from the spirit of the invention. All falling within the scope of the present invention.
Example 1
In this example, the heat-resistant polymer as the matrix was Polybenzimidazole (PBI). The method specifically comprises the following steps:
step 1: polybenzimidazole (PBI) was dissolved in dimethylacetamide (DMAc) at 120 ℃, incubated at 120 ℃ and subjected to vigorous stirring for 10 hours to give a Polybenzimidazole (PBI) (5 wt%) solution A;
step 2: the solution A is poured and coated on a glass substrate, and is solidified into a film B after being dried;
and step 3: washing the film B cured in the step 3 with water, and drying to obtain a substrate film C;
and 4, step 4: immersing the base film C cured in step 4 in molten cesium hydrogen perphosphate (CsH) at 160 DEG C5(PO4)2) And (5) preserving the heat for 24 hours to finally obtain the intermediate-temperature proton exchange membrane.
Example 2
In this example, the heat-resistant polymer as the matrix was Polybenzimidazole (PBI). The method specifically comprises the following steps:
step 1: polybenzimidazole (PBI) was dissolved in Dimethylformamide (DMF) at 120 ℃ and incubated at 120 ℃ and subjected to vigorous stirring for 10 hours to give a Polybenzimidazole (PBI) (5 wt%) solution A;
step 2: the solution A is poured and coated on a glass substrate, and is solidified into a film B after being dried;
and step 3: washing the film B cured in the step 3 with water, and drying to obtain a substrate film C;
and 4, step 4: immersing the base film C cured in step 4 in molten cesium hydrogen perphosphate (CsH) at 160 DEG C5(PO4)2) And (5) preserving the heat for 1h to finally obtain the intermediate-temperature proton exchange membrane.
Example 3
In this example, the heat-resistant polymer as the matrix was Polybenzimidazole (PBI). The method specifically comprises the following steps:
step 1: polybenzimidazole (PBI) was dissolved in dimethyl sulfoxide (DMSO) at 120 ℃, incubated at 120 ℃ and subjected to vigorous stirring for 10 hours to give a Polybenzimidazole (PBI) (5 wt%) solution A;
step 2: the solution A is poured and coated on a glass substrate, and is solidified into a film B after being dried;
and step 3: washing the film B cured in the step 3 with water, and drying to obtain a substrate film C;
and 4, step 4: immersing the base film C cured in step 4 in molten cesium hydrogen perphosphate (CsH) at 160 DEG C5(PO4)2) In the middle, the temperature is kept for 150h,finally obtaining the intermediate-temperature proton exchange membrane.
Example 4
In this example, the heat-resistant polymer as the matrix was polyvinylidene fluoride (PVDF). The method specifically comprises the following steps:
step 1: dissolving polyvinylidene fluoride (PVDF) in dimethylacetamide (DMAc) at 120 ℃, preserving heat at 120 ℃ and strongly stirring for 10 hours to obtain a polyvinylidene fluoride (PVDF) (15 wt%) solution A;
step 2: the solution A is poured and coated on a glass substrate, and is solidified into a film B after being dried;
and step 3: washing the film B cured in the step 3 with water, and drying to obtain a substrate film C;
and 4, step 4: immersing the base film C cured in step 4 in molten cesium hydrogen perphosphate (CsH) at 160 DEG C5(PO4)2) And (5) preserving the heat for 24 hours to finally obtain the intermediate-temperature proton exchange membrane.
Example 5
In this example, the heat-resistant polymer as the matrix was Polybenzimidazole (PBI). The method specifically comprises the following steps:
step 1: polybenzimidazole (PBI) was dissolved in dimethylacetamide (DMAc) at 120 ℃, incubated at 120 ℃ and subjected to vigorous stirring for 10 hours to give a Polybenzimidazole (PBI) (5 wt%) solution A;
step 2: the solution A is poured and coated on a glass substrate, and is solidified into a film B after being dried;
and step 3: washing the film B cured in the step 3 with water, and drying to obtain a substrate film C;
and 4, step 4: immersing the substrate film C solidified in the step 4 into melted potassium hydrogen perphosphate (KH) at 160 DEG C5(PO4)2) And (5) preserving the heat for 24 hours to finally obtain the intermediate-temperature proton exchange membrane.
