CN115881996A - Perfluoro ionic polymer with phenanthroline side group, synthetic method thereof, proton exchange membrane and membrane electrode for fuel cell - Google Patents
Perfluoro ionic polymer with phenanthroline side group, synthetic method thereof, proton exchange membrane and membrane electrode for fuel cell Download PDFInfo
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- CN115881996A CN115881996A CN202111300402.XA CN202111300402A CN115881996A CN 115881996 A CN115881996 A CN 115881996A CN 202111300402 A CN202111300402 A CN 202111300402A CN 115881996 A CN115881996 A CN 115881996A
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- 239000012528 membrane Substances 0.000 title claims abstract description 163
- DGEZNRSVGBDHLK-UHFFFAOYSA-N [1,10]phenanthroline Chemical compound C1=CN=C2C3=NC=CC=C3C=CC2=C1 DGEZNRSVGBDHLK-UHFFFAOYSA-N 0.000 title claims abstract description 55
- 239000000446 fuel Substances 0.000 title claims abstract description 51
- 229920000831 ionic polymer Polymers 0.000 title claims abstract description 46
- -1 Perfluoro Chemical group 0.000 title claims description 13
- 238000010189 synthetic method Methods 0.000 title abstract description 4
- 229920000642 polymer Polymers 0.000 claims abstract description 95
- 238000005342 ion exchange Methods 0.000 claims abstract description 40
- 239000000126 substance Substances 0.000 claims abstract description 37
- OBTWBSRJZRCYQV-UHFFFAOYSA-N sulfuryl difluoride Chemical class FS(F)(=O)=O OBTWBSRJZRCYQV-UHFFFAOYSA-N 0.000 claims abstract description 23
- 239000011347 resin Substances 0.000 claims abstract description 16
- 229920005989 resin Polymers 0.000 claims abstract description 16
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 42
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 37
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 32
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 32
- 238000001035 drying Methods 0.000 claims description 31
- 238000006243 chemical reaction Methods 0.000 claims description 28
- UQSQSQZYBQSBJZ-UHFFFAOYSA-N fluorosulfonic acid Chemical group OS(F)(=O)=O UQSQSQZYBQSBJZ-UHFFFAOYSA-N 0.000 claims description 28
- 238000000034 method Methods 0.000 claims description 28
- 239000003054 catalyst Substances 0.000 claims description 21
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 18
- 238000011282 treatment Methods 0.000 claims description 16
- 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
- 239000003153 chemical reaction reagent Substances 0.000 claims description 12
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- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 9
- 239000008367 deionised water Substances 0.000 claims description 8
- 229910021641 deionized water Inorganic materials 0.000 claims description 8
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical group C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 6
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- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 4
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- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 3
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- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 19
- 239000001257 hydrogen Substances 0.000 description 19
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 18
- 229910052760 oxygen Inorganic materials 0.000 description 18
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- 150000003460 sulfonic acids Chemical class 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
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- 125000000542 sulfonic acid group Chemical group 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
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- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 229910000420 cerium oxide Inorganic materials 0.000 description 2
- 238000002144 chemical decomposition reaction Methods 0.000 description 2
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- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 2
- KJFMBFZCATUALV-UHFFFAOYSA-N phenolphthalein Chemical compound C1=CC(O)=CC=C1C1(C=2C=CC(O)=CC=2)C2=CC=CC=C2C(=O)O1 KJFMBFZCATUALV-UHFFFAOYSA-N 0.000 description 2
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- 238000001308 synthesis method Methods 0.000 description 2
- 229910052684 Cerium Inorganic materials 0.000 description 1
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 1
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical group C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 1
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- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 1
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- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
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- 125000002943 quinolinyl group Chemical group N1=C(C=CC2=CC=CC=C12)* 0.000 description 1
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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 relates to a perfluorinated ion polymer with a phenanthroline side group, a synthetic method thereof, a proton exchange membrane and a membrane electrode for a fuel cell. The perfluorinated ionic polymer provided by the invention retains the structural advantages of perfluorinated sulfonyl fluoride resin in the chemical structure, and introduces a structural phenanthroline structural unit for capturing or quenching free radicals in the structure by adopting a chemical grafting mode, so that the purpose of resisting free radical attack can be fundamentally realized from the polymer, the degradation of the polymer is effectively weakened, and the chemical stability of the perfluorinated ionic polymer is improved. In addition, the phenanthroline structural unit introduced into the structure of the obtained perfluorinated ion polymer can regulate and control the ion exchange capacity of the perfluorinated ion polymer, and the obtained perfluorinated ion polymer can simultaneously achieve the purpose of effectively regulating and controlling the ion exchange capacity and the chemical stability. The invention also provides a proton exchange membrane for the fuel cell and a membrane electrode for the anti-free radical type fuel cell, which have longer service life.
Description
Technical Field
The invention belongs to the technical field of fluorine-containing high polymer materials, and particularly relates to a perfluorinated ion polymer with a phenanthroline side group, a synthetic method of the perfluorinated ion polymer, a proton exchange membrane and a membrane electrode for a fuel cell.
Background
The perfluorinated ion polymer has an ultra-stable perfluorinated main chain skeleton- (CF) 2 CF 2 )m-(CF 2 CF) n-with the side chain often being a sulfonic acid group (-SO) 3 H) The perfluoro ether structure is an end group, thereby endowing the polymer with higher chemical stability and good thermal stability. The perfluorinated ion polymer is a high molecular functional material capable of conducting and exchanging ion groups, and one of important applications is to prepare an ion exchange membrane for the field of proton exchange membrane fuel cells.
The proton exchange membrane fuel cell is an electrochemical device with high energy conversion efficiency, is environment-friendly, and the only product in the energy conversion process is water (the total reaction equation can be summarized as 2H) 2 +O 2 ＝2H 2 O), can avoid causing environmental pollution, and is an efficient and environment-friendly energy conversion device. The proton exchange membrane fuel cell has the distinct advantages in new energy transportation, industrial engineering, household home, mobile equipment and military and civilian industriesThe method has encouraging application prospect in aspects of use and the like. The Proton Exchange Membrane (PEM) is the core component of a Proton Exchange Membrane Fuel Cell (PEMFC) and serves both as a separator to separate fuel and oxidant, preventing them from reacting directly, and as an electrolyte to conduct protons. The proton exchange membrane widely applied at present is a perfluorosulfonic acid polymer proton exchange membrane, and the molecular structure of the proton exchange membrane comprises a perfluorosulfonic acid main chain skeleton- (CF) 2 CF 2 )m-(CF 2 CF) n-, and with a sulfonic acid group (-SO) 3 H) A perfluoroether structure side chain which is a terminal group. Besides the ionic conductivity of the ion exchange membrane prepared from the perfluorinated ionic polymer, the chemical stability of the perfluorinated ionic polymer, which is a key material of the clean energy technology, is one of the factors that must be considered, because the chemical stability of the perfluorinated ionic polymer directly determines the long-term operation life of the proton exchange membrane fuel cell.
The present research suggests that the chemically stable degradation process of perfluoroionic polymers is mainly free radical (HO. Cndot.)&HOO.) attacks the main chain or side chain of the polymer to "zipper-like" degradation, ultimately leading to overall degradation of the polymer. During the synthesis of the perfluoroionomer, the initiator inevitably generates, for example, -CF = CF at the molecular chain end 2 、-COOH、-CF 2 SO 3 H and-CF 2 H and the like, and chemical degradation often occurs at the tail end of the incompletely fluorinated molecular chain with the unstable group, and free radicals attack the unstable group to cause degradation reaction. Therefore, it is an important subject to design and synthesize a perfluoroionomer having high chemical stability. At present, aiming at chemical degradation of a polymer caused by free radical attack, the chemical stability of the polymer is improved by two means: (1) Inhibiting the generation of free radicals during polymer application; (2) The polymer structure is optimized to quench or capture the generated free radicals. In optimizing The polymer structure, ramani et al [ The Journal of Physical Chemistry B,2007,111 (30), 8684-8690]The cerium oxide is added into the ion exchange membrane to capture free radicals in the system, so that the attack of the cerium oxide on the ion exchange membrane is relieved, and the chemical stability of the ion exchange membrane is improved. The results show that the ion exchange with the addition of cerium oxideThe film has good chemical stability. Xiao et al (Chinese patent: CN 102479956A) in Chinese academy of sciences well improve the chemical stability of the membrane by modifying the micro-morphology of the proton exchange membrane. The method firstly prepares the polymer into the ion exchange membrane, then adopts a post-treatment strategy to resist the attack of free radicals for the ion exchange membrane, and does not adopt measures to quench or capture the generated free radicals at the source of the polymer and the synthesis process thereof. The disadvantages of such methods mainly include: 1) The compatibility of the inorganic additive and the perfluorinated sulfonic acid polymer is poor, the inorganic additive is distributed unevenly in the membrane, and aggregation is easy to occur; 2) The added substances do not contain ionic groups, so that the strength and the conductivity of the membrane are reduced; 3) The small molecular additive can be degraded and lost continuously in the long-term use process, and cannot play a role in protection for a long time. The invention synthesizes the perfluorinated ionic polymer with high chemical stability by the design optimization of the polymer structure, thereby achieving the purpose of enhancing the chemical stability of the polymer from the source.
Disclosure of Invention
Aiming at the defects of the perfluorinated ionic polymer in the prior art, the invention provides a perfluorinated ionic polymer with a phenanthroline side group and a synthesis method thereof, the perfluorinated ionic polymer retains the structural advantages of perfluorosulfonyl fluororesin in the chemical structure, and simultaneously introduces a structure (phenanthroline structural unit) for capturing or quenching free radicals into the structure by adopting a chemical grafting mode, so that the purpose of resisting the attack of the free radicals can be fundamentally realized from the polymer, the degradation of the polymer is effectively weakened, and the chemical stability of the perfluorinated ionic polymer is improved. In addition, the phenanthroline structural unit introduced into the structure of the obtained perfluorinated ionic polymer can regulate and control the Ion Exchange Capacity (IEC) of the perfluorinated ionic polymer, so that the obtained perfluorinated ionic polymer can simultaneously achieve the aim of effectively regulating and controlling the Ion Exchange Capacity (IEC) and chemical stability.
The invention also provides a proton exchange membrane for a fuel cell, which is prepared from the perfluorinated ion polymer with the phenanthroline side group, and the obtained proton exchange membrane has higher mechanical strength, good thermal stability and stronger chemical stability, and can effectively capture or quench free radicals, so that the degradation of the proton exchange membrane is weakened or slowed down, and the service life of the proton exchange membrane is prolonged.
The invention also provides a membrane electrode for the anti-free radical fuel cell, wherein a catalyst layer of the membrane electrode contains the perfluorinated ionic polymer with the phenanthroline side group, so that free radicals can be effectively captured or quenched, attack of the free radicals is resisted, the stability of the membrane electrode is improved, and the service life is prolonged.
The technical scheme of the invention is as follows:
1. a perfluorinated ionic polymer with phenanthroline side groups has a structure shown in a formula (I):
the structure of the formula (I) comprises an A unit and a B unit; the A unit is a phenanthroline structural unit, the unit comprises a phenanthroline group M and a perfluoroether structural unit, and the B unit 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; most 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; y/(y + z) is defined as the graft ratio;
the structure of the monomer reagent for providing the phenanthroline group M in the unit A is shown as a formula II,
wherein R is 1 ～R 8 The radical being-NH 2 、-CH 2 NH 2 Ph (Ph represents a benzene ring) and PhNH 2 、-PhCOOH、-Cl、-O-CH 3 、-CH 3 、-H、-F、-Br、CH 3 CH 2 -、(CH 3 ) 2 CH-or (CH) 3 ) 3 C-；
R 1 ～R 8 In which at least one group contains-NH 2 The other groups are electron-withdrawing groups or electron-donating groups or-H, and the other groups are not electron-withdrawing groups at the same time, and the number of the electron-withdrawing groups is at most 3;
wherein the electron donating group of the above groups comprises: -NH 2 、-CH 2 NH 2 、-Ph、-PhNH 2 、-PhCOOH、-O-CH 3 、-CH 3 、CH 3 CH 2 -、(CH 3 ) 2 CH-、(CH 3 ) 3 C-; electron withdrawing groups include-F, -Br, -Cl;
the electron-withdrawing ability of the electron-withdrawing groups is ordered as follows: -F > -Cl > -Br.
In the invention, the electron-donating group is favorable for forming a conjugated system with a pyridine ring, can be combined with free radicals, and prolongs the service life of the perfluorinated ionic polymer.
According to a preferred embodiment of the present invention, R is 1 is-NH 2 、-CH 2 NH 2 、-Ph、-PhNH 2 、-PhCOOH、-Cl、-O-CH 3 、-CH 3 or-H; r 2 is-H, -NH 2 、-PhNH 2 -F, -PhCOOH or-CH 3 ；R 3 is-H, -NH 2 、-PhNH 2 -PhCOOH, -Br, -Ph or-CH 3 ；R 4 is-H, -NH 2 、-PhNH 2 -PhCOOH, -Br, -Ph or-CH 3 ；R 5 is-H, -NH 2 、-PhNH 2 -Br or-CH 3 ；R 6 is-NH 2 、-H、-CH 2 NH 2 、-CH 3 or-Ph,; r 7 is-NH 2 、-H、-CH 2 NH 2 、-CH 3 or-Ph,; r is 8 is-NH 2 、-CH 2 NH 2 -Ph or-H.
Further preferably, R is 1 is-NH 2 、-PhNH 2 or-H; r 2 is-NH 2 -H or-PhNH 2 ；R 3 is-NH 2 、-PhNH 2 or-CH 3 ；R 4 is-NH 2 、-PhNH 2 or-CH 3 ；R 5 is-H, -NH 2 or-CH 3 ；R 6 is-H or-Ph; r 7 is-NH 2 -H or-Ph; r 8 is-NH 2 or-H.
According to a preferred embodiment of the present invention, R is 1 ～R 8 Do not simultaneously contain-NH 2 ；R 1 ～R 8 In (2) contains-NH 2 The number is at most 3.
In at least one preferred embodiment of the present invention, R 1 、R 2 、R 3 、R 4 、R 5 、R 6 、R 7 is-H, R 8 is-NH 2 。
In at least one preferred embodiment of the present invention, R 1 、R 2 is-H, R3, R4 are-CH 3, R 5 、R 6 、R 7 is-H, R 8 is-NH 2 。
In at least one preferred embodiment of the present invention, R 1 、R 2 、R 3 、R 4 、R 5 is-H, R 6 is-Ph, R 7 is-H, R 8 is-NH 2 。
According to the present invention, the number average molecular weight of the perfluoroionomer represented by formula (i) is preferably 20 to 100 ten thousand, more preferably 20 to 60 ten thousand, and most preferably 30 to 50 ten thousand.
In the present invention, the perfluoroionomer represented by formula (I) has the following advantages: (1) The superior unit- (CF) of the perfluoro sulfonyl fluorine resin ultrastable is reserved 2 CF 2 ) x Ensuring sufficient mechanical strength and thermal stability of the polymer; (2) The chemical grafting is carried out by utilizing the end group of the side chain of the perfluorinated ion polymer, and the introduced functional phenanthroline structural unit can effectively capture or quench free radicals, so that the degradation of the polymer is weakened or slowed down; (3) The perfluorinated ionic polymer synthesized by the method can simultaneously meet the requirements of high Ion Exchange Capacity (IEC) and strong chemical stability, has wide applicability, and can be prepared by regulating and controlling PhilowThe occupation ratio of the quinoline structure unit, namely the grafting ratio, is used for synthesizing the perfluorinated ion polymer which meets various requirements and has Ion Exchange Capacity (IEC) and chemical stability.
2. The synthesis method of the perfluoroionic polymer with the phenanthroline side group comprises the following steps:
(1) Selecting perfluorosulfonyl fluoride resin and a monomer reagent for providing a phenanthroline group M to perform one-step grafting reaction in an organic solvent to synthesize an intermediate product;
or, firstly, pre-swelling the perfluorosulfonyl fluororesin in an organic solvent, then adding a monomer reagent for providing the phenanthroline group M to perform a grafting reaction, and synthesizing an intermediate product;
the reaction formula is as follows:
(2) Respectively treating the intermediate product obtained in the step (1) by alkali and acid to complete ion exchange, and treating unreacted sulfonyl fluoride group-SO 2 Conversion of F to perfluorosulfonic acid group-SO 3 H, washing and drying to obtain the perfluoroionomer with the phenanthroline side group;
the reaction formula is as follows:
according to the present invention, 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.
According to a preferred embodiment of the present invention, the molar ratio of the perfluorosulfonyl fluoride resin to the monomer reagent for providing the phenanthroline group M in step (1) is 1.
According to the invention, the mass volume ratio of the perfluorosulfonyl fluororesin to the organic solvent in the step (1) is preferably 1 to 10,g/mL; more preferably 1 to 5,g/mL; most preferably 1 to 2,g/mL.
Preferably, according to the invention, the temperature of the grafting reaction in step (1) is 15 to 150 ℃, preferably 25 to 80 ℃; the reaction time is 1 to 48 hours, preferably 8 to 12 hours.
According to the invention, the pre-swelling in the step (1) is to swell the perfluorosulfonyl fluoride resin in the organic solvent for 60-100 min at 40-80 ℃.
According to the invention, the alkali in the step (2) is one of sodium hydroxide and potassium hydroxide, and the concentration of the sodium hydroxide is 5-50 wt%, preferably 15-40 wt%; the acid is one of hydrochloric acid, sulfuric acid and nitric acid, and the concentration of the sulfuric acid or nitric acid is 5-50 wt%, preferably 25-40 wt%.
According to the invention, preferably, the washing in the step (2) is carried out by using deionized water, and the drying is carried out for 18-36 h at the temperature of 55-65 ℃.
The prepared perfluorinated ionic polymer with the phenanthroline side group can determine the ion exchange capacity and the proportion of the phenanthroline structural unit through acid-base titration. According to the requirements of product performance, the grafting rate of the reaction can be regulated and controlled by regulating and controlling the reaction time and the reaction temperature in the step (1), and further the ion exchange capacity of the perfluorinated ion polymer and the ratio of the phenanthroline structural unit can be regulated and controlled.
3. The application of the perfluorinated ionic polymer with the phenanthroline side group in one or more of the following items: 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 exchange membrane for a fuel cell, and the component of the proton exchange membrane comprises the perfluorinated ion polymer with the phenanthroline side group.
A proton exchange membrane for a fuel cell, said proton exchange membrane having a structure selected from one of:
1) The proton exchange membrane is prepared by the perfluorinated ion polymer with the phenanthroline side group;
2) The proton exchange membrane is prepared by the mixture of the perfluorinated ion polymer with the phenanthroline side group and the perfluorinated sulfonic acid polymer.
The above production method includes spin coating, screen printing, dip coating, ink jet printing, solution casting, spray pyrolysis method and the like, and the solution casting method is preferable.
According to the invention, the ion exchange capacity of the proton exchange membrane is preferably 0.9-1.2 mmol/g, the ionic conductivity is 50-200 mS/cm, the thermal degradation temperature is 280-330 ℃, and after a Fenton test for 200 hours, the retention rate of the ion exchange capacity is more than 93%, and the retention rate of the ionic conductivity is more than 93%.
Preferably, according to the present invention, the thickness of the proton exchange membrane is 10 to 200 μm.
5. The preparation method of the proton exchange membrane for the fuel cell comprises the following steps:
dissolving the perfluorinated ionic polymer with the phenanthroline side group in an organic solvent to prepare a perfluorinated ionic polymer solution, and directly preparing the proton exchange membrane by adopting a solution tape casting method;
or adding the perfluorinated ionic polymer with the phenanthroline side group as a free radical quencher into a conventional perfluorinated sulfonic acid polymer solution to prepare a perfluorinated ionic polymer composite solution, and preparing the composite proton exchange membrane by adopting a solution casting method.
Preferably, according to the invention, the concentration of the perfluoroionomer solution is between 5 and 35wt%, preferably between 10 and 25wt%.
