CN113416982B - Composite proton exchange membrane and preparation method thereof - Google Patents
Composite proton exchange membrane and preparation method thereof Download PDFInfo
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- CN113416982B CN113416982B CN202110699742.8A CN202110699742A CN113416982B CN 113416982 B CN113416982 B CN 113416982B CN 202110699742 A CN202110699742 A CN 202110699742A CN 113416982 B CN113416982 B CN 113416982B
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Abstract
A composite proton exchange membrane and its preparing process are disclosed. The composite proton exchange membrane comprises perfluorinated sulfonic acid resin and non-perfluorinated sulfonic acid resin; wherein the perfluorinated sulfonic acid resin has a perfluorinated main chain structure; the non-perfluorinated sulfonic acid resin has a partially fluorinated or non-fluorinated backbone structure; the perfluorinated sulfonic acid resin and the non-perfluorinated sulfonic acid resin both have a proton exchange function; the composite proton exchange membrane is doped with metal oxide or metal nano particles; the mass percentage of the non-perfluorinated sulfonic acid resin relative to the total mass of the composite proton exchange membrane is 1-30%. The composite proton exchange membrane has the advantages of prolonged service life, reduced hydrogen cross permeation and lower cost.
Description
Technical Field
The invention belongs to the technical field of hydrogen energy, and particularly relates to a novel composite proton exchange membrane for polymer electrolyte membrane water electrolysis and a preparation method thereof.
Background
Polymer Electrolyte Membrane Water Electrolysis (PEMWE) is an important technology for converting electrical energy into chemical energy, in the context of climate change and the related requirements for energy conversion.
However, the PEMWE technology is currently limited by the following problems that cannot be popularized and used in a large scale:
(1) because of using noble metal catalyst and proton exchange membrane, the disposable input cost is too high;
(2) proton exchange membranes have a limited long-term service life;
(3) since a thin Polymer Electrolyte Membrane (PEM) is used in a PEMWE cell, it tends to produce gas crossover phenomena, particularly crossover of hydrogen in the anode compartment, when it is used. Since the lower explosive limit for hydrogen in oxygen is about 4 vol%, a value of 2 vol% safety margin cannot be achieved without a reasonable gas crossover mitigation strategy.
Therefore, a new composite proton exchange membrane for water electrolysis of polymer electrolyte membrane and a preparation method thereof are needed to solve the above technical problems.
Disclosure of Invention
In order to solve the technical problems, the invention provides a novel composite proton exchange membrane for polymer electrolyte membrane water electrolysis.
The composite proton exchange membrane comprises perfluorinated sulfonic acid resin and non-perfluorinated sulfonic acid resin,
the perfluorinated sulfonic acid resin has a perfluorinated main chain structure;
the non-perfluorinated sulfonic acid resin has a partially fluorinated or non-fluorinated backbone structure;
the perfluorinated sulfonic acid resin and the non-perfluorinated sulfonic acid resin have a proton exchange function;
the composite proton exchange membrane is doped with metal oxide or metal nano particles;
wherein the mass percentage of the metal oxide relative to the total mass of the composite proton exchange membrane is 0.1-2%;
wherein the mass percentage of the metal nano particles relative to the total mass of the composite proton exchange membrane is 0.01-1%.
Wherein the mass percentage of the non-perfluorinated sulfonic acid resin relative to the total mass of the composite proton exchange membrane is 1-30%.
Wherein the metal oxide comprises one or more of Ce oxide and Mn oxide.
The metal nanoparticles comprise one or more of Au nanoparticles, Pt nanoparticles and Ru nanoparticles.
Wherein a main chain of the non-perfluorosulfonic acid resin having a partially fluorinated main chain structure includes one or more of polyvinyl fluoride (PVF), polyvinylidene fluoride (PVDF) or ethylene-tetrafluoroethylene copolymer (ETFE), and a molecular side chain of the non-perfluorosulfonic acid resin having a partially fluorinated main chain contains sulfonic acid (-SO) 3 H) A functional group.
Wherein the main chain of the non-perfluorinated sulfonic acid resin with the non-fluorinated main chain structure comprises one or more of sulfonated polyether ether ketone (sPEEK), sulfonated polyether sulfone (sPES) and sulfonated polyaryl ether sulfone (sAES).
The invention also provides a preparation method of the composite proton exchange membrane, which comprises the following steps:
(1) dissolving perfluorosulfonic acid resin (PFSA) in a mixed solvent to form a solution A;
(2) adding metal oxide or metal nano particles into the solution A to form a solution B;
(3) adding non-perfluorinated sulfonic acid resin into the solution B to form a solution C;
(4) and coating the solution C on a base material, and drying to obtain the composite proton exchange membrane.
The invention also provides another preparation method of the composite proton exchange membrane, which comprises the following steps:
(i) dissolving perfluorosulfonic acid resin (PFSA) and non-perfluorosulfonic acid resin in a mixed solvent to form a solution D;
(ii) adding metal oxide or metal nano particles into the solution D to form a solution E;
(iii) and coating the solution E on a base material, and drying to obtain the composite proton exchange membrane.
Wherein, in the step (1) or (i), the mixed solvent comprises a lipophilic solvent and a hydrophilic solvent; wherein the lipophilic solvent is selected from one or more of N, N-Dimethylformamide (DMF), N-dimethylacetamide (DMAc), N-methylpyrrolidone (NMP) and dimethyl sulfoxide (DMSO); the hydrophilic solvent is selected from one or more of tert-butyl alcohol, n-propyl alcohol, isopropyl alcohol, ethanol and water.
Wherein, in the mixed solvent, the volume ratio of the lipophilic solvent to the hydrophilic solvent is 1-3:8, preferably 2: 8.
Wherein, in the step (1) or (i), the mass ratio of the perfluorinated sulfonic acid resin to the mixed solvent is 8-12:90, preferably 10: 90.
Wherein in the step (3) or (i), the mass ratio of the non-perfluorinated sulfonic acid resin to the perfluorinated sulfonic acid resin is 15-40: 100.
Wherein, in the step (1) or (i), the solution A or the solution D is formed by dissolving for 3 to 6 days under the condition of 45 to 55 ℃ (preferably 50 ℃).
Wherein in the step (2) or (ii), the mass ratio of the added metal oxide to the perfluorosulfonic acid resin is 0.3-0.8:100 (preferably 0.5: 100); the mass ratio of the added metal nanoparticles to the perfluorosulfonic acid resin is 0.5-1.5:2000 (preferably 1:2000)
Wherein, in the step (2) or (ii), the solution B or the solution E is formed by dissolving for 0.5 to 2 days (preferably 1 day) under the condition of 45 to 55 ℃ (preferably 50 ℃).
Wherein, in the step (3), the solution A or the solution D is formed by dissolving for 0.5 to 2 days (preferably 1 day) under the condition of 45 to 55 ℃ (preferably 50 ℃).
Wherein, in the step (4) or (iii), the coating mode is knife coating, dipping, spin coating, and the like.
Wherein, in the step (4) or (iii), the drying manner is drying for 2-4h (preferably 3h) at 95-115 ℃ (preferably 100 ℃) under normal pressure.
The invention also provides the application of the composite proton exchange membrane in the water electrolysis of the polymer electrolyte membrane.
The invention also provides a polymer electrolyte membrane water electrolyzer, which comprises the composite proton exchange membrane.
The beneficial technical effects of the invention are embodied in the following aspects:
(1) the metal oxide is added as a free radical quencher, so that the service life of the proton exchange membrane can be prolonged by 2-5 times;
(2) the noble metal nano particles are used as a gas composite catalyst, so that the problem of overhigh hydrogen content in the anode gas caused by gas cross permeation can be solved;
(3) the sulfonic acid membrane having a partially fluorinated backbone or a non-fluorinated backbone has a lower hydrogen cross-permeation rate than the sulfonic acid membrane having a perfluorinated backbone, and thus the addition of a sulfonic acid resin having a partially fluorinated backbone or a non-fluorinated backbone to the composite membrane can reduce the hydrogen cross-permeation.
The above effects (2) and (3) in combination can reduce the hydrogen content in the anode gas to below 0.1 vol.% at a rated power load of the polymer electrolyte membrane water electrolyzer of 20% to 100%.
(4) The cost of the sulfonic acid resin having a partially fluorinated backbone or a non-fluorinated backbone relative to the perfluorosulfonic acid resin is about 1/5 to 1/2 of the perfluorosulfonic acid resin, which helps to reduce the cost of the water electrolyzer.
Brief description of the drawings
FIG. 1 shows N-CeO in example 1 2 Electrolytic polarization profiles of P30 membrane and Nafion 115 membrane of comparative example.
FIG. 2 shows N-CeO in example 1 2 P30 Membrane and Nafion 115 Membrane of comparative exampleThe hydrogen concentration in oxygen at the time of electrolysis.