Example 6
In this example, the heat-resistant polymer as the matrix was Polybenzimidazole (PBI). The method specifically comprises the following steps:
step 1: polybenzimidazole (PBI) was dissolved in dimethylacetamide (DMAc) at 120 ℃, incubated at 120 ℃ and subjected to vigorous stirring for 10 hours to give a Polybenzimidazole (PBI) (5 wt%) solution A;
step 2: the solution A is poured and coated on a glass substrate, and is solidified into a film B after being dried;
and step 3: washing the film B cured in the step 3 with water, and drying to obtain a substrate film C;
and 4, step 4: immersing the substrate film C solidified in the step 4 into molten rubidium hydrogen peroxide phosphate (RbH) at 160 DEG C5(PO4)2) And (5) preserving the heat for 24 hours to finally obtain the intermediate-temperature proton exchange membrane.
Example 7
In this example, the heat-resistant polymer as the matrix was Polybenzimidazole (PBI). The method specifically comprises the following steps:
step 1: polybenzimidazole (PBI) was dissolved in dimethylacetamide (DMAc) at 120 ℃, incubated at 120 ℃ and subjected to vigorous stirring for 10 hours to give a Polybenzimidazole (PBI) (5 wt%) solution A;
step 2: the solution A is poured and coated on a glass substrate, and is solidified into a film B after being dried;
and step 3: washing the film B cured in the step 3 with water, and drying to obtain a substrate film C;
and 4, step 4: dipping the substrate film C solidified in the step 4 into the melted KH with the temperature of 160 DEG C5(AsO4)2And (5) preserving the heat for 24 hours to finally obtain the prepared intermediate-temperature proton exchange membrane.
Example 8
In this example, the heat-resistant polymer as the matrix was Polybenzimidazole (PBI). The method specifically comprises the following steps:
step 1: polybenzimidazole (PBI) was dissolved in dimethylacetamide (DMAc) at 120 ℃, incubated at 120 ℃ and subjected to vigorous stirring for 10 hours to give a Polybenzimidazole (PBI) (5 wt%) solution A;
step 2: the solution A is poured and coated on a glass substrate, and is solidified into a film B after being dried;
and step 3: washing the film B cured in the step 3 with water, and drying to obtain a substrate film C;
and 4, step 4: immersing the substrate film C solidified in the step 4 into molten CsH at 160 DEG C2PO4And (5) preserving the heat for 24 hours to finally obtain the intermediate-temperature proton exchange membrane.
Example 9
In this example, the heat-resistant polymer as the matrix was Polybenzimidazole (PBI). The method specifically comprises the following steps:
step 1: polybenzimidazole (PBI) was dissolved in dimethylacetamide (DMAc) at 120 ℃, incubated at 120 ℃ and subjected to vigorous stirring for 10 hours to give a Polybenzimidazole (PBI) (5 wt%) solution A;
step 2: the solution A is poured and coated on a glass substrate, and is solidified into a film B after being dried;
and step 3: washing the film B cured in the step 3 with water, and drying to obtain a substrate film C;
and 4, step 4: dipping the substrate film C solidified in the step 4 into molten NH with the temperature of 160 DEG C4H2PO4And (5) preserving the heat for 24 hours to finally obtain the intermediate-temperature proton exchange membrane.
Example 10
In this example, the heat-resistant polymer as the matrix was Polybenzimidazole (PBI). The method specifically comprises the following steps:
step 1: polybenzimidazole (PBI) was dissolved in dimethylacetamide (DMAc) at 120 ℃, incubated at 120 ℃ and subjected to vigorous stirring for 10 hours to give a Polybenzimidazole (PBI) (5 wt%) solution A;
step 2: the solution A is poured and coated on a glass substrate, and is solidified into a film B after being dried;
and step 3: washing the film B cured in the step 3 with water, and drying to obtain a substrate film C;
and 4, step 4: dipping the substrate film C solidified in the step 4 into molten RbH at 160 DEG C2PO4And (5) preserving the heat for 24 hours to finally obtain the intermediate-temperature proton exchange membrane.
Example 11
In this example, the heat-resistant polymer as the matrix was Polybenzimidazole (PBI). The method specifically comprises the following steps:
step 1: polybenzimidazole (PBI) was dissolved in dimethylacetamide (DMAc) at 120 ℃, incubated at 120 ℃ and subjected to vigorous stirring for 10 hours to give a Polybenzimidazole (PBI) (5 wt%) solution A;
step 2: the solution A is poured and coated on a glass substrate, and is solidified into a film B after being dried;
and step 3: washing the film B cured in the step 3 with water, and drying to obtain a substrate film C;
and 4, step 4: dipping the substrate film C solidified in the step 4 into the melted KH with the temperature of 160 DEG C2PO4And (5) preserving the heat for 24 hours to finally obtain the intermediate-temperature proton exchange membrane.
