CN114597463A - Preparation method and application of microporous framework based blend membrane - Google Patents
Preparation method and application of microporous framework based blend membrane Download PDFInfo
- Publication number
- CN114597463A CN114597463A CN202210241297.5A CN202210241297A CN114597463A CN 114597463 A CN114597463 A CN 114597463A CN 202210241297 A CN202210241297 A CN 202210241297A CN 114597463 A CN114597463 A CN 114597463A
- Authority
- CN
- China
- Prior art keywords
- pim
- membrane
- microporous
- drying
- cpim
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000012528 membrane Substances 0.000 title claims abstract description 67
- 239000000203 mixture Substances 0.000 title claims abstract description 44
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 229920000642 polymer Polymers 0.000 claims abstract description 21
- 238000002156 mixing Methods 0.000 claims abstract description 20
- 239000000463 material Substances 0.000 claims description 25
- 238000001035 drying Methods 0.000 claims description 20
- 239000000843 powder Substances 0.000 claims description 17
- 238000006243 chemical reaction Methods 0.000 claims description 16
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- 230000015572 biosynthetic process Effects 0.000 claims description 14
- 238000003786 synthesis reaction Methods 0.000 claims description 14
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 12
- 238000005406 washing Methods 0.000 claims description 11
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 10
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 10
- 239000002904 solvent Substances 0.000 claims description 10
- 229910052720 vanadium Inorganic materials 0.000 claims description 10
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 8
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 claims description 8
- 239000002253 acid Substances 0.000 claims description 8
- 230000004913 activation Effects 0.000 claims description 8
- 229910052731 fluorine Inorganic materials 0.000 claims description 8
- 239000011737 fluorine Substances 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 7
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- PCRSJGWFEMHHEW-UHFFFAOYSA-N 2,3,5,6-tetrafluorobenzene-1,4-dicarbonitrile Chemical compound FC1=C(F)C(C#N)=C(F)C(F)=C1C#N PCRSJGWFEMHHEW-UHFFFAOYSA-N 0.000 claims description 5
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 5
- AVXURJPOCDRRFD-UHFFFAOYSA-N Hydroxylamine Chemical compound ON AVXURJPOCDRRFD-UHFFFAOYSA-N 0.000 claims description 4
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- 238000001291 vacuum drying Methods 0.000 claims description 4
- 239000004696 Poly ether ether ketone Substances 0.000 claims description 3
- 239000004693 Polybenzimidazole Substances 0.000 claims description 3
- 229920002480 polybenzimidazole Polymers 0.000 claims description 3
- 229920002530 polyetherether ketone Polymers 0.000 claims description 3
- 239000008213 purified water Substances 0.000 claims description 3
- 238000002791 soaking Methods 0.000 claims description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 3
- 239000004695 Polyether sulfone Substances 0.000 claims description 2
- 239000004642 Polyimide Substances 0.000 claims description 2
- 238000007605 air drying Methods 0.000 claims description 2
- 238000001914 filtration Methods 0.000 claims description 2
- 229920006393 polyether sulfone Polymers 0.000 claims description 2
- 229920001721 polyimide Polymers 0.000 claims description 2
- 238000005303 weighing Methods 0.000 claims description 2
- 101001001642 Xenopus laevis Serine/threonine-protein kinase pim-3 Proteins 0.000 claims 7
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 abstract description 2
- 125000004093 cyano group Chemical group *C#N 0.000 abstract description 2
- 230000037427 ion transport Effects 0.000 abstract description 2
- 229920006120 non-fluorinated polymer Polymers 0.000 abstract 1
- 101000595531 Homo sapiens Serine/threonine-protein kinase pim-1 Proteins 0.000 description 28
- 102100036077 Serine/threonine-protein kinase pim-1 Human genes 0.000 description 28
- 239000013316 polymer of intrinsic microporosity Substances 0.000 description 28
- 239000000243 solution Substances 0.000 description 23
- 238000012360 testing method Methods 0.000 description 15
- 229920002465 poly[5-(4-benzoylphenoxy)-2-hydroxybenzenesulfonic acid] polymer Polymers 0.000 description 9
- 229910001456 vanadium ion Inorganic materials 0.000 description 8
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 description 7
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 6
- 150000002500 ions Chemical class 0.000 description 6
- 230000008961 swelling Effects 0.000 description 6
- 238000010521 absorption reaction Methods 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 230000010220 ion permeability Effects 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 3
- 238000004364 calculation method Methods 0.000 description 3
- 238000009792 diffusion process Methods 0.000 description 3
- 239000003792 electrolyte Substances 0.000 description 3
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 3
- 229910052719 titanium Inorganic materials 0.000 description 3
- 239000010936 titanium Substances 0.000 description 3
- 238000012546 transfer Methods 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 238000002835 absorbance Methods 0.000 description 2
- 238000005266 casting Methods 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- 230000035515 penetration Effects 0.000 description 2
- 230000002829 reductive effect Effects 0.000 description 2
