CN114361544A - Cross-linked proton exchange membrane and preparation method thereof - Google Patents
Cross-linked proton exchange membrane and preparation method thereof Download PDFInfo
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- 239000012528 membrane Substances 0.000 title claims abstract description 83
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 239000011347 resin Substances 0.000 claims abstract description 57
- 229920005989 resin Polymers 0.000 claims abstract description 57
- 125000000467 secondary amino group Chemical class [H]N([*:1])[*:2] 0.000 claims abstract description 49
- 238000004132 cross linking Methods 0.000 claims abstract description 44
- 239000004693 Polybenzimidazole Substances 0.000 claims abstract description 38
- 229920002480 polybenzimidazole Polymers 0.000 claims abstract description 38
- 125000000524 functional group Chemical group 0.000 claims abstract description 35
- UQSQSQZYBQSBJZ-UHFFFAOYSA-N fluorosulfonic acid Chemical group OS(F)(=O)=O UQSQSQZYBQSBJZ-UHFFFAOYSA-N 0.000 claims abstract description 30
- 238000006243 chemical reaction Methods 0.000 claims abstract description 29
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims abstract description 13
- 150000003460 sulfonic acids Chemical class 0.000 claims abstract description 11
- 238000009826 distribution Methods 0.000 claims abstract description 4
- 238000000034 method Methods 0.000 claims description 40
- 238000005266 casting Methods 0.000 claims description 31
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 15
- 238000010438 heat treatment Methods 0.000 claims description 14
- 239000002904 solvent Substances 0.000 claims description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 9
- 239000000178 monomer Substances 0.000 claims description 8
- 239000003054 catalyst Substances 0.000 claims description 7
- 229910052736 halogen Inorganic materials 0.000 claims description 7
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 6
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 6
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 6
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 6
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 5
- 150000002367 halogens Chemical class 0.000 claims description 5
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 claims description 5
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 4
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical compound C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- OBTWBSRJZRCYQV-UHFFFAOYSA-N sulfuryl difluoride Chemical compound FS(F)(=O)=O OBTWBSRJZRCYQV-UHFFFAOYSA-N 0.000 claims description 4
- 230000009471 action Effects 0.000 claims description 3
- 229910052794 bromium Inorganic materials 0.000 claims description 3
- 229910052801 chlorine Inorganic materials 0.000 claims description 3
- 238000007334 copolymerization reaction Methods 0.000 claims description 3
- 229910052740 iodine Inorganic materials 0.000 claims description 3
- 239000011736 potassium bicarbonate Substances 0.000 claims description 3
- 229910000028 potassium bicarbonate Inorganic materials 0.000 claims description 3
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 3
- 230000008569 process Effects 0.000 claims description 3
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical compound O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 claims description 3
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 3
- 238000010382 chemical cross-linking Methods 0.000 abstract description 5
- 239000002131 composite material Substances 0.000 abstract description 4
- 210000004379 membrane Anatomy 0.000 description 67
- 239000000243 solution Substances 0.000 description 29
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 16
- 238000000576 coating method Methods 0.000 description 12
- 239000011248 coating agent Substances 0.000 description 9
- 230000008961 swelling Effects 0.000 description 9
- 238000001035 drying Methods 0.000 description 8
- 229940006460 bromide ion Drugs 0.000 description 7
- 239000003999 initiator Substances 0.000 description 7
- 239000003014 ion exchange membrane Substances 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 238000001878 scanning electron micrograph Methods 0.000 description 6
- 230000009286 beneficial effect Effects 0.000 description 5
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- 239000000463 material Substances 0.000 description 4
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- 230000000052 comparative effect Effects 0.000 description 3
- 239000004744 fabric Substances 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- -1 functional group halogen Chemical class 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- ZVXOHSHODRJTCP-UHFFFAOYSA-N 1,1,2,2,3,3,4-heptafluoro-4-(trifluoromethyl)cyclobutane Chemical compound FC(F)(F)C1(F)C(F)(F)C(F)(F)C1(F)F ZVXOHSHODRJTCP-UHFFFAOYSA-N 0.000 description 2
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 2
- YSTVLPSZAHXMQI-UHFFFAOYSA-N 6-bromo-1,1,2-trifluorohex-1-ene Chemical compound FC(F)=C(F)CCCCBr YSTVLPSZAHXMQI-UHFFFAOYSA-N 0.000 description 2
