CN117844149A - Modified fluorine-containing sulfonic acid resin, membrane and application thereof in field of flow batteries - Google Patents
Modified fluorine-containing sulfonic acid resin, membrane and application thereof in field of flow batteries Download PDFInfo
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- CN117844149A CN117844149A CN202311727447.4A CN202311727447A CN117844149A CN 117844149 A CN117844149 A CN 117844149A CN 202311727447 A CN202311727447 A CN 202311727447A CN 117844149 A CN117844149 A CN 117844149A
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- acid resin
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- sulfonic acid
- ion exchange
- titanium dioxide
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- 239000011347 resin Substances 0.000 title claims abstract description 59
- 229920005989 resin Polymers 0.000 title claims abstract description 59
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 title claims abstract description 25
- 239000012528 membrane Substances 0.000 title claims abstract description 25
- 125000001153 fluoro group Chemical class F* 0.000 title 1
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical class [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 claims abstract description 48
- 238000006277 sulfonation reaction Methods 0.000 claims abstract description 28
- 239000003014 ion exchange membrane Substances 0.000 claims abstract description 22
- 150000002500 ions Chemical class 0.000 claims abstract description 18
- 150000003460 sulfonic acids Chemical class 0.000 claims abstract description 18
- 150000002221 fluorine Chemical class 0.000 claims abstract description 14
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000011737 fluorine Substances 0.000 claims abstract description 9
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 9
- 230000008961 swelling Effects 0.000 claims abstract description 6
- 239000008186 active pharmaceutical agent Substances 0.000 claims abstract description 4
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 42
- 239000007788 liquid Substances 0.000 claims description 24
- 239000007787 solid Substances 0.000 claims description 23
- 238000005266 casting Methods 0.000 claims description 22
- 238000010438 heat treatment Methods 0.000 claims description 22
- 239000002904 solvent Substances 0.000 claims description 20
- 238000005342 ion exchange Methods 0.000 claims description 16
- UQSQSQZYBQSBJZ-UHFFFAOYSA-N fluorosulfonic acid Chemical class OS(F)(=O)=O UQSQSQZYBQSBJZ-UHFFFAOYSA-N 0.000 claims description 14
- 239000011248 coating agent Substances 0.000 claims description 12
- 238000000576 coating method Methods 0.000 claims description 12
- 239000006185 dispersion Substances 0.000 claims description 10
- -1 polytetrafluoroethylene Polymers 0.000 claims description 10
- 230000003014 reinforcing effect Effects 0.000 claims description 10
- 239000000835 fiber Substances 0.000 claims description 9
- 230000010220 ion permeability Effects 0.000 claims description 7
- 229920000642 polymer Polymers 0.000 claims description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 6
- 239000004642 Polyimide Substances 0.000 claims description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 4
- 229920001721 polyimide Polymers 0.000 claims description 4
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 4
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 3
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 3
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 3
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 2
- 229920001774 Perfluoroether Polymers 0.000 claims description 2
- 239000004693 Polybenzimidazole Substances 0.000 claims description 2
- 239000004695 Polyether sulfone Substances 0.000 claims description 2
- 239000004698 Polyethylene Substances 0.000 claims description 2
- 239000004743 Polypropylene Substances 0.000 claims description 2
- 229920006221 acetate fiber Polymers 0.000 claims description 2
- 239000000919 ceramic Substances 0.000 claims description 2
- 229920001577 copolymer Polymers 0.000 claims description 2
- 238000007598 dipping method Methods 0.000 claims description 2
- 238000007606 doctor blade method Methods 0.000 claims description 2
- 235000019253 formic acid Nutrition 0.000 claims description 2
- 239000002557 mineral fiber Substances 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 229920001643 poly(ether ketone) Polymers 0.000 claims description 2
- 229920002480 polybenzimidazole Polymers 0.000 claims description 2
- 229920006393 polyether sulfone Polymers 0.000 claims description 2
- 229920000573 polyethylene Polymers 0.000 claims description 2
- 229920001155 polypropylene Polymers 0.000 claims description 2
- 239000004800 polyvinyl chloride Substances 0.000 claims description 2
- 229920000915 polyvinyl chloride Polymers 0.000 claims description 2
- 229920000131 polyvinylidene Polymers 0.000 claims description 2
- 238000005507 spraying Methods 0.000 claims description 2
- 230000002787 reinforcement Effects 0.000 claims 2