- 230000032258 transport Effects 0.000 description 2
- 238000000627 alternating current impedance spectroscopy Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- JUPQTSLXMOCDHR-UHFFFAOYSA-N benzene-1,4-diol;bis(4-fluorophenyl)methanone Chemical compound OC1=CC=C(O)C=C1.C1=CC(F)=CC=C1C(=O)C1=CC=C(F)C=C1 JUPQTSLXMOCDHR-UHFFFAOYSA-N 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000000635 electron micrograph Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 229920000295 expanded polytetrafluoroethylene Polymers 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 239000011256 inorganic filler Substances 0.000 description 1
- 229910003475 inorganic filler Inorganic materials 0.000 description 1
- 230000000670 limiting effect Effects 0.000 description 1
- 238000003760 magnetic stirring Methods 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 230000003204 osmotic effect Effects 0.000 description 1
- 238000002047 photoemission electron microscopy Methods 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 229920001483 poly(ethyl methacrylate) polymer Polymers 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- 238000006277 sulfonation reaction Methods 0.000 description 1
- 125000000542 sulfonic acid group Chemical group 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000000870 ultraviolet spectroscopy Methods 0.000 description 1
- UUUGYDOQQLOJQA-UHFFFAOYSA-L vanadyl sulfate Chemical compound [V+2]=O.[O-]S([O-])(=O)=O UUUGYDOQQLOJQA-UHFFFAOYSA-L 0.000 description 1
- 229910000352 vanadyl sulfate Inorganic materials 0.000 description 1
- 230000037303 wrinkles Effects 0.000 description 1
Images
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/18—Regenerative fuel cells, e.g. redox flow batteries or secondary fuel cells
-
- 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
Landscapes
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Sustainable Development (AREA)
- Sustainable Energy (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Conductive Materials (AREA)
Abstract
The invention discloses a preparation method and application of a microporous framework based blend membrane. The framework polymer is one of cyano-group PIM (PIM-1), oximido-group PIM (AO-PIM-1), carboxyl-group PIM (cPIM-1) and sulfonic-group PIM (sPIM-1), and the basal membrane is made of a non-fluorinated polymer with high proton conductivity. The invention provides a blending membrane strategy with simple preparation process and strong supporting framework for the first time, and effectively improves the mechanical stability of the ion-conducting membrane. On the one hand, the base film provides a large number of ion transport channels; on the other hand, the helical backbone polymer restricts the movement of the chains and thus improves the stability of the membrane. The mixing provides a new strategy for improving the service strength of the diaphragm.
Description
Technical Field
The invention relates to a preparation method and application of a blending membrane based on a microporous framework, and belongs to the technical field of vanadium redox flow batteries.
Background
Vanadium Redox Flow Battery (VRFB), a large energy storage technology, has been proven to be effective in utilizing renewable energy with intermittent characteristics due to its environmentally friendly, high efficiency, adjustable power and capacity, long cycle life, low maintenance cost, etc., Proton Exchange Membrane (PEM) not only plays a role in separating positive and negative electrolytes, but also provides a channel for proton transmission, is one of the main important components in VRFB systems, and its performance can greatly affect the performance of the battery system. The currently most commonly used all-coated sulfonic acid group membrane has excellent proton conductivity and excellent stability, but its higher vanadium ion permeability, lower mechanical strength and high manufacturing cost severely limit its further development. Therefore, there is a need to develop a new generation of high performance PEMs for VRFBs.
The addition of a backbone polymer is one of the effective methods to enhance the stabilization capability of the PEM. The problem of interface compatibility caused by inorganic filler can be well solved by selecting the organic polymeric framework material, and meanwhile, the method can be used for further modifying the selected material according to actual requirements so as to facilitate better application. Materials such as PTFE, ePTFE and PBI are used for preparing high-performance PEM so far, but most of the reinforced framework materials are hydrophobic materials, and the proton conductivity of the materials is greatly sacrificed while the penetration of vanadium ions is hindered.
Disclosure of Invention
The invention provides a blending membrane for an all-vanadium redox flow battery, a preparation method and application aiming at the existing technical problems.
The purpose of the invention can be realized by the following technical scheme
A blending membrane based on microporous frameworks is characterized in that a sulfonated non-fluorine material is used as a base membrane, a rigid spiral framework polymer is mixed in the base membrane to be used as a supporting material, and the supporting material is composed of a hydrophilic inherent microporous polymer.
In the technical scheme of the invention, the base membrane is made of one or more of sulfonated polyether ether ketone, sulfonated polyimide, sulfonated polybenzimidazole and sulfonated polyether sulfone.