- SPWMKPHRQTUEIX-UHFFFAOYSA-N C=COC(C(C(C(F)=S(=O)=O)(F)F)(C(F)(F)F)F)(F)F Chemical compound C=COC(C(C(C(F)=S(=O)=O)(F)F)(C(F)(F)F)F)(F)F SPWMKPHRQTUEIX-UHFFFAOYSA-N 0.000 description 2
- 210000002469 basement membrane Anatomy 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- 238000006073 displacement reaction Methods 0.000 description 2
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- 239000000126 substance Substances 0.000 description 2
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- ZQZMAJGEFXFVCR-UHFFFAOYSA-N 2-chloro-1,1,3,4,4-pentafluorobuta-1,3-diene Chemical compound FC(F)=C(F)C(Cl)=C(F)F ZQZMAJGEFXFVCR-UHFFFAOYSA-N 0.000 description 1
- 229910006095 SO2F Inorganic materials 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
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- 239000003011 anion exchange membrane Substances 0.000 description 1
- 125000000751 azo group Chemical group [*]N=N[*] 0.000 description 1
- PFKFTWBEEFSNDU-UHFFFAOYSA-N carbonyldiimidazole Chemical compound C1=CN=CN1C(=O)N1C=CN=C1 PFKFTWBEEFSNDU-UHFFFAOYSA-N 0.000 description 1
- 230000008859 change Effects 0.000 description 1
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- 125000004122 cyclic group Chemical group 0.000 description 1
- DUQAODNTUBJRGF-UHFFFAOYSA-N difluorodiazene Chemical group FN=NF DUQAODNTUBJRGF-UHFFFAOYSA-N 0.000 description 1
- REAOZOPEJGPVCB-UHFFFAOYSA-N dioxygen difluoride Chemical compound FOOF REAOZOPEJGPVCB-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
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Images
Abstract
The invention discloses a preparation method of a cross-linking proton exchange membrane, which comprises the steps of preparing sulfonic acid resin containing functional groups and polybenzimidazole containing secondary amine through chemical cross-linking, wherein the EW value of the perfluorinated sulfonic acid resin containing the functional groups is 800-1200, the molecular weight is 20-50 ten thousand, and the molecular weight distribution is 1.05-1.8; in the polybenzimidazole containing secondary amine, the molar content of secondary amine groups is 5-40%, and the molecular weight of the polybenzimidazole containing secondary amine is 10-50 ten thousand; the molar ratio of the functional group in the perfluorinated sulfonic acid resin to the secondary amine in the polybenzimidazole is 0.1-1. According to the preparation method, the non-composite high-strength crosslinking type perfluorosulfonic acid proton exchange membrane is prepared by the perfluorosulfonic acid containing functional groups and the polybenzimidazole containing secondary amine through a chemical crosslinking reaction, so that the mechanical property and the size stability of the proton membrane are effectively improved.
Description
Technical Field
The invention belongs to the technical field of high polymer materials, and particularly relates to a cross-linked proton exchange membrane and a preparation method thereof.
Background
At present, scientific researchers seek clean energy sources due to the increasing shortage of fossil energy and the increasing serious environmental pollution. The fuel cell is a green energy conversion device which directly converts chemical energy into electric energy, the proton exchange membrane is one of the core components of the fuel cell, and the commercial proton exchange membranes are all perfluorinated sulfonic acid resin ion exchange membranes. The perfluorosulfonic acid ion exchange membrane has excellent chemical stability, electrochemical stability and thermal stability due to the unique perfluoromain chain structure, and therefore, is widely applied to the fields of fuel cells, electrolytic water, electrodialysis, flow batteries and the like. The perfluorinated sulfonic acid resin ion exchange membrane homogeneous membrane has poor dimensional stability due to high swelling degree and high water absorption, and under the application working condition of alternate dry and wet change, wet stress can be formed inside the ion membrane, the mechanical property of the ion membrane can be degraded due to the wet stress, the membrane structure can be damaged under the long-term cyclic use working condition, and the service life of the ion membrane and the operation safety of a fuel cell stack are finally influenced.
At present, the mechanical strength of the composite proton exchange membrane is enhanced mostly by a porous filling mode, but the prepared enhanced composite proton exchange membrane has the problems of insufficient filling degree and insufficient bonding force of two-phase interfaces, so that the problems of low ionic conductivity, low mechanical property and poor dimensional stability are caused, and meanwhile, the preparation process is complex and the preparation process is difficult to stabilize.
Therefore, there is a need for an improved proton exchange membrane preparation method to improve the mechanical strength and stability of the proton exchange membrane.
Disclosure of Invention
The present invention is based on the discovery and recognition by the inventors of the following facts and problems: in addition to a porous filling composite mode, crosslinking is also an effective method which can effectively inhibit swelling and simultaneously give consideration to proton conductivity of an ion exchange membrane, and the homogeneous proton exchange membrane prepared by adding a crosslinking agent and perfluorinated sulfonic acid resin for chemical crosslinking can avoid the problem of interface falling caused by insufficient filling, so that good mechanical property and dimensional stability are maintained, and an ordered proton channel is constructed to improve the proton conductivity. CN101764234A discloses a preparation method of a cross-linked proton exchange membrane, which comprises dissolving carbonyldiimidazole and perfluorosulfonic acid ion exchange resin in an organic solvent to prepare a perfluorosulfonic acid solution (perfluorocasting solution); and adding a cross-linking agent into the casting solution, uniformly stirring, pouring the casting solution on the surface of a horizontal glass plate or a Hastelloy steel plate, and evaporating an organic solvent to obtain the cross-linked ion exchange membrane. However, when a crosslinking mode is adopted, the molecular weight of the crosslinking agent and the bonding force between the crosslinking agent and the perfluorinated sulfonic acid resin have great influence on the mechanical strength of the ion exchange membrane, and the mechanical strength of the formed ion exchange membrane cannot be effectively increased under the condition of insufficient crosslinking degree.
The present invention is directed to solving, at least to some extent, one of the technical problems in the related art. Therefore, the embodiment of the invention provides a preparation method of a crosslinking type proton exchange membrane, which is characterized in that a compound-free high-strength crosslinking type perfluorosulfonic acid proton exchange membrane is prepared by a perfluorosulfonic acid containing functional groups and a polybenzimidazole containing secondary amine (-NH) through a chemical crosslinking reaction, and the mechanical property and the size stability of the proton membrane are effectively improved.
The preparation method of the cross-linking proton exchange membrane comprises the step of chemically cross-linking sulfonic acid resin containing functional groups and polybenzimidazole containing secondary amine, wherein,
the sulfonic acid resin containing functional groups comprises a repeating unit shown as a formula I, wherein X is more than 0 and less than 0.1, y is more than 0 and less than 0.6, a is more than 1 and less than 6, b is 1,2 or 3, c is 1,2 or 3, X is at least one of Cl, Br and I,
the polybenzimidazole containing secondary amine comprises a repeating unit with a structural formula shown as formula II, R is selected from O, CH2、CH2-O-CH2、(CH2)2、(CH2)3、(CH2)4、(CH2)5、(CH2)6At least one of
The preparation method of the cross-linked proton exchange membrane provided by the embodiment of the invention brings advantages and technical effects, 1, in the method provided by the embodiment of the invention, the cross-linked proton exchange membrane is prepared by chemically cross-linking sulfonic acid resin containing functional groups and (-NH) polybenzimidazole containing secondary amine, and a porous enhancement layer is not required to be added for compounding, so that the preparation method is simple; 2. in the method of the embodiment of the invention, secondary amine groups in the polybenzimidazole and functional group halogen crosslinking sites on the sulfonic acid resin can easily perform a displacement reaction, which is beneficial to the proceeding of a crosslinking reaction, so that the crosslinking degree of the crosslinking reaction can be effectively controlled by controlling the contents of the functional groups in the sulfonic acid resin and the secondary amine groups in the (-NH) polybenzimidazole containing secondary amine, and the mechanical strength of the proton exchange membrane is increased; 3. the method of the embodiment of the invention effectively improves the mechanical property and the dimensional stability of the proton exchange membrane, the tensile strength can reach more than 80MPa, and the swelling ratio is reduced to be less than 3%.
In some embodiments, the perfluorosulfonic acid resin containing functional groups has an EW value of 800-1200, a molecular weight of 20-50 ten thousand and a molecular weight distribution of 1.05-1.8.
In some embodiments, the functional group of the perfluorinated sulfonic acid resin containing the functional group
The molar content of (A) is 5-15%.
In some embodiments, the molar content of secondary amine groups in the secondary amine-containing polybenzimidazole is from 5 to 40%.
In some embodiments, the secondary amine-containing polybenzimidazole has a molecular weight of 10 to 50 million.
In some embodiments, the method of preparing a cross-linked proton exchange membrane comprises the steps of:
a. dissolving perfluorosulfonic acid resin containing functional groups and polybenzimidazole containing secondary amine in a solvent, and performing crosslinking reaction under the action of a catalyst to obtain a casting solution, wherein the solvent comprises at least one of water, ethanol, n-propanol, isopropanol, pyrrolidone, dimethylformamide, dimethylacetamide and dimethyl sulfoxide, and the catalyst comprises Na2CO3、NaHCO3、K2CO3、KHCO3At least one of NaH and LiH;
b. and c, preparing the cross-linking proton exchange membrane from the membrane casting solution obtained in the step a by a solution casting method.
In some embodiments, in the step a, the method for preparing the perfluorosulfonic acid resin containing a functional group comprises: prepared by radical copolymerization of a halogen-containing long-side chain monomer, tetrafluoroethylene, and a sulfonyl fluoride vinyl ether.
In some embodiments, in step a, the molar ratio of the functional group in the perfluorosulfonic acid resin to the secondary amine in the polybenzimidazole is from 0.1 to 1.
In some embodiments, in step a, the crosslinking reaction temperature is 20 ℃ to 200 ℃ and the reaction time is 0.5 to 24 hours; and/or in the step b, the concentration of the casting solution is 5 wt% -25 wt%, the heating temperature of the solution casting method is 100 ℃ and 250 ℃, and the heating time is 5-30 minutes.
The embodiment of the invention also provides a cross-linked proton exchange membrane which is prepared by the method of the embodiment of the invention. The cross-linked proton exchange membrane disclosed by the embodiment of the invention has excellent mechanical properties and dimensional stability, and the tensile strength can reach more than 80 MPa.
Drawings
FIG. 1 is a scanning electron micrograph of a proton exchange membrane prepared according to example 1;
FIG. 2 is a scanning electron micrograph of a proton exchange membrane prepared according to example 2;
FIG. 3 is a scanning electron micrograph of a proton exchange membrane prepared in example 3.
Detailed Description
Reference will now be made in detail to embodiments of the present invention, examples of which are illustrated in the accompanying drawings. The embodiments described below with reference to the drawings are illustrative and intended to be illustrative of the invention and are not to be construed as limiting the invention.
The preparation method of the cross-linking proton exchange membrane comprises the step of chemically cross-linking sulfonic acid resin containing functional groups and polybenzimidazole containing secondary amine, wherein,
the sulfonic acid resin containing functional groups comprises a repeating unit shown as a formula I, wherein X is more than 0 and less than 0.1, y is more than 0 and less than 0.6, a is more than 1 and less than 6, b is 1,2 or 3, c is 1,2 or 3, X is at least one of Cl, Br and I,
the polybenzimidazole containing secondary amine comprises a repeating unit with a structural formula shown as formula II, R is selected from O, CH2、CH2-O-CH2、(CH2)2、(CH2)3、(CH2)4、(CH2)5、(CH2)6At least one of
According to the preparation method of the cross-linked proton exchange membrane, sulfonic acid resin containing functional groups and secondary amine-containing (-NH) polybenzimidazole are subjected to chemical cross-linking to prepare the cross-linked proton exchange membrane, a porous reinforcing layer is not required to be added for compounding, and the preparation method is simple; in the method of the embodiment of the invention, secondary amine groups in the polybenzimidazole and functional group halogen crosslinking sites on the sulfonic acid resin can easily perform a displacement reaction, which is beneficial to the proceeding of a crosslinking reaction, so that the crosslinking degree of the crosslinking reaction can be effectively controlled by controlling the contents of the functional groups in the sulfonic acid resin and the secondary amine groups in the (-NH) polybenzimidazole containing secondary amine, and the mechanical strength of the proton exchange membrane is increased; the method of the embodiment of the invention effectively improves the mechanical property and the dimensional stability of the proton exchange membrane, the tensile strength can reach more than 80MPa, and the swelling ratio is reduced to be less than 3%.
In some embodiments, the perfluorosulfonic acid resin containing functional groups preferably has an EW value of 800-1200, a molecular weight of 20-50 ten thousand, and a molecular weight distribution of 1.05-1.8. Preferably, in the perfluorosulfonic acid resin containing functional groups, the functional groups are
The molar content of (a) is not more than 10%, and more preferably 5 to 15%. In the method of the embodiment of the invention, the content of the functional group in the perfluorinated sulfonic acid resin is further optimized, which is beneficial to improving the mechanical property and the proton conductivity of the proton exchange membrane, and the excessive content of the functional group can influence the regularity of the perfluorinated sulfonic acid resin and reduce the crystallization property of the resinBut rather, the mechanical strength of the proton exchange membrane is reduced.
In some embodiments, the molar content of secondary amine groups in the secondary amine-containing polybenzimidazole is preferably no more than 40%, preferably 5 to 40%. More preferably, the molecular weight of the polybenzimidazole containing secondary amine is 10-50 ten thousand, and the tensile strength is more than or equal to 100 MPa. In the method of the embodiment of the invention, the content of secondary amine groups in the polybenzimidazole is further optimized, which is beneficial to improving the mechanical property and the proton conductivity of the proton exchange membrane, the secondary amine groups with excessive content can remain in the proton exchange membrane, quaternary ammonium groups are formed by peroxidation in the using process at the later stage, and finally the proton exchange membrane is converted into an anion exchange membrane.
In some embodiments, the method of preparing a cross-linked proton exchange membrane comprises the steps of:
a. dissolving perfluorosulfonic acid resin containing functional groups and polybenzimidazole containing secondary amine in a solvent, and performing crosslinking reaction under the action of a catalyst to obtain a casting solution;
b. and c, preparing the cross-linking proton exchange membrane from the membrane casting solution obtained in the step a by a solution casting method.
In some embodiments, in step a, the solvent comprises at least one of water, ethanol, n-propanol, isopropanol, pyrrolidone, dimethylformamide, dimethylacetamide, and dimethylsulfoxide, and the catalyst comprises Na2CO3、NaHCO3、K2CO3、KHCO3At least one of NaH and LiH. In the method of the embodiment of the invention, the solvent and the catalyst adopted in the crosslinking process are preferred, which is favorable for further promoting the crosslinking reaction.
In some embodiments, in the step a, the method for preparing the perfluorosulfonic acid resin containing a functional group comprises: prepared by radical copolymerization of a halogen-containing long-side chain monomer, tetrafluoroethylene, and a sulfonyl fluoride vinyl ether. Wherein the halogen-containing long side chain monomer contains functional groups
Perfluoroolefin of (2), preferablyAlternatively, 2-chloropentafluoro-1, 3-butadiene, 6-bromo-1, 1, 2-trifluorohexene and the like may be mentioned.
Preferably, the preparation method of the perfluorosulfonic acid resin containing functional groups comprises the following steps: (1) halogen-containing long-side-chain monomer, tetrafluoroethylene, and sulfonyl fluoride vinyl ether are mixed in a molar ratio of 1-5: 0.1-5: 5-15, adding the mixture into a reaction kettle according to the proportion of the solvent: adding a solvent according to the mass ratio of the monomers of 5-10:1, vacuumizing the reaction kettle, introducing N2 for ten minutes, sealing, and stirring and heating; (2) when the temperature rises to 20-120 ℃, adding an initiator, wherein the initiator is selected from N2F2, perfluoroperoxide, peroxide and azo initiators, the concentration of the initiator is 0.1-10 wt%, the reaction pressure is 0.1-10 MPa, and the reaction time is 3-24 h. Preferably, the initiator is added in portions, and the initiator is added once in half an hour for reaction, and added in 2 to 10 portions. After the reaction is finished, pressure is released, unreacted monomers are evaporated out by heating, the solvent is recovered, a powdery product is obtained, the product is further extracted by methanol for three times, and the product is dried for 8 hours at the temperature of 100 ℃, so that the ion exchange resin containing the crosslinking sites is obtained.
In some embodiments, in step a, the molar ratio of the functional group in the perfluorosulfonic acid resin to the secondary amine in the polybenzimidazole is from 0.1 to 1. In the method of the embodiment of the invention, the molar ratio of the functional group in the perfluorosulfonic acid resin to the secondary amine in the polybenzimidazole is preferably selected, which is beneficial to the proceeding of the crosslinking reaction, effectively controls the crosslinking degree, further improves the mechanical property and proton conductivity of the proton exchange membrane, and keeps the dimensional stability.
In some embodiments, in step a, the crosslinking reaction temperature is 20 ℃ to 200 ℃ and the reaction time is 0.5 to 24 hours; in the step b, the concentration of the casting solution is 5 wt% -25 wt%, the heating temperature of the solution casting method is 100 ℃ and 250 ℃, and the heating time is 5-30 minutes. In the method of the embodiment of the invention, the proton exchange membrane is prepared by adopting a solution casting method for the membrane casting solution obtained by the crosslinking reaction, and the preparation method is simple and is easy for industrial application.
The embodiment of the invention also provides a cross-linked proton exchange membrane which is prepared by the method of the embodiment of the invention. Preferably, the thickness of the cross-linked proton exchange membrane is 8-15 μm. The cross-linked proton exchange membrane disclosed by the embodiment of the invention has excellent mechanical properties and dimensional stability, and the tensile strength can reach more than 80 MPa.
The present invention is described in detail below with reference to the drawings and examples.
Example 1
(1) Preparation of Bromide ion-containing perfluorosulfonic acid resin
Washing and drying a reaction kettle, and mixing 6-bromo-1, 1, 2-trifluorohexene, tetrafluoroethylene and perfluoro-2- (2-sulfuryl fluoroethyl) propyl vinyl ether (CF)2＝CFOCF2CFCF3OF2CF2SO2F) Mixing according to the mol ratio of 2:5:4, adding a solvent perfluoromethyl cyclobutane, vacuumizing the reaction kettle, filling nitrogen, and circulating for three times. The temperature was raised to 90 ℃ while the pressure was raised to 2 MPa. Dissolving an initiator peroxide perfluoropropionyl compound in perfluoromethylcyclobutane, adding the solution into a reaction kettle in batches every half an hour, reacting for 10 hours, stopping the reaction, cooling, and relieving pressure. Pouring out the materials, transferring the materials into a glass flask, distilling out unreacted monomers and solvent to obtain a powdery product, further washing the product with methanol for a plurality of times, and drying the product at 100 ℃ for 8h to obtain the perfluorinated sulfonic acid resin containing bromide ions, wherein the molar content of the bromide ions is 10%.
(2) 90g of dimethylformamide is placed in a 250mL three-neck flask, and then 9g of the bromide ion-containing perfluorosulfonic acid resin prepared in the step (1) and 1g of secondary amine-containing PBI resin (commercially available) are added, wherein the mixed solid content of the two resins is 10 wt%, the molar content of the secondary amine groups in the PBI resin is 30%, and the molar ratio of bromide ions to the secondary amine groups is 4: 10.
(3) Adding 0.1g LiH as a crosslinking reaction catalyst, introducing nitrogen for 10 minutes to replace the air in the flask, stirring and heating to start crosslinking reaction, heating to the temperature of 80 ℃, and reacting for 6 hours to obtain a casting solution.
(4) And (2) defoaming the casting solution in vacuum until no obvious bubbles exist, filtering the casting solution by 0.5um filter cloth, coating by adopting a scraper coating method, flatly placing the basement membrane on a vacuum adsorption platform of a scraper coater, starting a vacuum pump to fix the basement membrane, pouring the casting solution, and then starting the scraper coater. And (3) standing for 1min after blade coating is finished, taking down the wet membrane, drying in an oven at 200 ℃ for 15 min, and removing the proton exchange membrane after drying is finished.
The SEM image of the cross-linked proton exchange membrane prepared in this example is shown in FIG. 1.
The cross-linked proton exchange membrane prepared in this example had a thickness of 8.1um, a tensile strength of 65.44MPa, an elongation at break of 67.04%, an electrical conductivity of 0.095S/cm, and a swelling ratio of 2-3% (membrane dimensions were measured and compared with the original dimensions after soaking in pure water at 80 ℃ for 24 hours).
Example 2
(1) The same procedure as in example 1 was conducted except that the molar content of bromide ions in the obtained bromide-containing perfluorosulfonic acid resin was 6%.
(2) And (2) putting 90g of dimethylformamide into a 250mL three-neck flask, and then adding 9g of the bromide ion-containing perfluorosulfonic acid resin prepared in the step (1) and 1g of secondary amine-containing PBI resin, wherein the mixed solid content of the two resins is 10 wt%, the molar content of the secondary amine groups in the PBI resin is 15%, and the molar ratio of bromide ions to the secondary amine groups is 6: 10.
(3) Adding 0.1g LiH as a crosslinking reaction catalyst, introducing nitrogen for 10 minutes to replace the air in the flask, stirring and heating to start crosslinking reaction, heating to the temperature of 80 ℃, reacting for 6 hours, and taking out the casting solution.
(4) And (3) defoaming the casting solution in vacuum until no obvious bubble exists, filtering the casting solution by 0.5-micrometer filter cloth, coating by adopting a slit coating method, fixing a bottom membrane on an operation platform of a slit coater, pumping the casting solution into a film head of the slit coater, wherein the flow rate is 15mL/min, and the coating wet thickness is 350 micrometers. Standing for 1 minute after coating, taking down the wet membrane, drying in an oven at 200 ℃ for 15 minutes, and taking down the proton exchange membrane after drying.
The SEM image of the cross-linked proton exchange membrane prepared in this example is shown in FIG. 2.
The thickness of the cross-linked proton exchange membrane prepared by the embodiment is 8.6um, the tensile strength is 66.72MPa, the elongation at break is 65.13%, the electrical conductivity is 0.102S/cm, and the swelling ratio is 1.5-2.5%.
Example 3
(1) The molar content of bromide ions in the prepared bromide ion-containing perfluorosulfonic acid resin was 6% in the same manner as in example 2.
(2) And (2) taking 80g of dimethylacetamide in a 250mL three-neck flask, and then adding 18g of the bromide ion-containing perfluorosulfonic acid resin prepared in the step (1) and 2g of secondary amine-containing PBI resin, wherein the mixed solid content of the two resins is 20 wt%, the mole content of bromide ions in the perfluorosulfonic acid resin is 6%, the mole content of secondary amine groups in the secondary amine-containing PBI resin is 15%, and the mole ratio of bromide ions to secondary amine groups is 6: 10.
(3) Taking 0.1g LiH as a crosslinking reaction catalyst, heating while stirring to start a crosslinking reaction, heating to 150 ℃, reacting for 10 hours, and taking out the casting solution.
(4) And (3) defoaming the casting solution in vacuum until no obvious bubble exists, filtering the casting solution by using 0.5um filter cloth, and coating by using a slit coating method. And (3) fixing a bottom film on an operation platform of the slit coating machine, and pumping the film casting solution into a film head of the slit coating machine at the flow rate of 15 mL/min. Standing for 1 minute after coating, taking down the wet membrane, drying in an oven at 200 ℃ for 15 minutes, and taking down the proton exchange membrane after drying.
The SEM image of the cross-linked proton exchange membrane prepared in this example is shown in FIG. 3.
The thickness of the cross-linked proton exchange membrane prepared in the embodiment is 13um, the tensile strength is 83.72MPa, the breaking elongation is 68.07%, the electrical conductivity is 0.099S/cm, and the swelling rate is 2-3%.
Comparative example 1
The same procedure as in example 3, except that step 3 was omitted, the crosslinking reaction was not conducted, and the mixed solution of the two resins obtained in step 2 was subjected to the procedure of step (4) to obtain a proton exchange membrane.
The proton exchange membrane prepared by the embodiment has the thickness of 13.3um, the tensile strength of 35MPa, the elongation at break of 40 percent, the electrical conductivity of 0.09S/cm and the swelling ratio of 6-7 percent.
Comparative example 2
The same procedure as in example 1, except that the molar content of bromide ion in the bromide ion-containing perfluorosulfonic acid resin obtained in step (1) was 30%.
The proton exchange membrane prepared in comparative example 2 has a thickness of 8.2um, a tensile strength of 47MPa, an elongation at break of 59.9%, an electrical conductivity of 0.091S/cm and a swelling ratio of 4.5-5.5%.
In the present disclosure, the terms "one embodiment," "some embodiments," "an example," "a specific example," or "some examples" and the like mean that a specific feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the present disclosure. In this specification, the schematic representations of the terms used above are not necessarily intended to refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples. Furthermore, various embodiments or examples and features of different embodiments or examples described in this specification can be combined and combined by one skilled in the art without contradiction.
Although embodiments of the present invention have been shown and described above, it is understood that the above embodiments are exemplary and should not be construed as limiting the present invention, and that variations, modifications, substitutions and alterations can be made to the above embodiments by those of ordinary skill in the art within the scope of the present invention.
Claims (10)
1. A preparation method of a cross-linking proton exchange membrane is characterized by comprising the step of chemically cross-linking sulfonic acid resin containing functional groups and polybenzimidazole containing secondary amine, wherein,
the sulfonic acid resin containing functional groups comprises a repeating unit shown as a formula I, wherein X is more than 0 and less than 0.1, y is more than 0 and less than 0.6, a is more than 1 and less than 6, b is 1,2 or 3, c is 1,2 or 3, X is at least one of Cl, Br and I,
the polybenzimidazole containing secondary amine comprises a repeating unit with a structural formula shown as formula II, R is selected from O, CH2、CH2-O-CH2、(CH2)2、(CH2)3、(CH2)4、(CH2)5、(CH2)6At least one of
2. The method for preparing a cross-linked proton exchange membrane according to claim 1, wherein the perfluorosulfonic acid resin containing functional groups has an EW value of 800-1200, a molecular weight of 20-50 ten thousand and a molecular weight distribution of 1.05-1.8.
3. The method for preparing a cross-linked proton exchange membrane according to claim 1, wherein the functional group in the perfluorinated sulfonic acid resin containing the functional group
The molar content of (A) is 5-15%.
4. The method for preparing a cross-linked proton exchange membrane according to claim 1, wherein the molar content of the secondary amine group in the polybenzimidazole containing the secondary amine is 5-40%.
5. The method for preparing a crosslinked proton exchange membrane according to claim 1 or 5, wherein the molecular weight of the polybenzimidazole containing a secondary amine is 10 to 50 ten thousand.
6. The method for preparing a cross-linked proton exchange membrane according to claim 1, comprising the steps of:
a. dissolving perfluorosulfonic acid resin containing functional groups and polybenzimidazole containing secondary amine in a solvent, and performing crosslinking reaction under the action of a catalyst to obtain a casting solution, wherein the solvent comprises water, ethanol, n-propanol and isopropanolAt least one of alcohol, pyrrolidone, dimethylformamide, dimethylacetamide and dimethyl sulfoxide, wherein the catalyst comprises Na2CO3、NaHCO3、K2CO3、KHCO3At least one of NaH and LiH;
b. and c, preparing the cross-linking proton exchange membrane from the membrane casting solution obtained in the step a by a solution casting method.
7. The method for preparing a cross-linked proton exchange membrane according to claim 1 or 6, wherein in the step a, the method for preparing the perfluorosulfonic acid resin containing functional groups comprises: prepared by radical copolymerization of a halogen-containing long-side chain monomer, tetrafluoroethylene, and a sulfonyl fluoride vinyl ether.
8. The method for preparing a cross-linked proton exchange membrane according to claim 1 or 6, wherein in the step a, the molar ratio of the functional group in the perfluorosulfonic acid resin to the secondary amine in the polybenzimidazole is 0.1-1.
9. The method for preparing the cross-linked proton exchange membrane according to claim 6, wherein in the step a, the cross-linking reaction temperature is 20 ℃ to 200 ℃, and the reaction time is 0.5 h to 24 h; and/or in the step b, the concentration of the casting solution is 5 wt% -25 wt%, the heating temperature of the solution casting method is 100 ℃ and 250 ℃, and the heating time is 5-30 minutes.
10. A cross-linked proton exchange membrane obtainable by the process of any one of claims 1 to 9.
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| CN115353579A (en) * | 2022-10-20 | 2022-11-18 | 国家电投集团氢能科技发展有限公司 | Anti-swelling amphoteric ion exchange resin, preparation method thereof, ion exchange membrane and application |
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| CN101367903A (en) * | 2008-08-07 | 2009-02-18 | 同济大学 | Enhancement type composite proton exchanging film based on semi-interpenetrating network |
| CN101764234A (en) * | 2009-11-13 | 2010-06-30 | 山东东岳高分子材料有限公司 | Interpenetrating crosslinked perfluorinated sulfonic acid ion exchange membrane and preparation method thereof |
| US20140242368A1 (en) * | 2013-02-22 | 2014-08-28 | National Research Council Of Canada | Process for producing ion exchange membranes by melt-processing of acidic pfsa ionomers |
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| CN101367903A (en) * | 2008-08-07 | 2009-02-18 | 同济大学 | Enhancement type composite proton exchanging film based on semi-interpenetrating network |
| CN101764234A (en) * | 2009-11-13 | 2010-06-30 | 山东东岳高分子材料有限公司 | Interpenetrating crosslinked perfluorinated sulfonic acid ion exchange membrane and preparation method thereof |
| US20140242368A1 (en) * | 2013-02-22 | 2014-08-28 | National Research Council Of Canada | Process for producing ion exchange membranes by melt-processing of acidic pfsa ionomers |
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| CN115353579A (en) * | 2022-10-20 | 2022-11-18 | 国家电投集团氢能科技发展有限公司 | Anti-swelling amphoteric ion exchange resin, preparation method thereof, ion exchange membrane and application |
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Inventor after: Gan Zhiqiang Inventor after: Wang Jie Inventor after: Li Zhenkang Inventor after: Xia Fengjie Inventor after: Liu Zhen Inventor after: Li Daoxi Inventor after: Liu Hao Inventor after: Zhou Mingzheng Inventor after: Tang Haolin Inventor after: Liu Pinyang Inventor after: Fang Liang Inventor after: Wang Fuyao Inventor after: Liu Fei Inventor before: Gan Zhiqiang Inventor before: Xia Fengjie Inventor before: Liu Zhen Inventor before: Li Daoxi Inventor before: Liu Hao Inventor before: Liu Pinyang Inventor before: Fang Liang Inventor before: Wang Fuyao Inventor before: Liu Fei Inventor before: Wang Jie Inventor before: Li Zhenkang |