- BZPCMSSQHRAJCC-UHFFFAOYSA-N 1,2,3,3,4,4,5,5,5-nonafluoro-1-(1,2,3,3,4,4,5,5,5-nonafluoropent-1-enoxy)pent-1-ene Chemical compound FC(F)(F)C(F)(F)C(F)(F)C(F)=C(F)OC(F)=C(F)C(F)(F)C(F)(F)C(F)(F)F BZPCMSSQHRAJCC-UHFFFAOYSA-N 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 claims 1
- XIUFWXXRTPHHDQ-UHFFFAOYSA-N prop-1-ene;1,1,2,2-tetrafluoroethene Chemical group CC=C.FC(F)=C(F)F XIUFWXXRTPHHDQ-UHFFFAOYSA-N 0.000 claims 1
- 239000002131 composite material Substances 0.000 abstract description 8
- 239000002861 polymer material Substances 0.000 abstract description 2
- 238000010521 absorption reaction Methods 0.000 abstract 1
- 229910021645 metal ion Inorganic materials 0.000 abstract 1
- 230000035699 permeability Effects 0.000 abstract 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract 1
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical group OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 33
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 30
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 24
- 239000002105 nanoparticle Substances 0.000 description 16
- 239000000243 solution Substances 0.000 description 16
- 238000006243 chemical reaction Methods 0.000 description 15
- 239000004408 titanium dioxide Substances 0.000 description 15
- 238000005406 washing Methods 0.000 description 11
- 229910010413 TiO 2 Inorganic materials 0.000 description 10
- 238000003756 stirring Methods 0.000 description 10
- 238000001132 ultrasonic dispersion Methods 0.000 description 10
- 238000001291 vacuum drying Methods 0.000 description 10
- 239000012298 atmosphere Substances 0.000 description 9
- 239000000463 material Substances 0.000 description 9
- 230000007935 neutral effect Effects 0.000 description 7
- 239000003795 chemical substances by application Substances 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 238000000034 method Methods 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 239000003792 electrolyte Substances 0.000 description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- 229910001456 vanadium ion Inorganic materials 0.000 description 3
- 239000004812 Fluorinated ethylene propylene Substances 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 239000004020 conductor Substances 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 239000002608 ionic liquid Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 229920009441 perflouroethylene propylene Polymers 0.000 description 2
- 229910052720 vanadium Inorganic materials 0.000 description 2
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 2
- KEQGZUUPPQEDPF-UHFFFAOYSA-N 1,3-dichloro-5,5-dimethylimidazolidine-2,4-dione Chemical compound CC1(C)N(Cl)C(=O)N(Cl)C1=O KEQGZUUPPQEDPF-UHFFFAOYSA-N 0.000 description 1
- OVGRCEFMXPHEBL-UHFFFAOYSA-N 1-ethenoxypropane Chemical class CCCOC=C OVGRCEFMXPHEBL-UHFFFAOYSA-N 0.000 description 1
- 229920003934 Aciplex® Polymers 0.000 description 1
- 229920003935 Flemion® Polymers 0.000 description 1
- 229920000557 Nafion® Polymers 0.000 description 1
- 239000004696 Poly ether ether ketone Substances 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 1
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- XTHPWXDJESJLNJ-UHFFFAOYSA-N chlorosulfonic acid Substances OS(Cl)(=O)=O XTHPWXDJESJLNJ-UHFFFAOYSA-N 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- HQQADJVZYDDRJT-UHFFFAOYSA-N ethene;prop-1-ene Chemical group C=C.CC=C HQQADJVZYDDRJT-UHFFFAOYSA-N 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000007306 functionalization reaction Methods 0.000 description 1
- 150000002460 imidazoles Chemical class 0.000 description 1
- 239000010954 inorganic particle Substances 0.000 description 1
- 239000012982 microporous membrane Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 229920002530 polyetherether ketone Polymers 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 150000003852 triazoles Chemical class 0.000 description 1
Classifications
-
- 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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- Manufacture Of Macromolecular Shaped Articles (AREA)
Abstract
The invention belongs to the technical field of high polymer materials, and relates to a modified fluorine-containing sulfonic acid resin, a membrane and application thereof in the field of flow batteries, wherein the modified fluorine-containing sulfonic acid resin consists of 90-99.9 wt% of fluorine-containing sulfonic acid resin, 0.1-10 wt% of sulfonated titanium dioxide, and the sulfonation degree DS of the sulfonated titanium dioxide is 60% -75%. When the modified fluorine-containing sulfonic acid resin and the membrane prepared by the invention are applied to a flow battery, the permeability and the swelling rate of metal ions can be reduced, the water absorption capacity of the perfluorinated sulfonic acid resin membrane is improved, the proton conduction capacity of the perfluorinated sulfonic acid resin membrane is improved, and the composite ion exchange membrane with high ion selectivity and excellent battery performance is obtained.