In the technical scheme of the invention, the hydrophilic inherent microporous polymer is composed of one or more of cyano-group PIM (PIM-1), oximido-group PIM (AO-PIM-1), carboxyl-group PIM (cPIM-1) and sulfonic-group PIM (sPIM-1);
preferably: uniformly mixing 5,5',6,6' -tetrahydroxy-3, 3,3',3' -tetramethyl-1, 1' -spirobiindole and tetrafluoroterephthalonitrile with a solvent, heating the mixture at 50-500 ℃ for 3-8 hours, adding potassium carbonate in the reaction process, washing after the reaction is finished, recrystallizing and drying to obtain PIM-1 powder;
preferably: synthesis of cPIM-1: mixing PIM-1 with a solvent, adding sodium hydroxide, stirring, heating the mixture at 110-130 ℃ for 5-9 days, cooling to room temperature after the reaction is finished, washing, performing acid activation treatment, and drying to obtain cPIM-1 powder;
preferably: synthesis of sPIM-1: adding cPIM-1 into concentrated sulfuric acid, mixing and stirring, pouring into purified water, washing to neutrality, and drying to obtain sPIM-1;
preferably: synthesis of AO-PIM-1: weighing the PIM-1 powder and tetrahydrofuran, uniformly mixing, reacting at 60-70 ℃ for 18-22 h, adding hydroxylamine dropwise in a nitrogen protection device during the reaction, and filtering and drying after the reaction is finished to obtain AO-PIM-1 powder.
In the technical scheme of the invention, the weight ratio of the hydrophilic inherent microporous polymer in the blended membrane is 0.1-50%, preferably 1-30%.
In the technical scheme of the invention, the thickness of the blend film is 10-100 μm.
In the technical scheme of the invention, synthesis of PIM-1 comprises the following steps: uniformly mixing 5,5',6,6' -tetrahydroxy-3, 3,3',3' -tetramethyl-1, 1' -spirobiindole and tetrafluoroterephthalonitrile with a solvent in a mass ratio of 1-5: 1-5, heating the mixture at 40-550 ℃ for 4-6 hours, adding potassium carbonate in the reaction process, cooling to room temperature, then sequentially pouring into water for washing, recrystallizing and drying to obtain PIM-1 powder; synthesis of cPIM-1: adding PIM-1 into a solvent, adding sodium hydroxide, stirring, and heating the mixture at 110-130 ℃ for 6-8 days; after the reaction is finished, cooling to room temperature, washing, carrying out acid activation treatment, and drying to obtain the cPIM-1 powder.
The preparation method of the blending membrane based on the microporous framework comprises the following steps: preparing a rigid spiral skeleton polymer solution, and preparing a sulfonated non-fluorine material solution; and mixing the rigid spiral skeleton polymer solution and the sulfonated non-fluorine material solution, pouring the mixture in a culture dish, and performing forced air drying to obtain the blend membrane.
In the method, the solvent in the rigid spiral skeleton polymer solution and the sulfonated non-fluorine material solution is one or a mixture of N, N-Dimethylformamide (DMF), N-Dimethylacetamide (DMAC) and dimethyl sulfoxide (DMSO).
In the method, after air blast drying, vacuum drying is adopted, and the drying temperature is 30-150 ℃; the drying time is 10-15 h.
The method comprises the following steps: soaking the blended film in an acid solution for activation treatment; preferably: the acid solution is 0.1-4M sulfuric acid solution.
The technical scheme of the invention is as follows: the blend membrane based on the microporous framework is applied to the blend membrane of the all-vanadium flow battery.
In some embodiments, the hydrophilic intrinsically microporous polymer is cyano PIM (PIM-1), oximo PIM (AO-PIM-1), carboxy PIM (cPIM-1), sulfonate PIM (sPIM-1) for increasing blend membrane mechanical strength, inhibiting swelling ratio, and increasing coulombic efficiency.
The invention has the beneficial effects that:
the invention reasonably mixes the porous PIMs material into the proton exchange polymer to improve the performance of the obtained hybrid membrane, including optimizing the vanadium resistance of the membrane and improving the stability, thereby developing a new generation of high-performance PEM for the application of VRFB system. In the invention, PIMs with different hydrophilic groups are added into a polymer base material, so that the related performance of the VRFB can be respectively improved. The vanadium resistance of the film is greatly enhanced by introducing PIMs, so that the Coulombic Efficiency (CE) is increased.
Drawings
FIG. 1 is a) a PIM-1 nuclear magnetic spectrum and b) PIM-1 and cPIM-1 infrared images. c) PIM-1 and cPIM-1BET test profiles and d) thermogravimetric profiles of cPIM-1 and SPEEK.