FIG. 3 shows N-CeO of example 1 2 Stability of the P30 film on electrolysis.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
Example 1
A preparation method of a composite proton exchange membrane comprises the following steps:
(1) dissolving a perfluorosulfonic acid resin (PFSA) in a mixed solvent of NMP and water (the volume ratio of the NMP to the water is 2:8), wherein the mass ratio of the PFSA to the mixed solvent is 10:90, and dissolving the mixed solution at 50 ℃ for 3 days to form a solution A;
(2) adding cerium oxide nanoparticles into the solution A, wherein the mass ratio of cerium oxide to PFSA is 0.2:100, and dissolving the mixed solution at 50 ℃ for 1 day to form a solution B;
(3) adding polyvinylidene fluoride-g-styrene sulfonic acid (PVDF-g-PSSA) into the solution B, wherein the mass ratio of PVDF-g-PSSA to PFSA is 30:100, and dissolving the mixed solution at 50 ℃ for 1 day to form a solution C;
(4) scraping the solution C on a base material, and then drying the base material for 3 hours at the temperature of 100 ℃ under normal pressure to obtain N-CeO 2 -P30 composite proton exchange membrane.
Example 2
A preparation method of a composite proton exchange membrane comprises the following steps:
(1) dissolving a perfluorosulfonic acid resin (PFSA) in a mixed solvent of NMP and water (the volume ratio of the NMP to the water is 2:8), wherein the mass ratio of the PFSA to the mixed solvent is 10:90, and dissolving the mixed solution at 50 ℃ for 3 days to form a solution A;
(2) adding Pt nanoparticles into the solution A, wherein the mass ratio of Pt to PFSA is 1: 2000; dissolving the mixed solution at 50 ℃ for 1 day to form a solution B;
(3) adding polyvinylidene fluoride-g-styrene sulfonic acid (PVDF-g-PSSA) into the solution B, wherein the mass ratio of PVDF-g-PSSA to PFSA is 20:100, and dissolving the mixed solution at 50 ℃ for 1 day to form a solution C;
(4) coating the solution C on a base material in a scraping manner, and then drying the base material for 3 hours at 100 ℃ under normal pressure to obtain an N-Pt-P20 composite membrane;
example 3
A preparation method of a composite proton exchange membrane comprises the following steps:
(1) dissolving a perfluorosulfonic acid resin (PFSA) and a polyvinylidene fluoride-g-styrene sulfonic acid (PVDF-g-PSSA) resin in a mixed solvent of NMP and water (the volume ratio of the NMP to the water is 2:8), wherein the mass ratio of the PFSA to the mixed solvent is 10:90, the mass ratio of the PVDF-g-PSSA to the PFSA is 30:100, and the mixed solution is dissolved at 50 ℃ for 5 days to form a solution D;
(2) adding cerium oxide nanoparticles into the solution D, wherein the mass ratio of cerium oxide to PFSA is 0.5:100, and dissolving the mixed solution at 50 ℃ for 1 day to form a solution E;
(3) scraping the solution E on a base material, and then drying for 3 hours at the temperature of 100 ℃ under normal pressure to obtain N-CeO 2 -P30 composite proton exchange membrane.
Performance testing
The membrane of example 1 was fabricated into a membrane electrode for PEM electrolyzed water experiments. In addition, for comparison, experiments were simultaneously conducted using a Nafion 115 membrane manufactured by dupont as a comparative example. The loading capacity of the membrane electrode catalyst is respectively anode IrO 2 2mg/cm 2 Cathode 70% Pt/C catalyst 1mg/cm 2 And the temperature of the electrolyzed pure water is 80 ℃, and a performance test, a hydrogen in oxygen test and a durability test are respectively carried out. The results are shown in FIGS. 1, 2 and 3, respectively.
As can be seen from FIG. 1, N-CeO of example 1 2 When the-P30 film is used as a proton exchange membrane for electrolyzing water, the current density is 1.5A/cm 2 When is N-CeO 2 The electrolytic voltage of-P30 and Nafion 115 membranes was 1.76V and 1.74V, respectively, indicating that the two membranes performed comparably.
As can be seen from FIG. 2, when the electrolytic current density is more than 0.5A/cm 2 When using the N-CeO of example 1 2 Hydrogen content in oxygen for electrolysis of P30 membranesAll below 0.1 vol.%, well below the lower explosive limit of hydrogen.
As can be seen from FIG. 3, when the N-CeO2-P30 membrane of example 1 was used as a proton exchange membrane for electrolyzed water, the electrolytic voltage did not increase after a long time of electrolysis of 700 hours, indicating that the membrane had good durability.