Description
Technical Field
The invention relates to the technical field of high polymer materials, in particular to a modified fluorine-containing sulfonic acid resin, a membrane and application thereof in the field of flow batteries.
Background
Flow Batteries (RFBs) achieve storage and release of electricity with their excellent battery efficiency, rapid response speed, long cycle life, and unique modular design, and are attractive in the fields of electrical and chemical energy. The ion exchange membrane (PEM) serves as a key component of a Vanadium Redox Flow Battery (VRFB) system, isolating the positive and negative electrolytes, and providing the necessary proton transport channels. The excellent PEM should have high proton conductivity, low vanadium ion permeability, excellent cell performance, and low cost.
The simple perfluorinated sulfonic acid resin ion exchange membrane is widely applied due to the excellent mechanical property and chemical stability, but the proton conductivity is closely related to the swelling of the membrane, and too high proton conductivity can cause the swelling to rise, so that the ion permeation of the ion exchange membrane and the service life of the membrane are affected, and the application of the battery is limited to a certain extent. The mechanical strength and ion permeation blocking capacity of the membrane can be improved by adding the inorganic nano particles such as titanium dioxide, and the inorganic nano particles such as titanium dioxide can interact with the ion resin to enable the composite membrane structure to be more compact and limit the swelling behavior of the composite membrane, so that the high-performance ion exchange membrane is prepared. However, when titanium dioxide is simply added, the problems of difficult dispersion and easy agglomeration exist, the mechanical properties are affected, and the proton conducting capacity of the membrane is reduced to a certain extent.
Chinese patent document CN111333892A provides a perfluorinated sulfonic acid resin/cationic ionic liquid modified inorganic particle amphoteric ion conductive composite membrane, which has the characteristics of excellent ion selectivity, high conductivity and good chemical stability, and can be applied to redox flow batteries. However, the patent uses an anionic ionic liquid as a modifier, which is expensive and has a complex preparation process. Chinese patent document CN112582657A discloses a preparation method of an ultrathin high proton conductivity proton exchange composite membrane, which is prepared by taking a PTFE microporous membrane as a base membrane, taking perfluorinated sulfonic acid resin liquid and nano-phosphorylated titanium dioxide as proton conductor materials and taking a free radical quencher as an additive. The prepared composite membrane has high proton conductivity, high mechanical strength, thin thickness and good uniformity. Although the proton conductivity of the invention is high, too high proton conductivity can lead to high ion permeability, and in practical application, can lead to cross-permeation of electrolyte, thereby influencing the service life and the use cost of the electrolyte. The proton exchange membrane is formed by compositing inorganic nano particles grafted by an azacyclo compound and perfluorinated sulfonic acid resin in the Chinese patent document CN101604757A, has higher proton conducting capacity, has stable battery performance and can avoid the occurrence of catalyst poisoning. The nitrogen heterocyclic compound is imidazole, triazole or imidazole derivative with similar physical and chemical properties; the inorganic nano particles are silica, zirconium dioxide or titanium dioxide nano particles with similar physical and chemical properties; the perfluorinated sulfonic acid resin is Nafion resin, aciplex or Flemion proton conductor polymer, and the weight ratio of the inorganic nano particles grafted by the nitrogen heterocyclic compound to the perfluorinated sulfonic acid resin is 1:20-1:1. The preparation process of the invention is complex, in particular to a grafting method, the grafting rate is low, and the cost is higher when a catalyst is used.
Disclosure of Invention
The invention provides a modified fluorine-containing sulfonic acid resin, a membrane and application thereof in the field of flow batteries, and aims to solve the problem that the proton conductivity and ion permeation of the perfluorinated sulfonic acid resin can not be combined to cause low ion selectivity.