Fig. 2 is a digital photograph a) a cPIM/SPEEK-X membrane casting solution image, b) a cPIM/SPEEK-X membrane image, and c) an infrared spectrum of the cPIM/SPEEK-X (X ═ 0,5,10,15,20,25, 30%).
Fig. 3 is a cross-sectional electron micrograph of cPIM/SPEEK-X (X ═ 0,5,10,15,20,25, 30%).
Fig. 4 is a) tensile strength, b) water absorption and swelling ratio, c) vanadium ion permeability curve and d) proton conductivity and ion selectivity water absorption and swelling ratio (X ═ 0,5,10,15,20,25, 30%) of cPIM/SPEEK-X.
FIG. 5 is a performance graph of an all vanadium flow battery a) a schematic flow battery, b) CE, c) VE, d) EE at a current density of 20-240mA cm-2.
FIG. 6 is a graph of sPIM/SPEEK-X membrane performance in an all vanadium flow battery
Detailed Description
The invention is further illustrated by the following examples, without limiting the scope of the invention:
EXAMPLE 1 preparation of PIM-1
Synthesis of PIM-1: 5.00g of 5,5',6,6' -tetrahydroxy-3, 3,3',3' -tetramethyl-1, 1' -spirobiindole (CAS: 77-08-7, TTSBI) and 3.00g of tetrafluoroterephthalonitrile were added to a 250mL three-necked flask, then 100mL of DMF solution was added and mixed well, the mixture was heated at 150 ℃ for 5 hours, and 4.2292g of potassium carbonate was added during the reaction. After cooling to room temperature, the mixture was poured into water for washing, recrystallized 3 times or more with chloroform/methanol system to remove impurities, and then vacuum-dried at 120 ℃ for 24 hours to obtain PIM-1 powder as shown in fig. 1 (a).
Example 2 preparation of cPIM-1
Synthesis of cPIM-1: 4.8g of PIM-1 prepared in example 1 was charged in a 250mL three-necked flask, then 100mL of a mixed solution of water and ethanol (mass ratio: 1) was added thereto, 40g of sodium hydroxide was added thereto, and the mixture was stirred and heated at 120 ℃ for 7 days. After completion, the reaction mixture was cooled to room temperature, washed with water several times to remove impurities, and finally subjected to activation treatment with a 1M hydrochloric acid solution, followed by vacuum drying at 120 ℃ for 24 hours to obtain cPIM-1 powder as shown in FIG. 1(b) and FIG. 1 (c).
EXAMPLE 3 preparation of sPIM-1
synthesis of sPIM-1: 2g of cPIM-1 prepared in example 2 was added to 20mL of concentrated sulfuric acid at a mass to volume ratio of 1:10(cPIM-1 mass: 1, concentrated sulfuric acid volume: 10), mixed and stirred for 24h, poured into purified water and washed to neutrality, and then vacuum-dried at 120 ℃ for 24h to obtain sPIM-1.
EXAMPLE 4 preparation of AO-PIM-1
Synthesis of AO-PIM-1: 4.8g of the PIM-1 powder prepared in example 1 were weighed out, dissolved in tetrahydrofuran and poured into a three-necked flask and heated to 65 ℃ for 20 hours, during which a nitrogen blanket was always used and 50mL of hydroxylamine solution (CAS: 7803-49-8) were added dropwise. After completion of the reaction, the mixture was poured into 1L of ethanol and filtered to collect a solid. Vacuum drying at 120 ℃ for 24h to obtain AO-PIM-1 powder.
Example 5 preparation of cPIM-1/SPEEK blend Membrane
SPEEK was prepared by sulfonating PEEK in sulfuric acid (98 wt.%) at 50 c for 10h, with a SPEEK sulfonation degree of 0.98. The cPIM-1/SPEEK blend membrane was then prepared by the following method.
1g of cPIM-1 powder and 1g of SPEEK were dissolved in 50mL of dimethyl sulfoxide, respectively. Then, 12.5mL of SPEEK solution and 6.25mL of cPIM-1 solution were weighed out based on the mass of each membrane (0.25g) and mixed well. The new mixture was stirred well for 24 hours and sonicated for 2 hours to form a homogeneous cPIM-1/SPEEK-5 mixture. And pouring the prepared mixture into a culture dish. The mixture is placed in a 60 ℃ oven for shaping operation for 2h and then is moved to a 120 ℃ vacuum oven for drying for 12 h. And after drying, soaking the membrane in 1M sulfuric acid solution for activation treatment. The activated membrane is immersed in pure water for storage. The configured blend membrane is denoted cPIM/SPEEK-X, where X represents the mass ratio of cPIM-1 to the membrane as a whole.