Example 12
In this example, the heat-resistant polymer as the matrix was Polybenzimidazole (PBI). The method specifically comprises the following steps:
step 1: polybenzimidazole (PBI) was dissolved in dimethylacetamide (DMAc) at 120 ℃, incubated at 120 ℃ and subjected to vigorous stirring for 10 hours to give a Polybenzimidazole (PBI) (5 wt%) solution A;
step 2: the solution A is poured and coated on a glass substrate, and is solidified into a film B after being dried;
and step 3: washing the film B cured in the step 3 with water, and drying to obtain a substrate film C;
and 4, step 4: impregnating the substrate film C cured in step 4 into molten CsHSO at 160 ℃4And (5) preserving the heat for 24 hours to finally obtain the intermediate-temperature proton exchange membrane.
Example 13
In this example, the heat-resistant polymer as the matrix was Polybenzimidazole (PBI). The method specifically comprises the following steps:
step 1: polybenzimidazole (PBI) was dissolved in dimethylacetamide (DMAc) at 120 ℃, incubated at 120 ℃ and subjected to vigorous stirring for 10 hours to give a Polybenzimidazole (PBI) (5 wt%) solution A;
step 2: the solution A is poured and coated on a glass substrate, and is solidified into a film B after being dried;
and step 3: washing the film B cured in the step 3 with water, and drying to obtain a substrate film C;
and 4, step 4: dipping the substrate film C solidified in the step 4 into the melted KHSO with the temperature of 160 DEG C4And (5) preserving the heat for 24 hours to finally obtain the intermediate-temperature proton exchange membrane.
Example 14
In this example, the heat-resistant polymer as the matrix was Polybenzimidazole (PBI). The method specifically comprises the following steps:
step 1: polybenzimidazole (PBI) was dissolved in dimethylacetamide (DMAc) at 150 ℃ and incubated at 150 ℃ and subjected to vigorous stirring for 5 hours to give a Polybenzimidazole (PBI) (5 wt%) solution A;
step 2: the solution A is poured and coated on a glass substrate, and is solidified into a film B after being dried;
and step 3: washing the film B cured in the step 3 with water, and drying to obtain a substrate film C;
and 4, step 4: dipping the substrate film C solidified in the step 4 into molten RbHSO at 160 DEG C4And (5) preserving the heat for 24 hours to finally obtain the intermediate-temperature proton exchange membrane.
Examples Performance testing
Using a JSM-7800F field emission scanning electron microscope to obtain a cross-section picture of a prepared sample, using a DMA8000 dynamic mechanical analyzer to perform mechanical property test on the prepared sample, wherein the size of the test sample is 3mm × mm (the width is × long), the test condition is that the tensile speed is 0.3N/min at room temperature, proton conductivity test is performed, using conductive silver glue to respectively prepare two parallel electrodes with equal length on the test sample, using an impedance spectrometer (SI-1260, Solartron) to test the proton conductivity, placing the sample with the test alternating voltage of 20 mv. into an oven, and performing test under the condition that 80 ℃ saturated water vapor is introduced into the oven, wherein the proton conductivity test temperature is within the range of 100--2The activated area of the carbon paper is 5cm2The hydrogen and the oxygen are respectively led into the cathode and the anode of the single cell, and the gas flow rates of the hydrogen and the oxygen are both 60cm3min-1And by adding 0.12ml min–1Water for humidifying hydrogen gas, fuel cell performanceThe testing temperature is within the range of 100-400 ℃.
CsH loading in the matrix prepared in example 15(PO4)2The medium temperature proton exchange membrane of (1), as shown in figure 1. The prepared medium-temperature proton exchange membrane has good flexibility and mechanical property.
As can be seen from fig. 2, the proton conductivity of the medium-temperature proton exchange membrane prepared in example 1 increases with increasing temperature. Specifically, in the temperature region of 100-–5–10–3S cm–1This is because CsH5(PO4)2Has a melting point of about 150 ℃ in the CsH range5(PO4)2Still in the solid state, the proton conductivity is at a lower level; at a temperature of 140-5(PO4)2Melting occurs, resulting in a rapid increase in proton conductivity, up to 10–3–10–2S cm–1(ii) a In the temperature region of 160-5(PO4)2When the material is in a molten state, the proton conductivity is slowly improved along with the temperature increase; above 250 ℃ due to CsH5(PO4)2Such that the proton concentration is reduced, resulting in a slight decrease in proton conductivity.
