CN112436170B - High-tolerance perfluorinated proton membrane and preparation method thereof - Google Patents
High-tolerance perfluorinated proton membrane and preparation method thereof Download PDFInfo
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- CN112436170B CN112436170B CN202011374149.8A CN202011374149A CN112436170B CN 112436170 B CN112436170 B CN 112436170B CN 202011374149 A CN202011374149 A CN 202011374149A CN 112436170 B CN112436170 B CN 112436170B
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- H—ELECTRICITY
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
- H01M8/1018—Polymeric electrolyte materials
- H01M8/1041—Polymer electrolyte composites, mixtures or blends
- H01M8/1046—Mixtures of at least one polymer and at least one additive
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- H01M8/10—Fuel cells with solid electrolytes
- H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
- H01M8/1018—Polymeric electrolyte materials
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- H01M8/1081—Polymeric electrolyte materials characterised by the manufacturing processes starting from solutions, dispersions or slurries exclusively of polymers
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Abstract
The invention relates to the technical field of functional polymer composite materials, in particular to a high-tolerance perfluorinated proton membrane and a preparation method thereof. The high-tolerance perfluorinated proton membrane is 5-50 mu m thick, consists of perfluorinated sulfonic acid resin and an additive, wherein the content of the additive is 0.01-5 wt% of the mass of the perfluorinated sulfonic acid resin, the additive has a specific structure, has strong scavenging capacity on oxygen-containing free radicals, particularly hydroxyl free radicals, is particularly suitable for being used in a fuel cell environment to scavenge the generated hydroxyl free radicals, and has low influence and low water washing performance on the performance of the fuel cell, so that the tolerance of the membrane is increased by geometric progression. The high-tolerance perfluorinated proton membrane has high free radical oxidation tolerance and long service life; the invention also provides a preparation method of the composition.
Description
Technical Field
The invention relates to the technical field of functional polymer composite materials, in particular to a high-tolerance perfluorinated proton membrane and a preparation method thereof.
Background
Proton Exchange Membrane Fuel Cells (PEMFCs), which convert reactants, i.e., a fuel (e.g., hydrogen) and an oxidant (e.g., oxygen or air), to generate electric energy, are considered to be the first clean and efficient power generation technology in the 21 st century. Proton exchange membranes are a key material of PEMFCs.
The polymer electrolyte membrane serves as a separator to prevent mixing of reactive gases and as an electrolyte to transport protons from the anode to the cathode. During operation of the fuel cell, a small amount of oxygen will always permeate through the membrane from the cathode to the anode and react with the hydrogen attached to the platinum-carbon catalyst to form hydrogen peroxide. The hydrogen peroxide diffuses into the membrane and reacts with trace metal ion impurities in the membrane, such as iron ions, which have a Fenton catalytic effect, and copper ions catalyze the decomposition of the hydrogen peroxide to generate hydroxyl radicals (. OH) or peroxy radicals (. OOH) with strong oxidizing property.
In order to improve the durability of the polymer electrolyte membrane, the membranes currently used are mostly perfluorinated ion exchange membranes. But due to the fact thatDuring the synthesis of the perfluorinated ion exchange resin, unstable carboxyl (-COOH) groups are inevitably introduced, so that generated hydroxyl groups (. OH) or peroxy groups (. OOH) attack weak groups (such as carboxylic acid groups) on the molecular chain of the ionomer. Hydroxyl groups attack unstable end groups of the polymer leading to chain scission and/or can also attack SO under dry conditions3-The groups thus break the polymer chains, both attacks degrading the membrane and eventually leading to membrane rupture, thinning or pinhole formation, the rate of membrane degradation increasing significantly with increasing operating time and decreasing relative humidity of the inlet air (RH).
To improve the performance and/or durability of the film, several approaches have been proposed to address these issues. For example, in a method (US5547551, US 56565041, US5599614) for filling a Nafion ionic conducting solution in Gore-Select series composite membrane solution developed by w.l.gore company, a polytetrafluoroethylene microporous membrane is added as a reinforcing layer of the membrane, so that the membrane has excellent oxidation stability, can locally slow down the degradation of a fuel cell membrane, and cannot fundamentally solve the problem.
Another solution to the long term free radical oxidative stability of the membrane is to add a catalyst to the membrane that can promote free radical degradation, including 1) adding an aqueous material to the membrane for preventing the fuel cell from operating at low humidity (e.g., US 200701564); 2) adding metal element or alloy with free radical trapping effect into the membrane (such as US 2004043283); 3) the free radical scavenger of phenol and hindered amine is added into the film to eliminate hydroxyl free radical.
The above techniques can partially solve the problem of radical tolerance of the membrane, but cannot fundamentally solve the problem. Their major difficulties mainly include: 1) the added water-retaining substances have a limited water content and cannot fundamentally increase the humidity of the reaction environment and solve the dehydration problem of the membrane, and the added substances also reduce the strength and conductivity of the membrane: 2) the added metal or alloy trapping agent requires very precise control of the content and distribution in the membrane, because these metallic species, in addition to having the effect of trapping hydroxyl radicals, also catalyse the degradation of hydrogen peroxide, and if too large an amount will increase the concentration of hydroxyl radicals in the membrane, further promoting the degradation of the membrane. However, because the metal substance has higher density and hydrophilic surface, the metal substance has spontaneous action due to sedimentation and phase separation aggregation with the perfluorinated ion exchange membrane mainly composed of hydrophobic chains in the membrane preparation process. This phenomenon causes unavoidable increases in the local concentration of the metal element leading to accelerated hydrogen peroxide degradation and deterioration of the film. 3) Some added phenol, hindered amine and other substances are used as polymerization inhibitors in free radical polymerization, namely, the added phenol, hindered amine and other substances have very good reactivity to carbon radicals, but the reactivity to oxygen-containing hydroxyl radicals is greatly reduced. Moreover, they are also degraded continuously and disappear finally when scavenging free radicals, are easy to dissolve in water, can be dissolved out of the membrane along with water generated during working, and cannot play a role in protection.
Disclosure of Invention
The invention aims to provide a high-tolerance perfluorinated proton membrane which has high free radical oxidation tolerance and long service life; the invention also provides a preparation method of the composition.
The high-tolerance perfluorinated proton membrane is 5-50 mu m thick, and consists of perfluorinated sulfonic acid resin and an additive, wherein the content of the additive is 0.01-5 wt% of the mass of the perfluorinated sulfonic acid resin;
the chemical structure of the additive is selected from one or more of the following structures:
(Ⅰ)
(Ⅱ)
(Ⅲ)
(Ⅳ)
(Ⅴ)
(Ⅵ)
(Ⅶ)
(Ⅷ)
wherein R is1，R2，R3，R4Is H, OH, CH3(CH2)nO、CH3(CH2)n、NH2、CH2OH、C6H5、CF3(CF2)n、CF3(CF2)nO, COOH, n is an integer from 0 to 10.
Preferably, the additive is present in an amount of 0.1 to 2 wt% of the perfluorosulfonic acid resin.
The perfluorinated sulfonic acid resin is selected from one or more of long-chain branched perfluorinated sulfonic acid resin or short-chain branched perfluorinated sulfonic acid resin.
The number average molecular weight of the perfluorinated sulfonic acid resin is 15-70 ten thousand, and the exchange capacity is 0.85-1.6 mmol/g.
Preferably, the perfluorinated ion exchange resin has a number average molecular weight of 20 to 60 ten thousand and an exchange capacity of 0.9 to 1.4 mmol/g.
The disclosed additives are selected based on the expected high rate of hydrogen peroxide decomposition reaction, low impact on fuel cell performance, and low water washability. The compound is a good free radical scavenger or hydrogen peroxide decomposer, can capture and scavenge free hydroxyl groups more quickly, and prevents the attack of the free radicals on active sites, thereby improving the tolerance of the membrane. The amount of additive used in the high tolerance proton membrane depends on several factors, and it is preferred to use the minimum amount of additive to achieve these results.
The preparation method of the high-tolerance perfluorinated proton membrane comprises the following steps:
(1) adding perfluorinated sulfonic acid resin and an additive into a solvent to form a dispersion liquid;
(2) and (2) forming the dispersion liquid in the step (1) into a film by adopting a tape casting, pouring, screen printing process, blade coating, spraying or dipping mode, and heating to volatilize the solvent to obtain the high-tolerance perfluorinated proton membrane.