It should be understood that the above examples are only for clarity of illustration and are not intended to limit the embodiments. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. And obvious variations or modifications therefrom are within the scope of the invention.
Claims (10)
1. The preparation method of the composite proton exchange membrane is characterized in that the composite proton exchange membrane comprises perfluorinated sulfonic acid resin and non-perfluorinated sulfonic acid resin;
wherein the perfluorosulfonic acid resin has a perfluorinated backbone structure;
the non-perfluorinated sulfonic acid resin has a partially fluorinated or non-fluorinated backbone structure;
the perfluorinated sulfonic acid resin and the non-perfluorinated sulfonic acid resin both have a proton exchange function;
the composite proton exchange membrane is doped with metal oxide or metal nano particles;
the mass percentage of the non-perfluorinated sulfonic acid resin relative to the total mass of the composite proton exchange membrane is 1-30%;
the main chain of the non-perfluorinated sulfonic acid resin with the partially fluorinated main chain structure comprises one or more of polyvinyl fluoride, polyvinylidene fluoride or ethylene-tetrafluoroethylene copolymer, and the molecular side chain of the non-perfluorinated sulfonic acid resin with the partially fluorinated main chain structure contains sulfonic acid functional groups;
the non-perfluorinated sulfonic acid resin with a non-fluorinated main chain structure comprises one or more of sulfonated polyether ether ketone, sulfonated polyether sulfone and sulfonated polyaryl ether sulfone;
wherein the preparation method comprises the following steps:
(1) dissolving perfluorosulfonic acid resin in a mixed solvent to form a solution A;
(2) adding metal oxide or metal nano particles into the solution A to form a solution B;
(3) adding non-perfluorinated sulfonic acid resin into the solution B to form a solution C;
(4) coating the solution C on a base material, and drying to obtain the composite proton exchange membrane;
alternatively, the preparation method comprises:
(i) dissolving perfluorinated sulfonic acid resin and non-perfluorinated sulfonic acid resin in a mixed solvent to form a solution D;
(ii) adding metal oxide or metal nano particles into the solution D to form a solution E;
(iii) coating the solution E on a base material, and drying to obtain the composite proton exchange membrane;
wherein, in the step (1) or (i), the mixed solvent comprises a lipophilic solvent and a hydrophilic solvent;
wherein in the step (3) or (i), the mass ratio of the non-perfluorinated sulfonic acid resin to the perfluorinated sulfonic acid resin is 15-40: 100.
2. The method for preparing a composite proton exchange membrane according to claim 1, wherein the mass percentage of the metal oxide relative to the total mass of the composite proton exchange membrane is 0.1-2%.
3. The method for preparing a composite proton exchange membrane according to claim 1, wherein the mass percentage of the metal nanoparticles to the total mass of the composite proton exchange membrane is 0.01-1%.
4. The method of preparing a composite proton exchange membrane according to claim 1, wherein the metal oxide comprises one or more of Ce oxide and Mn oxide.
5. The method of claim 1, wherein the metal nanoparticles comprise one or more of Au nanoparticles, Pt nanoparticles, and Ru nanoparticles.
6. The method for preparing a composite proton exchange membrane according to claim 1, wherein in the step (1) or (i), the mass ratio of the perfluorinated sulfonic acid resin to the mixed solvent is 8-12: 90.
7. The method for preparing a composite proton exchange membrane according to claim 1, wherein the volume ratio of the lipophilic solvent to the hydrophilic solvent in the mixed solvent is 1-3: 8.
8. A composite proton exchange membrane prepared by the method of preparing a composite proton exchange membrane according to any one of claims 1 to 7.
9. Use of the composite proton exchange membrane of claim 8 for water electrolysis of polymer electrolyte membranes.
10. A polymer electrolyte membrane water electrolyzer comprising the composite proton exchange membrane of claim 8.
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| CN118127564B (en) * | 2024-05-08 | 2024-08-20 | 山东东岳未来氢能材料股份有限公司 | Hypotonic hydrogen proton exchange membrane and preparation method and application thereof |
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| CN101079487A (en) * | 2006-05-26 | 2007-11-28 | 中国科学院大连化学物理研究所 | Multi-layer moisture making compound film for proton exchange film fuel cell and its making method |
| CN101777655B (en) * | 2009-12-07 | 2012-09-19 | 山东华夏神舟新材料有限公司 | Inorganic composite metal oxide doped fluorine-containing proton exchange membrane for fuel cell |
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