A unit cell of a fuel cell was assembled based on the middle-temperature proton exchange membrane of example 1, and the test temperature was 200 ℃, as shown in fig. 3, the Open Circuit Voltage (OCV) thereof reached 1.02V, exhibiting good output performance of the fuel cell.
The composition ratio and performance of the medium-temperature proton exchange membrane prepared in each example, and the performance of the fuel cell assembled using the electrolyte are shown in table 1.
TABLE 1
In conclusion, the medium-temperature proton exchange membrane prepared by the invention not only has high proton conductivity and good thermal stability, but also has excellent mechanical properties. It is suitable for working in the temperature range of 100-400 ℃ and the operating temperature is lower than that of the molten carbonate electrolyte, so that the flexible polymer with high mechanical strength can be used as a supporting matrix for loading the molten oxysalt. The molten proton conductor electrolyte membrane disclosed by the invention is simple and convenient in preparation process and suitable for industrial production; meanwhile, the cheap raw materials of the electrolyte membrane are beneficial to reducing the cost of the electrolyte membrane and the fuel cell, and the electrolyte membrane is expected to be widely applied to the field of medium-temperature fuel cells and the related field needing the medium-temperature proton conduction electrolyte membrane.
The foregoing description of specific embodiments of the present invention has been presented. It is to be understood that the present invention is not limited to the specific embodiments described above, and that various changes or modifications may be made by one skilled in the art within the scope of the appended claims without departing from the spirit of the invention. The embodiments and features of the embodiments of the present application may be combined with each other arbitrarily without conflict.
Claims (6)
1. The medium-temperature proton exchange membrane is characterized by consisting of a heat-resistant polymer matrix and oxysalt, wherein the oxysalt is loaded in the heat-resistant polymer matrix;
the preparation method of the medium-temperature proton exchange membrane comprises the following steps:
s1, dissolving the heat-resistant polymer in a solvent to obtain a solution A;
s2, casting the solution A on a substrate, drying and curing to form a film C;
s3, washing the membrane C with water, and drying to obtain a membrane D;
s4, soaking the membrane D in molten oxysalt, and treating residual oxysalt on the surface of the membrane after soaking to obtain the medium-temperature proton exchange membrane;
in step S4, the film D is soaked in molten oxysalt, the soaking temperature is 5-20 ℃ higher than the melting temperature of the oxysalt, and the soaking time is 1-24 h;
the oxysalt is CsH5(PO4)2、KH5(PO4)2、CsH2PO4、RbH2PO4、KH2PO4One of (1);
the weight ratio of the heat-resistant polymer matrix to the oxysalt is 1: (0.41 to 1).
2. A medium-temperature proton exchange membrane according to claim 1, wherein said heat-resistant polymer is one or more of heat-resistant hydrocarbon polymer and fluorine polymer, and said oxysalt is MHXO4、MH2X’O4、MH5(X’O4)2Wherein M is Cs, Rb, K or NH4 +X is S or Se, and X' is P or As.
3. A medium-temperature proton exchange membrane according to claim 2, wherein said heat-resistant hydrocarbon polymer is polybenzimidazole; the fluoropolymer is polyvinylidene fluoride.
4. An intermediate-temperature proton exchange membrane according to claim 1, wherein in step S1, the solvent is one or more selected from dimethylformamide, dimethylacetamide, N-methylpyrrolidone, dimethyl sulfoxide, acetone, ethanol, methyl acetone, and methyl ethyl acetone.
5. A medium-temperature proton exchange membrane according to claim 1, wherein in step S1, the dissolving temperature is 10-50 ℃ lower than the boiling point of the solvent, and the dissolving time is 5-15 h.