In the step (1), the solvent is one or more of dimethylformamide, dimethyl sulfoxide, N-methylpyrrolidone, water, methanol, ethanol, N-propanol, isopropanol, N-butanol, isobutanol, ethylene glycol, propylene glycol, glycerol, acetonitrile, acetone, butanone and dimethylacetamide.
The content of the perfluorosulfonic acid resin in the dispersion is 5 to 40 wt%.
Compared with the prior art, the invention has the following beneficial effects:
the additive adopted by the invention has stronger scavenging capability to oxygen-containing free radicals, particularly hydroxyl free radicals, and is particularly suitable for being used in the fuel cell environment to scavenge the generated hydroxyl free radicals; and the voltage attenuation of the fuel cell caused by the pollution related to the dissolution of the catalyst and the degradation of the ionomer electrolyte is reduced; meanwhile, the additive has lower influence on the performance of the fuel cell and low water washability, so that the tolerance of the membrane is increased geometrically.
Detailed Description
The present invention is described in further detail below with reference to the accompanying tables and examples, which are intended to facilitate the understanding of the present invention without limiting it in any way. In the examples, the percentages are by weight unless otherwise specified.
Example 1
Selecting short-chain branch perfluorosulfonic acid resin with exchange capacity of 1.25mmol/g and number average molecular weight of 45 ten thousand and a component accounting for 0.5 wt% of the mass of the perfluorosulfonic acid resin, wherein R in the component1，R2Is OCH3；R3，R4Is H.
Dissolving perfluorosulfonic acid resin in DMSO to form 20 wt% resin dispersion, adding the resin dispersion of formula (I), stirring and dispersing uniformly, forming a film by tape casting, and heating to volatilize the solvent to obtain the perfluoroproton membrane with the thickness of 15 μm.
Example 2
Selecting long-chain branched perfluorosulfonic acid resin with exchange capacity of 1.1mmol/g and number average molecular weight of 35 ten thousand and a formula (IV) accounting for 1 wt% of the mass of the perfluorosulfonic acid resin, wherein R in the formula (IV)1Is H; r2Is OH.
Dissolving perfluorinated sulfonic acid resin in a propanol-water system to form 22 wt% resin dispersion, adding the resin dispersion of formula (IV), stirring and dispersing uniformly, forming a film by tape casting, and heating to volatilize the solvent to obtain the perfluorinated proton membrane with the thickness of 20 microns.
Example 3
Selecting long-chain branched perfluorosulfonic acid resin with exchange capacity of 1.01mmol/g and number average molecular weight of 30 ten thousand and a component (VII) accounting for 2 wt% of the mass of the perfluorosulfonic acid resin, wherein R in the component (VII)1Is NH2；R2，R3，R4Is H.
Dissolving perfluorosulfonic acid resin in DMF to form 27 wt% resin dispersion, adding the resin dispersion of formula (VII), stirring and dispersing uniformly, casting to form a film, and heating to volatilize the solvent to obtain the perfluorinated proton membrane with the thickness of 30 μm.
Example 4
Selecting short-chain branch perfluorosulfonic acid resin with exchange capacity of 1.35mmol/g and number average molecular weight of 40 ten thousand and a formula (III) accounting for 3.5 wt% of the mass of the perfluorosulfonic acid resin, wherein R in the formula (III) is1，R2Is COOH.
Dissolving perfluorosulfonic acid resin in DMSO to form 27 wt% resin dispersion, adding the resin dispersion of formula (III), stirring and dispersing uniformly, forming a film by tape casting, and heating to volatilize the solvent to obtain the perfluoroproton membrane with the thickness of 35 μm.
Example 5
Selecting long-chain branched perfluorosulfonic acid resin with exchange capacity of 0.9mmol/g and number average molecular weight of 50 ten thousand and a formula (I) accounting for 4.5 wt% of the mass of the perfluorosulfonic acid resin, wherein R in the formula (I)1，R2Is C4H9；R3，R4Is H.
Dissolving perfluorosulfonic acid resin in DMF to form 35 wt% resin dispersion, adding the resin of formula (II), stirring for dispersing uniformly, forming a film by tape casting, and heating to volatilize the solvent to obtain the perfluorinated proton membrane with the thickness of 50 μm.
Example 6
Selecting short-chain branch perfluorosulfonic acid resin with exchange capacity of 1.4mmol/g and number average molecular weight of 55 ten thousand and a formula (II) accounting for 2.5 wt% of the mass of the perfluorosulfonic acid resin, wherein R in the formula (II)1，R2Is OH; r3，R4Is H.
Dissolving perfluorinated sulfonic acid resin in an ethanol-water system to form 30 wt% resin dispersion, adding the resin dispersion of the formula (II), stirring and dispersing uniformly, forming a film by tape casting, and heating to volatilize the solvent to obtain the perfluorinated proton membrane with the thickness of 40 microns.
Example 7
Selecting short-chain branch perfluorosulfonic acid resin with exchange capacity of 1.3mmol/g and number average molecular weight of 25 ten thousand and a component (I) accounting for 0.1 wt% of the mass of the perfluorosulfonic acid resin, wherein R in the component (I)1，R4Is C6H5；R3，R2Is H.
Dissolving perfluorosulfonic acid resin in DMSO to form 17 wt% resin dispersion, adding the resin dispersion of formula (I), stirring and dispersing uniformly, forming a film by tape casting, and heating to volatilize the solvent to obtain the perfluoroproton membrane with the thickness of 8 μm.
Comparative example 1
Selecting short-chain branch perfluorosulfonic acid resin with exchange capacity of 1.25mmol/g and number average molecular weight of 40 ten thousand, dissolving the resin in DMF to form 22 wt% resin dispersion, adding no additive, stirring and dispersing uniformly, forming a film by tape casting, and heating to volatilize the solvent to obtain the perfluorinated proton membrane with the thickness of 25 mu m.
The perfluor proton membranes prepared in examples 1-7 and comparative example 1 were subjected to performance test as follows.
(1) Accelerated oxidation test.
The experimental test is carried out by a Fenton reagent method, and the method comprises the following specific steps:
80ppm Fe was added to 100mL of 30% hydrogen peroxide solution2+Weighing a certain mass (0.06-0.1g) of perfluorinated proton membrane, placing in the perfluorinated proton membrane, keeping at 80 ℃ for 8h, taking out a sample from the solution, cleaning with deionized water,the mixture was dried at 80 ℃ for 2 hours and weighed, and the weight loss was calculated.
(2) And (5) durability test.
The perfluorinated proton membrane sample was bonded between cathode and anode electrodes to prepare an MEA, both cathode and anode having a density of 0.4mg/cm2Pt loading of (a). MEA samples were used to assemble a 41cm thick section2Active area fuel cell, 5 different fuel cells were tested simultaneously using the stack. The durability or chemical stability of the MEA samples was evaluated at 30% Relative Humidity (RH) and 90 c at Open Circuit Voltage (OCV) to provide hydrogen and air gas flow rates of 3.43slpm and 8.37slpm, respectively. OCV of each cell in the stack was monitored over time. OCV of any of 5 cells in the stack reaches 0.8V or H2Crossover is more than 10mA/cm2And ending the test and stopping the test.
The test results are shown in table 1.
Table 1 results of performance test of the perfluorinated proton membranes of examples 1-7 and comparative example 1
| Item | Mass loss (%) | OCV(h) |
| Example 1 | 3.26 | 235 |
| Example 2 | 3.89 | 200 |
| Example 3 | 4.02 | 180 |
| Example 4 | 3.68 | 215 |
| Example 5 | 2.93 | 250 |
| Example 6 | 2.5 | 270 |
| Example 7 | 4.53 | 170 |
| Comparative example 1 | 5.43 | 130 |
As can be seen from table 1, the perfluorinated proton membranes of examples 1-7, to which the additives were added, reduced the degradation rate of the membranes and effectively improved the durability of the membranes, compared to comparative example 1.
Claims (9)
1. A high-tolerance perfluorinated proton membrane is characterized in that: the thickness is 5-50 μm, and the resin is composed of perfluorosulfonic acid resin and additive, wherein the content of the additive is 0.01-5 wt% of the mass of the perfluorosulfonic acid resin;
the chemical structure of the additive is selected from one or more of the following structures:
(Ⅰ)
(Ⅱ)
(Ⅳ)
(Ⅷ)
wherein R is1，R2，R3，R4Is H, OH, CH3(CH2)nO、CH3(CH2)n、NH2、CH2OH、C6H5、CF3(CF2)n、CF3(CF2)nO, COOH, n is an integer from 0 to 10.
2. The highly tolerant perfluorinated proton membrane according to claim 1, wherein: the content of the additive is 0.1-2 wt% of the perfluorosulfonic acid resin.
3. The highly tolerant perfluorinated proton membrane according to claim 1, wherein: the perfluorinated sulfonic acid resin is selected from one or more of long-chain branched perfluorinated sulfonic acid resin or short-chain branched perfluorinated sulfonic acid resin.
4. The highly tolerant perfluorinated proton membrane according to claim 1, wherein: the number average molecular weight of the perfluorinated sulfonic acid resin is 15-70 ten thousand, and the exchange capacity is 0.85-1.6 mmol/g.
5. The highly tolerant perfluorinated proton membrane according to claim 1, wherein: the number average molecular weight of the perfluorinated sulfonic acid resin is 20-60 ten thousand, and the exchange capacity is 0.9-1.4 mmol/g.
6. A method for preparing a high-tolerance perfluorinated proton membrane according to any one of claims 1 to 5, wherein the method comprises the following steps: the method comprises the following steps:
(1) adding perfluorinated sulfonic acid resin and an additive into a solvent to form a dispersion liquid;
(2) and (3) forming a film by using the dispersion liquid obtained in the step (1), and heating to volatilize the solvent to obtain the high-tolerance perfluorinated proton membrane.
7. The method for preparing a perfluorinated proton membrane with high tolerance according to claim 6, wherein the method comprises the following steps: in the step (1), the solvent is one or more of dimethylformamide, dimethyl sulfoxide, N-methylpyrrolidone, water, methanol, ethanol, N-propanol, isopropanol, N-butanol, isobutanol, ethylene glycol, propylene glycol, glycerol, acetonitrile, acetone, butanone and dimethylacetamide.
8. The method for preparing a perfluorinated proton membrane with high tolerance according to claim 6, wherein the method comprises the following steps: in the step (1), the content of the perfluorosulfonic acid resin in the dispersion liquid is 5-40 wt%.
9. The method for preparing a perfluorinated proton membrane with high tolerance according to claim 6, wherein the method comprises the following steps: in the step (2), the film forming mode is casting, pouring, silk screen printing process, blade coating, spraying or dipping.
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| CN104134813A (en) * | 2013-05-02 | 2014-11-05 | 山东东岳高分子材料有限公司 | Long-life polyelectrolyte membrane and preparation method thereof |
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| CN110444793A (en) * | 2019-08-16 | 2019-11-12 | 上海元城汽车技术有限公司 | A kind of durability proton exchange, preparation method and applications |
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| DE112005000196T5 (en) * | 2004-01-20 | 2006-11-30 | E.I. Dupont De Nemours And Co., Wilmington | A process for producing stable proton exchange membranes and a catalyst for use therein |
| CN102522576B (en) * | 2011-12-24 | 2013-12-04 | 山东东岳高分子材料有限公司 | Fuel cell membrane with high tolerance and its preparation method |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102687328A (en) * | 2009-11-10 | 2012-09-19 | 戴姆勒股份公司 | Composite proton conducting membrane with low degradation and membrane electrode assembly for fuel cells |
| CN104134813A (en) * | 2013-05-02 | 2014-11-05 | 山东东岳高分子材料有限公司 | Long-life polyelectrolyte membrane and preparation method thereof |
| CN110256913A (en) * | 2019-06-17 | 2019-09-20 | 深圳市通用氢能科技有限公司 | A kind of preparation method of antioxidant, water-retaining agent, mixture, denatured fuel cell membrane-electrode |
| CN110444793A (en) * | 2019-08-16 | 2019-11-12 | 上海元城汽车技术有限公司 | A kind of durability proton exchange, preparation method and applications |
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