According to the present invention, the organic solvent is preferably at least one of N, N-dimethylformamide, N-dimethylacetamide, N-methylpyrrolidone, ethanol, an ethanol/water mixed solvent, an isopropanol/water mixed solvent, dimethyl sulfoxide, or ethyl acetate.
More preferably, the volume ratio of ethanol to water in the ethanol/water mixed solvent is 8-9; the volume ratio of the isopropanol to the water in the isopropanol/water mixed solvent is 8-9.
Preferably, according to the present invention, the total polymer concentration in the perfluoroionic polymer composite solution is 5 to 30%.
According to a preferred embodiment of the present invention, the solution casting method comprises the steps of: coating the perfluorinated ionic polymer solution or the perfluorinated ionic 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 exchange membrane is prepared, the ionic conductivity and the chemical stability of the proton exchange membrane can be regulated and controlled by regulating the proportion of the perfluorinated ionic polymer according to the requirement of product performance, so that the service life of the proton exchange membrane can be regulated and controlled.
6. The invention also provides a membrane electrode for the anti-free radical fuel cell, and a catalyst layer of the membrane electrode comprises the perfluorinated ion polymer with the phenanthroline side group.
The membrane electrode for free radical resisting fuel cell consists of electrode layer and proton exchange membrane, the electrode layer includes gas diffusion layer and catalyst layer, and the electrode layer is separated into hydrogen electrode and oxygen electrode for contacting fuel hydrogen and oxygen in the membrane electrode, and the proton exchange membrane is located between the hydrogen electrode and the oxygen electrode.
The proton exchange membrane can be the proton exchange membrane for the fuel cell of the invention or other conventional proton exchange membranes for the fuel cell.
7. The preparation method of the membrane electrode for the anti-free radical fuel cell comprises the following steps:
(1) Dissolving the perfluorinated ionic polymer with the phenanthroline side group in a water/alcohol mixed solvent to prepare a perfluorinated ionic polymer solution or adding the perfluorinated ionic polymer into a conventional perfluorinated sulfonic acid polymer solution to prepare a perfluorinated ionic polymer composite solution, then adding a 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 due to the fact that the electrode layer is in contact with fuel hydrogen and oxygen in the membrane 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, carrying out hot pressing treatment, naturally cooling, and taking out the prepared membrane electrode.
The Gas Diffusion Layer (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.
According to the invention, in the step (1), the alcohol in the water/alcohol mixed solvent is ethanol or isopropanol, and the volume ratio of water to alcohol is 1-2.
Preferably, according to the present invention, the concentration of the perfluoroionomer in the perfluoroionomer solution or the perfluoroionomer composite solution in the step (1) is 5 to 15wt%.
According to the invention, the time of the ultrasonic treatment in the step (1) is preferably 30-200 min.
Preferably, according to the present invention, the platinum loading of the catalyst layer in the step (2) is 0.3 to 0.6mg/cm 2 More preferably 0.4mg/cm 2 。
According to the present invention, in step (2), the gas diffusion layer is a carbon paper hydrophobically treated with PTFE.
According to the invention, the heat treatment in step (2) is preferably carried out at 80-130 ℃ for 30-200 min.
Preferably, the proton exchange membrane in step (3) may be the above-mentioned proton exchange membrane for fuel cell of the present invention or other conventional proton exchange membrane for fuel cell.
According to the present invention, the conditions of the hot pressing treatment in the step (3) are preferably: the pressure is 0.1-5 MPa, the temperature is 80-140 ℃, and the duration is 30-150 s.
In 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 perfluorinated ion polymer according to the requirement of product performance, thereby regulating and controlling the service life of the membrane electrode.
Has the advantages that:
the invention prepares a kind of perfluoroionomer with phenanthroline side group, and compared with the methods for resisting or slowing down free radical attack (CN 102479956A, CN 101281967A and CN 108878993A), the perfluoroionomer prepared by the invention has the following advantages:
1. the superior stable unit- (CF) of the perfluorosulfonyl fluoride polymer is reserved 2 CF 2 ) x-ensures that the prepared perfluorinated ion polymer has enough mechanical strength and thermal stability;
2. the functional phenanthroline structural unit is introduced into the polymer structure, so that the ion exchange capacity and the chemical stability of the perfluorinated ion polymer can be regulated and controlled; therefore, the prepared perfluorinated ionic polymer can simultaneously meet the requirements of mechanical strength, thermal stability and ion exchange capacity, and has higher chemical stability;
3. the invention designs and synthesizes a perfluorinated ion polymer with a side chain containing a functional phenanthroline structural unit from a polymer source, and can effectively capture or quench free radicals, thereby weakening or slowing down the degradation of the polymer; in the polymer synthesis process, the grafting rate can be effectively regulated and controlled according to the product requirements;
4. after the perfluorinated ionic polymer prepared by the method is tested for 102 days by free radical attenuation, the retention rate of Ion Exchange Capacity (IEC) is up to more than 90%, and the obtained perfluorinated ionic polymer is proved to have higher capability of resisting free radical attack and can effectively prolong the service life of the perfluorinated sulfonic acid polymer;
5. the perfluorinated ionic polymer prepared by the method can be used for preparing a corresponding ion exchange membrane, has the function of resisting free radical attack, and has high chemical stability and long service life;
6. after the proton exchange membrane prepared by the invention is tested for 102 days by the attenuation of free radicals, the retention rate of the ionic conductivity is up to more than 90 percent, and the proton exchange membrane has higher capability of resisting the attack of the free radicals and can effectively prolong the service life of the proton exchange membrane.
7. The perfluorinated ion polymer prepared by the method can be used as an additive material to prepare a composite proton exchange membrane, so that the purposes of resisting free radical attack and prolonging the service life are achieved; the content of the perfluorinated ion polymer as an additive can be effectively regulated and controlled according to the product requirements;
8. the invention provides a membrane electrode for a free radical resistant fuel cell, which takes the perfluorinated ion polymer prepared by the invention as a raw material or an additive, and can effectively prolong the service life of the membrane electrode;
drawings
FIG. 1 is a graph of the infrared characterization result of intermediate A1.
FIG. 2 is a graph showing the ion exchange capacity retention rate of the objective product A2.
FIG. 3 is a graph of the ionic conductivity retention of the proton exchange membrane prepared in example 2.
Detailed Description
The present invention is described in detail below with reference to specific examples, which are only for illustrating the present invention in detail and are not intended to limit the scope of the present invention. The invention is not limited to the following embodiments, and other combinations derived from the invention are within the scope of the invention. The raw materials and reagents mentioned in the examples are all common commercial products unless otherwise specified; the experimental methods mentioned in the examples are all conventional technical means in the field unless otherwise specified.
In the examples, fenton test is used to accelerate the oxidation of the target product, so as to achieve the purpose of investigating the chemical stability of the target product. The chemical stability of the target product was evaluated by testing the retention rate (RV%) of the Ion Exchange Capacity (IEC) of the target product before and after the Fenton experiment.