In order to achieve the above purpose, the present invention adopts the following technical scheme:
a modified fluorine-containing sulfonic acid resin is composed of fluorine-containing sulfonic acid resin and sulfonated titanium dioxide, and comprises 90-99.9wt% of fluorine-containing sulfonic acid resin, 0.1-10wt% of sulfonated titanium dioxide, and the sulfonation degree DS of the sulfonated titanium dioxide is 60% -75%.
Wherein, the sulfonation degree DS is the mol ratio of S element and Ti element in the sulfonated titanium dioxide.
Preferably, the mass content of the sulfonated titanium dioxide in the modified fluorine-containing sulfonic acid resin is 2.5-3.5%.
Preferably, the fluorine-containing sulfonic acid resin comprises one or more of a perfluorosulfonic acid resin and a partial fluorine-containing sulfonic acid resin, wherein the perfluorosulfonic acid resin is preferred; further preferably, the ion exchange capacity of the perfluorinated sulfonic acid resin is 0.5-2.5 mmol/g, and the molecular weight is 15-80 ten thousand; preferably, the ion exchange capacity is 0.8-1.8 mmol/g, and the molecular weight is 20-60 ten thousand; most preferably, the ion exchange capacity is 0.9-1.25 mmol/g, and the molecular weight is 20-40 ten thousand.
A modified ion exchange membrane comprises the modified fluorine-containing sulfonic acid resin and a reinforcing layer, wherein the thickness of the membrane is 40-100 mu m, the swelling rate is 4-10%, and the conductivity is more than or equal to 20ms/cm 2 Ion permeability of 5-8 x 10 -7 cm -2 ·min -1 Ion selectivity is 5-7X 10 3 S·min/cm 3 。
Preferably, the reinforcing layer is a porous nonwoven polymer, wherein the thickness of the reinforcing layer is: 5 to 50. Mu.m, preferably 5 to 25. Mu.m; the non-woven polymer is one or more of polytetrafluoroethylene, polyvinylidene fluoride-Co-hexafluoropropylene, polyethylene, polypropylene, polyethylene-Co-propylene, acetate fiber, polyimide, polyvinyl chloride, fluorinated Ethylene Propylene (FEP), fluorinated propyl vinyl ether fiber, perfluoroalkoxy vinyl ether copolymer fiber (PFA), ceramic fiber, mineral fiber, oxide fiber, polyethersulfone, polyetherketone, polyimide, polybenzimidazole and sulfonated and phosphorylated derivatives thereof.
Preferably, the number of the reinforcing layers is 0 to 10, preferably 0 to 3. When the reinforcing layer is 0 layers, the reinforcing layer is a homogeneous film, and when the number of the reinforcing layer is 1-3 layers, the reinforcing layer is a composite reinforcing film.
The invention provides a preparation method of the modified ion exchange membrane, which comprises the following steps:
a. mixing the modified fluorine-containing sulfonic acid resin and a solvent to form uniform dispersion liquid, wherein the solid content is 5-40%; the solvent is one or more of N, N-dimethylformamide, N-dimethylacetamide, N-methylpyrrolidone, 1-5 carbon chain alcohol, formic acid or acetic acid;
b. and (c) carrying out solution casting, wire rod coating, doctor blade coating, spraying or dipping on the dispersion liquid obtained in the step (a) to form a film, and heating at 50-80 ℃ to volatilize the solvent to obtain the modified ion exchange membrane.
The invention also provides application of the modified ion exchange membrane in the field of flow batteries.
Compared with the prior art, the invention has at least the following advantages:
1. the modified fluorine-containing sulfonic acid resin provided by the invention is prepared by modifying the fluorine-containing sulfonic acid resin through sulfonated titanium dioxide, solves the problem of poor ion permeation and proton conductivity of an ion exchange membrane in the prior art, has ultrahigh ion selectivity and excellent comprehensive performance, is convenient to apply to the field of flow batteries, and is favorable for realizing the use requirements of long service life and high performance of the ion exchange membrane.
2. The invention prepares the composite ion exchange membrane by using sulfonic acid functionalized titanium dioxide and fluorine-containing sulfonic acid ion resin, and can be applied to the field of flow batteries under different current densities.
3. The invention controls the sulfonation reaction time and temperature to precisely control the sulfonation degree to 60-75%, and greatly improves the interaction force between the sulfonated titanium dioxide and the fluorine-containing sulfonic acid resin, thereby having high ion selectivity. And has lower vanadium ion permeability and higher proton conductivity, thus solving the problem that proton conduction and ion permeation can not be combined. When the sulfonation degree of the titanium dioxide is 65%, the sulfonated titanium dioxide and the perfluorinated sulfonic acid resin have the most stable interaction force and the most ion selectivity.
Detailed Description
The present invention will be described in further detail with reference to examples. The starting materials used in the present invention, unless otherwise specified, may be prepared by any of the methods available commercially or by existing methods.
The sulfonated titanium dioxide of the present invention is preferably prepared by the following method, which comprises the steps of: a. dispersing titanium dioxide into a solvent to prepare titanium dioxide dispersion liquid; b. adding a functionalizing agent into the titanium dioxide dispersion liquid in the step a for sulfonic acid functionalization reaction, wherein the reaction temperature is 25-100 ℃, the reaction time is 1-48 h, and the reaction pressure is 0.05-10 MPa; c. and d, precipitating the dispersion liquid after the reaction in the step b, and washing to neutrality and drying to obtain the sulfonated titanium dioxide.
In step a, the concentration of titanium dioxide in the titanium dioxide dispersion is 0.1-0.3g/ml; the solvent is at least one selected from N, N-dimethylformamide, N-dimethylacetamide, N-methylpyrrolidone and alcohols with 1-5 carbon chains. In the step b, the functionalizing agent is at least one selected from dilute sulfuric acid, chlorosulfonic acid, sulfurous acid and sodium sulfate; the molar ratio of the titanium dioxide to the functionalizing agent is 1:1-1:10.
Preferably, the concentration of titanium dioxide in the titanium dioxide dispersion liquid is 0.2g/ml, the reaction temperature is 80 ℃, the reaction time is 24-42, the reaction pressure is normal pressure, the functionalizing agent is dilute sulfuric acid, the solvent is methanol, and the molar ratio of the titanium dioxide to the functionalizing agent is 1:2.34.
Example 1
1g of TiO 2 The nanoparticles were dispersed in 5ml of methanol, then 15ml of 2mol/L sulfuric acid solution was added, then placed in an ultrasonic apparatus for ultrasonic dispersion for 2 hours, transferred to a three-necked flask, N 2 Heating at 80℃for 24 hours under an atmosphere. Washing to neutrality after the reaction is finished, and vacuum drying to obtain white powdery solid, namely sulfonated titanium dioxide with the sulfonation degree of 60 percent.
A perfluorinated sulfonic acid resin having an IEC value of 1.0mmol/g and a molecular weight of 30 ten thousand was mixed with sulfonated titanium dioxide having a sulfonation degree of 60%, wherein the sulfonated titanium dioxide content was 3% by weight. Dispersing the mixed material in N, N-dimethylformamide, carrying out ultrasonic stirring to obtain a casting film liquid with the solid content of 30%, coating the casting film liquid with a wire rod to form a film, and heating and volatilizing a dry solvent to obtain the ion exchange film with the thickness of 50 mu m.
Example 2
1g of TiO 2 The nanoparticles were dispersed in 5ml of methanol, then 15ml of 2mol/L sulfuric acid solution was added, then placed in an ultrasonic apparatus for ultrasonic dispersion for 2 hours, and then transferred to a three-necked flask, N 2 Heating at 80deg.C for 30 hr under atmosphere. Washing to neutrality after the reaction is finished, and vacuum drying to obtain white powdery solid, namely sulfonated titanium dioxide with 65 percent of sulfonation degree.
The perfluorosulfonic acid resin having an IEC value of 1.0mmol/g and a molecular weight of 30 ten thousand was mixed with sulfonated titanium dioxide having a sulfonation degree of 65%, the sulfonated titanium dioxide content being 3% by weight. Dispersing in N, N-dimethylformamide, ultrasonic stirring to obtain casting film liquid with solid content of 30%, coating to form film by using a wire rod, and volatilizing the dry solvent by heating to obtain the ion exchange film with thickness of 50 μm.
Example 3
1g of TiO 2 The nanoparticles were dispersed in 5ml of methanol, then 15ml of 2mol/L sulfuric acid solution was added, then placed in an ultrasonic apparatus for ultrasonic dispersion for 2 hours, and then transferred to a three-necked flask, N 2 Heating at 80deg.C for 42 hr under atmosphere. Washing to neutrality after the reaction is finished, and vacuum drying to obtain white powdery solid, namely sulfonated titanium dioxide with the sulfonation degree of 75 percent.
Dissolving a perfluorinated sulfonic acid resin with IEC of 1.0mmol/g and molecular weight of 30 ten thousand in N, N-dimethylformamide, preparing a mixed solution with sulfonated titanium dioxide with sulfonation degree of 75%, preparing a casting solution with solid content of 30% after the sulfonated titanium dioxide content is 3wt% and ultrasonic stirring uniformly, coating the casting solution into a film through a wire rod, and volatilizing a dry solvent through heating to obtain the ion exchange membrane with thickness of 50 mu m.
Example 4
1g of TiO 2 The nanoparticles were dispersed in 5ml of methanol, then 15ml of 2mol/L sulfuric acid solution was added, then placed in an ultrasonic apparatus for ultrasonic dispersion for 2 hours, and then transferred to a three-necked flask, N 2 Heating at 80deg.C under atmospheric conditions for 30Hours. And after the reaction is finished, washing to be neutral, and vacuum drying to obtain white powdery solid, namely the sulfonated titanium dioxide with the sulfonation degree of 65%.
A perfluorinated sulfonic acid resin with a molecular weight of 25 ten thousand and 0.9mmol/g IEC was mixed with sulfonated titanium dioxide with a sulfonation degree of 65%, the sulfonated titanium dioxide content being 3% by weight. Dispersing the mixed material in N, N-dimethylformamide, carrying out ultrasonic stirring to obtain a casting film liquid with the solid content of 30%, coating the casting film liquid with a wire rod to form a film, and heating and volatilizing a dry solvent to obtain the ion exchange film with the thickness of 50 mu m.
Example 5
1g of TiO 2 The nanoparticles were dispersed in 5ml of methanol, then 15ml of 2mol/L sulfuric acid solution was added, then placed in an ultrasonic apparatus for ultrasonic dispersion for 2 hours, and then transferred to a three-necked flask, N 2 Heating at 80deg.C for 30 hr under atmosphere. And after the reaction is finished, washing to be neutral, and vacuum drying to obtain white powdery solid, namely the sulfonated titanium dioxide with the sulfonation degree of 65%.
A perfluorinated sulfonic acid resin having an IEC of 1.25mmol/g and a molecular weight of 50 ten thousand was mixed with sulfonated titanium dioxide having a sulfonation degree of 65%, the sulfonated titanium dioxide content being 3% by weight. Dispersing the mixed material in N, N-dimethylformamide, carrying out ultrasonic stirring to obtain a casting film liquid with the solid content of 30%, coating the casting film liquid with a wire rod to form a film, and heating and volatilizing a dry solvent to obtain the ion exchange film with the thickness of 50 mu m.
Example 6
1g of TiO 2 The nanoparticles were dispersed in 5ml of methanol, then 15ml of 2mol/L sulfuric acid solution was added, then placed in an ultrasonic apparatus for ultrasonic dispersion for 2 hours, and then transferred to a three-necked flask, N 2 Heating at 80deg.C for 30 hr under atmosphere. And after the reaction is finished, washing to be neutral, and vacuum drying to obtain white powdery solid, namely the sulfonated titanium dioxide with the sulfonation degree of 65%.
The perfluorosulfonic acid resin having an IEC value of 1.0mmol/g and a molecular weight of 30 ten thousand was mixed with sulfonated titanium dioxide having a sulfonation degree of 65%, and the sulfonated titanium dioxide content was 0.1% by weight. Dispersing the mixed material in N, N-dimethylformamide, carrying out ultrasonic stirring to obtain a casting film liquid with the solid content of 30%, coating the casting film liquid with a wire rod to form a film, and heating and volatilizing a dry solvent to obtain the ion exchange film with the thickness of 50 mu m.
Example 7
1g of TiO 2 The nanoparticles were dispersed in 5ml of methanol, then 15ml of 2mol/L sulfuric acid solution was added, then placed in an ultrasonic apparatus for ultrasonic dispersion for 2 hours, and then transferred to a three-necked flask, N 2 Heating at 80deg.C for 30 hr under atmosphere. And after the reaction is finished, washing to be neutral, and vacuum drying to obtain white powdery solid, namely the sulfonated titanium dioxide with the sulfonation degree of 65%.
A perfluorinated sulfonic acid resin having an IEC value of 1.0mmol/g and a molecular weight of 30 ten thousand was mixed with sulfonated titanium dioxide having a sulfonation degree of 65%, the sulfonated titanium dioxide content being 10% by weight. Dispersing the mixed material in N, N-dimethylformamide, carrying out ultrasonic stirring to obtain a casting film liquid with the solid content of 30%, coating the casting film liquid with a wire rod to form a film, and heating and volatilizing a dry solvent to obtain the ion exchange film with the thickness of 50 mu m.
Example 8
1g of TiO 2 The nanoparticles were dispersed in 5ml of methanol, then 15ml of 2mol/L sulfuric acid solution was added, then placed in an ultrasonic apparatus for ultrasonic dispersion for 2 hours, and then transferred to a three-necked flask, N 2 Heating at 80deg.C for 30 hr under atmosphere. And after the reaction is finished, washing to be neutral, and vacuum drying to obtain white powdery solid, namely the sulfonated titanium dioxide with the sulfonation degree of 65%.
A perfluorinated sulfonic acid resin having an IEC value of 1.0mmol/g and a molecular weight of 30 ten thousand was mixed with sulfonated titanium dioxide having a sulfonation degree of 65%, the sulfonated titanium dioxide content being 3% by weight. Dispersing the mixed material in N, N-dimethylformamide, carrying out ultrasonic stirring to obtain casting solution with the solid content of 30%, selecting polytetrafluoroethylene porous non-woven polymer with the thickness of 10 mu m, coating the polymer into a film by a wire rod, and volatilizing the dry solvent by heating to obtain the single reinforced ion exchange film with the thickness of 50 mu m.
Comparative example 1
The IEC value is 1.0mmol/g, the perfluorosulfonic acid resin with the molecular weight of 30 ten thousand is dispersed in N, N-dimethylformamide to obtain casting solution with the solid content of 30 percent, the casting solution is coated by a wire rod to form a film, and the film is heated to volatilize a dry solvent to obtain the ion exchange film with the thickness of 50 mu m.
Comparative example 2
1g of TiO 2 The nanoparticles were dispersed in 5ml of methanol, then 15ml of 2mol/L sulfuric acid solution was added, then placed in an ultrasonic apparatus for ultrasonic dispersion for 2 hours, and then transferred to a three-necked flask, N 2 Heating at 80deg.C for 30 hr under atmosphere. And after the reaction is finished, washing to be neutral, and vacuum drying to obtain white powdery solid, namely the sulfonated titanium dioxide with the sulfonation degree of 65%.
The perfluorosulfonic acid resin having an IEC value of 1.0mmol/g and a molecular weight of 30 ten thousand was mixed with sulfonated titanium dioxide having a sulfonation degree of 65% and a sulfonated titanium dioxide content of 13% by weight. Dispersing the mixed material in N, N-dimethylformamide, carrying out ultrasonic stirring to obtain a casting film liquid with the solid content of 30%, coating the casting film liquid with a wire rod to form a film, and heating and volatilizing a dry solvent to obtain the ion exchange film with the thickness of 50 mu m.
Comparative example 3
1g of TiO 2 The nanoparticles were dispersed in 5ml of methanol, then 15ml of 2mol/L sulfuric acid solution was added, then placed in an ultrasonic apparatus for ultrasonic dispersion for 2 hours, and then transferred to a three-necked flask, N 2 Heating at 80deg.C for 30 hr under atmosphere. And after the reaction is finished, washing to be neutral, and vacuum drying to obtain white powdery solid, namely the sulfonated titanium dioxide with the sulfonation degree of 65%.
A sulfonated polyetheretherketone resin (molecular weight 328) having a degree of sulfonation of 67% was mixed with a sulfonated titanium dioxide having a degree of sulfonation of 65%, the content of the sulfonated titanium dioxide being 3% by weight. Dispersing the mixed material in N, N-dimethylformamide, carrying out ultrasonic stirring to obtain a casting film liquid with the solid content of 30%, coating the casting film liquid with a wire rod to form a film, and heating and volatilizing a dry solvent to obtain the ion exchange film with the thickness of 50 mu m.
Table 1 shows the results of the ion exchange membranes obtained in the various examples and comparative examples. Wherein the conductivity is measured by an electrochemical impedance tester, and the testing condition temperature is 25 ℃ and 30% RH. The ion penetration test method adopts national standard GB/T33339-2016. Table 2 shows the current density of 160mA/cm for the various examples and comparative examples 2 The following cell efficiencies were compared.
