CN117106270A - Composite ion exchange membrane and preparation method and application thereof - Google Patents

Composite ion exchange membrane and preparation method and application thereof Download PDF

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Publication number
CN117106270A
CN117106270A CN202310988917.6A CN202310988917A CN117106270A CN 117106270 A CN117106270 A CN 117106270A CN 202310988917 A CN202310988917 A CN 202310988917A CN 117106270 A CN117106270 A CN 117106270A
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acid
ion exchange
exchange membrane
sulfonated
cerium
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张亚欢
刘昊
张泽天
刘卫霞
马亚敏
邓颖姣
焦佳佳
鹿传睿
周明正
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Spic Hydrogen Energy Technology Development Co Ltd
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Spic Hydrogen Energy Technology Development Co Ltd
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    • 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
    • H01M8/10—Fuel cells with solid electrolytes
    • H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
    • H01M8/1018—Polymeric electrolyte materials
    • H01M8/1041—Polymer electrolyte composites, mixtures or blends
    • H01M8/1046—Mixtures of at least one polymer and at least one additive
    • H01M8/1051—Non-ion-conducting additives, e.g. stabilisers, SiO2 or ZrO2
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G83/00—Macromolecular compounds not provided for in groups C08G2/00 - C08G81/00
    • C08G83/008—Supramolecular polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/20—Manufacture of shaped structures of ion-exchange resins
    • C08J5/22—Films, membranes or diaphragms
    • C08J5/2206—Films, membranes or diaphragms based on organic and/or inorganic macromolecular compounds
    • C08J5/2275—Heterogeneous membranes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2325/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Derivatives of such polymers
    • C08J2325/18—Homopolymers or copolymers of aromatic monomers containing elements other than carbon and hydrogen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2327/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers
    • C08J2327/02—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment
    • C08J2327/12—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
    • C08J2327/18—Homopolymers or copolymers of tetrafluoroethylene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2381/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing sulfur with or without nitrogen, oxygen, or carbon only; Polysulfones; Derivatives of such polymers
    • C08J2381/06—Polysulfones; Polyethersulfones
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2487/00—Characterised by the use of unspecified macromolecular compounds, obtained otherwise than by polymerisation reactions only involving unsaturated carbon-to-carbon bonds

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  • Chemical Kinetics & Catalysis (AREA)
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  • Polymers & Plastics (AREA)
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  • Life Sciences & Earth Sciences (AREA)
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  • Materials Engineering (AREA)
  • Composite Materials (AREA)
  • Manufacture Of Macromolecular Shaped Articles (AREA)

Abstract

The invention belongs to the field of high polymer materials and functional materials, and particularly relates to a composite ion exchange membrane, a preparation method and application thereof. The embodiment of the invention discloses a composite ion exchange membrane, which comprises 90-99.99% of ion exchange resin and 0.01-10% of cerium-based coordination polymer by mass percent. The organic ligand in the cerium-based coordination polymer in the composite ion exchange membrane has better compatibility when being blended with the ion exchange membrane, so that the composite ion exchange membrane has better chemical stability.

Description

Composite ion exchange membrane and preparation method and application thereof
Technical Field
The invention belongs to the field of high polymer materials and functional materials, and particularly relates to a composite ion exchange membrane and a preparation method thereof.
Background
The ion exchange membrane is widely applied to the fields of fuel cell proton exchange membranes, chlor-alkali industrial membranes, flow battery membranes, water electrolysis hydrogen production proton exchange membranes, separation membranes, protective materials and the like. In fuel cells, the degradation of other components such as catalysts and gas diffusion layers generally only leads to the degradation of cell performance, but the damage of the ion exchange membrane directly leads to the mixing of cathode and anode reaction gases, so that the cell directly fails and even safety accidents occur. The preparation of proton exchange membranes with high performance and high durability is critical to the development of fuel cells.
In the operation process of the fuel cell, the proton exchange membrane is easy to attack by hydroxyl radicals, so that the performance of the proton exchange membrane is reduced, even perforations appear, and the degradation of the proton exchange membrane and even the failure of the cell are caused. Therefore, it is highly desirable to improve the chemical durability to overcome the problems of performance degradation and lifetime shortening caused by hydroxyl radical attack.
Disclosure of Invention
The present invention has been made based on the findings and knowledge of the inventors regarding the following facts and problems:
cerium ions, cerium-based metal salts or cerium-based metal oxides are doped into ion exchange resins, and cerium element can play a role of a free radical quencher, so that the chemical stability of the proton exchange membrane is improved. The prior art impregnates ion exchange membranes with cerium ion solutions or doped cerium-based metal salts/metal oxides to produce fuel cell proton exchange membranes of high chemical durability. Although the method for impregnating cerium ions is simple, the proton transmission capacity of the proton exchange membrane is obviously reduced, and the electrochemical performance is sacrificed; unmodified cerium-based metal salts/metal oxides have poor compatibility with polymers, are unevenly dispersed in the membrane material, have limited doping levels, and limit the application of cerium-doped ion exchange membranes.
The present invention aims to solve at least one of the technical problems in the related art to some extent. Therefore, the embodiment of the invention provides a composite ion exchange membrane, and the organic ligand in the cerium-based coordination polymer has better compatibility with the ion exchange membrane when being blended, so that the composite ion exchange membrane has better chemical stability.
The composite ion exchange membrane provided by the embodiment of the invention comprises 90-99.99% of ion exchange resin and 0.01-10% of cerium-based coordination polymer by mass percent.
The composite ion exchange membrane provided by the embodiment of the invention has the advantages and technical effects that 1, in the embodiment of the invention, the composite ion exchange membrane is prepared by using the cerium-based coordination polymer and the ion exchange resin, the existence of the organic ligand in the coordination polymer can overcome the problem of uneven dispersion of cerium-based metal salt and metal oxide in the ion exchange resin, so that cerium element has good dispersibility in the ion exchange resin, and the problem of conductivity reduction caused by direct contact of cerium ions and sulfonic acid functional groups in the ion exchange resin can be avoided; 2. in the embodiment of the invention, cerium ions in the coordination center of the cerium-based coordination polymer can be used as a hydroxyl radical quencher, so that the chemical durability of the composite ion exchange membrane is obviously improved; 3. in the embodiment of the invention, the ion exchange membrane can be used in the fields of polyelectrolyte membranes, proton exchange membranes for hydrogen production by water electrolysis, acid primary battery membranes, secondary battery membranes such as lithium batteries, polyelectrolytes in super capacitors, polyelectrolyte membranes for metal recovery batteries, sensors and the like, and has wide application prospects.
In some embodiments, the metal ion of the coordination center of the cerium-based coordination polymer comprises Ce 3+ And Ce (Ce) 4+ At least one of them.
In some embodiments, the cerium-based coordination polymer includes at least one of a coordination polymer of one-dimensional structure, a coordination network of two-dimensional structure, and a coordination network of three-dimensional structure;
wherein the organic ligand of the cerium-based coordination polymer comprises at least one of sulfonic acid organic ligand and carboxylic acid organic ligand; preferably, the organic ligand comprises at least one of ethylenediamine tetraacetic acid disodium salt, N- (4-benzoyloxy) iminodiacetic acid, (5-ethoxycarbonyl-6-phenyl-1, 6-dihydropyrimidin-2-one-4-yl) methanesulfonic acid, R-2- (4- (4-carboxybenzyloxy) phenoxy) propionic acid, (5-ethoxycarbonyl-6-bromophenyl-1, 6-dihydropyrimidin-2-one-4-yl) methanesulfonic acid, 1' -ferrocenedicarboxylic acid, (5-ethoxycarbonyl-6-methyl-1, 6-dihydropyrimidin-2-one-4-yl) methanesulfonic acid, 1, 10-phenanthroline-2, 9-dicarboxylic acid, (5-ethoxycarbonyl-6-hydrogen-1, 6-dihydropyrimidin-2-one-4-yl) methanesulfonic acid, 5-aminoisophthalic acid, and pivalic acid.
In some embodiments, the coordination polymer of one-dimensional structure, coordination network of two-dimensional structure, and coordination network of three-dimensional structure have a unit cell volume of Preferably +.>More preferably +.>
In some embodiments, the cerium-based coordination polymer includes at least one of a two-dimensional porous MOF and a three-dimensional porous MOF;
wherein the two-dimensional porous MOF or the three-dimensional porous MOF has a particle size of 5 to 800nm and a BET specific surface area of 40 to 3000m 2 Per gram, micropore volume is 0.01-1.5 cm 3 /g；
Preferably, the organic ligands of the cerium-based coordination polymer include sulfonic acid-based organic ligands;
further preferred, at least one of a dicarboxylic acid-based organic ligand, a tricarboxylic acid-based organic ligand, a tetracarboxylic acid-based organic ligand, and a sulfonic acid-functionalized organic ligand is included;
more preferably, the di-, tri-or tetracarboxylic acid organic ligands include 2,2 '-thiodicarboxylic acid, 1,3, 5-tribenzoylbenzene, 2' -dithiodicarboxylic acid, 3, 6-benzobutane dicarboxylic acid, 1, 4-phthalic acid, 4'4 "-tricarboxylic acid triphenylamine, 2, 6-naphthalene dicarboxylic acid, 2,4, 6-tris (4-carboxyphenyl) -1,3, 5-triazine, 4' -biphthalic acid, benzene-1, 2,4, 5-tetracarboxylic acid, naphthalene-1, 4-dicarboxylic acid, naphthalene-2, 3,6, 7-tetracarboxylic acid, 4,5,9, 10-tetrahydropyrene-2, 7-dicarboxylic acid, [1,1 '-biphenyl ] -3,3',5 '-tetracarboxylic acid, pyrene-2, 7-dicarboxylic acid, 4',5 '-bis (4-carboxyphenyl) - [1,1':2',1" -terphenyl ] -4,4 "-dicarboxylic acid, [1,1': at least one of 4',1" -terphenyl ] -4,4 "-dicarboxylic acid, 1,3,6, 8-tetracarboxylic pyrene, 1,3, 5-benzene tricarboxylic acid, 4',4",4 '"-methane tetra-tetrabenzoic acid, [1,1' -biphenyl ] -3,4', 5-tricarboxylic acid, and 5',5" -bis (4-carboxyphenyl) - [1,1':3',1":3",1 "-tetrabiphenyl ] -4,4" -dicarboxylic acid;
More preferably, the sulfonic acid functionalized diacid organic ligand comprises at least one of 2-sulfonic acid terephthalic acid, 3, 7-disulfonaphthyl-2, 6-dicarboxylic acid, 5-sulfonic isophthalic acid, 4, 8-disulfonaphthyl-2, 6-dicarboxylic acid, 2, 5-disulfonic acid terephthalic acid, 3 '-disulfo- [1,1' -biphenyl ] -4,4 '-dicarboxylic acid, 5, 7-disulfonaphthyl-1, 4-dicarboxylic acid, 4-sulfonic acid-4' 4 "-dicarboxylic acid triphenylamine, 6-sulfenaphthyl-1, 4-dicarboxylic acid, and [1,1 '-biphenyl ] -4' -sulfonic acid-3, 5-dicarboxylic acid.
In some embodiments, the ion exchange resin comprises at least one of perfluorosulfonic acid resin, perfluorosulfonimide resin, polyacid side chain type perfluororesin, sulfonated polytrifluorostyrene, sulfonated polysulfone, sulfonated polyethersulfone, sulfonated polyetheretherketone, sulfonated polyaryletherketone, sulfonated polyarylethernitrile, sulfonated polyphosphazene, sulfonated polyphenylene ether, sulfonated polyphenylnitrile, sulfonated polyimide, and sulfonated polybenzimidazole; preferably comprises at least one of perfluorinated sulfonic acid resin, perfluorinated sulfonimide resin, polyacid side chain type perfluorinated resin, sulfonated polytrifluorostyrene, sulfonated polyether ether ketone, sulfonated polyaryletherketone and sulfonated polyarylethernitrile; more preferably at least one of perfluorosulfonic acid resin, perfluorosulfonimide resin, polyacid side chain type perfluororesin, and sulfonated polytrifluorostyrene.
In some embodiments, the composite ion exchange membrane has a membrane thickness of 3 to 500 μm and an ion exchange capacity of 0.1 to 4.2mmol/g.
The embodiment of the invention also provides a preparation method of the composite ion exchange membrane, which comprises the following steps:
(1) Dispersing ion exchange resin and cerium-based coordination polymer in a solvent to obtain a dispersion liquid;
(2) And (3) carrying out casting, casting or coating on the dispersion liquid prepared in the step (1), and drying to obtain the composite ion exchange membrane.
The preparation method of the composite ion exchange membrane provided by the embodiment of the invention has the advantages and technical effects that 1, in the embodiment of the invention, the prepared composite ion exchange membrane has better flatness, uniform thickness distribution and better performance; 2. the method provided by the embodiment of the invention has the advantages of simple process, convenient operation, high production efficiency and convenient wide application in industrial production; 3. the dispersion liquid in the preparation process can be used for preparing coatings, hydrogels and adhesives of porous membranes such as desalination membranes (nanofiltration membranes) and ultra/micro filtration membranes, various fabrics in the biomedical field such as surgical gloves, medical protective clothing and sterile cloth sheets, and protective equipment in the biochemical battlefield such as military protective clothing, and has wide application fields.
In some embodiments, in the step (2), the method further comprises loading the dispersion liquid prepared in the step (1) on a reinforced membrane, and drying to obtain a composite ion exchange membrane; preferably, the reinforcing membrane is a porous membrane.
In some embodiments, the mass content of the reinforced membrane is 0.1-90% of the composite ion exchange membrane, and the thickness of the reinforced membrane is 2-400 μm.
In some embodiments, the material of the reinforced film comprises at least one of a non-fluorinated polyolefin, a fluoropolymer, and an aromatic polymer; preferably, the non-fluorinated polyolefin comprises at least one of polyethylene, polypropylene and ethylene-propylene copolymer; the fluorine-containing polymer comprises at least one of polytetrafluoroethylene, tetrafluoroethylene-hexafluoropropylene copolymer, tetrafluoroethylene-propylene copolymer, ethylene-tetrafluoroethylene copolymer, tetrafluoroethylene-hexafluoropropylene-ethylene copolymer, polyvinylidene fluoride, vinylidene fluoride-hexafluoropropylene copolymer, tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer, vinylidene fluoride-tetrafluoroethylene-hexafluoropropylene copolymer, polyvinyl fluoride, polychlorotrifluoroethylene and ethylene-chlorotrifluoroethylene copolymer; the aromatic polymer membrane comprises at least one of polyaryletherketone, polysulfone, polyethersulfone ketone, polybenzimidazole, polyaramid, polyimide and polyetheretherketone.
The embodiment of the invention also provides application of the composite ion exchange membrane in polyelectrolyte membranes in chlor-alkali industry, proton exchange membranes for hydrogen production by water electrolysis, secondary battery membranes such as acid primary battery membranes and lithium batteries, polyelectrolytes in supercapacitors, polyelectrolyte membranes for metal recovery batteries or sensors.
Drawings
FIG. 1 is a cross-sectional SEM image of a C-PEM-3 made according to example 22 prior to Fenton reagent treatment;
FIG. 2 is a cross-sectional SEM image of a C-PEM-3 made according to example 22 after Fenton reagent treatment;
FIG. 3 is a cross-sectional SEM image of a D-C-PEM-7 prepared according to comparative example 8 prior to Fenton reagent treatment;
FIG. 4 is a cross-sectional SEM image of a D-C-PEM-7 of comparative example 8 after Fenton reagent treatment;
FIG. 5 is a graph of the power density of the C-PEM-3 prepared in example 22 and the D-C-PEM-7 prepared in comparative example 8 before and after Fenton reagent treatment.
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 by referring to the drawings are illustrative and intended to explain the present invention and should not be construed as limiting the invention.
The composite ion exchange membrane provided by the embodiment of the invention comprises 90-99.99% of ion exchange resin and 0.01-10% of cerium-based coordination polymer by mass percent.
The composite ion exchange membrane provided by the embodiment of the invention is prepared by using the cerium-based coordination polymer and the ion exchange resin, the problem of uneven dispersion of cerium-based metal salt and metal oxide in the ion exchange resin can be overcome due to the existence of the organic ligand in the coordination polymer, so that cerium element has good dispersibility in the ion exchange resin, and the problem of conductivity reduction caused by counter ion crosslinking when cerium ions are directly contacted with sulfonic acid functional groups in the ion exchange resin can be avoided; cerium ions in the coordination center of the cerium-based coordination polymer can be used as a hydroxyl radical quencher, so that the chemical durability of the composite ion exchange membrane is remarkably improved; the ion exchange membrane can be used in the fields of polyelectrolyte membranes, proton exchange membranes for hydrogen production by water electrolysis, secondary battery membranes such as acid primary battery membranes, lithium batteries and the like, polyelectrolytes in super capacitors, polyelectrolyte membranes for metal recovery batteries, sensors and the like, and has wide application prospects.
In some embodiments, preferably, the metal ion of the coordination center of the cerium-based coordination polymer comprises Ce 3+ And Ce (Ce) 4+ At least one of them.
In some embodiments, preferably, the cerium-based coordination polymer includes at least one of a coordination polymer of one-dimensional structure, a coordination network of two-dimensional structure, and a coordination network of three-dimensional structure;
Wherein the organic ligand of the cerium-based coordination polymer comprises at least one of sulfonic acid organic ligand and carboxylic acid organic ligand; preferably, the organic ligand comprises at least one of the following tables:
in the embodiment of the invention, the preferred topological structure is a one-dimensional structure, a two-dimensional structure or a three-dimensional structure, and when the topological structure is a one-dimensional structure, the cerium-based coordination polymer with a linear one-dimensional structure is small in size, large in specific surface area and higher in quenching efficiency on hydroxyl free radicals; the two-dimensional structure or the three-dimensional structure can prolong the transmission path of gas and small organic molecules to improve the barrier property of the material, and can also be used as an inorganic filler of a high polymer material to enhance the mechanical strength of the composite ion exchange membrane.
In some embodiments, it is preferred that the unit cell volume of the one-dimensional structured coordination polymer, two-dimensional structured coordination network, and three-dimensional structured coordination network isPreferably +.>More preferably
In the embodiment of the invention, the unit cell volume of the coordination polymer is optimized, which is favorable for the dispersion of the coordination polymer in the ion exchange resin, so that the composite ion exchange membrane has better performance.
In some embodiments, the coordination polymer after dry-forming is preferably treated to a suitable size using physical methods of milling and/or ball milling. Further preferably, the particle size of the coordination polymer material after treatment is 1nm to 1000nm, preferably 2nm to 600nm, more preferably 3nm to 300nm.
In some embodiments, preferably, the cerium-based coordination polymer includes at least one of a two-dimensional porous MOF and a three-dimensional porous MOF;
wherein the two-dimensional porous MOF or the three-dimensional porous MOF has a particle size of 5 to 800nm and a BET specific surface area of 40 to 3000m 2 Per gram, micropore volume is 0.01-1.5 cm 3 /g; preferably, the granulesThe diameter is 10-500 nm, and the BET specific surface area is 100-2500 m 2 Per gram, micropore volume is 0.02-1.2 cm 3 /g; more preferably, the particle diameter is 30 to 300nm, and the BET specific surface area is 120 to 2200m 2 Per gram, micropore volume is 0.02-0.9 cm 3 /g；
Preferably, the organic ligands of the cerium-based coordination polymer include sulfonic acid-based organic ligands;
further preferred, at least one of a dicarboxylic acid-based organic ligand, a tricarboxylic acid-based organic ligand, a tetracarboxylic acid-based organic ligand, and a sulfonic acid-functionalized organic ligand is included;
more preferably, the di-, tri-, or tetracarboxylic acid-based organic ligand comprises at least one of the following tables:
more preferably, the sulfonic acid functionalized diacid organic ligand comprises at least one of the following tables:
in the embodiment of the invention, the organic ligand of the coordination polymer is preferably a two-dimensional porous MOF or a three-dimensional porous MOF, and when the topological structure is the two-dimensional porous MOF or the three-dimensional porous MOF, the formed cerium-based coordination polymer is beneficial to proton conduction and prolongs the transmission paths of gas and small organic molecules, thereby improving the conductivity and the barrier property of the composite ion exchange membrane and improving the mechanical strength of the composite ion exchange membrane.
In some embodiments, preferably, the ion exchange resin comprises at least one of perfluorosulfonic acid resin, perfluorosulfonimide resin, polyacid side chain type perfluororesin, sulfonated polytrifluorostyrene, sulfonated polysulfone, sulfonated polyethersulfone, sulfonated polyetheretherketone, sulfonated polyaryletherketone, sulfonated polyarylethernitrile, sulfonated polyphosphazene, sulfonated polyphenylene ether, sulfonated polyphenylnitrile, sulfonated polyimide, and sulfonated polybenzimidazole; preferably comprises at least one of perfluorinated sulfonic acid resin, perfluorinated sulfonimide resin, polyacid side chain type perfluorinated resin, sulfonated polytrifluorostyrene, sulfonated polyether ether ketone, sulfonated polyaryletherketone and sulfonated polyarylethernitrile; more preferably at least one of perfluorosulfonic acid resin, perfluorosulfonimide resin, polyacid side chain type perfluororesin, sulfonated polytrifluorostyrene;
preferably, the perfluorinated sulfonic acid resin is classified into acid type perfluorinated sulfonic acid resin, alkali metal type perfluorinated sulfonic acid resin and other cationic perfluorinated sulfonic acid resin according to different cations, wherein the structural general formula of the acid type perfluorinated sulfonic acid resin is as follows:
wherein m=0 to 6, n=2 to 5, x mainly determines the ion exchange Equivalent (EW) of the acid form perfluorosulfonic acid resin, and y mainly determines the molecular weight of the acid form perfluorosulfonic acid resin;
The structural general formula of the alkali metal type perfluorinated sulfonic acid resin is as follows:
wherein m=0 to 6, n=2 to 5, m is lithium, sodium, potassium, rubidium or cesium, x mainly determines EW of the alkali metal type perfluorosulfonic acid resin, and y mainly determines molecular weight of the alkali metal type perfluorosulfonic acid resin;
preferably, the perfluorinated sulfonyl imide resin is divided into acid type perfluorinated sulfonyl imide resin, alkali metal type perfluorinated sulfonyl imide resin and other cationic perfluorinated sulfonyl imide resin according to different cations, and the structural general formulas of the acid type perfluorinated sulfonyl imide resin and the alkali metal type perfluorinated sulfonyl imide resin are as follows:
wherein m=0 to 6, n=2 to 5, p=0 to 5, m ' is hydrogen, lithium, sodium, potassium, rubidium, cesium or other cations, x ' mainly determines the EW of the perfluorosulfonimide resin, and y ' mainly determines the molecular weight of the perfluorosulfonimide resin.
Preferably, the polyacid side-chain type perfluorinated resins are classified into acid type polyacid side-chain type perfluorinated resins, alkali metal type polyacid side-chain type perfluorinated resins and other cationic type polyacid side-chain type perfluorinated resins according to different cations, and the structural formulas of the acid type and alkali metal type polyacid side-chain type perfluorinated resins are as follows:
wherein m=0 to 6, n=2 to 5, p=0 to 5, m "is hydrogen, lithium, sodium, potassium, rubidium, cesium or other cations, x" mainly determines EW of the polyacid side chain type perfluorinated resin, and y "mainly determines molecular weight of the polyacid side chain type perfluorinated resin.
Preferably, the sulfonated polytrifluorostyrene has a structural formula:
wherein M' "is hydrogen, lithium, sodium, potassium, rubidium, cesium or other cations, X 1 Selected from H, F or CF 3 X ' ", y '" and z ' "primarily determine the molecular weight and EW of the sulfonated polytrifluorostyrene.
The cation comprises at least one of ammonium ion, alkaline earth metal ion, iron ion, vanadium ion, titanium ion, cobalt ion, chromium ion, nickel ion, copper ion, aluminum ion, silver ion, zinc ion, manganese ion and tin ion.
In some embodiments, the composite ion exchange membrane preferably has a membrane thickness of 3 to 500 μm and an ion exchange capacity of 0.1 to 4.2mmol/g. Further preferably, the composite ion exchange membrane has a membrane thickness of 4 to 320 μm and an ion exchange capacity of 0.15 to 3.0mmol/g. More preferably, the composite ion exchange membrane has a membrane thickness of 5 to 200 μm and an ion exchange capacity of 0.2 to 2.5mmol/g.
The embodiment of the invention also provides a preparation method of the composite ion exchange membrane, which comprises the following steps:
(1) Dispersing ion exchange resin and cerium-based coordination polymer in a solvent to obtain a dispersion liquid;
(2) And (3) carrying out casting, casting or coating on the dispersion liquid prepared in the step (1), and drying to obtain the composite ion exchange membrane.
According to the preparation method of the composite ion exchange membrane, the prepared composite ion exchange membrane has good flatness, uniform thickness distribution and better performance; the process is simple and convenient to operate, has high production efficiency, and is convenient to be widely applied to industrial production; the dispersion liquid in the preparation process can also be used for preparing coating layers, hydrogel and adhesives of porous membranes such as desalination membranes (nanofiltration membranes), ultra/micro filtration membranes and the like, various fabrics in the biomedical field such as surgical gloves, medical protective clothing, sterile cloth sheets and the like, and protective equipment in the biochemical battlefield such as military protective clothing and the like, and has wide application fields.
In some embodiments, preferably, in the step (1), the solvent includes at least one of water, a high boiling point organic solvent, tetrahydrofuran, and a lower aliphatic alcohol; the high boiling point organic solvent comprises at least one of ethylene glycol, propylene glycol, glycerol, DMF, DMAc, DMSO, hexamethylphosphoric triamide and NMP, and the lower aliphatic alcohol comprises at least one of methanol, ethanol, isopropanol and n-propanol.
In some embodiments, preferably, the dispersing temperature is 10-240 ℃, the pressure is normal pressure-20 MPa, and the dispersing time is 0.1-24 h; the dispersing adopts a method comprising at least one of stirring, shaking and ultrasonic treatment.
In some embodiments, preferably, in the step (2), the drying temperature is 20 to 180 ℃.
In some embodiments, preferably, in the step (2), the method further includes loading the dispersion liquid prepared in the step (1) on a reinforced membrane, and drying to obtain a composite ion exchange membrane; preferably, the reinforcing membrane is a porous membrane.
In some embodiments, the mass content of the reinforced membrane is preferably 0.1 to 90% of the composite ion exchange membrane, and the thickness of the reinforced membrane is 2 to 400 μm. Further preferably, the mass content of the reinforced membrane is 1-70% of that of the composite ion exchange membrane, and the thickness of the reinforced membrane is 2-300 μm. More preferably, the mass content of the reinforced membrane is 3-50% of that of the composite ion exchange membrane, and the thickness of the reinforced membrane is 2-180 μm.
In some embodiments, preferably, the material of the reinforced film comprises at least one of a non-fluorinated polyolefin, a fluoropolymer, and an aromatic polymer; preferably, the non-fluorinated polyolefin comprises at least one of polyethylene, polypropylene and ethylene-propylene copolymer; the fluorine-containing polymer comprises at least one of polytetrafluoroethylene, tetrafluoroethylene-hexafluoropropylene copolymer, tetrafluoroethylene-propylene copolymer, ethylene-tetrafluoroethylene copolymer, tetrafluoroethylene-hexafluoropropylene-ethylene copolymer, polyvinylidene fluoride, vinylidene fluoride-hexafluoropropylene copolymer, tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer, vinylidene fluoride-tetrafluoroethylene-hexafluoropropylene copolymer, polyvinyl fluoride, polychlorotrifluoroethylene and ethylene-chlorotrifluoroethylene copolymer; the aromatic polymer membrane comprises at least one of polyaryletherketone, polysulfone, polyethersulfone ketone, polybenzimidazole, polyaramid, polyimide and polyetheretherketone.
The embodiment of the invention also provides application of the composite ion exchange membrane in polyelectrolyte membranes in chlor-alkali industry, proton exchange membranes for hydrogen production by water electrolysis, secondary battery membranes such as acid primary battery membranes and lithium batteries, polyelectrolytes in supercapacitors, polyelectrolyte membranes for metal recovery batteries or sensors.
The embodiment of the invention also provides a preparation method of the cerium-based coordination polymer, which comprises the following steps:
when the cerium-based coordination polymer is at least one of a coordination polymer with a one-dimensional structure, a coordination network with a two-dimensional structure and a coordination network with a three-dimensional structure, the preparation method comprises the following steps: dispersing cerium salt and organic ligand in solvent, carrying out hydrothermal reaction under acidic condition, cooling to room temperature, filtering, washing and drying to obtain coordination polymer.
Wherein the cerium salt comprises at least one of cerium nitrate, cerium chloride, cerium sulfate and cerium acetate, and the organic ligand comprises at least one of sulfonic acid organic ligand and carboxylic acid organic ligand;
the molar ratio of the cerium salt to the organic ligand is 1:0.5-4, preferably 1:1-3;
the solvent comprises at least one of water, methanol, ethanol, acetonitrile, diethyl ether, dimethylformamide (DMF), dimethylacetamide (DMAc), dimethylsulfoxide (DMSO), and N-methylpyrrolidone (NMP);
The pH value of the acidic condition is 1-6, preferably 1-5; the solution for adjusting the pH value comprises at least one of sulfuric acid solution, hydrochloric acid solution, trifluoroacetic acid solution, triethylamine and sodium hydroxide solution;
the temperature of the hydrothermal reaction is 20-200 ℃, and the time of the hydrothermal reaction is 12-84 hours;
the solvent used for washing comprises at least one of water, methanol, ethanol, acetonitrile, DMF and DMAc.
When the cerium-based coordination polymer is at least one of a two-dimensional porous MOF and a three-dimensional porous MOF, a hydrothermal synthesis method is adopted, and comprises at least one of the following synthesis methods:
synthesis method one
(1) Dissolving an organic ligand in a high-boiling point organic solvent to form an organic ligand solution, and dissolving cerium salt in the high-boiling point organic solvent to form a cerium salt solution; wherein the molar ratio of the organic ligand to the cerium salt is 1 (2-5), each 0.005 millimole cerium salt corresponds to 0.5-3 mL of organic solvent, and the volume ratio of the organic ligand solution to the cerium salt solution is 1 (2-10); respectively ultrasonically treating the organic ligand solution and the cerium salt solution for 0.5-2 hours at room temperature, and slowly dripping the cerium salt solution into the organic ligand solution;
(2) Continuing ultrasonic treatment of the mixed solution for 1-2 hours, and then dropwise adding ammonia water or sodium hydroxide solution to adjust the pH to 4-5; transferring the suspension into a hydrothermal reaction kettle, and performing sealed reaction in a blast oven for 18-48 hours at a reaction temperature of 100-200 ℃;
(3) After the reaction is finished, after the container is naturally cooled to room temperature, washing with a high boiling point organic solvent and ethanol in sequence, centrifugally separating, transferring the obtained white or pale yellow precipitate to a vacuum oven for drying, and finally obtaining white or pale yellow powder at the drying temperature of 150-200 ℃.
Synthesis method II
(11) Adding an organic ligand into an ethanol-water solution, adding ammonia water or 1mol/L sodium hydroxide solution to form an organic ligand solution, and simultaneously adding cerium salt into the ethanol-water solution to form a cerium salt solution; wherein the molar ratio of the organic ligand to the cerium salt is 1 (2-5), the volume ratio of water and ethanol in the ethanol-water solution is 1 (2-4), the volume ratio of ammonia water or sodium hydroxide solution to the ethanol-water solution is 5 (6-10), each 0.1 millimole of cerium salt corresponds to 4-8 mL of ethanol-water solution, and the volume ratio of the ethanol-water solution in the organic ligand solution and the cerium salt solution is (2-5): 1;
(12) Heating and stirring the organic ligand solution until the organic ligand solution is completely dissolved, slowly dripping cerium salt solution into the cooled organic ligand solution after ultrasonic treatment for 2-5 hours at room temperature, and continuously stirring the mixed solution for 12-24 hours at room temperature;
(13) After the reaction is finished, washing with ultrapure water and ethanol in sequence, centrifugally separating, transferring the obtained white or pale yellow precipitate to a vacuum oven for drying, and finally obtaining white or pale yellow powder at the drying temperature of 150-200 ℃.
Synthesis method III
(21) Adding an organic ligand, cerium salt and formic acid into a high-boiling-point organic solvent at the same time, wherein the molar ratio of the organic ligand to the cerium salt is 1 (2-5), each 0.1 millimole of cerium salt corresponds to 4-8 mL of the high-boiling-point organic solvent and 0.2-1 mL of formic acid, and carrying out ultrasonic treatment on the mixed solution for 0.5-2 hours at room temperature;
(22) Transferring the mixed solution after ultrasonic treatment into a hydrothermal reaction kettle, and sealing and reacting for 18-48 hours in a blast oven at the reaction temperature of 100-200 ℃;
(23) After the reaction is finished, after the container is naturally cooled to room temperature, washing with a high boiling point organic solvent and ethanol in sequence, centrifugally separating, transferring the obtained white or pale yellow precipitate to a vacuum oven for drying, and finally obtaining white or pale yellow powder at the drying temperature of 150-200 ℃.
Wherein the high boiling point organic solvent comprises at least one of DMF, DMAc, DMSO and NMP; the cerium salt comprises at least one of cerium nitrate, cerium chloride, cerium sulfate and cerium acetate.
The technical scheme of the present invention is described in detail below with reference to specific embodiments and drawings.
Cerium salt and organic ligand used in the embodiment of the invention are from chemical reagent suppliers such as Allatin, microphone reagent, piobtained pharmaceutical industry, music research reagent and the like; the perfluorosulfonic acid resin is derived from komu, 3M and sorrow; polyacid side chain type perfluorinated resins are derived from 3M; the porous polyethersulfone membrane is from Zhejiang Tailin organism; the perfluorinated sulfonimide resin and the porous polytetrafluoroethylene membrane (ePTFE) are self-made, and other solvents are common chemical reagents.
The perfluorinated sulfonyl imide resin is prepared by free radical copolymerization of perfluorinated sulfonyl imide vinyl ether monomer and tetrafluoroethylene monomer:
specifically, the perfluorinated sulfonimide vinyl ether monomer and tetrafluoroethylene monomer (TFE) are in Na 2 HPO 4 /NaH 2 PO 4 The buffer solution is prepared from (NH) 4 ) 2 S 2 O 8 /NaHSO 3 As initiator, continuous copolymerization was carried out. First Na is added to 2 HPO 4 ·7H 2 O and NaH 2 PO 4 Fully dissolving in de-aerated deionized water (a proper amount of surfactant can be added) to prepare a solution 1; subsequently, perfluorosulfonimide vinyl ether monomer 1 was added to solution 1, and the solution was cooled to 8 ℃ with continuous nitrogen, and then initiator was added to prepare solution 2. The autoclave was evacuated and after 3 purges with nitrogen over 5 minutes the initiator was added to solution 2; adding the solution 2 into a metering pump reservoir, and degassing with helium for more than 20 min; solution 2 was drawn into a fully evacuated autoclave and a suitable amount of de-aerated deionized water was added to make the solution half the volume of the reactor. When the reactor temperature reached 10 ℃, TFE was added to a pressure of 150psi and the continuous addition pump was started to maintain the pressure between 145 and 150psi throughout the process by adding TFE; and finally, acidifying the filtrate with 70% hydrochloric acid to obtain a precipitated polymer, washing the polymer with water until the polymer is neutral, and drying the polymer in full vacuum at 50 ℃ for more than 12 hours to obtain the perfluorinated sulfonyl imide resin.
Porous polytetrafluoroethylene films are prepared by a common biaxial stretching method: (1) 75 parts of PTFE powder (Cormu 605 XTX) and 25 parts of auxiliary oil (aviation kerosene) are mixed and stirred uniformly, and then cured, shaped and extruded for calendering to prepare a calendering belt containing the auxiliary oil; (2) Drying the calendaring belt to obtain a degreasing film, stretching the degreasing film in the MD direction, stretching the degreasing film in the TD direction, and performing heat setting to obtain the porous polytetrafluoroethylene film. The MD stretch ratio was 7 times and the TD stretch ratio was 22 times. Wherein the direction of the mechanical force is MD, and the direction transverse to the mechanical force is TD.
Example 1
Mixing 1, 10-phenanthroline-2, 9-dicarboxylic acid and (CeNO) in a molar ratio of 1:1 3 ) 3 ·6H 2 Adding O into water, uniformly mixing, adjusting the pH to 1 by using sulfuric acid solution, and sealing in a hydrothermal reaction kettle; heating to 180 ℃, reacting for 72 hours, gradually cooling to room temperature to obtain brown rod-shaped crystals, filtering, washing with distilled water and DMF sequentially, and drying to obtain the cerium coordination polymer { [ Ce ] with one-dimensional chain structure and high thermal stability 2 (PDA) 2 (SO 4 )(H 2 O) 6 ](H 2 O) 3 N, unit cell volumeIs that After ball milling treatment, the particle size distribution of the coordination polymer material is 3 nm-10 nm, which is named CPs-1.PDA is deprotonated 1, 10-phenanthroline-2, 9-dicarboxylic acid, and has the following structure:
Example 2
The molar ratio of (CeNO 3 ) 3 ·6H 2 Adding O and pivalic acid into methanol solvent, adding triethylamine, stirring thoroughly to dissolve, and filtering. The filtrate is slowly evaporated at room temperature to form needle-shaped crystals, and the needle-shaped crystals are washed by methanol and dried to prepare the cerium coordination polymer [ Ce (piv) with one-dimensional chain structure 3 (MeOH) 2 ]n, unit cell volume isThe grain size is 0.25X0.15X0.10 mm 3 The particle size distribution of the milled coordination polymer powder is 50-300 nm, and the particle size distribution is named CPs-2.piv is deprotonated pivalic acid, which has the structure:
example 3
1,1' -ferrocenedicarboxylic acid, ce (NO) 3 ) 3 ·6H 2 O is placed into a beaker according to the mol ratio of 1.5:1, 10mL of deionized water is added for fully stirring, so that the deionized water and the deionized water are uniformly mixed, and then a proper amount of sodium hydroxide solution is added and transferred into the inner container of the hydrothermal reaction kettle. Sealing the reaction kettle, putting the reaction kettle into a baking oven, heating to 110 ℃ for crystallization for 12 days, slowly cooling to room temperature, and alternately washing with water and ethanol to obtain the two-dimensional coordination polymer { [ Ce 2 (fcd) 3 ·H 2 O]·H 2 O } n, unit cell volume ofAfter ball milling, powder with the particle size distribution of 30 nm-120 nm is obtained and named CPs-3.fcd is a dianion [ Fe (C) formed by removing two protons from 1,1' -ferrocenedicarboxylic acid 5 H 4 COO) 2 ] 2- 。
Example 4
CeCl with the mol ratio of 1:3 3 ·7H 2 O and [ 5-ethoxycarbonyl-6- (4-bromophenyl) -1, 6-dihydropyrimidinone]Adding methanesulfonic acid (HL 1) into a beaker, adding a mixed solvent of water and ethanol, stirring, dissolving, filtering the solution into the beaker, standing and volatilizing at room temperature to obtain colorless flaky crystals { [ Ce (L1) 2 (H 2 O) 6 ](L1)(C 2 H 5 OH) 2 ·3H 2 O } n, unit cell volume ofThe grain size is 0.05X0.10X0.25 mm 3 After ball milling, powder with the particle size distribution of 50 nm-150 nm is obtained and named CPs-4. The coordination polymer has a two-dimensional molecular structure.
Example 5
The tridentate aromatic carboxylic acid ligand N- (4-benzoic acid group) iminodiacetic acid (H) with the molar ratio of 1:1 2 L2) and (CeNO) 3 ) 3 ·6H 2 Adding O into a polytetrafluoroethylene reaction kettle, adding acetonitrile and water mixed solution with the volume ratio of 1:1, stirring at room temperature for 20min, regulating the pH value of a system to be=2 by using 1M HCl solution, sealing the reaction mixture, then placing the reaction mixture into an electrothermal blowing drying oven, heating to 120 ℃, and keeping the temperature constant for 3 days. Cooling to room temperature at a rate of 5℃per hour to give colorless crystals { [ Ce (H) 3 L2)(H 2 O)]N, unit cell volume ofThe powder with the particle size distribution of 50 nm-100 nm is obtained and is named CPs-5.Ce (III) and carboxylic acid are linked to form one-dimensional chains, which are linked by three carboxylic acid groups of the ligandAnd forming a two-dimensional double-layer planar structure.
Example 6
5-Aminoisophthalic acid (H) in a molar ratio of 1:2 2 aip) and (CeNO) 3 ) 3 ·6H 2 Placing O and water in a hydrothermal tank, refluxing at 150deg.C in an oven for 3 days, cooling, and filtering to obtain colorless blocky crystal, cerium-based complex { [ Ce (aip) (Haip) (H) 2 O) 2 ]·H 2 O } n, unit cell volume 0.90307 (18) nm 3 After ball milling, powder with the particle size distribution of 10 nm-100 nm is obtained and named CPs-6.
Example 7
The bidentate carboxylic acid ligand R-2- (4- (4-carboxybenzyloxy) phenoxy) propionic acid (H) in a molar ratio of 1:1 2 L3) and (CeNO) 3 ) 3 ·6H 2 Adding O into a polytetrafluoroethylene reaction kettle, adding acetonitrile and water mixed solution with the volume ratio of 1:1, stirring for 30min at room temperature, regulating the pH value of a system to be=2 by using 25% trifluoroacetic acid solution, sealing the reaction mixture, and then placing the reaction mixture into an electrothermal blowing drying oven, heating to 120 ℃, and keeping the temperature constant for 3 days. Cooling to room temperature at a rate of 5 ℃ per hour to obtain colorless block-shaped { [ Ce 2 (H 2 L3) 3 (H 2 O) 3 ]·H 2 O·CH 3 CN } n, unit cell volume ofThe powder with the particle size of 30 nm-120 nm is obtained after grinding and ball milling, and is named CPs-7, and the coordination polymer has a three-dimensional molecular structure.
Example 8
The molar ratio of (CeNO) was 1:1.5 3 ) 3 ·6H 2 O, 2' -thiodicarboxylic acid (H) 2 TDA) and KOH are added into a polytetrafluoroethylene reaction kettle, deionized water is added for full dissolution, the mixture is sealed and placed into an electrothermal blowing drying box for heating to 120 ℃, the temperature is kept for 24 hours, the mixture is naturally cooled to room temperature, the mixture is washed with deionized water for 3 times, the dried mixture is dried to obtain the MOF material with a two-dimensional porous structure, the thickness of the formed nano-sheet is 80-150 nm, the transverse dimension is 2-4 mu m, and the powder is obtained after ball milling and named MOF-1.
Example 9
And preparing the MOF-2 with a three-dimensional porous structure by adopting the hydrothermal synthesis method I.
Wherein the organic ligand is 1, 4-phthalic acid, the high boiling point organic solvent is DMF, and the cerium salt is (CeNO 3 ) 3 ·6H 2 O, the molar ratio of the organic ligand to the cerium salt is 1:2.5, each 0.005 millimole of cerium salt corresponds to 3mL of organic solvent, the volume ratio of the organic ligand solution to the cerium salt solution is 1:5, and the cerium salt solution is slowly added into the organic ligand solution after ultrasonic treatment for 1 hour under the room temperature condition.
Continuously carrying out ultrasonic treatment on the mixed solution for 1 hour, and then dropwise adding sodium hydroxide solution to adjust the pH to 4-5; the suspension was transferred to a hydrothermal reaction kettle and reacted in a sealed air oven for 18 hours at a reaction temperature of 120 ℃.
And (3) drying the white precipitate in a vacuum oven for 24 hours after the reaction is finished, wherein the drying temperature is 150 ℃, and finally obtaining white powder.
Example 10
And preparing the MOF-3 with a three-dimensional porous structure by adopting the hydrothermal synthesis method II.
Wherein the organic ligand is 4,5,9, 10-tetrahydropyrene-2, 7-dicarboxylic acid, and the cerium salt is CeCl 3 ·7H 2 O, the molar ratio of the organic ligand to the cerium salt is 1:5, the volume ratio of water to ethanol in the ethanol-water solution is 1:2, the volume ratio of ammonia water to the ethanol-water solution is 5:8, each 0.1 millimole cerium salt corresponds to 8mL of the ethanol-water solution, and the volume ratio of the ethanol-water solution in the organic ligand solution and the cerium salt solution is 2:1.
The organic ligand solution is heated and stirred until the organic ligand solution is completely dissolved, cerium salt solution is slowly dripped into the cooled organic ligand solution after being sonicated for 5 hours at room temperature, and the mixed solution is continuously stirred for 24 hours at room temperature.
After the reaction, washing with ultrapure water and ethanol in sequence, centrifugally separating to obtain pale yellow precipitate, transferring the pale yellow precipitate to a vacuum oven for drying, and drying at the temperature of 200 ℃ to finally obtain pale yellow powder.
Example 11
And preparing the MOF-4 with a three-dimensional porous structure by adopting the hydrothermal synthesis method III.
Wherein the organic ligand is 2,4, 6-tris (4-carboxyphenyl) -1,3, 5-triazine, the cerium salt is cerium (III) acetate hydrate, the organic ligand, cerium salt and formic acid are added into DMAc at the same time, wherein the molar ratio of the organic ligand to the cerium salt is 1:2, each 0.1 millimole of cerium salt corresponds to 4mL of DMAc and 1mL of formic acid, and the mixed solution is sonicated for 2 hours at room temperature.
The mixed solution after ultrasonic treatment was transferred to a hydrothermal reaction kettle, and the reaction was sealed in a forced air oven for 48 hours at a reaction temperature of 200 ℃.
After the reaction is finished, washing with DMF and ethanol in sequence and centrifugally separating to obtain pale yellow precipitate, transferring to a vacuum oven for drying for 24 hours, and drying at 150-200 ℃ to finally obtain pale yellow powder.
Example 12
Unlike example 11, the organic ligand was 5',5 "-bis (4-carboxyphenyl) - [1,1':3',1":3",1" -tetrabiphenyl ] -4,4 "-dicarboxylic acid, the molar ratio of organic ligand to cerium salt was 1:3, the other conditions were identical, and finally a white powder MOF-5 was obtained. MOF-5 is a three-dimensional porous structure.
Example 13
Unlike example 9, in which the organic ligand was 2-sulfoterephthalic acid, the reaction was carried out in a forced air oven for 48 hours at 200℃under the same conditions, and MOF-6 as a pale yellow powder was finally obtained. MOF-6 is a three-dimensional porous structure.
Example 14
In contrast to example 10, the organic ligand was 3,3' -disulfo- [1,1' -biphenyl ] -4,4' -dicarboxylic acid, the cerium salt was cerium (IV) sulfate tetrahydrate, and the other conditions were identical, to finally obtain a pale yellow powder MOF-7.MOF-7 is a three-dimensional porous structure.
Example 15
In contrast to example 12, the organic ligand was 4, 8-disulfonaphthyl-2, 6-dicarboxylic acid, the other conditions being identical, a pale yellow powder MOF-8 being obtained. MOF-8 is a three-dimensional porous structure.
Example 16
40mg of each of the coordination polymers in examples 1 to 7 (diluted in 0.5mL of isopropanol) was weighed and added to 200g of a D520 resin dispersion (Kemu, perfluorosulfonic acid resin mass content 5%, EW 980g/mol, solvent water, a mixed solvent of ethanol and n-propanol) respectively. Stirring and mixing for 24 hours at room temperature, scraping and coating on a release film by a scraper, drying for 1 hour at 80 ℃, and carrying out heat treatment for 15 minutes at 150 ℃ to obtain the ion exchange film with the thickness of 50+/-3 mu m. The chemical structure of the perfluorosulfonic acid resin in the D520 resin dispersion liquid is as follows:
Example 17
1g of 3M800 resin (3M Co., EW: 800 g/mol) was weighed and dissolved in 4mL of DMSO at 80℃with stirring, and 0.1mg, 1mg, 5mg, 10mg and 20mg of the coordination polymer CPs-1 of example 1 (CPs-1 diluted in 1mL of DMSO) were added, respectively, and dispersed by sonication for 10 minutes to obtain a dispersion. The dispersion was cast in a super flat dish and dried at 180℃for 6 hours to give an ion exchange membrane having a thickness of 50.+ -. 4. Mu.m.
The chemical structure of the 3M800 resin is:
example 18
90mg of each of the MOFs in examples 8 to 15 was weighed and added to 50g of a D72 resin dispersion (Sorvy, perfluorosulfonic acid resin mass content 40%, EW 720g/mol, solvent water). Stirring and mixing for 24 hours at room temperature, scraping and coating on a release film by a scraper, drying for 1 hour at 80 ℃, and heat-treating for 15 minutes at 150 ℃ to obtain the ion exchange film with the thickness of 50+/-3 mu m. The chemical structure of the perfluorosulfonic acid resin in the D72 resin dispersion liquid is as follows:
example 19
10g of the 3M800 resin of example 17 was weighed and dissolved in 40g of a hydroalcoholic mixed solvent (water to ethanol mass ratio: 2:3) at room temperature with stirring, 360mg of the coordination polymer CPs-1 of example 1 was added, and the dispersion was obtained by ultrasonic dispersion for 10 minutes. The ion exchange membranes PEM-21 and PEM-22 with different thicknesses are prepared by doctor blade coating on a release membrane, drying at 100 ℃ for 15min, and heat treatment at 150 ℃ for 5min, and controlling the clearance of the doctor blade.
Example 20
Unlike example 19, which uses a release film as the substrate, a composite ion exchange membrane C-PEM-1 was prepared by the same heat treatment method using doctor blade coating on both sides of the ePTFE film. The ePTFE film has a thickness of 3+ -0.5 μm, a porosity of 75%, and a pore size distribution of 200-300 nm.
Example 21
9g of the 3M800 resin of example 17 was weighed and dissolved in 40g of DMF at room temperature with stirring, 1g of the coordination polymer MOF-8 of example 15 was added, and dispersion was obtained by ultrasonic dispersion for 10 min. The separation membrane is taken as a substrate, the separation membrane is coated on two sides of the porous polyethersulfone membrane by a slit, and is dried for 1 hour at 100 ℃, and is subjected to heat treatment for 15min at 160 ℃, so that the composite ion exchange membrane C-PEM-2 is prepared. The thickness of the porous polyethersulfone is 120-140 μm and the average pore diameter is 0.45 μm.
Example 22
10g of ion exchange resin solid is weighed, and dissolved and dispersed in a hydroalcoholic mixed solvent (water, ethanol, n-propanol, isopropanol and n-butanol with the mass ratio of 2:1:1:1:1) at 60 ℃ to obtain resin dispersion liquid. 50mg of MOF-8 of example 18 was added to the resin dispersion, dispersed uniformly by sonication for 15min, slit coated on both sides of the ePTFE membrane, dried at 90℃for 3min, and heat treated at 180℃for 10min to give different ion exchange membranes having a thickness of 15.+ -. 2. Mu.m, namely composite ion exchange membranes C-PEM-3, C-PEM-4, C-PEM-5 and C-PEM-6. The ePTFE film has a thickness of 7+ -1.5 μm, a porosity of 72%, and a pore size distribution of 180-270 nm.
Wherein the ion exchange resin solid is 3M800, BAM3G, perfluorinated sulfonyl imide resin or PFIA;
3M800 is the same as in example 17;
BAM3G is sulfonated polytrifluorostyrene resin from Barad with EW value of 407G/mol and structural formula:
wherein X is 1 Is F or CF 3 The ratio of the 2 substituents is not defined;
the perfluorinated sulfimide resin is obtained by copolymerizing tetrafluoroethylene and sulfimide monomers, the EW value is 1200g/mol, and the structural formula is as follows:
PFIA is polyacid side chain type perfluorinated resin, from 3M, with EW value of 625g/mol, and structural formula:
comparative example 1
Unlike example 16, an ion exchange membrane D-PEM-1 having a thickness of 50.+ -.3 μm was produced without adding a coordination polymer to the dispersion.
Comparative example 2
Unlike example 17, ion exchange membrane D-PEM-2 was prepared to a thickness of 50.+ -.4. Mu.m, without adding CPs-1 to the dispersion.
Comparative example 3
Unlike example 18, ion exchange membrane D-PEM-3 was prepared with a thickness of 50.+ -.3. Mu.m, without adding MOF to the dispersion.
Comparative example 4
Unlike example 19, ion exchange membranes D-PEM-4 and D-PEM-5 of different thicknesses were produced without adding CPs-1 to the dispersion.
Comparative example 5
Unlike example 20, composite ion exchange membrane D-C-PEM-1 was prepared without adding CPs-1 to the dispersion.
Comparative example 6
Unlike example 21, a composite ion exchange membrane D-C-PEM-2 was prepared without adding MOF-8 to the dispersion.
Comparative example 7
Unlike example 22, the ion exchange resin was 3M800, and 50mg of nano cerium oxide (CeO) was added to the dispersion 2 ) And MOF-8 is not added to prepare the composite ion exchange membrane D-C-PEM-3.
Comparative example 8
In contrast to example 22, composite ion exchange membranes D-C-PEM-4, D-C-PEM-5, D-C-PEM-6 and D-C-PEM-7 were made using ion exchange resins BAM3G, perfluorosulfonimide resin, PFIA and 3M800, respectively, without adding MOF-8 to the dispersion.
Test examples
Unit cell volume of coordination polymer: measured by single crystal X-ray diffraction method.
MOF particle size distribution: observation was performed using SEM.
BET specific surface area of MOF: the measurement was performed by using ASIQ-MI001-5 physical adsorption apparatus (America Kang Da).
Micropore volume of MOF: calculated by the t-plot method.
The test methods of conductivity, EW, IEC, tensile strength, tensile strain at break and water absorption are described in GB/T20042.3-2022 section 3 of proton exchange membrane fuel cell: proton exchange membrane test methods; wherein the conductivity is measured at 80℃and 95% relative humidity.
Fuel cell polarization curve: test methods refer to GB/T20042.5-2022 section 5 of proton exchange Membrane Fuel cell: membrane electrode test methods.
Radical resistance of ion exchange membranes: the ion exchange membrane was immersed in Fenton (Fenton) reagent at 80℃for 8 hours, and mass loss and conductivity decay before and after immersion were compared. Preparation of Fenton reagent: to 50mL of H with mass fraction of 3% 2 O 2 0.1mL of Fe with the mass concentration of 0.01mol/L is added dropwise into the solution 2+ The solution is prepared into the Fenton reagent which is prepared and used at present. The smaller the mass loss percentage of the ion exchange membrane is after Fenton reagent treatment, the better the durability is; the smaller the conductivity decay, the better the radical resistance.
(1) Table 1 shows the particle size distribution and unit cell volume of the coordination polymers obtained in examples 1 to 7.
TABLE 1
(2) Table 2 shows the particle sizes, BET specific surface areas and micropore volumes of the MOF materials prepared in examples 8 to 15.
TABLE 2
MOF Particle size (nm) BET specific surface area (m) 2 /g) Micropore volume (cm) 3 /g)
Example 8 MOF-1 30～60 127 0.06
Example 9 MOF-2 50～100 670 0.34
Example 10 MOF-3 30～70 1250 0.59
Example 11 MOF-4 50～80 1430 0.79
Example 12 MOF-5 30～40 2160 0.88
Example 13 MOF-6 30～50 1120 0.62
Example 14 MOF-7 200～300 1580 0.79
Example 15 MOF-8 30～40 1650 0.80
(3) The composite ion exchange membranes prepared in example 16 and comparative example 1 were subjected to Fenton reagent treatment, and the mass loss after the treatment is shown in Table 3.
TABLE 3 Table 3
As can be seen from the data of table 3, the radical durability of the composite ion exchange membrane is significantly improved and the mass loss of the composite ion exchange membrane is significantly reduced after doping the cerium-based coordination polymer as compared with comparative example 1; the better radical durability enables better safety and reliability in long-term operation.
(4) The IEC, water absorption rate and mass loss of the ion exchange membrane after the Fenton reagent treatment were tested for the added amounts of the composite ion exchange membranes of different CPs-1 prepared in example 17 and comparative example 2, and the results are shown in table 4.
TABLE 4 Table 4
As can be seen from the data of table 4, IEC and water absorption of the composite ion exchange membrane were less changed and radical durability was improved after doping a small amount of cerium-based coordination polymer as compared with comparative example 2; even an ion exchange membrane PEM-8 with a CPs-1 mass content of about 0.01% has a significantly reduced mass loss compared to D-PEM-2.
(5) The composite ion exchange membranes prepared in example 18 and comparative example 3 were treated with Fenton reagent, and the mass loss after the treatment is shown in Table 5.
TABLE 5
As can be seen from the data in table 5, compared with comparative example 3, the mass loss of the composite ion exchange membrane after being treated with the Fenton reagent is also significantly reduced, the free radical resistance is significantly improved, and the cerium-based MOF has a good effect as a hydroxyl radical quencher.
(6) The thicknesses of the composite ion exchange membranes and the mass loss after Fenton reagent treatment in examples 19 to 21 and comparative examples 4 to 6 were tested and are shown in Table 6.
TABLE 6
As can be seen from the data of table 6, the composite ion exchange membranes of the doped cerium-based coordination polymers prepared in examples 19 to 21 have significantly reduced mass loss and significantly improved free radical resistance, as compared to the ion exchange membranes of comparative examples 4 to 6, which are not doped with cerium-based coordination polymers. The chemical compositions of the PEM-21 and the PEM-22 are basically consistent, but the thicknesses are different, so that the difference exists in free radical resistance, and the PEM-22 benefits from the larger thickness, so that the permeation of hydroxyl radicals can be delayed to a certain extent, and the degradation of internal materials by the attack of the hydroxyl radicals is reduced. The same is true for the difference in the free radical resistance of C-PEM-1 and C-PEM-2, D-C-PEM-1 and D-C-PEM-2. The cerium-based polymer can improve the free radical resistance of ion exchange membranes and composite ion exchange membranes with different thicknesses, and can meet more application scenes.
(7) The resin types of the composite ion exchange membranes in example 22, comparative example 7 and comparative example 8 are shown in the following table 7, the IEC, water absorption rate, and mass loss after the Fenton reagent treatment of the composite ion exchange membrane are tested, the results are shown in table 6, and the tensile strength, elongation at break, and electrical conductivity before and after the Fenton reagent treatment of the composite ion exchange membrane are shown in table 8.
TABLE 7
TABLE 8
As can be seen from the data in table 7, the MOF-8 doped composite ion exchange membrane has higher IEC, water absorption and less mass loss when the ion exchange resin is the same as the cerium oxide doped composite ion exchange membrane. This is because cerium oxide is converted into cerium ions under the acidic condition of the ion exchange membrane to crosslink with sulfonic acid, resulting in a decrease in IEC and water absorption, and at the same time, sulfonic acid functional groups in MOF-8 can increase IEC and water absorption. Compared with a solid structure of cerium oxide, the porous structure of MOF-8 has larger specific surface area and stronger free radical quenching inactivation property, so that the composite ion exchange membrane has less mass loss and better durability.
As can be seen from the data in Table 8, the composite ion exchange membrane composed of the ion exchange resin, the enhancement layer and the MOF-8 has good mechanical properties and electrical conductivity, and can be applied to the proton exchange membrane of the fuel cell. After Fenton reagent treatment, the composite ion exchange membrane containing MOF-8 has low conductivity reduction degree and better durability. C-PEM-3 has higher tensile strength, elongation at break and electrical conductivity than D-C-PEM-3 doped with ceria.
SEM scanning of the cross section of the C-PEM-3 obtained in example 22 before and after the Fenton reagent treatment is performed, and the results are shown in FIGS. 1 and 2; SEM scans of sections of the D-C-PEM-7 prepared in comparative example 8 before and after Fenton reagent treatment were performed, and the results are shown in FIGS. 3 and 4. Because of the deviation of the thicknesses of different positions of the membrane, the membrane thickness is different, but compared with D-C-PEM-7, the morphology of the C-PEM-3 is less changed after Fenton reagent treatment, and the joint of the intermediate ePTFE enhancement layer and the upper and lower ion exchange resin layers is relatively flat. After the treatment of the Fenton reagent, the junction of the intermediate ePTFE enhancement layer and the upper and lower ion exchange resin layers becomes uneven, and the influence of the attack of hydroxyl radicals is larger.
The power densities of the C-PEM-3 and D-C-PEM-7 before and after Fenton reagent treatment were tested and the results are shown in FIG. 5. The performance of the single cell of the fuel cell engine of the C-PEM-3 before and after the Fenton reagent treatment is better than that of the D-C-PEM-7. The introduction of MOF-8 not only improves the durability of the composite ion exchange membrane, but also improves the electrochemical performance of the composite ion exchange membrane, and the comprehensive performance is obviously improved.
For purposes of this disclosure, the terms "one embodiment," "some embodiments," "example," "a particular example," or "some examples," etc., mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention. In this specification, schematic representations of the above terms are not necessarily directed 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, the different embodiments or examples described in this specification and the features of the different embodiments or examples may be combined and combined by those skilled in the art without contradiction.
While the above embodiments have been shown and described, it should be understood that the above embodiments are illustrative and not to be construed as limiting the invention, and that variations, modifications, alternatives, and variations of the above embodiments may be made by those of ordinary skill in the art without departing from the scope of the invention.

Claims (12)

1. A composite ion exchange membrane is characterized by comprising 90-99.99% of ion exchange resin and 0.01-10% of cerium-based coordination polymer by mass percent.
2. The composite ion exchange membrane of claim 1 wherein the metal ion of the coordination center of the cerium-based coordination polymer comprises Ce 3+ And Ce (Ce) 4+ At least one of them.
3. The composite ion exchange membrane of claim 1 or 2, wherein the cerium-based coordination polymer comprises at least one of a coordination polymer of one-dimensional structure, a coordination network of two-dimensional structure, and a coordination network of three-dimensional structure;
wherein the organic ligand of the cerium-based coordination polymer comprises at least one of sulfonic acid organic ligand and carboxylic acid organic ligand; preferably, the organic ligand comprises at least one of ethylenediamine tetraacetic acid disodium salt, N- (4-benzoyloxy) iminodiacetic acid, (5-ethoxycarbonyl-6-phenyl-1, 6-dihydropyrimidin-2-one-4-yl) methanesulfonic acid, R-2- (4- (4-carboxybenzyloxy) phenoxy) propionic acid, (5-ethoxycarbonyl-6-bromophenyl-1, 6-dihydropyrimidin-2-one-4-yl) methanesulfonic acid, 1' -ferrocenedicarboxylic acid, (5-ethoxycarbonyl-6-methyl-1, 6-dihydropyrimidin-2-one-4-yl) methanesulfonic acid, 1, 10-phenanthroline-2, 9-dicarboxylic acid, (5-ethoxycarbonyl-6-hydrogen-1, 6-dihydropyrimidin-2-one-4-yl) methanesulfonic acid, 5-aminoisophthalic acid, and pivalic acid.
4. The composite ion exchange membrane of claim 3 wherein the coordination polymer of one-dimensional structure, coordination network of two-dimensional structure and coordination network of three-dimensional structure have a unit cell volume ofPreferably isMore preferably +.>
5. The composite ion exchange membrane of claim 1 or 2, wherein the cerium-based coordination polymer comprises at least one of a two-dimensional porous MOF and a three-dimensional porous MOF;
wherein the two-dimensional porous MOF or the three-dimensional porous MOF has a particle size of5 to 800nm, BET specific surface area of 40 to 3000m 2 Per gram, micropore volume is 0.01-1.5 cm 3 /g；
Preferably, the organic ligands of the cerium-based coordination polymer include sulfonic acid-based organic ligands;
further preferred, at least one of a dicarboxylic acid-based organic ligand, a tricarboxylic acid-based organic ligand, a tetracarboxylic acid-based organic ligand, and a sulfonic acid-functionalized organic ligand is included;
more preferably, the di-, tri-or tetracarboxylic acid organic ligands include 2,2 '-thiodicarboxylic acid, 1,3, 5-tribenzoylbenzene, 2' -dithiodicarboxylic acid, 3, 6-benzobutane dicarboxylic acid, 1, 4-phthalic acid, 4'4 "-tricarboxylic acid triphenylamine, 2, 6-naphthalene dicarboxylic acid, 2,4, 6-tris (4-carboxyphenyl) -1,3, 5-triazine, 4' -biphthalic acid, benzene-1, 2,4, 5-tetracarboxylic acid, naphthalene-1, 4-dicarboxylic acid, naphthalene-2, 3,6, 7-tetracarboxylic acid, 4,5,9, 10-tetrahydropyrene-2, 7-dicarboxylic acid, [1,1 '-biphenyl ] -3,3',5 '-tetracarboxylic acid, pyrene-2, 7-dicarboxylic acid, 4',5 '-bis (4-carboxyphenyl) - [1,1':2',1" -terphenyl ] -4,4 "-dicarboxylic acid, [1,1': at least one of 4',1" -terphenyl ] -4,4 "-dicarboxylic acid, 1,3,6, 8-tetracarboxylic pyrene, 1,3, 5-benzene tricarboxylic acid, 4',4",4 '"-methane tetra-tetrabenzoic acid, [1,1' -biphenyl ] -3,4', 5-tricarboxylic acid, and 5',5" -bis (4-carboxyphenyl) - [1,1':3',1":3",1 "-tetrabiphenyl ] -4,4" -dicarboxylic acid;
More preferably, the sulfonic acid functionalized diacid organic ligand comprises at least one of 2-sulfonic acid terephthalic acid, 3, 7-disulfonaphthyl-2, 6-dicarboxylic acid, 5-sulfonic isophthalic acid, 4, 8-disulfonaphthyl-2, 6-dicarboxylic acid, 2, 5-disulfonic acid terephthalic acid, 3 '-disulfo- [1,1' -biphenyl ] -4,4 '-dicarboxylic acid, 5, 7-disulfonaphthyl-1, 4-dicarboxylic acid, 4-sulfonic acid-4' 4 "-dicarboxylic acid triphenylamine, 6-sulfenaphthyl-1, 4-dicarboxylic acid, and [1,1 '-biphenyl ] -4' -sulfonic acid-3, 5-dicarboxylic acid.
6. The composite ion exchange membrane of claim 1, wherein the ion exchange resin comprises at least one of perfluorosulfonic acid resin, perfluorosulfonimide resin, polyacid side chain type perfluororesin, sulfonated polytrifluorostyrene, sulfonated polysulfone, sulfonated polyethersulfone, sulfonated polyetheretherketone, sulfonated polyaryletherketone, sulfonated polyarylethernitrile, sulfonated polyphosphazene, sulfonated polyphenylene oxide, sulfonated polyphenylnitrile, sulfonated polyimide, and sulfonated polybenzimidazole; preferably comprises at least one of perfluorinated sulfonic acid resin, perfluorinated sulfonimide resin, polyacid side chain type perfluorinated resin, sulfonated polytrifluorostyrene, sulfonated polyether ether ketone, sulfonated polyaryletherketone and sulfonated polyarylethernitrile; more preferably at least one of perfluorosulfonic acid resin, perfluorosulfonimide resin, polyacid side chain type perfluororesin, and sulfonated polytrifluorostyrene.
7. The composite ion exchange membrane according to claim 1, wherein the composite ion exchange membrane has a membrane thickness of 3 to 500 μm and an ion exchange capacity of 0.1 to 4.2mmol/g.
8. The method for producing a composite ion exchange membrane according to any one of claims 1 to 7, comprising the steps of:
(1) Dispersing ion exchange resin and cerium-based coordination polymer in a solvent to obtain a dispersion liquid;
(2) And (3) carrying out casting, casting or coating on the dispersion liquid prepared in the step (1), and drying to obtain the composite ion exchange membrane.
9. The method according to claim 8, wherein in the step (2), the dispersion liquid obtained in the step (1) is supported on a reinforced membrane, and the reinforced membrane is dried to obtain the composite ion exchange membrane; preferably, the reinforcing membrane is a porous membrane.
10. The method for preparing a composite ion exchange membrane according to claim 9, wherein the mass content of the reinforced membrane is 0.1-90% of the composite ion exchange membrane, and the thickness of the reinforced membrane is 2-400 μm.
11. The method of preparing a composite ion exchange membrane according to claim 9 or 10, wherein the material of the reinforcing membrane comprises at least one of a non-fluorinated polyolefin, a fluoropolymer, and an aromatic polymer; preferably, the non-fluorinated polyolefin comprises at least one of polyethylene, polypropylene and ethylene-propylene copolymer; the fluorine-containing polymer comprises at least one of polytetrafluoroethylene, tetrafluoroethylene-hexafluoropropylene copolymer, tetrafluoroethylene-propylene copolymer, ethylene-tetrafluoroethylene copolymer, tetrafluoroethylene-hexafluoropropylene-ethylene copolymer, polyvinylidene fluoride, vinylidene fluoride-hexafluoropropylene copolymer, tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer, vinylidene fluoride-tetrafluoroethylene-hexafluoropropylene copolymer, polyvinyl fluoride, polychlorotrifluoroethylene and ethylene-chlorotrifluoroethylene copolymer; the aromatic polymer membrane comprises at least one of polyaryletherketone, polysulfone, polyethersulfone ketone, polybenzimidazole, polyaramid, polyimide and polyetheretherketone.
12. Use of a composite ion exchange membrane according to any one of claims 1 to 7 in polyelectrolyte membranes in the chlor-alkali industry, proton exchange membranes for hydrogen production by hydrolysis, acid primary battery membranes, secondary battery membranes for lithium batteries and the like, polyelectrolytes in supercapacitors, polyelectrolyte membranes for metal recovery batteries or sensors.
CN202310988917.6A 2023-08-07 2023-08-07 Composite ion exchange membrane and preparation method and application thereof Pending CN117106270A (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN117721498A (en) * 2024-02-07 2024-03-19 宁波中科氢易膜科技有限公司 Preparation method of organic-inorganic hybrid ion composite membrane

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN117721498A (en) * 2024-02-07 2024-03-19 宁波中科氢易膜科技有限公司 Preparation method of organic-inorganic hybrid ion composite membrane
CN117721498B (en) * 2024-02-07 2024-05-07 宁波中科氢易膜科技有限公司 Preparation method of organic-inorganic hybrid ion composite membrane

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