Fig. 2 is a digital photograph a) a cPIM/SPEEK-X membrane casting solution image, b) a cPIM/SPEEK-X membrane image, and c) an infrared spectrum (X ═ 0,5,10,15,20,25, 30%) of the cPIM/SPEEK-X, and fig. 3 is a cPIM/SPEEK-X cross-sectional electron microscope image (X ═ 0,5,10,15,20,25, 30%), and as the content of cPIM-1 increases, corresponding fig. 3(a), 3(b), 3(c), 3(d), 3(e), and 3(f) show that the thickness of the prepared blend film is 70 μm. The cross-section of the membrane shows more wrinkles and is evenly distributed over the whole cross-sectional area. Indicating that the compatibility between the cPIM-1 and the SPEEK is better and the cPIM-1 can be uniformly dispersed.
Test method
Swelling ratio and Water absorption
SR (swelling ratio) and WU (water absorption) of the film are obtained from the following two equations, respectively:
where d and W are the diameter and mass of the membrane in the wet and dry states, respectively.
Mechanical Properties
At a tension speed of 5mmmin-1The mechanical properties of the film were obtained on a universal tester. The samples were cut into 35mm by 10mm strips and wiped with water on the wet film surface before testing. To reduce test error, three samples were tested for each film and the resulting data was averaged. The tensile strength calculation formula of the film sample is as follows:
in the formula, FMaxIs the maximum tension; w and D are the width and thickness of the sample film, respectively.
Proton transfer rate
The proton transfer rate of the membrane was measured on an electrochemical workstation (Solartron analytical 1470E +1260A) using an ac impedance spectroscopy test. The sample is clamped between two circular titanium sheets, and the titanium sheets are fixed by button cell clamps. Test frequency at 103To 106Between hertz, the ac amplitude is 5 mV. The proton transfer rate of the membrane was measured using the latest method of the li professor group, and the calculation formula was as follows:
where σ is the proton transport rate of the membrane. L is the thickness of the sample. R is the resistance of the film. And A is the effective area of the film, namely the area of the titanium sheet.
The membrane area resistance can be calculated by the following formula:
RA＝R×A
RAis the film surface resistance.
Vanadium ion permeation Rate and ion Selectivity
In an effective area of 1.77cm2Type H versus diffusion cell. 50mL of 1.5M VOSO are filled in the diffusion cell at one side4/3.0M H2SO4Solution, diffusion cell on the other side was filled with the same volume of 1.5M MgSO4/3.0M H2SO4Solutions to balance ionic strength and osmotic pressure and magnetic stirring was used to reduce concentration polarization during testing. Every 24h at MgSO4/H2SO4The solution was measured and absorbance was measured at 762nm with an ultraviolet-visible spectrophotometer. VO was determined using a standard absorbance/concentration curve2+The concentration of (c). The vanadium permeation rate can be calculated using the following formula:
wherein VBIs MgSO4/H2SO4The volume of the solution, this experiment is 50 ml; cB(t) is MgSO at time t4/H2SO4VO in solution2+The concentration of the ions; cAIs VOSO4/H2SO4VO in solution2+Concentration, which can be considered constant in case the test time is not too long, to simplify the calculation; A. l is the effective membrane area and the membrane thickness respectively; p is the penetration rate of vanadium ions.
Ion selectivity is defined as the proton transport ratio and VO2+The ratio of the permeation rates is calculated according to the following formula:
fundamental characterization of membranes
The tensile strength test in fig. 4(a) shows that the doped framework material cPIM-1 can improve the mechanical strength of the membrane, and the double reduction of the water absorption and swelling ratio in fig. 4(b) shows that the framework material inhibits the movement dispersion of the flexible chain. Fig. 4(c) the significant decrease in vanadium ion mobility rate with increasing doping levels demonstrates that the framework chain inhibits bulk ion transport. FIG. 4(d) proton conductivity decreased but H/V ion selectivity increased.
Cell performance
The performance of VRFB was tested using a self-made flow cell system consisting of a membrane (effective distance 10.5 cm)2) Two carbon felt electrodes, two graphite plate current collectors and a pair of shells. Membrane-separated negative electrode electrolyte (10 ml1.5MV)2+/V3+3MH2SO4) And a positive electrode electrolyte (10ml of 1.5M VO)2+/VO2+3MH2SO4) And sandwiched between the two electrodes. For the charge and discharge test, the cut-off voltages for charging and discharging were 1.7V and 0.8V, respectively, and the current densities for the test were 40, 60, 80, 100 and 120mA cm-2. For the cycling test, the constant current density was 120mA cm-2The test was carried out at the same cut-off voltage. During the test, nitrogen blanket was used. The Coulombic Efficiency (CE), Voltage Efficiency (VE) and Energy Efficiency (EE) of the cell were calculated by the following formulas:
wherein C isdAnd CcDischarge capacity and charge capacity, respectively; edAnd EcRespectively, a discharge energy and a charge energy.
VRFB Performance of the cPIM/SPEEK-X blend membranes was evaluated (at 40-120mA cm)-2At a range of current densities). As shown in fig. 5, (a) is a schematic diagram of cell test, and it can be seen from the graph (b) that the coulombic efficiency of the SPEEK membrane can be significantly improved and the vanadium ion permeability can be reduced by mixing the cPIM-1, and it can be seen from the graph (b) and the graph (c) that the energy efficiency is not changed obviously although the voltage efficiency is slightly reduced, and the incorporation of the porous PIMs material into the polymer is indeed an effective way to develop a high-performance PEM to the energy field in consideration of the above cell line data.
Test of vanadium ion permeability
Fig. 6 is a graph of doped film cell data for a low dose doped backbone material. (a) The coulomb efficiency shows that the ion blocking capability of the separator is enhanced, and the efficiency graphs of (b) and (c) show that the doping of the framework material with small dose has obvious effect on the improvement of the battery performance.
Claims (11)
1. A blending membrane based on microporous frameworks is characterized in that a sulfonated non-fluorine material is used as a base membrane, a rigid spiral framework polymer is mixed in the base membrane to be used as a supporting material, and the supporting material is composed of a hydrophilic inherent microporous polymer.
2. The microporous framework based blend membrane according to claim 1, wherein the base membrane is selected from one or more of sulfonated polyether ether ketone, sulfonated polyimide, sulfonated polybenzimidazole, and sulfonated polyether sulfone.
3. The microporous-framework-based blend membrane of claim 1, wherein the hydrophilic intrinsically microporous polymer is one or more of cyano-PIM (PIM-1), oximo-PIM (AO-PIM-1), carboxy-PIM (cPIM-1), and sulfo-PIM (sPIM-1);
preferably: uniformly mixing 5,5',6,6' -tetrahydroxy-3, 3,3',3' -tetramethyl-1, 1' -spirobiindole and tetrafluoroterephthalonitrile with a solvent, heating the mixture at 50-500 ℃ for 3-8 hours, adding potassium carbonate in the reaction process, washing after the reaction is finished, recrystallizing and drying to obtain PIM-1 powder;
preferably: synthesis of cPIM-1: mixing PIM-1 with a solvent, adding sodium hydroxide, stirring, heating the mixture at 110-130 ℃ for 5-9 days, cooling to room temperature after the reaction is finished, washing, performing acid activation treatment, and drying to obtain cPIM-1 powder;
preferably: synthesis of sPIM-1: adding cPIM-1 into concentrated sulfuric acid, mixing and stirring, pouring into purified water, washing to neutrality, and drying to obtain sPIM-1;
preferably: synthesis of AO-PIM-1: weighing the PIM-1 powder and tetrahydrofuran, uniformly mixing, reacting at 60-70 ℃ for 18-22 h, adding hydroxylamine dropwise in a nitrogen protection device during the reaction, and filtering and drying after the reaction is finished to obtain AO-PIM-1 powder.
4. The microporous-backbone-based blend membrane according to claim 1, wherein the weight ratio of the hydrophilic intrinsically microporous polymer in the blend membrane is 0.1 to 50%, preferably 1 to 30%.
5. The microporous skeleton-based blend membrane of claim 1, wherein the blend membrane has a thickness of 10 to 100 μm.
6. The microporous framework based blend membrane of claim 3, wherein the synthesis of PIM-1: uniformly mixing 5,5',6,6' -tetrahydroxy-3, 3,3',3' -tetramethyl-1, 1' -spirobiindole and tetrafluoroterephthalonitrile with a solvent in a mass ratio of 1-5: 1-5, heating the mixture at 40-550 ℃ for 4-6 hours, adding potassium carbonate in the reaction process, cooling to room temperature, then sequentially pouring into water for washing, recrystallizing and drying to obtain PIM-1 powder;
synthesis of cPIM-1: adding PIM-1 into a solvent, adding sodium hydroxide, stirring, and heating the mixture at 110-130 ℃ for 6-8 days; after the reaction is finished, cooling to room temperature, washing, carrying out acid activation treatment, and drying to obtain the cPIM-1 powder.
7. The preparation method of the microporous framework based blend membrane according to claim 1, which comprises the following steps: preparing a rigid spiral skeleton polymer solution, and preparing a sulfonated non-fluorine material solution; and mixing the rigid spiral skeleton polymer solution and the sulfonated non-fluorine material solution, pouring the mixture in a culture dish, and performing forced air drying to obtain the blend membrane.
8. The method for preparing the microporous framework based blend membrane according to claim 7, wherein the solvent in the solution of the rigid helical framework polymer and the solution of the sulfonated non-fluorine material is one or more of N, N-Dimethylformamide (DMF), N-Dimethylacetamide (DMAC) and Dimethylsulfoxide (DMSO).
9. The preparation method of the microporous framework based blend membrane according to claim 7, characterized in that after air-blast drying, vacuum drying is adopted, and the drying temperature is 30-150 ℃; the drying time is 10-15 h.
10. The preparation method of the microporous framework based blend membrane according to claim 7, which comprises the following steps: soaking the blended film in an acid solution for activation treatment; preferably: the acid solution is 0.1-4M sulfuric acid solution.
11. The microporous framework based blended membrane of claim 1, wherein the microporous framework based blended membrane is used as a blended membrane of an all-vanadium flow battery.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210241297.5A CN114597463A (en) | 2022-03-11 | 2022-03-11 | Preparation method and application of microporous framework based blend membrane |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210241297.5A CN114597463A (en) | 2022-03-11 | 2022-03-11 | Preparation method and application of microporous framework based blend membrane |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN114597463A true CN114597463A (en) | 2022-06-07 |
Family
ID=81817798
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210241297.5A Pending CN114597463A (en) | 2022-03-11 | 2022-03-11 | Preparation method and application of microporous framework based blend membrane |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114597463A (en) |
Citations (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102639614A (en) * | 2009-12-04 | 2012-08-15 | 北京普能世纪科技有限公司 | Polymer blend proton exchange membrane and preparation method thereof |
| US20120264589A1 (en) * | 2009-11-12 | 2012-10-18 | Naiying Du | Polymers of intrinsic microporosity containing tetrazole groups |
| US20130252137A1 (en) * | 2010-12-10 | 2013-09-26 | Dalian Rongke Power Co., Ltd | Use of porous membrane and composite membrane thereof in redox flow energy storage battery |
| CN105789668A (en) * | 2016-03-03 | 2016-07-20 | 中国科学院化学研究所 | Preparation method of metal-organic framework material/polymer composite proton exchange membrane |
| CN109585888A (en) * | 2018-11-07 | 2019-04-05 | 大连理工大学 | A kind of blending type anion-exchange membrane and preparation method thereof |
| CN110128686A (en) * | 2019-04-29 | 2019-08-16 | 天津大学 | A kind of preparation method of the proton exchange membrane with chemical stability |
| CN110336052A (en) * | 2019-06-25 | 2019-10-15 | 大连理工大学 | A kind of mixed-matrix type cation-exchange membrane and preparation method thereof |
| CN112321818A (en) * | 2020-11-20 | 2021-02-05 | 复旦大学 | High molecular functional polymer with self-micropore structure and super-assembly preparation method thereof |
| CN112852101A (en) * | 2021-01-22 | 2021-05-28 | 中国石油大学(北京) | Sulfonated polyether ether ketone based proton exchange membrane and preparation method and application thereof |
| CN113036174A (en) * | 2019-12-09 | 2021-06-25 | 中国科学院大连化学物理研究所 | Organic framework copolymer supported porous ion-conducting membrane and preparation and application thereof |
| CN113067001A (en) * | 2021-03-24 | 2021-07-02 | 南京工业大学 | Mixed membrane for all-vanadium redox flow battery, preparation method and application |
| CN114149580A (en) * | 2022-01-12 | 2022-03-08 | 吉林大学 | Rigid twisted microporous polymer-sulfonated polyether sulfone porous composite membrane and preparation method and application thereof |
-
2022
- 2022-03-11 CN CN202210241297.5A patent/CN114597463A/en active Pending
Patent Citations (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20120264589A1 (en) * | 2009-11-12 | 2012-10-18 | Naiying Du | Polymers of intrinsic microporosity containing tetrazole groups |
| CN102639614A (en) * | 2009-12-04 | 2012-08-15 | 北京普能世纪科技有限公司 | Polymer blend proton exchange membrane and preparation method thereof |
| US20130252137A1 (en) * | 2010-12-10 | 2013-09-26 | Dalian Rongke Power Co., Ltd | Use of porous membrane and composite membrane thereof in redox flow energy storage battery |
| CN105789668A (en) * | 2016-03-03 | 2016-07-20 | 中国科学院化学研究所 | Preparation method of metal-organic framework material/polymer composite proton exchange membrane |
| CN109585888A (en) * | 2018-11-07 | 2019-04-05 | 大连理工大学 | A kind of blending type anion-exchange membrane and preparation method thereof |
| CN110128686A (en) * | 2019-04-29 | 2019-08-16 | 天津大学 | A kind of preparation method of the proton exchange membrane with chemical stability |
| CN110336052A (en) * | 2019-06-25 | 2019-10-15 | 大连理工大学 | A kind of mixed-matrix type cation-exchange membrane and preparation method thereof |