The Fenton experiment has the specific conditions that: 20ppm of Fe 2+ Ion addition 30wt% H 2 O 2 In the preparation of FentAnd (3) on reagent. And then, immersing the target product in a Fenton reagent in a water bath at the temperature of 80 ℃, and testing the Ion Exchange Capacity (IEC) of the target product after soaking for a certain time, thereby judging the chemical stability of the target product. In order to ensure the concentration of OH free radicals, the Fenton reagent needs to be replaced every 3 h.
Titration of Ion Exchange Capacity (IEC): accurately weighing a certain weight of dry target product, then treating for 1h in 80 ℃ water bath by using a Fenton reagent, carrying out ion exchange for more than 12h by using a NaCl aqueous solution with the concentration of about 1M, collecting the solution after the ion exchange, using phenolphthalein as an indicator, and titrating by using 0.1M NaOH standard solution until the solution turns pink, wherein the Ion Exchange Capacity (IEC) value of the target product can be calculated according to the following formula:
IEC＝(V NaOH ×C NaOH )/m
in the formula:
V NaOH the volume of NaOH standard consumed, mL,
C NaOH -the molar concentration of NaOH standard solution, mmol/mL,
m is the mass of the dry target product, g.
Retention of Ion Exchange Capacity (IEC):
RV％＝(IEC 1 -IEC 0 )/IEC 0
in the formula:
IEC 1 and IEC 0 Respectively represent the Ion Exchange Capacity (IEC) of the target product after and before the Fenton experiment.
Ion conductivity determination of proton exchange membrane: the resistance R of a sample 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 (cm) of the membrane,
r is the resistance of the membrane (omega),
σ is the conductivity (S/cm) of the sample,
s is the area (cm) of the test portion of the sample 2 )。
Retention of proton exchange membrane ionic conductivity:
RV％＝(σ 1 -σ 0 )/σ 0
in the formula:
σ 1 and σ 0 Respectively represent the ion conductivity of the proton exchange membrane after and before 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.
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 process for synthesizing the perfluoro-ionic polymer with phenanthroline lateral group includes providing the monomer reagent (R) containing phenanthroline group M by 1, 10-phenanthroline-5-amino group 1 ～R 7 Are all-H, R 8 is-NH 2 ) Reacting with perfluorosulfonyl fluoride resin (m =1,n =2, the number average molecular weight is 40 ten thousand, and the x value is 10) to synthesize a target product, and specifically, the method comprises the following steps:
(1) Cleaning a 150mL reaction kettle, adding 30g of perfluorosulfonyl fluoride resin into 50mL of N, N-dimethylformamide, starting a stirring device, heating to 60 ℃, swelling for 60min in advance, vacuumizing, filling high-purity nitrogen for three times, adding 0.1g of 1, 10-phenanthroline-5-amino, slowly heating to 80 ℃ after completely dissolving, and reacting, wherein the molar ratio of the perfluorosulfonyl fluoride resin to the 1, 10-phenanthroline-5-amino is about 1:7, reacting for 10 hours at 80 ℃ under mechanical stirring, cooling to room temperature, filtering the product, washing the product for multiple times by using ethanol and deionized water to remove unreacted 1, 10-phenanthroline-5-amino, and drying to obtain an intermediate product, which is marked as A1; 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) Its characteristic peak is 1467cm -1 Nearby, characteristic peaks of C = N double bond and S-N bond of connecting group in phenanthroline structural unit appear simultaneously, and the characteristic peaks are respectively 1670cm -1 And 1398cm -1 Nearby; the infrared result proves that the intermediate product A1 is successfully synthesized;
(2) Respectively treating the intermediate product A1 obtained in the step (1) by 30wt% of sodium hydroxide and 25wt% of sulfuric acid to complete ion exchange, and treating unreacted sulfonyl fluoride group-SO 2 F is completely converted into perfluorosulfonic acid group-SO 3 H, washing the product with deionized water, and drying the product at 60 ℃ for 30H to obtain a target product, which is marked as A2; 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 2, after the free radical decay test is carried out for 102 days, the retention rate of the Ion Exchange Capacity (IEC) is up to more than 90%, and the obtained perfluorinated ion polymer is proved to have higher capability of resisting the attack of free radicals, so that the service life of the perfluorinated ion polymer can be effectively prolonged.
The IEC of the obtained target product A2 is 1.02mmol/g, and y/(y + z) =0.25 (namely, the grafting ratio) in the structure of the obtained target product A2 is determined by the Ion Exchange Capacity (IEC).
Example 2
The preparation method of the proton exchange membrane for the fuel cell comprises the following specific steps:
dissolving the target product A2 prepared in example 1 in N, N-dimethylformamide to prepare a 15wt% perfluorinated ionic polymer solution, then coating the perfluorinated ionic polymer 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 demoulding to prepare the proton exchange membrane for the fuel cell.
The ion exchange capacity IEC of the proton exchange membrane was determined by titration to be 1.02mmol/g.
The ion conductivity of the proton exchange membrane at room temperature (25 ℃) is 120mS/cm.
The stability of the proton exchange membrane is tested by a Fenton test, and the result is shown in figure 3, after the proton exchange membrane is tested for 102 days by a free radical attenuation test, the retention rate of the ionic conductivity is up to more than 90%, and the obtained proton exchange membrane is proved to have higher capability of resisting the attack of free radicals and can effectively prolong the service life of the proton exchange membrane.
Example 3
Synthesis of perfluoroionic polymer with phenanthroline side group, which selects dimethyl-1, 10-phenanthroline-5-amino as monomer reagent (R3, R4 are-CH 3, R4 is-CH 3) 1 、R 2 、R 5 ～R 7 Are all-H, R 8 is-NH 2 ) Reacting with perfluorosulfonyl fluoride resin (m =1,n =2, the number average molecular weight is 42 ten thousand, and the x value is 6) to synthesize a target product, and specifically, the method comprises the following steps:
(1) Cleaning a 150mL reaction kettle, adding 50mL of N, N-dimethylformamide, starting a stirring device, vacuumizing, filling high-purity nitrogen for three times, replacing, adding 0.1g of dimethyl-1, 10-phenanthroline-5-amino, slowly heating to 80 ℃, adding 30g of perfluorosulfonyl fluororesin after the perfluorosulfonyl fluororesin is completely dissolved, wherein the molar ratio of the perfluorosulfonyl fluororesin to the dimethyl-1, 10-phenanthroline-5-amino is about 1:6, reacting for 24 hours at 80 ℃ under mechanical stirring, cooling to room temperature, filtering the product, washing the product for multiple times by using ethanol and deionized water to remove unreacted dimethyl-1, 10-phenanthroline-5-amino, and drying to obtain an intermediate product, which is marked as A3; the reaction formula is as follows:
(2) Respectively treating the intermediate product A3 obtained in the step (1) by 30wt% of sodium hydroxide and 25wt% of sulfuric acid to complete ion exchange, and treating unreacted sulfonyl fluoride groups-SO 2 F is completely converted into perfluorosulfonic acid group-SO 3 And H, washing the product with deionized water, and drying at 60 ℃ for 30H to obtain a target product, which is marked as A4 and has the following reaction formula:
the IEC of the obtained target product A4 is 0.98mmol/g, and y/(y + z) =0.30 (i.e. grafting ratio) in the structure of the obtained target product A4 is determined by Ion Exchange Capacity (IEC).
Example 4
A preparation method of a proton exchange membrane for a fuel cell comprises the following specific steps:
the target product A4 prepared in example 3 is dissolved in an isopropanol/water (volume ratio = 8.
The ion exchange capacity IEC of the proton exchange membrane was determined by titration to be 0.98mmol/g.
The ion conductivity of the proton exchange membrane at room temperature (25 ℃) is 110mS/cm.
Example 5
A process for synthesizing the perfluoro-ionic polymer with phenanthroline lateral group includes providing the phenanthroline radical M with 7-phenyl-1, 10-phenanthroline-5-amino group 1 ～R 5 Are all-H, R 6 is-Ph, R 7 is-H, R 8 is-NH 2 ) Reacting with perfluorosulfonyl fluoride resin (m =1,n =2, the number average molecular weight is 40 ten thousand, and the value of x is 6) to synthesize a target product, and specifically, the method comprises the following steps:
(1) Cleaning a 150mL reaction kettle, adding 50mL of N, N-dimethylacetamide, starting a stirring device, vacuumizing, filling high-purity nitrogen for three times, replacing, adding 0.2g of 7-phenyl-1, 10-phenanthroline-5-amino, slowly heating to 80 ℃, adding 40g of perfluorosulfonyl fluorine resin after the perfluorosulfonyl fluorine resin is completely dissolved, wherein the molar ratio of the perfluorosulfonyl fluorine resin to the 7-phenyl-1, 10-phenanthroline-5-amino is about 1:7, reacting for 30 hours at 80 ℃ under mechanical stirring, cooling to room temperature, filtering the product, washing the product for multiple times by using ethanol and deionized water to remove unreacted 7-phenyl-1, 10-phenanthroline-5-amino, and drying to obtain an intermediate product, which is marked as A5; the reaction formula is as follows:
(2) Respectively treating the intermediate product A5 obtained in the step (1) by 30wt% of sodium hydroxide and 25wt% of sulfuric acid to complete ion exchange, and treating unreacted sulfonyl fluoride group-SO 2 F is completely converted into perfluorosulfonic acid group-SO 3 H, washing the product with deionized water, and drying the product at 60 ℃ for 30 hours to obtain a target product, which is marked as A6 and has the following reaction formula:
the IEC of the obtained target product A6 is 0.95mmol/g, and y/(y + z) =0.32 (i.e. grafting ratio) in the structure of the obtained target product A6 is determined by Ion Exchange Capacity (IEC).
Example 6
The preparation method of the proton exchange membrane for the fuel cell comprises the following specific steps:
the target product A6 prepared in example 5 was dissolved in a mixed solvent of ethanol/water (volume ratio = 9.
The ion exchange capacity IEC of the proton exchange membrane is determined by titration to be 0.95mmol/g.
The ion conductivity of the proton exchange membrane at room temperature (25 ℃) is 100mS/cm.
Example 7
A preparation method of a composite proton exchange membrane for a fuel cell comprises the following specific steps:
(1) The target product A2 obtained in example 1 was dissolved in an isopropanol/water (volume ratio = 8;
(2) Taking a perfluorosulfonic acid polymer, wherein the Ion Exchange Capacity (IEC) of the perfluorosulfonic acid polymer is 1.15mmol/g, the number average molecular weight is 40 ten thousand, the structural formula is shown in the specification, and the value of a is 6; dissolving in an isopropanol/water (volume ratio = 8);
(3) Adding the solution A7 into the solution A8, uniformly mixing by adopting a mechanical stirring mode, wherein the concentration of a target product A2 in the mixed solution is 5wt%, coating the obtained mixed solution on a clean and smooth quartz surface vessel, pre-drying at 80 ℃, placing in a drying oven at 145 ℃ for drying for 90 minutes, taking out, demolding, and preparing the composite proton exchange membrane for the fuel cell, wherein the mass content of A2 in the obtained composite proton exchange membrane is 25%.
The Ion Exchange Capacity (IEC) of the composite proton exchange membrane is determined to be 1.13mmol/g.
The ion conductivity of the composite proton exchange membrane at room temperature (25 ℃) is 125.5mS/cm.
Example 8
A preparation method of a composite proton exchange membrane for a fuel cell comprises the following specific steps:
(1) The target product A4 obtained in example 3 was dissolved in an isopropanol/water (volume ratio = 8;
(2) Taking a perfluorosulfonic acid polymer, wherein the Ion Exchange Capacity (IEC) of the perfluorosulfonic acid polymer is 1.15mmol/g, the number average molecular weight is 42 ten thousand, the value of a is 6, the structural formula is shown in example 7, and the perfluorosulfonic acid polymer is dissolved in an isopropanol/water (volume ratio = 8);
(3) Adding the solution A9 into the solution A10, and uniformly mixing in a mechanical stirring manner, wherein the concentration of a target product A4 in the mixed solution is 8wt%; and coating the obtained mixed solution on a clean and smooth quartz surface vessel, pre-drying at 80 ℃, putting the vessel in an oven at 145 ℃ for drying for 90 minutes, taking out the vessel and demoulding to prepare the composite proton exchange membrane for the fuel cell, wherein the mass content of A4 in the obtained composite proton exchange membrane is 40%.
The Ion Exchange Capacity (IEC) of the composite proton exchange membrane is determined to be 1.05mmol/g.
The ionic conductivity of the composite proton exchange membrane at room temperature (25 ℃) is 100.8mS/cm.
Example 9
The preparation process of membrane electrode for free radical resisting fuel cell includes the following steps:
(1) Dissolving the target product A2 in example 1 in a mixed solvent of water and isopropanol (volume ratio is 2;
(2) Coating the perfluorinated ion polymer solution in the step (1) on a clean and smooth quartz surface dish, pre-drying at 80 ℃, placing the coated membrane in a drying oven at 145 ℃ for drying for 90 minutes, taking out the membrane, and demolding to prepare a proton exchange membrane;
(3) Spraying the membrane electrode slurry obtained in the step (1) onto a gas diffusion layer of 2cm multiplied by 2cm subjected to hydrophobic treatment by a spray gun to form a catalyst layer, and carrying out heat treatment at 130 ℃ for 90min to obtain a platinum loading capacity of 0.4mg/cm on the surface of the catalyst layer 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 due to the difference that the electrode layer contacts with fuel hydrogen and oxygen in the membrane 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 exchange 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) Diluting A8 in example 7 in a mixed solvent of water/isopropanol (volume ratio is 2; then adding 10mL of composite solution into a Pt/C catalyst, and carrying out ultrasonic treatment for 150min to obtain membrane electrode slurry, wherein the mass fraction of the total polymers in the slurry is 5%, and the mass ratio of A2 in the total polymers is 30%;
(2) Coating the perfluorinated ion polymer composite solution in the step (1) on a clean and smooth quartz surface dish, pre-drying at 80 ℃, placing the solution in an oven at 145 ℃ for drying for 90 minutes, taking out the solution and demoulding to prepare a composite proton exchange membrane;
(3) Spraying the membrane electrode slurry obtained in the step (1) onto a gas diffusion layer of 2cm multiplied by 2cm subjected to hydrophobic treatment by a spray gun to form a catalyst layer, and carrying out heat treatment at 130 ℃ for 90min to obtain a platinum loading capacity of 0.4mg/cm on the surface of the catalyst layer 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 due to the difference that the electrode layer contacts with fuel hydrogen and oxygen in the membrane 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 exchange 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 exchange membrane is prepared by taking unmodified perfluorosulfonic acid polymer as a raw material, and comprises the following specific steps:
the perfluorosulfonic acid polymer in example 7 was dissolved in an isopropanol/water (volume ratio =8: 2) mixed solvent to prepare a 20wt% perfluorosulfonic acid polymer solution A8, no additive was added, the obtained solution was coated on a clean and smooth quartz watch glass, pre-dried at 80 ℃, placed in an oven at 145 ℃ for drying for 90 minutes, taken out and demolded to prepare a perfluorosulfonic acid proton exchange membrane.
The IEC determination shows that the obtained proton exchange membrane IEC is 1.02mmol/g.
Comparative example 2
The membrane electrode is prepared by taking unmodified perfluorosulfonic acid polymer as a raw material, and the method comprises the following specific steps:
(1) Diluting the perfluorosulfonic acid polymer solution A8 in the mixed solvent of isopropanol/water (volume ratio is 8;
(2) Coating 5wt% of perfluorosulfonic acid polymer 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 the perfluorosulfonic acid proton exchange 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 catalyst layer, and performing heat treatment at 130 ℃ for 90min, wherein the platinum loading capacity of the surface of the catalyst 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 due to the difference that the electrode layer contacts with fuel hydrogen and oxygen in the membrane 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 exchange 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.
Comparative example 3
The preparation of proton exchange membrane directly adopts 1, 10-phenanthroline-5-amino as additive component of proton exchange membrane, and its concrete steps are as follows:
1, 10-phenanthroline-5-amino is directly added into the perfluorosulfonic acid polymer solution A8 described in example 7, the mixture is uniformly mixed by adopting a mechanical stirring mode, the molar ratio of the perfluorosulfonic acid polymer to the 1, 10-phenanthroline-5-amino in the mixed solution is about 1.
The Ion Exchange Capacity (IEC) of the proton exchange membrane was determined to be 0.96mmol/g.
The ion conductivity of the proton exchange membrane at room temperature (25 ℃) was 65.5mS/cm.
Comparative example 4
The preparation of membrane electrode directly adopts 1, 10-phenanthroline-5-amino as the additive component of membrane electrode, and its concrete steps are as follows:
(1) Diluting A8 in example 7 in a water/isopropanol (volume ratio is 2;
(2) Coating the perfluorinated ion polymer composite solution in the step (1) on a clean and smooth quartz surface dish, pre-drying at 80 ℃, placing the coated solution in an oven at 145 ℃ for drying for 90 minutes, taking out the coated solution and demoulding to prepare a proton exchange membrane;
(3) Spraying the membrane electrode slurry obtained in the step (1) onto a gas diffusion layer of 2cm multiplied by 2cm subjected to hydrophobic treatment by a spray gun to form a catalyst layer, and carrying out heat treatment at 130 ℃ for 90min to obtain a platinum loading capacity of 0.4mg/cm on the surface of the catalyst layer 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 due to the difference that fuel hydrogen and oxygen contact in the membrane 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 exchange membrane (3 cm multiplied by 3 cm) in the step (2), aligning up and down, perfectly matching, carrying out 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 to obtain the membrane electrode.
And (3) performance testing:
the perfluor ionic polymer, the proton exchange membrane and the membrane electrode which are prepared by the method are subjected to performance tests, and the results are shown in tables 1-3:
TABLE 1 chemical stability test results for perfluoroionomer
| IEC retention (%), after 200h Fenton test | Thermal degradation temperature (. Degree.C.) | |
| Example 1 | 94.6 | 310 |
| Example 1 corresponding unmodified perfluorosulfonic acid Polymer | 85.2 | 300 |
| Example 3 | 95.4 | 300 |
| Example 3 corresponding unmodified perfluorosulfonic acid Polymer | 80.6 | 280 |
| Example 5 | 96.0 | 280 |
| Example 5 corresponding unmodified perfluorosulfonic acid Polymer | 85.2 | 260 |
As can be seen from Table 1, after the perfluoroionic polymer prepared by the method disclosed by the invention is tested by a Fenton test for 200 hours, the IEC of the perfluoroionic polymer is more than 94%, the thermal degradation temperature of the perfluoroionic polymer is more than 280 ℃, and 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 perfluorinated ionic polymer with the phenanthroline side group prepared by the invention has high chemical stability, weakens or slows down the degradation of the polymer, and has sufficient mechanical strength and thermal stability.
TABLE 2 Performance test results for proton exchange membranes
As can be seen from Table 2, after the proton exchange membrane prepared by the perfluorinated ionic polymer with the phenanthroline side group is tested by a Fenton test for 200 hours, the IEC of the proton exchange membrane is over 95%, the retention rate of the ionic conductivity of the proton exchange membrane is over 95%, and the thermal degradation temperature of the proton exchange membrane is over 300 ℃; after a Fenton test is carried out for 200 hours, the IEC of the composite proton exchange membrane prepared from the perfluorinated ion polymer with the phenanthroline side group is over 93%, the retention rate of the ionic conductivity is over 93%, and the thermal degradation temperature of the composite proton exchange membrane is over 280 ℃; compared with proton exchange membranes (comparative examples 1 and 3) prepared from the perfluorinated sulfonic acid polymer which is not subjected to modification treatment, the proton exchange membrane has the advantages that the chemical stability, the mechanical strength and the thermal stability are obviously improved, and the service life of the proton exchange membrane is effectively prolonged. In the comparative example 3, 1, 10-phenanthroline-5-amino is directly added into the conventional perfluorinated sulfonic acid polymer to prepare the proton exchange membrane, and small molecules are easy to agglomerate and run off, do not contain ionic groups and have poor compatibility with the polymer, so that the mechanical property and the conductivity of the proton exchange membrane are reduced, and the service life is influenced.
TABLE 3 Performance test results of Membrane electrode
| Example 9 | Example 10 | Comparative example 2 | Comparative example 4 | |
| Duration (h) | 200.3 | 220.5 | 140.6 | 80.8 |
As can be seen from Table 3, the membrane electrode prepared from the perfluoroionic polymer having phenanthroline side groups according to 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 polymer without modification treatment (comparative example 2) has a duration of 140.6 hours, and the membrane electrode prepared by directly adding 1, 10-phenanthroline-5-amino group to the conventional perfluorosulfonic acid polymer has a duration of 80.8 hours. The durability of the membrane electrode prepared by the invention is effectively improved.
Claims (10)
1. A perfluorinated ionic polymer with a phenanthroline side group is characterized in that the structure is shown as formula (I):
the structure of formula (I) comprises an A unit and a B unit; a unit is a phenanthroline structural unit, the unit comprises a phenanthroline group M and a perfluoroether structural unit, and B unit 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; n is an integer of 1 to 6;
in the structure of the formula (I), x is an integer of 1-30, and x + y/(x + y + z) = 0.05-0.8; y/(y + z) = 0.2-0.6;
the structure of the monomer reagent for providing the phenanthroline group M in the unit A is shown as a formula II,
wherein R is 1 ～R 8 The radical being-NH 2 、-CH 2 NH 2 Ph (Ph represents a benzene ring) and PhNH 2 、-PhCOOH、-Cl、-O-CH 3 、-CH 3 、-H、-F、-Br、CH 3 CH 2 -、(CH 3 ) 2 CH-or (CH) 3 ) 3 C-；R 1 ～R 8 In which at least one group contains-NH 2 。
2. The perfluoroionomer of claim 1, wherein in the structure of formula (I), m is an integer from 1 to 3; n is an integer of 1 to 3; most preferably, m =1,n =2;
preferably, in the structure of formula (I), x + y/(x + y + z) =0.15 to 0.4; y/(y + z) =0.2 to 0.4.
3. The perfluoroionomer of claim 1, wherein R is 1 is-NH 2 、-CH 2 NH 2 、-Ph、-PhNH 2 、-PhCOOH、-Cl、-O-CH 3 、-CH 3 or-H; r 2 is-H, -NH 2 、-PhNH 2 -F, -PhCOOH or-CH 3 ；R 3 is-H, -NH 2 、-PhNH 2 -PhCOOH, -Br, -Ph or-CH 3 ；R 4 is-H, -NH 2 、-PhNH 2 -PhCOOH, -Br, -Ph or-CH 3 ；R 5 is-H, -NH 2 、-PhNH 2 -Br or-CH 3 ；R 6 is-NH 2 、-H、-CH 2 NH 2 、-CH 3 or-Ph,; r is 7 is-NH 2 、-H、-CH 2 NH 2 、-CH 3 or-Ph,; r 8 is-NH 2 、-CH 2 NH 2 -Ph or-H.
Further preferably, R is 1 is-NH 2 、-PhNH 2 or-H; r 2 is-NH 2 -H or-PhNH 2 ；R 3 is-NH 2 、-PhNH 2 or-CH 3 ；R 4 is-NH 2 、-PhNH 2 or-CH 3 ；R 5 is-H, -NH 2 or-CH 3 ；R 6 is-H or-Ph; r 7 is-NH 2 -H or-Ph; r 8 is-NH 2 or-H.
Preferably, R 1 ～R 8 In (2) contains-NH 2 The number is at most 3.
4. The perfluoroionomer of claim 1, wherein the perfluoroionomer of formula (i) has a number average molecular weight of 20 to 100 ten thousand, more preferably 20 to 60 ten thousand, and most preferably 30 to 50 ten thousand.
5. The method for synthesizing the phenanthroline-pendant group-containing perfluoroionic polymer according to claim 1, comprising the steps of:
(1) Selecting perfluorosulfonyl fluoride resin and a monomer reagent for providing a phenanthroline group M to perform one-step grafting reaction in an organic solvent to synthesize an intermediate product;
or, firstly, pre-swelling the perfluorosulfonyl fluororesin in an organic solvent, then adding a monomer reagent for providing the phenanthroline group M to perform a grafting reaction, and synthesizing an intermediate product;
the reaction formula is as follows:
(2) Respectively treating the intermediate product obtained in the step (1) by alkali and acid to complete ion exchange, and treating unreacted sulfonyl fluoride group-SO 2 Conversion of F to perfluorosulfonic acid group-SO 3 H, washing and drying to obtain the perfluoroionomer with the phenanthroline side group;
the reaction formula is as follows:
6. the method of claim 5, wherein step (1) satisfies one or more of the following conditions:
i. 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 fluoride resin to the monomer reagent for providing the phenanthroline group M in the step (1) is 1;
the mass volume ratio of the perfluorosulfonyl fluororesin to the organic solvent in the step (1) is 1-10 g/mL; more preferably 1 to 5,g/mL; most preferably 1 to 2,g/mL;
the temperature of the grafting reaction in the step (1) is 15-150 ℃, preferably 25-80 ℃; the reaction time is 1 to 48 hours, preferably 8 to 12 hours;
v, swelling the perfluorosulfonyl fluoride resin in the organic solvent at the temperature of between 40 and 80 ℃ for 60 to 100min in the pre-swelling step (1).
7. The method according to claim 5, wherein the alkali in step (2) is one of sodium hydroxide and potassium hydroxide, and the concentration is 5-50 wt%, preferably 15-40 wt% of sodium hydroxide; the acid is one of hydrochloric acid, sulfuric acid and nitric acid, and the concentration of the acid is 5-50 wt%, preferably 25-40 wt% 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.
8. Use of the phenanthroline pendant group-bearing perfluoroionomer of claim 1 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 proton exchange membrane for a fuel cell, wherein the proton exchange membrane component comprises the perfluoroionomer having pendant phenanthroline groups of claim 1.
10. A membrane electrode for a radical scavenging fuel cell, characterized in that a catalyst layer of the membrane electrode comprises the perfluoroionomer having a phenanthroline side group according to claim 1.
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| CN106832326A (en) * | 2017-03-28 | 2017-06-13 | 河北医科大学 | A kind of high-thermal-stability cerium coordination polymer and its preparation method and application |
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| CN105037604A (en) * | 2015-05-25 | 2015-11-11 | 上海交通大学 | Short chain perfluorosulfonamide anion ionomer for fuel cells, preparation and applications thereof |
| CN106832326A (en) * | 2017-03-28 | 2017-06-13 | 河北医科大学 | A kind of high-thermal-stability cerium coordination polymer and its preparation method and application |
| CN110734515A (en) * | 2019-09-25 | 2020-01-31 | 中盐金坛盐化有限责任公司 | imidazole iron polymer, synthetic method, battery and battery system |
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