6. A fuel cell prepared on the basis of an intermediate-temperature proton exchange membrane according to any one of claims 1 to 5.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710326667.4A CN107331883B (en) | 2017-05-10 | 2017-05-10 | Intermediate-temperature proton exchange membrane and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710326667.4A CN107331883B (en) | 2017-05-10 | 2017-05-10 | Intermediate-temperature proton exchange membrane and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN107331883A CN107331883A (en) | 2017-11-07 |
| CN107331883B true CN107331883B (en) | 2020-07-14 |
Family
ID=60193726
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710326667.4A Active CN107331883B (en) | 2017-05-10 | 2017-05-10 | Intermediate-temperature proton exchange membrane and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107331883B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101319051A (en) * | 2008-07-15 | 2008-12-10 | 山东东岳神舟新材料有限公司 | Fibre reinforcement inorganics doped multi-layer fluorine ion exchange containing film |
| 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 |
| CN101330150A (en) * | 2008-07-29 | 2008-12-24 | 山东东岳神舟新材料有限公司 | Inorganic doping cross-linking multilayer ion membrane containing fluorine and preparation method thereof |
| 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 |
-
2017
- 2017-05-10 CN CN201710326667.4A patent/CN107331883B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN101319051A (en) * | 2008-07-15 | 2008-12-10 | 山东东岳神舟新材料有限公司 | Fibre reinforcement inorganics doped multi-layer fluorine ion exchange containing film |
| CN101330150A (en) * | 2008-07-29 | 2008-12-24 | 山东东岳神舟新材料有限公司 | Inorganic doping cross-linking multilayer ion membrane containing fluorine and preparation method thereof |
| 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 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN107331883A (en) | 2017-11-07 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Oono et al. | Influence of the phosphoric acid-doping level in a polybenzimidazole membrane on the cell performance of high-temperature proton exchange membrane fuel cells | |
| JP6300985B2 (en) | Method for producing polymer electrolyte membrane | |
| Oono et al. | Influence of operating temperature on cell performance and endurance of high temperature proton exchange membrane fuel cells | |
| JP6235554B2 (en) | POLYMER ELECTROLYTE MEMBRANE, METHOD FOR PRODUCING THE SAME, AND MEMBRANE-ELECTRODE ASSEMBLY CONTAINING THE SAME | |
| KR102018913B1 (en) | Gas diffusion layer comprising carbon nanofiber spun for fuel cell | |
| Chien et al. | Characteristics of high-water-uptake activated carbon/Nafion hybrid membranes for proton exchange membrane fuel cells | |
| CN107324316A (en) | A kind of preparation method of graphene film positive electrode and its application in aluminium ion battery | |
| CN111129529B (en) | Covalent organic framework material used for fuel cell self-humidifying membrane electrode and preparation method thereof | |
| CN101475699A (en) | Preparation of proton conduction membrane | |
| CN107331883B (en) | Intermediate-temperature proton exchange membrane and preparation method thereof | |
| CN107240705B (en) | Medium-temperature molten proton conductor electrolyte membrane and application | |
| CN102376961A (en) | High temperature proton exchange membrane for fuel cell, and preparation method thereof | |
| Das et al. | Electrophoretic deposition of zirconia thin film on nonconducting substrate for solid oxide fuel cell application | |
| Wang et al. | Polyimide‐Based Self‐Standing Polymer Electrolyte Membrane for Lithium‐Ion Batteries | |
| Park et al. | Durability analysis of Nafion/hydrophilic pretreated PTFE membranes for PEMFCs | |
| JP2008034212A (en) | Ionic conductor, energy device, and fuel cell | |
| Jung et al. | Electrochemical performance and long-term durability of a reversible solid oxide fuel cell | |
| Modestov et al. | Influence of catalyst layer binder on catalyst utilization and performance of fuel cell with polybenzimidazole-H3PO4 membrane | |
| KR101630212B1 (en) | A composite membrane comprising nonwoven PAI-PTM and sulfonated poly(arylene ether sulfone) as hydrocarbon-based electrolyte therein and the use thereof | |
| KR20130004615A (en) | Composite electrolyte membrane for fuel cell and method for manufacturing the same | |
| CN107946621B (en) | Method for improving corrosion resistance of carbon fiber or carbon fiber composite material through functional graphene modification | |
| JP5336804B2 (en) | Porous electrode substrate, method for producing the same, membrane-electrode assembly, and polymer electrolyte fuel cell | |
| Hedayat et al. | A novel method to fabricate inert substrate-supported microtubular solid oxide fuel cells by selective leaching | |
| JP2011023170A (en) | Method for manufacturing electrode of fuel cell | |
| JP2011238496A (en) | Electrode for fuel cell, membrane electrode assembly and fuel cell using the same, and method for manufacturing electrode for fuel cell |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |