CN115873149A - Perfluoro sulfonic acid ionic polymer with triazole group, proton membrane and membrane electrode for fuel cell and preparation method thereof - Google Patents
Perfluoro sulfonic acid ionic polymer with triazole group, proton membrane and membrane electrode for fuel cell and preparation method thereof Download PDFInfo
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- 239000012528 membrane Substances 0.000 title claims abstract description 165
- UQSQSQZYBQSBJZ-UHFFFAOYSA-N fluorosulfonic acid Chemical compound OS(F)(=O)=O UQSQSQZYBQSBJZ-UHFFFAOYSA-N 0.000 title claims abstract description 81
- 229920000831 ionic polymer Polymers 0.000 title claims abstract description 51
- 239000000446 fuel Substances 0.000 title claims abstract description 49
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- 125000001425 triazolyl group Chemical group 0.000 title 1
- 229920000642 polymer Polymers 0.000 claims abstract description 79
- 150000003852 triazoles Chemical group 0.000 claims abstract description 63
- 239000000126 substance Substances 0.000 claims abstract description 30
- 238000005342 ion exchange Methods 0.000 claims abstract description 29
- 150000003460 sulfonic acids Chemical class 0.000 claims abstract description 21
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- 239000011347 resin Substances 0.000 claims description 37
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 34
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- 238000006243 chemical reaction Methods 0.000 claims description 30
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 29
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- 238000000034 method Methods 0.000 claims description 18
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 14
- 239000013067 intermediate product Substances 0.000 claims description 14
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- 238000005406 washing Methods 0.000 claims description 9
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 6
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- 239000003054 catalyst Substances 0.000 description 14
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- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 14
- 239000007789 gas Substances 0.000 description 13
- 230000014759 maintenance of location Effects 0.000 description 13
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 11
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- 229910052739 hydrogen Inorganic materials 0.000 description 11
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 11
- 125000000542 sulfonic acid group Chemical group 0.000 description 11
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 10
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- QARLOMBMXGVKNV-UHFFFAOYSA-N 1,2,2-trifluoroethenesulfonyl fluoride Chemical compound FC(F)=C(F)S(F)(=O)=O QARLOMBMXGVKNV-UHFFFAOYSA-N 0.000 description 8
- 238000010438 heat treatment Methods 0.000 description 8
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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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Abstract
The invention belongs to the field of proton membranes and membrane electrodes of fuel cells, and particularly relates to perfluorosulfonic acid ionic polymers with triazole groups, a proton membrane and a membrane electrode for a fuel cell, and a preparation method thereof. The perfluorosulfonic acid ionic polymer with triazole group can fundamentally achieve the purpose of resisting free radical attack from the polymer, effectively weaken the degradation of the polymer and improve the chemical stability of the perfluorosulfonic acid ionic polymer. In addition, the triazole structural unit introduced into the structure of the obtained polymer can regulate and control the ion exchange capacity of the perfluorosulfonic acid ionic polymer, so that the obtained perfluorosulfonic acid ionic polymer can simultaneously realize the purpose of effectively regulating and controlling the ion exchange capacity and the chemical stability; the proton membrane and the membrane electrode comprise perfluorinated sulfonic acid ionic polymer with triazole group, and the triazole group can effectively capture or quench free radicals, so that the degradation of the proton membrane and the membrane electrode is weakened or slowed down, and the service life of the proton membrane and the membrane electrode is prolonged.
Description
Technical Field
The invention belongs to the field of fuel cell proton exchange membranes and membrane electrodes, and particularly relates to a perfluorosulfonic acid ionic polymer with triazole groups, a proton membrane for a fuel cell, a membrane electrode and a preparation method thereof.
Background
Fuel cells are power generation devices that convert chemical energy stored in reactants directly into electrical energy without combustion. The fuel cell does not generate substances such as nitrogen, sulfur oxides and the like which pollute the environment in the working process, so the fuel cell is considered to be an environment-friendly device, and in addition, the fuel cell has the advantages of high energy conversion efficiency, high reliability, good compressibility, good maintainability and the like, and the fuel cell technology is considered to be one of novel environment-friendly and efficient power generation technologies in the 21 st century. The Proton Exchange Membrane Fuel Cell (PEMFC) has the advantages of a common fuel cell, low working temperature, high starting speed, light weight, long service life, no corrosion and loss of electrolyte, high specific power and specific energy and the like. PEMFCs have gradually become ideal power sources for electric vehicles, mobile communications, submarines, and the like. Currently, many countries around the world are driving fuel cell traffic power solutions. In 2015, the first automobile with PEMFC as the main power source was sold by the japan Toyota company, and a milestone of fuel cell technology for automobile power was established.
Currently, most representative of commercial proton exchange membranes used at home and abroad is Nafion series membranes manufactured by dupont in the 80 th century, which have been rapidly developed due to their excellent conductivity and good comprehensive properties and become a standard for measuring the performance of proton exchange membranes. The main component of the Nafion membrane is perfluorosulfonic acid ionic Polymer (PFSIs), and the high molecular chain of the Nafion membrane has an ultra-stable perfluoro main chain skeleton- (CF) 2 CF 2 )m-(CF 2 CF) n-and with a sulfonic acid group (-SO) 3 H) Is a side chain of a terminal group, thus having higher chemical stability and good thermal stability. The perfluorosulfonic acid proton exchange membrane prepared by PFSIs has been widely noticed due to its advantages of high chemical stability, high conductivity at high humidity, high current density at low temperature, small resistance, etc. The chemical stability of the perfluorosulfonic acid polymer directly determines the long-term operating life of the fuel cell, however, during the operation of the fuel cell, the perfluorosulfonic acid polymer carries-SO 3 The H side group is easily attacked by hydroxyl radicals and eventually leads to a zipper-like degradation of the polymer backbone. Therefore, improving the chemical stability of PFSIs is very important for the industrial development of fuel cells.
Current research suggests that the chemical degradation process of PFSIs is mainly: during the synthesis of the perfluoropolymer, the initiator inevitably generates, for example, -CF = CF at the molecular chain end 2 、-COOH、-CF 2 SO 3 H and-CF 2 H, etc., labile group, radical (HO. Cndot.)&HOO. Cndot.) attack on unstable group at molecular chain endClumps, resulting in "zipper-like" degradation of the polymer. Therefore, designing and synthesizing PFSIs with high chemical stability is an important issue. Currently, means for improving the chemical stability of PFSIs mainly include: (1) Inhibiting the generation of free radicals in the application process of the polymer, such as Chinese patent document CN 112436170A, adding an additive capable of removing the free radicals into a perfluorosulfonic acid proton exchange membrane to capture the free radicals in the system, thereby relieving the attack of the perfluorosulfonic acid proton exchange membrane and increasing the chemical stability of the membrane; (2) Quenching or capturing generated free radicals by optimizing the polymer structure, such as introducing Zr into a perfluorosulfonic proton exchange membrane by an ion exchange method in Chinese patent document CN 102479956A 4+ 、Ca 2+ 、Mg 2+ 、Al 3+ One or more than two metal ions in the proton exchange membrane modify the microscopic appearance of the proton exchange membrane, and the chemical stability of the membrane is well improved. The methods need to prepare the polymer into the proton membrane and then adopt post-treatment measures to resist the attack of free radicals, but the methods do not adopt measures to quench or capture the generated free radicals at the source of the polymer and the synthesis process thereof, so that the phenomenon that additives or adulterants are lost from the proton exchange membrane is easy to occur, and the synthesis of PFSIs with high chemical stability by optimizing and modifying polymer molecular chains has important significance for prolonging the service life of the proton exchange membrane.
Disclosure of Invention
The invention provides a perfluorosulfonic acid ionic polymer with triazole group and a preparation method thereof, aiming at solving the problem that the service life of the existing perfluorosulfonic acid ionic polymer is shortened due to easy degradation under the attack of free radicals. In addition, the triazole structural unit introduced into the obtained polymer structure can regulate and control the Ion Exchange Capacity (IEC) of the PFSIs, so that the obtained PFSIs can simultaneously realize the aim of effectively regulating and controlling the IEC and chemical stability.
The invention also provides a proton membrane for a fuel cell, which is prepared from the perfluorosulfonic acid ionic polymer and has higher mechanical strength and thermal stability, and the ionic conductivity of the proton membrane can be regulated and controlled by introducing the functional triazole group into the structure of the proton membrane, so that the free radical can be effectively captured or quenched, the degradation of the proton membrane is weakened or slowed down, and the service life of the proton membrane is prolonged.
The invention also provides a membrane electrode, wherein the catalyst layer of the membrane electrode contains the perfluorinated sulfonic acid ionic polymer with the triazole group, so that free radicals can be effectively captured or quenched, the stability of the membrane electrode is improved, and the service life of the membrane electrode is prolonged.
In order to achieve the purpose, the invention adopts the following technical scheme:
1. the perfluorinated sulfonic acid ionic polymer with the triazole group has a molecular structural formula shown as a formula (I):
the macromolecular chain structure of the formula (I) comprises a unit (A) and a unit (B), wherein the unit (A) is a triazole structural unit, the unit (A) comprises a triazole group M and a perfluoroether structural unit, and the unit (B) comprises an ionic group-SO 3 H and a perfluoroether structural unit;
in the structure of the formula (I), m is an integer of 0-10, preferably, m is an integer of 1-3; n is an integer of 1 to 6, preferably, n is an integer of 1 to 3; further preferably, m =1,n =2;
in the structure of the formula (I), x is an integer of 1-30, and x + y/(x + y + z) = 0.05-0.8, preferably, x + y/(x + y + z) = 0.15-0.4; y/(y + z) =0.2 to 0.6, preferably, y/(y + z) =0.2 to 0.4;
the structural formula of the reagent for providing the triazole group M in the unit (A) is shown as a formula (II),
in the formula (II), R 1 ～R 9 The radicals are each-H, -NH 2 、-PhNH 2 、-Cl、-Br、-PhCOOH、-CH 3 -Ph (Ph represents a benzene ring), -O-CH 3 、-NO 2 Any one of the above;
R 1 ～R 9 in which at least one group contains-NH 2 The other groups are electron-withdrawing groups or electron-donating groups or-H, and the number of the electron-withdrawing groups is at most 3;
wherein the electron donating group of the above groups comprises: -NH 2 、-Ph、-PhNH 2 、-PhCOOH、-O-CH 3 、-CH 3 (ii) a Electron withdrawing groups including-Cl, -Br, -NO 2 ；
The electron-withdrawing ability of the electron-withdrawing group is in the order: -NO 2 ＞-Cl＞-Br。
In the invention, the electron-donating group is favorable for forming a conjugated system with the triazole group, can be combined with free radicals, and prolongs the service life of the perfluorinated ionic polymer.
Preferably, said R 1 ～R 9 containing-NH 2 A number of up to 3;
preferably, R 1 is-H, -NH 2 、-PhNH 2 、-Cl、-Br、-PhCOOH、-CH 3 -Ph (Ph represents a benzene ring) or-O-CH 3 ；
R 2 is-H, -NH 2 、-PhNH 2 -Cl, -PhCOOH or-CH 3 ；
R 3 is-H, -NH 2 、-PhNH 2 、-Br、-PhCOOH、-CH 3 or-Ph;
R 4 is-H, -NH 2 、-PhNH 2 、-Br、-PhCOOH、-CH 3 or-Ph;
R 5 is-H, -NH 2 、-PhNH 2 -Br or-CH 3 ；
R 6 is-H, -NH 2 、-PhNH 2 、-Cl、-Br、-CH 3 or-O-CH 3 ；
R 7 is-H, -NH 2 、-PhNH 2 、-Br、-CH 3 or-NO 2 ；
R 8 is-H, -NH 2 、-PhNH 2 、-Br、-CH 3 or-NO 2 ；
R 9 is-H, -NH 2 、-PhNH 2 、-Cl、-Br、-CH 3 or-Ph.
Further preferably, R 1 、R 2 Are each-NH 2 、-H、-PhNH 2 One of (1); r 3 、R 4 Are respectively-H, -NH 2 、 -PhNH 2 、-CH 3 One of (1); r is 5 、R 8 Are respectively-H, -NH 2 、-CH 3 One of (1); r is 6 、R 9 Are respectively-H, -NH 2 、 -PhNH 2 One of (a) and (b); r 7 is-H, -NH 2 、-NO 2 One of (a) and (b);
in at least one preferred embodiment of the present invention, R 1 is-NH 2 ，R 2 ～R 9 Are all-H.
The number average molecular weight of the perfluorosulfonic acid ionomer in the formula (i) is 20 to 100 ten thousand, preferably 20 to 60 ten thousand, and more preferably 30 to 50 ten thousand.
The perfluorosulfonic acid ionomer has the following advantages: retention of the predominant units- (CF) of the Perfluoropolymer hyperstabilization 2 CF 2 ) x Ensuring sufficient mechanical strength and thermal stability of the polymer; the PFSIs side chain end group is used for chemical grafting, and the introduced functional triazole structural unit can effectively capture or quench free radicals, so that the degradation of the polymer is weakened or slowed down; the perfluorinated ionic polymer synthesized by the method can meet the requirements of high Ion Exchange Capacity (IEC) and strong chemical stability, has wide applicability, and can synthesize PFSIs (polymer-modified silicate polymers) meeting various requirements of IEC and chemical stability by regulating the proportion of triazole structural units, namely the grafting rate;
2. the preparation method of the perfluorinated sulfonic acid ionic polymer with the triazole group comprises the following steps:
(1) Performing one-step grafting reaction on perfluorosulfonyl fluoride resin (III) and a reagent containing triazole group M in an organic solvent to synthesize an intermediate product (IV);
or pre-swelling the perfluorosulfonyl fluoride resin (III) in an organic solvent, and then carrying out a grafting reaction with a reagent containing a triazole group M to synthesize an intermediate product (IV);
the reaction formula is as follows:
(2) The intermediate product (IV) obtained in the step (1) is treated by alkali and acid in sequence to complete ion exchange, and unreacted sulfonyl fluoride group (-SO) 2 F) Conversion to perfluorosulfonic acid group (-SO) 3 H) Washing and drying to obtain the perfluorosulfonic acid ionic polymer (I) with triazole group, wherein the reaction formula is as follows:
preferably, the organic solvent in step (1) is at least one of N, N-dimethylformamide, N-dimethylacetamide, N-methylpyrrolidone, ethanol, isopropanol, dimethyl sulfoxide or ethyl acetate.
Preferably, in the structural formula (iii) of the perfluorosulfonyl fluoride resin polymer chain in the step (1), m =1 to 3, n =1 to 3,x is an integer of 1 to 15, and the number average molecular weight is 250000 to 500000; more preferably, m =1,n =2,x is 10, and the number average molecular weight is 350000 to 500000.
Preferably, the molar ratio of the perfluorosulfonyl fluororesin to the agent containing a triazole group M in the step (1) is 1:3 to 10.
Preferably, the mass-volume ratio of the perfluorosulfonyl fluororesin to the organic solvent in the step (1) is 1:1-30 g/mL; more preferably 1:1-20 g/mL; most preferably 1:1 to 10,g/mL.
Preferably, the grafting reaction temperature in step (1) is 15 to 150 ℃, more preferably 25 to 80 ℃, and the reaction time is 1 to 48 hours, more preferably 8 to 12 hours.
Preferably, the pre-swelling in step (1) is to swell the perfluorosulfonyl fluoride resin in an organic solvent at 40-80 ℃ for 60-100 min.
Preferably, in the step (2), the alkali is one of sodium hydroxide and potassium hydroxide, the concentration is 5 to 50wt%, and more preferably 15 to 40wt% of sodium hydroxide, the acid is one of hydrochloric acid, sulfuric acid and nitric acid, and the concentration is 5 to 50wt%, and more preferably 25 to 40wt% of sulfuric acid or nitric acid.
Preferably, the washing in the step (2) is washing with deionized water, and the drying is drying at 55-65 ℃ for 18-36 h.
The perfluorosulfonic acid ionic polymer (I) prepared by the method determines the Ion Exchange Capacity (IEC) and the proportion (grafting rate) of triazole structural units by acid-base titration. According to the product performance requirement, the grafting rate of the polymer can be regulated and controlled by regulating and controlling the reaction time and the reaction temperature in the step (1), so that the IEC of the perfluorosulfonic acid ionic polymer (I) and the proportion of the triazole structural unit can be regulated and controlled.
3. The use of the above perfluorosulfonic acid ionomer (i) having a triazole group in one or more of: 1) Use in the manufacture of an ion exchange membrane in a fuel cell or electrolyser; 2) The application of the super acid in chemical catalysis; 3) Use in electrodialysis; 4) The application in seawater desalination; 5) Use in gas separation; 6) The application in preparing membrane electrode for fuel cell; 7) The application in sewage treatment.
4. The invention also provides a proton membrane for a fuel cell, which comprises the perfluorinated sulfonic acid ionic polymer with the triazole group.
The structure of the proton membrane is selected from one of the following:
1) Proton membrane prepared from the perfluorinated sulfonic acid ionic polymer with triazole group;
2) The compound proton membrane is formed by the mixture of the perfluorinated sulfonic acid ionic polymer with the triazole group and the perfluorinated sulfonic acid polymer.
According to the invention, the ion exchange capacity of the proton membrane is preferably 0.9-1.25 mmol/g, the ionic conductivity is 50-200 mS/cm, the thermal degradation temperature is 280-320 ℃, and after a Fenton test for 200 hours, the retention rate of the ion exchange capacity is more than 94% and the retention rate of the ionic conductivity is more than 93%.
Preferably, the thickness of the proton membrane is 10 to 200 μm.
5. The preparation method of the proton membrane for the fuel cell comprises the following steps:
dissolving the perfluorinated sulfonic acid ionic polymer with the triazole group in an organic solvent to prepare a perfluorinated sulfonic acid ionic polymer solution, and directly preparing a proton membrane by using the perfluorinated sulfonic acid ionic polymer solution;
or adding the perfluorinated sulfonic acid ionic polymer serving as a free radical quenching agent into a conventional perfluorinated sulfonic acid resin solution to prepare a polymer composite solution, and preparing a composite proton membrane by using the polymer composite solution;
methods for preparing the proton membrane using the polymer solution include spin coating, screen printing, dip coating, ink jet printing, solution casting, spray pyrolysis, and the like, and the solution casting method is preferred.
Preferably, the concentration of the perfluorosulfonic acid ionomer solution is 2 to 35wt%, preferably 5 to 30wt%.
Preferably, the organic solvent is at least one of N, N-dimethylformamide, N-dimethylacetamide, N-methylpyrrolidone, ethanol, isopropanol, an ethanol/water mixed solvent, an isopropanol/water mixed solvent, dimethyl sulfoxide, or ethyl acetate.
Preferably, the volume ratio of ethanol to water in the perfluorosulfonic acid ionomer solution is 8-9:1-2, and the volume ratio of isopropanol to water is 8-9:1-2.
Preferably, the total concentration of the polymers in the polymer composite solution is 5 to 30%.
Preferably, the solution casting method comprises the steps of:
coating the perfluorinated sulfonic acid ionic polymer solution or the polymer composite solution on a quartz watch glass, pre-drying at 80-90 ℃, drying at 140-150 ℃ for 90-100 min, taking out and demoulding.
In the invention, when the proton membrane is prepared, the conductivity, the chemical stability and the service life of the proton membrane can be regulated and controlled by adjusting the mass fraction of the perfluorosulfonic acid ionic polymer with the triazole group according to the product performance requirement.
6. The invention also provides a membrane electrode for the anti-free radical fuel cell, wherein the catalyst mixture component of the catalyst layer of the membrane electrode comprises the perfluorinated sulfonic acid ionic polymer with the triazole group;
the membrane electrode for the anti-free radical fuel cell consists of an electrode layer and a proton membrane, wherein the electrode layer comprises a gas diffusion layer and a catalyst layer, the electrode layer is divided into a hydrogen electrode and an oxygen electrode, and the proton membrane is positioned between the hydrogen electrode and the oxygen electrode;
the proton membrane can be the proton membrane for the fuel cell or other conventional proton membranes for the fuel cell;
the membrane electrode has the duration time of more than 200h under the conditions that the open-circuit voltage is 0.9-1.2V, the relative humidity is 30% and the temperature is 90 ℃.
7. The preparation method of the membrane electrode for the anti-free radical fuel cell comprises the following steps:
(1) Dissolving the perfluorinated sulfonic acid ionic polymer with the triazole group in a water/alcohol mixed solvent to prepare a perfluorinated ionic polymer solution or adding the obtained perfluorinated ionic polymer solution into a conventional perfluorinated sulfonic acid resin solution to prepare a perfluorinated ionic polymer composite solution, then adding a Pt/C platinum-based catalyst into the perfluorinated ionic polymer solution or the perfluorinated ionic polymer composite solution, and performing ultrasonic treatment to obtain membrane electrode slurry;
(2) Spraying membrane electrode slurry onto the gas diffusion layer subjected to hydrophobic treatment by using a spray gun to form a catalyst layer, and performing heat treatment to obtain an electrode layer consisting of the gas diffusion layer and the catalyst layer, wherein the obtained electrode layer is divided into a hydrogen electrode and an oxygen electrode;
(3) And placing the hydrogen electrode and the oxygen electrode which are cut into proper sizes on the upper side and the lower side of the proton exchange membrane, aligning up and down, perfectly matching, and naturally cooling by hot pressing treatment of a press to obtain the membrane electrode.
The gas diffusion layer is composed of a substrate layer, which is mostly porous carbon paper or carbon cloth, and a microporous layer, which is usually composed of conductive carbon black and a water repellent. The base layer is composed of a carbon substrate which is porous and non-woven and has a macroporous structure, and the substrate is subjected to hydrophobic treatment by PTFE (polytetrafluoroethylene), and then is coated with a single-layer or multi-layer microporous layer (MPL) to form a porous structure with different pores.
Preferably, in the water/alcohol mixed solvent in the step (1), the alcohol is ethanol or isopropanol, and the volume ratio of the water to the alcohol is 1-2:8-9.
Preferably, the concentration of the perfluorosulfonic acid ionomer having a triazole group in the polymer composite solution in the step (1) is 5 to 15wt%.
Preferably, the ultrasonic time in the step (1) is 30-200 min.
Preferably, the platinum loading of the catalytic layer in the step (2) is 0.35-0.45mg/cm 2 。
Preferably, the gas diffusion layer in step (2) is carbon paper hydrophobically treated with PTFE.
Preferably, the heat treatment process in the step (2) is heat treatment at 80-130 ℃ for 30-200 min.
Preferably, the pressure of the hot pressing treatment of the press in the step (3) is 0.1-5 MPa, the hot pressing temperature is 80-140 ℃, and the duration is 30-150 s.
Preferably, the proton exchange membrane in step (3) may be the above-mentioned proton membrane for fuel cell of the present invention or other conventional proton membrane for fuel cell.
According to the invention, when the membrane electrode for the fuel cell is prepared, the chemical stability of the membrane electrode for the fuel cell can be regulated and controlled by regulating the proportion of the perfluorosulfonic acid ionic polymer with the triazole group according to the requirements of product performance, so that the service life of the membrane electrode for the fuel cell can be regulated and controlled.
One or more technical solutions provided by the embodiments of the present invention at least have the following technical effects:
(1) The molecular chain of the perfluorosulfonic acid ionic polymer with triazole group in the invention retains the ultrastable main chain- (CF) of the perfluoropolymer 2 CF 2 ) x -sufficient mechanical strength and thermal stability of the polymer can be ensured;
(2) The perfluorosulfonic acid ionic polymer molecular chain side chain with the triazole group contains the triazole group, so that free radicals can be effectively captured or quenched, the degradation of the polymer is weakened or slowed down, the chemical stability of the polymer is improved, and the service life of the polymer is prolonged;
(3) The invention can achieve the technical effects of regulating and controlling the ion exchange capacity, the chemical stability and the service life of the target polymer by regulating and controlling the grafting rate;
(4) The side chain of the polymer molecular chain forming the proton membrane is grafted with a triazole group, and the triazole group has the function of resisting the attack of free radicals, so that the degradation of the proton membrane can be weakened or slowed down, and the service life of the proton membrane is prolonged;
(5) The catalyst layer of the membrane electrode comprises perfluorosulfonic acid ionic polymer with triazole group, has higher capability of resisting attack of free radicals, and can prolong the service life of the membrane electrode.
Drawings
FIG. 1 is a graph of the infrared characterization results of the target product A1 in example 1.
FIG. 2 is a graph showing the retention of the electric conductivity of the proton membrane for a fuel cell in example 2 in 0 to 115 days.
FIG. 3 is a graph showing the IEC retention of the target product A2 in 0 to 115 days in example 1.
Detailed Description
The present invention is further illustrated by, but not limited to, the following examples.
It should be noted that the experimental methods described in the following examples are all conventional methods unless otherwise specified; the reagents, materials and equipment are commercially available, unless otherwise specified.
The target polymer and the perfluorosulfonic acid resin in the examples were subjected to a Fenton test, respectively, to accelerate oxidation of the target polymer and the perfluorosulfonic acid resin to examine their chemical stability, and the chemical stability of the polymer was evaluated by testing the IEC retention (RV%) of the polymer before and after the Fenton test.
Fenton test method: adding the ferrous ion solution to 30wt% 2 O 2 In solution of Fe 2+ Preparing a Fenton reagent with the concentration of 20ppm, immersing the object to be tested in the Fenton reagent in a water bath at 80 ℃, and testing the IEC of the polymer after soaking for a certain time, thereby judging the chemical stability of the polymer. In order to ensure the concentration of the hydroxyl free radical, the Fenton reagent needs to be replaced every 3 hours.
Titration of ion exchange capacity IEC: accurately weighing a certain weight of dry polymer resin, then treating the dry polymer resin in deionized water at 80 ℃ for 1h, carrying out ion exchange for more than 12h by using a NaCl aqueous solution with the concentration of about 1M, collecting the exchanged solution, taking phenolphthalein as an indicator, and titrating the solution by using 0.1M NaOH standard solution until the solution turns pink, wherein the IEC value of the polymer can be calculated according to the following formula:
IEC＝(V NaOH ×c NaOH )/m
in the formula:
V NaOH the volume of NaOH solution consumed, in mL,
c NaOH the molar concentration of the NaOH solution in mmol/mL,
m-mass of dry polymer resin in g.
Retention of ion exchange capacity IEC:
RV％＝(IEC 1 -IEC 0 )/IEC 0
in the formula:
IEC 1 and IEC 0 Respectively represents the ion exchange capacity of the target product after and before the Fenton experiment.
Proton membrane ion conductivity measurement: the proton membrane resistance R is tested by adopting a two-electrode method, an instrument is an electrochemical workstation Autolab PGSTA302, the frequency interval is 106Hz-10Hz, and the conductivity is calculated by a calculation formula:
σ＝L/RS
in the formula:
l is the thickness of the membrane (cm), R is the resistance of the membrane (Ω), σ is the conductivity of the sample (S/cm), and S is the area of the test portion of the sample (cm) 2 )。
Retention rate of proton membrane ion conductivity:
RV％＝(σ 1 -σ 0 )/σ 0
in the formula:
σ 0 and σ 1 Respectively represents the ionic conductivity of the proton membrane before and after the Fenton experiment.
Thermal degradation temperature (defined as the temperature at which the polymer degrades by 5%): the test was carried out using a thermogravimetric analyzer, TAQ50, N manufactured by Perkin Elmer, USA 2 And (3) atmosphere, wherein the heating speed is 10 ℃/min, the temperature range is 50-800 ℃, and the sample is dried for 24 hours at the temperature of 60 ℃ before testing.
And (3) testing the durability of the membrane electrode:
the durability or chemical stability of the membrane electrode coupons 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 H 2 Crossover is more than 10mA/cm 2 And ending the test.
Example 1
A long-life perfluorosulfonic acid polymer with triazole groups and a preparation method thereof are specifically prepared by the following steps:
4-amino-3,5-di-2-pyridyl-4H-1,2,4-triazole is selected as a reagent (R) with a triazole group 1 is-NH 2 ，R 2 -R 9 All H) and perfluorovinyl sulfonyl fluoride resin (m =1, n =2, the number average molecular weight is 42 ten thousand, and the value of x is 10) to synthesize a target product, and the specific steps are as follows:
(1) Cleaning a 150mL reaction kettle, adding 30g of perfluorovinyl sulfonyl fluoride resin into 50mL of N, N-dimethylformamide, starting a stirring device, heating to 60 ℃, swelling for 60min in advance, vacuumizingAfter being replaced by high-purity nitrogen gas by air filling for three times, 0.15g of 4-amino-3,5-di-2-pyridyl-4H-1,2,4-triazole is added, after the mixture is completely dissolved, the mixture is slowly heated to 80 ℃ to react, and the molar ratio of the perfluorovinyl sulfonyl fluororesin to the 4-amino-3,5-di-2-pyridyl-4H-1,2,4-triazole is about 1. Under mechanical stirring at 80 ℃ (N) 2 Environment) reflux reaction for 10H, cooling to room temperature, washing the filtered product for multiple times by using ethanol and deionized water to remove unreacted 4-amino-3,5-di-2-pyridyl-4H-1,2,4-triazole, and drying to obtain an intermediate product, which is marked as A1, wherein the reaction formula is as follows:
the intermediate product A1 was subjected to infrared transmission spectrum measurement, and the measurement results are shown in FIG. 1, after the reaction, A1 still retains the sulfonyl fluoride group (-SO) in the perfluorosulfonyl fluororesin 2 F) The characteristic peak is 1467cm -1 Nearby, the characteristic peaks of C = N double bond, S-N bond of connecting group and N-H bond in triazole structural unit appear simultaneously, and the characteristic peaks are respectively 1670cm -1 、1398cm -1 And 3500cm -1 Nearby; the infrared result proves that the intermediate product A1 is successfully synthesized;
(2) The intermediate product A1 obtained in the step (1) is respectively treated by 30wt% of sodium hydroxide and 25wt% of sulfuric acid to complete ion exchange, and unreacted sulfonyl fluoride group (-SO) 2 F) All converted to perfluorosulfonic acid groups (-SO) 3 H) And washing the product for multiple times by deionized water, drying for 24h at 60 ℃ to obtain a target product, which is marked as A2, wherein the ion exchange capacity can be determined by titration, and the reaction formula is as follows:
the stability of the target product A2 is tested by a Fenton test, and the result is shown in figure 3, after 115 days of a free radical decay test, the retention rate of the Ion Exchange Capacity (IEC) is up to more than 90%, which proves that the obtained perfluorosulfonic acid ionomer has higher capability of resisting the attack of free radicals, and the service life of the perfluorosulfonic acid ionomer can be effectively prolonged.
Through Fourier transform infrared spectroscopy and IEC determination, y/(y + z) =0.28 in the obtained A2 high molecular structure, and the IEC of the obtained target product A2 is 1.06mmol/g.
Example 2
A proton membrane for fuel cell and its preparation method, the preparation step is as follows:
the target product A2 prepared in example 1 is dissolved in N, N-dimethylformamide to prepare a 15wt% polymer solution, then the solution is coated on a clean and smooth quartz surface dish, pre-dried at 80 ℃, placed in an oven at 145 ℃ for drying for 90 minutes, taken out and demoulded to prepare the long-life perfluorosulfonic acid proton membrane.
The ion exchange capacity IEC of the proton membrane was determined by titration to be 1.06mmol/g.
The ionic conductivity of the proton membrane in deionized water at 25 ℃ is 80mS/cm, and the conductivity is measured under the condition.
The stability of the proton membrane is tested by a Fenton test, and the result is shown in figure 2, after the proton membrane is tested for 115 days by a free radical decay test, the retention rate of the ionic conductivity is up to more than 90%, which proves that the obtained proton membrane has higher capability of resisting the attack of free radicals, and the service life of the proton membrane can be effectively prolonged.
Example 3
A perfluorosulfonic acid ionic polymer with triazole group and a preparation method thereof, the specific preparation method is as follows:
4-amino-3,5-di-2-pyridyl-4H-1,2,4-triazole is selected as a reagent (R) with a triazole group 1 -NH 2 ，R 2 -R 9 All of which are-H) and perfluorovinyl sulfonyl fluoride resin (m =0, n =2, number average molecular weight 42 ten thousand, x value is 8) to synthesize a target product, and the specific steps are as follows:
(1) Cleaning a 150mL reaction kettle, adding 10mL of N, N-dimethylformamide, starting a stirring device, vacuumizing, filling high-purity nitrogen for three times, and adding 0.15g of 4-amino-3,5-di-2-pyridinepyridine-4H-1,2,4-triazole, slowly heated to 80 ℃, after it is completely dissolved, 30g perfluorovinylsulfonyl fluoride resin is added, and the molar ratio of perfluorovinylsulfonyl fluoride resin to 4-amino-3,5-bis-2-pyridyl-4H-1,2,4-triazole is about 1. Under mechanical stirring at 80 ℃ (N) 2 Environment) reflux reaction for 24 hours, cooling to room temperature, washing the filtered product for multiple times by using ethanol and deionized water to remove unreacted 4-amino-3,5-di-2-pyridyl-4H-1,2,4-triazole, and drying to obtain an intermediate product, which is marked as A3, wherein the reaction formula is as follows:
(2) The intermediate product A3 obtained in the step (1) is treated by 30wt% of sodium hydroxide and 25wt% of sulfuric acid respectively to complete ion exchange, and unreacted sulfonyl fluoride group (-SO) 2 F) All converted to perfluorosulfonic acid groups (-SO) 3 H) The product is washed by deionized water for many times, dried for 24 hours at 60 ℃ to obtain a target product, marked as A4, the ion exchange capacity of the target product can be determined by titration, and the reaction process is as follows:
according to IEC determination, y/(y + z) =0.30 in the macromolecular structure of the obtained A4, and the IEC of the obtained A4 polymer is 1.26mmol/g.
Example 4
A proton membrane for fuel cell and its preparation method, the concrete preparation step is as follows:
the target product A4 obtained in example 3 is dissolved in an isopropanol/water (volume ratio = 8:2) mixed solvent to prepare a 20wt% perfluorosulfonic acid ionomer solution, then the solution is coated on a clean and smooth quartz surface dish, the dish is pre-dried at 80 ℃, then the dish is placed in an oven at 145 ℃ for drying for 90 minutes, and the dish is taken out and demoulded to prepare the long-life perfluorosulfonic acid proton membrane. The ionic conductivity of the proton membrane was 105mS/cm.
The ion exchange capacity IEC of the proton membrane was determined by titration to be 1.26mmol/g.
Example 5
A perfluorosulfonic acid ionic polymer with triazole group and a preparation method thereof, the specific implementation mode is as follows:
4-amino-3,5-di-2-pyridyl-4H-1,2,4-triazole is selected as a reagent (R) with a triazole group 1 -NH 2 ，R 2 -R 9 all-H) and perfluorovinyl sulfonyl fluoride resin (m =0, n =4, number average molecular weight 42 ten thousand, x value is 10) to synthesize a target product, and the specific experimental steps are as follows:
(1) After a 150mL reaction kettle is cleaned, 100mL of N, N-dimethylacetamide is added, a stirring device is started, the reaction kettle is vacuumized and filled with high-purity nitrogen for three times to replace, 0.15g of 4-amino-3,5-di-2-pyridyl-4H-1,2,4-triazole is added, after the reaction kettle is slowly heated to 80 ℃, 30g of perfluorovinyl sulfonyl fluoride resin is added after the reaction kettle is completely dissolved, and the molar ratio of the perfluorovinyl sulfonyl fluoride resin to 4-amino-3,5-di-2-pyridyl-4H-1,2,4-triazole is about 1. Under mechanical stirring at 80 ℃ (N) 2 Environment) reflux reaction for 30H, cooling to room temperature, washing the filtered product with ethanol and deionized water for multiple times to remove unreacted 4-amino-3,5-di-2-pyridyl-4H-1,2,4-triazole, drying to obtain an intermediate product, which is marked as A5, wherein the reaction process is as follows:
(2) The intermediate product A5 obtained in the step (1) is treated by 30wt% of sodium hydroxide and 25wt% of sulfuric acid respectively to complete ion exchange, and unreacted sulfonyl fluoride groups (-SO) 2 F) All converted to perfluorosulfonic acid groups (-SO) 3 H) The product is washed by deionized water for many times, dried for 24 hours at 60 ℃ to obtain a target product, marked as A6, the ion exchange capacity of the target product can be determined by titration, and the reaction process is as follows:
through the determination of an infrared spectrogram and IEC, the IEC of the obtained target product A6 is 1.16mmol/g, and y/(y + z) =0.32 in the obtained A6 macromolecular structure.
Example 6
A proton membrane for fuel cell and its preparation method, the concrete preparation step is as follows:
the target product A6 prepared in example 5 was dissolved in a mixed solvent of ethanol/water (volume ratio = 9:1) to prepare a 15wt% polymer solution, and then the solution was coated on a clean and smooth quartz surface dish, pre-dried at 80 ℃, placed in an oven at 145 ℃ for drying for 90 minutes, taken out and demolded to prepare a long-life perfluorosulfonic acid proton membrane. The ionic conductivity of the proton membrane is 90 mS/cm.
The ion exchange capacity IEC of the proton membrane was determined by titration to be 1.16mmol/g.
Example 7
A fuel cell composite proton membrane of perfluorosulfonic acid polymer with triazole group and a preparation method thereof comprise the following steps:
(1) The target product A2 obtained in example 1 was dissolved in an isopropanol/water (volume ratio = 8:2) mixed solvent to prepare a 20wt% polymer solution A7.
(2) A perfluorosulfonic acid resin (V) (the number average molecular weight of which is 40 ten thousand, the ion exchange capacity of which is 0.95mmol/g, the structural formula of which is shown in the specification, and the value of a is 10) is taken and dissolved in an isopropanol/water (volume ratio = 8:2) mixed solvent to prepare a 20wt% polymer solution A8.
(3) Adding the solution A7 into the solution A8, and uniformly mixing in a mechanical stirring manner, wherein the mass ratio of the solution A7 to the solution A is 1:9. And coating the obtained mixed solution on a clean and smooth quartz surface dish, pre-drying at 80 ℃, placing in an oven at 145 ℃ for drying for 90 minutes, taking out, and demolding to prepare the long-life perfluorosulfonic acid composite proton membrane.
The Ion Exchange Capacity (IEC) of the obtained composite proton membrane is determined to be 0.96mmol/g; the ionic conductivity of the composite proton membrane is 65mS/cm.
In the composite proton membrane, the mass fraction of the perfluorosulfonic acid ionomer A2 is 10%.
Example 8
A fuel cell composite proton membrane of perfluorosulfonic acid polymer with triazole group and a preparation method thereof comprise the following steps:
(1) The target product A2 obtained in example 1 was dissolved in an isopropyl alcohol/water (volume ratio = 8:2) mixed solvent to prepare a 20wt% polymer solution A9.
(2) The perfluorosulfonic acid resin (v) in example 7 was dissolved in a mixed solvent of isopropyl alcohol/water (volume ratio = 8:2) to prepare a 20wt% polymer solution a10.
(3) Adding the solution A9 into the solution A10, and uniformly mixing the solution A and the solution A in a mechanical stirring manner, wherein the mass ratio of the solution A to the solution A is 3:7; and coating the obtained mixed solution on a clean and smooth quartz surface dish, pre-drying at 80 ℃, placing in an oven at 145 ℃ for drying for 90 minutes, taking out, and demolding to prepare the long-life perfluorosulfonic acid composite proton membrane.
The Ion Exchange Capacity (IEC) of the composite proton membrane was determined to be 0.98mmol/g by IEC.
The ionic conductivity of the composite proton membrane is 75mS/cm.
In the composite proton membrane, the mass fraction of the perfluorosulfonic acid ionic polymer A2 is 30%.
Example 9
The preparation process of membrane electrode for free radical resisting fuel cell includes the following steps:
(1) Dissolving the resin (V) in example 7 in a water/isopropanol (volume ratio of 2:8) mixed solvent to prepare a 5wt% perfluorosulfonic acid resin solution, adding the target product A2 polymer in example 1 to prepare a mixed solution, adding 10mL of the mixed solution into a Pt/C catalyst, and performing ultrasonic treatment for 150min to obtain membrane electrode slurry, wherein the mass fraction of the polymer in the obtained slurry is 5%, and the mass ratio of A2 to V in the polymer is 3:7;
(2) Coating the perfluorinated sulfonic acid resin solution in the step (1) on a clean and smooth quartz surface dish, pre-drying at 80 ℃, placing the coated film in an oven at 145 ℃ for drying for 90 minutes, taking out the coated film and demoulding to prepare a proton membrane;
(3) Spraying the membrane electrode slurry obtained in the step (1) onto a gas diffusion layer which is subjected to hydrophobic treatment and is 2cm multiplied by 2cm by using a spray gun to form a catalytic layer, and carrying out heat treatment at 130 ℃ for 90min, wherein the platinum loading capacity on the surface of the catalytic layer is 0.4mg/cm 2 Obtaining an electrode layer consisting of a gas diffusion layer and a catalyst layer, wherein the obtained electrode layer is divided into a hydrogen electrode and an oxygen electrode;
(4) And (3) placing the hydrogen electrode and the oxygen electrode which are cut into proper sizes on the upper side and the lower side of the proton membrane (3 cm multiplied by 3 cm) in the step (2), aligning up and down, perfectly matching, performing hot pressing treatment by a press at the pressure of 0.8MPa and the hot pressing temperature of 140 ℃ for 60s, opening the press, naturally cooling, and taking out the prepared membrane electrode for the fuel cell.
Example 10
The preparation process of composite membrane electrode for free radical resisting fuel cell includes the following steps:
(1) Dissolving the perfluorosulfonic acid resin V in example 7 in a water/isopropanol (volume ratio of 2:8) mixed solvent to prepare a 5wt% perfluorosulfonic acid resin solution, then adding the target product A2 polymer in example 1 to prepare a mixed solution, adding 10mL of the mixed solution into a Pt/C catalyst, and performing ultrasonic treatment for 150min to obtain a membrane electrode slurry, wherein the mass fraction of the polymer in the membrane electrode slurry is 5%, and the mass ratio of A2 to V in the polymer is 3:7.
(2) Coating the mixed solution in the step (1) on a clean and smooth quartz surface dish, pre-drying at 80 ℃, then placing in an oven at 145 ℃ for drying for 90 minutes, taking out and demoulding to prepare a composite proton membrane;
(3) Spraying the membrane electrode slurry obtained in the step (1) onto a gas diffusion layer (2 cm multiplied by 2 cm) subjected to hydrophobic treatment by using a spray gun to form a catalytic layer, and carrying out heat treatment at 130 ℃ for 90min, wherein the platinum loading capacity on the surface of the catalytic layer is 0.4mg/cm 2 Obtaining an electrode layer consisting of a gas diffusion layer and a catalyst layer, wherein the obtained electrode layer is divided into a hydrogen electrode and an oxygen electrode;
(4) And (3) placing the hydrogen electrode and the oxygen electrode which are cut into proper sizes on the upper side and the lower side of the composite proton membrane (3 cm multiplied by 3 cm) in the step (2), aligning up and down, perfectly matching, performing hot pressing treatment by a press at the pressure of 0.8MPa and the hot pressing temperature of 140 ℃ for 60s, opening the press, naturally cooling, and taking out the prepared composite membrane electrode for the fuel cell.
Comparative example 1
The proton membrane is prepared by taking unmodified perfluorosulfonic acid resin (V) as a raw material, and comprises the following specific steps:
the perfluorosulfonic acid resin (V) in example 7 is taken and dissolved in isopropanol/water (volume ratio = 8:2) mixed solvent to prepare 20wt% perfluorosulfonic acid resin solution, no additive is added, the obtained solution is coated on a clean and smooth quartz surface dish, the solution is pre-dried at 80 ℃, then the dish is placed in an oven at 145 ℃ for drying for 90 minutes, and the membrane is taken out and demoulded to prepare the unmodified perfluorosulfonic acid proton membrane.
The IEC determination shows that the obtained proton membrane has the IEC of 0.95mmol/g and the ionic conductivity of 60mS/cm.
Comparative example 2
The membrane electrode is prepared by taking unmodified perfluorosulfonic acid resin (V) as a raw material, and the method comprises the following specific steps:
(1) The perfluorosulfonic acid resin (V) in example 7 was dissolved in isopropanol/water (volume ratio 8:2) mixed solvent to prepare a 5wt% perfluorosulfonic acid resin solution, 10mL of the 5wt% perfluorosulfonic acid resin solution was added to a Pt/C catalyst, and membrane electrode slurry was obtained by sonication for 100min, wherein the polymer mass fraction in the slurry was 5%.
(2) Coating 5wt% of perfluorosulfonic acid resin solution obtained in the step (1) on a clean and smooth quartz surface dish, pre-drying at 80 ℃, placing in a drying oven at 145 ℃ for drying for 80 minutes, taking out, and demolding to prepare an unmodified perfluorosulfonic acid proton membrane;
(3) Spraying the membrane electrode slurry obtained in the step (1) onto a gas diffusion layer which is subjected to hydrophobic treatment and is 2cm multiplied by 2cm by using a spray gun to form a catalytic layer, and performing heat treatment at 130 ℃ for 90min, wherein the platinum loading capacity on the surface of the catalytic layer is 0.4mg/cm 2 Obtaining an electrode layer consisting of a gas diffusion layer and a catalyst layer, the obtained electrode layer being divided into a hydrogen electrode and an oxygen electrodeA pole;
(4) And (3) placing the hydrogen electrode and the oxygen electrode which are cut into proper sizes on the upper side and the lower side of the proton membrane (3 cm multiplied by 3 cm) in the step (2), aligning up and down, perfectly matching, performing hot pressing treatment by a press at the pressure of 0.8MPa and the hot pressing temperature of 140 ℃ for 60s, opening the press, naturally cooling, and taking out the obtained unmodified membrane electrode.
Comparative example 3
A proton membrane for fuel cell and a membrane electrode for anti-free radical type fuel cell are prepared, which comprises the following steps:
directly adding 4-amino-3,5-di-2-pyridyl-4H-1,2,4-triazole as an additive into a perfluorosulfonic acid polymer solution A8, wherein the molar ratio of 4-amino-3,5-di-2-pyridyl-4H-1,2,4-triazole to perfluorosulfonic acid polymer in the mixed solution is about 1.8, coating the obtained mixed solution on a clean and smooth quartz surface dish, pre-drying at 80 ℃, placing in an oven at 145 ℃ for drying for 90 minutes, taking out and demolding to prepare the proton membrane for the fuel cell, wherein the mass content of the additive is 0.5%. The Ion Exchange Capacity (IEC) of the resulting composite proton membrane was determined to be 0.90mmol/g. The ionic conductivity of the composite proton membrane at room temperature (25 ℃) is 50.5mS/cm. Membrane electrode preparation and performance testing were performed using the proton membrane described above with reference to comparative example 2.
The perfluor sulfonic acid ionic polymer, the proton membrane and the membrane electrode which are prepared are subjected to performance tests, and the results are shown in tables 1 to 3:
TABLE 1 results of chemical stability test of perfluorosulfonic acid ionomer having triazole group and unmodified perfluorosulfonic acid polymer
As can be seen from Table 1, after the perfluoroionic polymer prepared by the method is tested by a Fenton test for 200 hours, the IEC of the perfluoroionic polymer is more than 94%, and the thermal degradation temperature of the perfluoroionic polymer is more than 290 ℃, so that the IEC retention rate and the thermal degradation temperature of the perfluoroionic polymer are obviously improved compared with those of an unmodified perfluorosulfonic acid polymer. The perfluorosulfonic acid ionic polymer with the triazole group prepared by the invention has higher chemical stability, reduces or slows down the degradation of the polymer, and has sufficient mechanical strength and thermal stability.
TABLE 2 Performance test results of proton membranes
As can be seen from Table 2, after the proton membrane prepared by the perfluorosulfonic acid ionic polymer with triazole groups is tested by a Fenton test for 200 hours, the retention rate of ionic conductivity is over 94%, and the thermal degradation temperature of the proton membrane is over 290 ℃; after a Fenton test is carried out for 200 hours, the retention rates of ionic conductivity of the composite proton exchange membrane prepared from the perfluorosulfonic acid ionic polymer with the triazole group are all over 95%, and the thermal degradation temperature of the composite proton exchange membrane is all over 280 ℃; compared with proton membranes (comparative examples 1 and 3) prepared from the unmodified perfluorosulfonic acid resin, the proton membrane provided by the invention has the advantages that the chemical stability and the thermal stability are obviously improved, and the service life of the proton membrane is effectively prolonged.
TABLE 3 Performance test results of Membrane electrode
As can be seen from Table 3, the membrane electrode prepared from the perfluoroionic polymer having triazole groups of the present invention has a duration of 200 hours or more at Open Circuit Voltage (OCV), 30% Relative Humidity (RH) and 90 ℃ while the membrane electrode prepared from the perfluorosulfonic acid resin without modification treatment (comparative example 2) has a duration of 95.3 hours, and the membrane electrode prepared by directly adding 4-amino-3,5-di-2-pyridyl-4H-1,2,4-triazole to the conventional perfluorosulfonic acid polymer has a duration of 82.5 hours. The durability of the membrane electrode prepared by the invention is greatly improved.
Claims (10)
1. The perfluorinated sulfonic acid ionic polymer with the triazole group is characterized in that the molecular structural formula of the polymer is shown as the formula (I):
wherein, the structure of the formula (I) comprises a unit (A) and a unit (B), the unit (A) is a triazole structural unit, the unit (A) comprises a triazole group M and a perfluoroether structural unit, and the unit (B) comprises an ionic group-SO 3 H and a perfluoroether structural unit;
in the structure of the formula (I), m is an integer of 0-10, and n is an integer of 1-6;
in the structure of the formula (I), x is an integer of 1-30, x + y/(x + y + z) = 0.05-0.8, y/(y + z) = 0.2-0.6;
the number average molecular weight of the perfluorinated sulfonic acid ionic polymer in the formula (I) is 20-100 ten thousand;
the structural formula of the reagent for providing the triazole group M in the unit (A) is shown as a formula (II),
wherein, R is 1 ～R 9 The radicals are each-H, -NH 2 、-PhNH 2 、-Cl、-Br、-PhCOOH、-CH 3 -Ph (Ph represents a benzene ring), -O-CH 3 、-NO 2 Any one of them.
2. The polymer according to claim 1, wherein m is an integer of 1 to 3, n is an integer of 1 to 3, x + y/(x + y + z) =0.15 to 0.4, y/(y + z) =0.2 to 0.4, and the number average molecular weight of the perfluorosulfonic acid ionomer in the formula (i) is 20 to 60 ten thousand; preferably, m =1,n =2, and the number average molecular weight of the perfluorosulfonic acid ionomer in the formula (i) is 30 to 50 ten thousand.
3. The polymer of claim 1, wherein R is of formula (II) 1 ～R 9 In the radical, 1 is less than or equal to-NH 2 The number is less than or equal to 3, and the number of the electron-withdrawing groups is less than or equal to 3.
4. The polymer of claim 3, wherein R is 1 is-H, -NH 2 、-PhNH 2 、-Cl、-Br、-PhCOOH、-CH 3 -Ph or-O-CH 3 ；
R 2 is-H, -NH 2 、-PhNH 2 -Cl, -PhCOOH or-CH 3 ；
R 3 is-H, -NH 2 、-PhNH 2 、-Br、-PhCOOH、-CH 3 or-Ph;
R 4 is-H, -NH 2 、-PhNH 2 、-Br、-PhCOOH、-CH 3 or-Ph;
R 5 is-H, -NH 2 、-PhNH 2 -Br or-CH 3 ；
R 6 is-H, -NH 2 、-PhNH 2 、-Cl、-Br、-CH 3 or-O-CH 3 ；
R 7 is-H, -NH 2 、-PhNH 2 、-Br、-CH 3 or-NO 2 ；
R 8 is-H, -NH 2 、-PhNH 2 、-Br、-CH 3 or-NO 2 ；
R 9 is-H, -NH 2 、-PhNH 2 、-Cl、-Br、-CH 3 or-Ph;
preferably, R 1 、R 2 Are each independently-NH 2 、-H、-PhNH 2 One of (1); r 3 、R 4 Each independently is-NH 2 、-H、-PhNH 2 、-CH 3 One of (1); r is 5 、R 8 Independently of one another are-H, -NH 2 、-CH 3 One of (1); r 6 、R 9 Independently of one another are-H, -NH 2 、-PhNH 2 One of (a) and (b); r 7 is-H, -NH 2 、-NO 2 One of (1);
further preferably, R 1 is-NH 2 ，R 2 ～R 9 Are all-H.
5. A process for the preparation of a polymer according to any one of claims 1 to 4, comprising the steps of:
(1) Selecting perfluorosulfonyl fluoride resin (III) and a reagent containing triazole group M to perform one-step graft reaction in an organic solvent to synthesize an intermediate product (IV);
or pre-swelling the perfluorosulfonyl fluoride resin (III) in an organic solvent, and then carrying out a grafting reaction with a reagent containing a triazole group M to synthesize an intermediate product (IV);
the reaction formula is as follows:
(2) The intermediate product (IV) obtained in the step (1) is treated by alkali and acid in sequence to complete ion exchange, and unreacted sulfonyl fluoride groups (-SO) 2 F) Conversion to perfluorosulfonic acid group (-SO) 3 H) Washing and drying to obtain the perfluorosulfonic acid ionic polymer (I) with triazole group, wherein the reaction formula is as follows:
6. the method for producing a polymer according to claim 5, wherein in the structural formula (III) of the perfluorosulfonyl fluoride resin polymer chain in the step (1), m =1 to 3,n =1 to 3,x is an integer of 1 to 15, and the number average molecular weight is 250000 to 500000; more preferably, m =1,n =2,x is 10, and the number average molecular weight is 350000 to 500000;
the organic solvent in the step (1) is at least one of N, N-dimethylformamide, N-dimethylacetamide, N-methylpyrrolidone, ethanol, isopropanol, dimethyl sulfoxide or ethyl acetate;
the molar ratio of the perfluorosulfonyl fluororesin to the reagent containing the triazole group M in the step (1) is 1:3-10;
the mass-volume ratio of the perfluorosulfonyl fluororesin to the organic solvent in the step (1) is 1:1-30 g/mL; preferably 1:1-20 g/mL; most preferably 1:1-10 g/mL;
in the step (1), the grafting reaction temperature is 15-150 ℃, the preferable temperature is 25-80 ℃, and the reaction time is 1-48 hours, the preferable time is 8-12 hours;
the pre-swelling in the step (1) is to swell the perfluorosulfonyl fluoride resin in an organic solvent for 60 to 100min at a temperature of between 40 and 50 ℃.
7. The method for preparing the polymer according to claim 5, wherein the base in step (2) is one of sodium hydroxide and potassium hydroxide, the concentration is 5 to 50wt%, preferably 15 to 40wt% of sodium hydroxide, the acid is one of hydrochloric acid, sulfuric acid and nitric acid, the concentration is 5 to 50wt%, preferably 25 to 40wt% of sulfuric acid and nitric acid;
in the step (2), deionized water is adopted for washing, and the drying is carried out at 55-65 ℃ for 18-36 h.
8. Use of a polymer as claimed in any one of claims 1 to 5 in one or more of: 1) Use in the manufacture of an ion exchange membrane in a fuel cell or electrolyser; 2) The application of the super acid in chemical catalysis; 3) Use in electrodialysis; 4) The application in seawater desalination; 5) Use in gas separation; 6) The application in preparing membrane electrode for fuel cell; 7) The application in sewage treatment.
9. A perfluorosulfonic proton membrane made with the polymer of any one of claims 1-5.
10. A membrane electrode for a radical scavenging fuel cell prepared from the polymer according to any one of claims 1 to 5.
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