TABLE 1 results of Performance test of different film samples
TABLE 2 different film samples at a current density of 160mA/cm 2 Lower battery efficiency
In all examples, the modified ion exchange membrane obtained in example 2 has the highest ion selectivity and the most excellent comprehensive performance, and by adding sulfonated titanium dioxide, the proton conductivity of the membrane is improved while the vanadium resistance of the membrane is improved. The addition of sulfonated titanium dioxide can influence the coulombic efficiency and the voltage efficiency of the battery by improving the proton conductivity and reducing the ion permeability, and the higher the proton conductivity is, the higher the voltage efficiency of the membrane is; the lower the vanadium ion permeability, the higher the coulombic efficiency of the membrane, with example 2 having the highest ion selectivity and therefore the highest energy efficiency.
Claims (10)
1. The modified fluorine-containing sulfonic acid resin is characterized by comprising 90-99.9 wt% of fluorine-containing sulfonic acid resin, 0.1-10 wt% of sulfonated titanium dioxide and the sulfonation degree DS of the sulfonated titanium dioxide is 60-75%.
2. The modified fluorosulfonic acid resin of claim 1, wherein the mass content of sulfonated titanium dioxide in said modified fluorosulfonic acid resin is 2.5-3.5%.
3. The modified fluorosulfonic acid resin of claim 1, wherein said fluorosulfonic acid resin comprises one or more of a perfluorosulfonic acid resin and a partially fluorosulfonic acid resin, preferably a perfluorosulfonic acid resin.
4. The modified fluorine-containing sulfonic acid resin according to claim 3, wherein the ion exchange capacity of the perfluorinated sulfonic acid resin is 0.5 to 2.5mmol/g and the molecular weight is 15 to 80 ten thousand; preferably, the ion exchange capacity is 0.8-1.8 mmol/g, and the molecular weight is 20-60 ten thousand; most preferably, the ion exchange capacity is 0.9-1.25 mmol/g, and the molecular weight is 20-40 ten thousand.
5. A modified ion exchange membrane comprising the modified fluorosulfonic acid resin of any one of claims 1 to 4 and a reinforcing layer, wherein the thickness of the membrane is 40 to 100. Mu.m, the swelling ratio is 4 to 10%, and the electrical conductivity is not less than 20ms/cm 2 Ion permeability of 5-8 x 10 -7 cm -2 ·min -1 Ion selectivity is 5-7X 10 3 S·min/cm 3 。
6. The modified ion exchange membrane of claim 5, wherein the reinforcement layer is a porous nonwoven polymer, and the nonwoven polymer is one or more of polytetrafluoroethylene, polyvinylidene fluoride-Co-hexafluoropropylene, polyethylene, polypropylene, polyethylene-Co-propylene, acetate fiber, polyimide, polyvinyl chloride, poly perfluoroethylene propylene fiber, poly perfluoropropyl vinyl ether fiber, perfluoroalkoxy vinyl ether copolymer fiber, ceramic fiber, mineral fiber, oxide fiber, polyethersulfone, polyetherketone, polyimide, polybenzimidazole, and sulfonated and phosphorylated derivatives thereof.
7. A modified ion exchange membrane according to claim 5, wherein the thickness of the reinforcement layer is 5-50 μm, preferably 5-25 μm.
8. A modified ion exchange membrane according to claim 5, wherein the enhancement layer is 0 to 10 layers, preferably 0 to 3 layers.
9. The method for producing a modified ion exchange membrane according to any one of claims 5 to 8, comprising the steps of:
a. mixing the modified fluorine-containing sulfonic acid resin and a solvent to form uniform dispersion liquid, wherein the solid content is 5-40%; the solvent is one or more of N, N-dimethylformamide, N-dimethylacetamide, N-methylpyrrolidone, 1-5 carbon chain alcohol, formic acid or acetic acid;
b. and (c) carrying out solution casting, wire rod coating, doctor blade coating, spraying or dipping on the dispersion liquid obtained in the step (a) to form a film, and heating at 50-80 ℃ to volatilize the solvent to obtain the modified ion exchange membrane.
10. Use of a modified ion exchange membrane according to any one of claims 5 to 8 in the field of flow batteries.
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