| CN113036174A (en) * | 2019-12-09 | 2021-06-25 | 中国科学院大连化学物理研究所 | Organic framework copolymer supported porous ion-conducting membrane and preparation and application thereof |
| CN112321818A (en) * | 2020-11-20 | 2021-02-05 | 复旦大学 | High molecular functional polymer with self-micropore structure and super-assembly preparation method thereof |
| CN112852101A (en) * | 2021-01-22 | 2021-05-28 | 中国石油大学(北京) | Sulfonated polyether ether ketone based proton exchange membrane and preparation method and application thereof |
| CN113067001A (en) * | 2021-03-24 | 2021-07-02 | 南京工业大学 | Mixed membrane for all-vanadium redox flow battery, preparation method and application |
| CN114149580A (en) * | 2022-01-12 | 2022-03-08 | 吉林大学 | Rigid twisted microporous polymer-sulfonated polyether sulfone porous composite membrane and preparation method and application thereof |
Non-Patent Citations (3)
| Title |
|---|
| 周佳慧: "自具微孔聚合物膜制备及离子选择特性研究", 《中国优秀博硕学位论文全文数据库（博士）工程科技Ⅰ辑, vol. 2021, no. 09, pages 2 * |
| 周佳慧: "自具微孔聚合物膜制备及离子选择特性研究", 《中国优秀博硕学位论文全文数据库（博士）工程科技I辑, vol. 2021, no. 09, 15 September 2021 (2021-09-15), pages 1 * |
| 鲁云华，等: "自具微孔聚合物ＰＩＭ－１基热致刚性膜材料的制备及气体分离性能", 材料导报Ｂ：研究篇, vol. 32, no. 8, pages 2877 - 2880 * |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Zhang et al. | Sulfonated polysulfone proton exchange membrane influenced by a varied sulfonation degree for vanadium redox flow battery | |
| Chen et al. | Advanced acid-base blend ion exchange membranes with high performance for vanadium flow battery application | |
| Li et al. | Sulfonated poly (ether ether ketone)/mesoporous silica hybrid membrane for high performance vanadium redox flow battery | |
| Bhushan et al. | High-performance membrane for vanadium redox flow batteries: Cross-linked poly (ether ether ketone) grafted with sulfonic acid groups via the spacer | |
| CN113067001B (en) | Mixed membrane for all-vanadium redox flow battery, preparation method and application | |
| Liao et al. | Fluoro-methyl sulfonated poly (arylene ether ketone-co-benzimidazole) amphoteric ion-exchange membranes for vanadium redox flow battery | |
| Che et al. | Anion exchange membranes based on long side-chain quaternary ammonium-functionalized poly (arylene piperidinium) s for vanadium redox flow batteries | |
| KR101802285B1 (en) | Ion Exchange Membrane and Method for Manufacturing the Same | |
| CN107394240B (en) | Preparation method and application of sulfonated polyaryletherketone ion exchange membrane | |
| CN111748096B (en) | Preparation and application of polybenzimidazole based single-ion polymer gel electrolyte | |
| Guo et al. | Crosslinked polybenzimidazole high temperature-proton exchange membranes with a polymers of intrinsic microporosity (PIM) macromolecular crosslinker | |
| Wang et al. | Sulfonated poly (phthalazinone ether sulfone) membrane as a separator of vanadium redox flow battery | |
| CN109659469A (en) | A kind of flow battery ion-conductive membranes and its preparation and application | |
| CN106558666A (en) | A kind of flow battery is with porous ion conductive membranes and its prepares and application | |
| Xia et al. | Rigidly and intrinsically microporous polymer reinforced sulfonated polyether ether ketone membrane for vanadium flow battery | |
| CA2241552A1 (en) | Blend membranes based on sulfonated poly(phenylene oxide) for enhanced polymer electrochemical cells | |
| Ban et al. | Efficient and durable vanadium flow batteries enabled by high-performance fluorinated poly (aryl piperidinium) membranes | |
| CN116613362A (en) | Composite amphoteric ion exchange membrane for vanadium battery and preparation method thereof | |
| US7714027B2 (en) | Crosslinked aromatic polymer electrolyte membrane and method for producing same | |
| CN115584046B (en) | Perfluorinated sulfonic acid/ketohexose composite ion exchange membrane for vanadium redox battery and preparation method thereof | |
| CN116053496B (en) | Metal carbide-organic framework composite membrane for all-vanadium redox flow battery, preparation method and application thereof | |
| CN114597463A (en) | Preparation method and application of microporous framework based blend membrane | |
| CN116315421A (en) | Preparation method of battery diaphragm with high lithium ion conductivity | |
| CN113185695B (en) | Polyether sulfone single-ion polymer and single-ion gel polymer electrolyte | |
| CN116154205A (en) | Application of side chain functionalized polybenzimidazole porous membrane in bromine-based flow battery |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |