CN117802532A - Composite diaphragm and preparation method and application thereof - Google Patents

Composite diaphragm and preparation method and application thereof Download PDF

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CN117802532A
CN117802532A CN202311804740.6A CN202311804740A CN117802532A CN 117802532 A CN117802532 A CN 117802532A CN 202311804740 A CN202311804740 A CN 202311804740A CN 117802532 A CN117802532 A CN 117802532A
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polymer
porous
ionomer
substituted
composite
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陈安琪
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Carbon Harmonic Technology Shanghai Co ltd
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Carbon Harmonic Technology Shanghai Co ltd
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Abstract

The application provides a composite diaphragm, a preparation method and application thereof, and belongs to the technical field of diaphragms. The composite membrane comprises a porous support layer and a porous hydrophilic layer; the porous hydrophilic layer covers at least one surface of the porous supporting layer in the thickness direction, and the porous hydrophilic layer is filled in the pores of the porous supporting layer; wherein the porous supporting layer is made of at least one of non-woven fabrics and porous fabrics; the porous hydrophilic layer comprises inorganic hydrophilic particles, a first polymer and a second polymer; the first polymer is an engineering plastic and the second polymer includes at least one of an ionomer and a cross-link of the ionomer. The composite membrane provided by the application has low surface resistance, low gas flux and high bubble point, and has good application prospect in the field of hydrogen production by alkaline water electrolysis.

Description

Composite diaphragm and preparation method and application thereof
Technical Field
The application relates to the technical field of diaphragms, in particular to a composite diaphragm and a preparation method and application thereof.
Background
The hydrogen production by water electrolysis refers to a mode that water molecules are dissociated under the action of direct current to generate oxygen and hydrogen, and the oxygen and the hydrogen are separated out from an anode and a cathode of an electrolytic tank respectively. The membrane for producing hydrogen by electrolyzing water is generally divided into an alkaline electrolytic water membrane, a proton exchange membrane, a solid oxide membrane and an anion exchange membrane according to different materials of the electrolytic cell membrane. The hydrogen production technology by adopting the alkaline water electrolysis diaphragm is mature, and the non-noble metal electrocatalyst (such as Ni, co, mn and the like) can be used under alkaline conditions, so that the catalyst in the electrolytic tank has lower manufacturing cost, low investment and operation cost and is suitable for industrial production.
The alkaline electrolyzed water diaphragm plays an important role in ion conduction and isolation of hydrogen and oxygen generated by the cathode and the anode respectively in the alkaline electrolyzer. The performance indexes of the alkaline electrolyzed water diaphragm are mainly the bubble point of the diaphragm, the gas flux of the diaphragm and the surface resistance of the diaphragm; an ideal alkaline electrolyzed water membrane should have a low sheet resistance, low gas flux, and a high bubble point. However, the existing alkaline electrolyzed water membrane cannot have a combination of low sheet resistance, low gas flux and high bubble point.
Therefore, the development of a diaphragm with low surface resistance, low gas flux and high bubble point has important significance for the development of the alkaline electrolyzed water field.
Disclosure of Invention
The invention aims to provide a composite diaphragm, a preparation method and application thereof, and aims to solve the technical problems that the existing diaphragm cannot have low surface resistance, low gas flux and high bubble point.
In a first aspect, the present application provides a composite separator comprising: a porous support layer and a porous hydrophilic layer; the porous hydrophilic layer covers at least one surface of the porous supporting layer in the thickness direction, and the porous hydrophilic layer is filled in the pores of the porous supporting layer; wherein the porous hydrophilic layer comprises inorganic hydrophilic particles, a first polymer and a second polymer; the first polymer is an engineering plastic and the second polymer includes at least one of an ionomer and a cross-link of the ionomer.
In the composite membrane provided by the application, the first polymer, the second polymer and the inorganic hydrophilic particles form a porous hydrophilic layer together, the porous hydrophilic layer covers at least one surface of the porous supporting layer in the thickness direction, the porous hydrophilic layer is filled in the pores of the porous supporting layer, and the first polymer and the second polymer have a synergistic effect, so that the composite membrane has lower surface resistance, lower gas flux and higher bubble point; the composite diaphragm provided by the application is used as an alkaline electrolyzed water composite diaphragm, so that the alkaline electrolyzed water composite diaphragm has higher safety and electrolysis water efficiency, and has good application prospect in the field of hydrogen production by alkaline electrolysis water.
With reference to the first aspect, in an alternative embodiment of the present application, the backbone of the ionomer has salt units; or/and, the ionomer has salt units in the side chains. Wherein the salt unit comprises: a first anionic unit covalently attached to the ionomer and a first cationic unit electrostatically bound to the first anionic unit; alternatively, the salt unit includes: a second cationic unit covalently attached to the ionomer and a second anionic unit electrostatically bound to the second cationic unit.
In the technical scheme, the composite diaphragm has lower surface resistance, lower gas flux and higher bubble point, and has good application prospect in the field of hydrogen production by alkaline water electrolysis.
Optionally, the first anionic unit comprises at least one of a sulfonic acid group anion and a carboxyl group anion; the first cation unit includes at least one of sodium ion, potassium ion, lithium ion, magnesium ion, and calcium ion.
Optionally, the second cationic unit comprises at least one of a quaternary ammonium based cation, a protonated primary amino cation, a protonated secondary amino cation, and a protonated tertiary amine based cation; the second anionic unit includes at least one of a halogen ion, a bicarbonate ion, a hydroxide ion, a trifluoromethanesulfonic acid anion, a para-trifluorobenzenesulfonic acid anion, a phosphorus hexafluoride anion, and a boron tetrafluoride anion.
With reference to the first aspect, in an alternative embodiment of the present application, the backbone of the ionomer has at least one of an aryl piperidine structure, a polyethylene structure, a polybenzimidazole structure, a polyphenylene ether structure, a polystyrene structure, a polyacrylic structure, an epoxy resin structure, a polyvinylpyridine structure, and a urea formaldehyde structure.
In the technical scheme, the composite diaphragm has lower surface resistance, lower gas flux and higher bubble point, and has good application prospect in the field of hydrogen production by alkaline water electrolysis.
Optionally, the backbone of the ionomer has at least one of an aryl piperidine type structure and a polystyrene type structure.
With reference to the first aspect, in an alternative embodiment of the present application, the ionomer comprises at least one of a first substance and a second substance; the structural formula of the first substance is as follows:
wherein m is 1 ＞0，n 1 ≥0；Ar 1 Ar, ar 2 Each independently selected from substituted or unsubstituted aryl; x is X 1 - Is an anion; r is R 1 R is as follows 2 Each independently is a substituted or unsubstituted alkyl group; r is R 3 Is a group containing a fluorine atom; the structural formula of the second substance is as follows:
wherein m is 2 ＞0，n 2 ＞0；Ar 3 Ar, ar 4 Each independently selected from substituted or unsubstituted aryl; x is X 2 - Is an anion; p is 1-6; r is R 4 Is a group containing fluorine atoms.
In the technical scheme, the surface resistance and the gas flux of the composite membrane are further reduced, the bubble point of the composite membrane is further improved, and the composite membrane has good application prospect in the field of hydrogen production by alkaline electrolysis of water.
Alternatively, m 1 And n 1 Ratio of m 2 And n 2 The ratio of (2) is greater than 1:1.
Alternatively, m 1 And n 1 Ratio of m 2 And n 2 The ratio of (2) to (20): 1, independently of each other.
Alternatively, ar 1 、Ar 2 、Ar 3 Ar, ar 4 Each independently selected from the group consisting of substituted or unsubstituted biphenyl, substituted or unsubstituted meta-terphenyl, substituted or unsubstituted para-terphenyl, substituted or unsubstituted tetrabiphenyl, substituted or unsubstituted pentabiphenyl, substituted or unsubstituted naphthalene, and substituted or unsubstituted fluorene.
Alternatively, X 1 - X is as follows 2 - Each independently selected from at least one of a halogen ion, a bicarbonate ion, a hydroxide ion, a trifluoromethanesulfonic acid anion, a p-trifluorobenzenesulfonic acid anion, a phosphorus hexafluoride anion, and a boron tetrafluoride anion.
Alternatively, R 3 R is as follows 4 Are trifluoromethyl groups.
Optionally, the alkyl group is selected from at least one of methyl, ethyl, propyl, butyl, pentyl, and hexyl.
In an alternative embodiment of the present application, in combination with the first aspect, the ionomer comprises a third substance having the following structural formula:wherein q is more than 0, r is more than or equal to 0, s is more than or equal to 0, and r and s are not simultaneously 0; r is R 4 + Is a positively charged cyclic amine group; x is X 3 - Is an anion; r is R 5 Selected from halogen substituted alkyl groups.
In the technical scheme, the surface resistance and the gas flux of the composite membrane are further reduced, the bubble point of the composite membrane is further improved, and the composite membrane has good application prospect in the field of hydrogen production by alkaline electrolysis of water.
Optionally, the positively charged cyclic amine group is selected from at least one of imidazolium, pyridinium, pyrazolium, pyrrolidinium, pyrimidinium, piperidinium, indolium, and triazinium.
Optionally, the positively charged cyclic amine group is selected from at least one of imidazolium and piperidinium.
Optionally, the positively charged cyclic amine group is selected from at least one of tetramethylimidazolium and N-methylpiperidinium.
Optionally, aGround, X 3 At least one selected from the group consisting of a hydroxyl group, a chlorine atom, a bromine atom, an iodine atom, a p-toluenesulfonyloxy group, a trifluoromethanesulfonic acid group and a methanesulfonyloxy group.
Alternatively, X 3 Selected from chlorine atoms.
Alternatively, R 5 At least one selected from chloromethyl, bromomethyl and iodomethyl.
Alternatively, the ratio of the sum of r and s to q is (1:2) - (9:1).
With reference to the first aspect, in an alternative embodiment of the present application, the first polymer is selected from at least one of polysulfone, polyethersulfone, and polyphenylsulfone; or/and the weight average molecular weight of the first polymer is 10000-500000; or/and, the inorganic hydrophilic particles comprise at least one of zirconia, barium sulfate, hydrotalcite, titanium dioxide and magnesium hydroxide; or/and the particle diameter of the inorganic hydrophilic particles is 1 nm-1 μm.
In the technical scheme, the composite diaphragm has lower surface resistance, lower gas flux and higher bubble point, and has good application prospect in the field of hydrogen production by alkaline water electrolysis.
Optionally, the first polymer is selected from at least one of polysulfone and polyethersulfone.
Optionally, the inorganic hydrophilic particles comprise at least one of zirconia and barium sulfate.
With reference to the first aspect, in an alternative embodiment of the present application, the mass fraction of the inorganic hydrophilic particles in the porous hydrophilic layer is 60% to 90%; the total mass of the first polymer and the second polymer accounts for 10% -40% of the mass of the porous hydrophilic layer, and the mass of the second polymer accounts for less than or equal to 70% of the total mass of the first polymer and the second polymer.
In the technical scheme, the composite diaphragm has lower surface resistance, lower gas flux and higher bubble point, and has good application prospect in the field of hydrogen production by alkaline water electrolysis.
Optionally, the mass fraction of the inorganic hydrophilic particles in the porous hydrophilic layer is 65% -85%, and the total mass of the first polymer and the second polymer accounts for 15% -35% of the mass of the porous hydrophilic layer.
Optionally, the mass of the second polymer is present in an amount of 0.01% to 50% of the total mass of the first polymer and the second polymer.
With reference to the first aspect, in an alternative embodiment of the present application, the thickness of the porous support layer is 30 μm to 500 μm; or/and the mesh number of the porous supporting layer is 20-150 meshes; or/and the porous supporting layer is made of at least one of non-woven fabrics and porous fabrics; or/and the thickness of the composite diaphragm is 200-800 μm.
In the technical scheme, the composite diaphragm has lower surface resistance, lower gas flux and higher bubble point, and has good application prospect in the field of hydrogen production by alkaline water electrolysis.
Optionally, the material of the porous supporting layer includes at least one of polypropylene, polyethylene, polysulfone, polyphenylene sulfide, polyamide, polyethersulfone, polyphenylsulfone, polyethylene terephthalate, polyetheretherketone, sulfonated polyetheretherketone, chlorotrifluoroethylene, copolymer of ethylene and tetrafluoroethylene, copolymer of ethylene and chlorotrifluoroethylene, polyimide, polyetherimide and meta-aramid.
In a second aspect, the present application provides a method for preparing the composite separator provided in any one of the first aspects, where the method includes: coating the slurry on the porous support layer so that part of the slurry is filled in the pores of the porous support layer and part of the slurry covers at least one surface of the porous support layer in the thickness direction; the coated system is placed in a coagulation bath for phase inversion treatment. Wherein the slurry comprises inorganic hydrophilic particles, a first polymer, a second polymer, and a pore-forming agent.
The preparation method of the composite membrane can enable the prepared composite membrane to have lower surface resistance, lower gas flux and higher bubble point; the composite diaphragm provided by the application is used as an alkaline electrolyzed water composite diaphragm, so that the alkaline electrolyzed water composite diaphragm has higher safety and electrolysis water efficiency, and has good application prospect in the field of hydrogen production by alkaline electrolysis water.
In a third aspect, the present application provides the use of a composite membrane for the preparation of a water electrolysis hydrogen production device and a secondary battery; wherein the composite membrane is the composite membrane provided in any one of the first aspect, or the composite membrane is the composite membrane manufactured by the manufacturing method of the composite membrane provided in the second aspect; the secondary battery includes at least one of a lithium battery and a sodium battery.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present application, the drawings that are needed in the embodiments will be briefly described below, it being understood that the following drawings only illustrate some embodiments of the present application and therefore should not be considered limiting the scope, and that other related drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 is a nuclear magnetic resonance hydrogen spectrum of a first monomer prepared in step (1) of example 1 of the present application.
FIG. 2 is a nuclear magnetic resonance spectrum of a polymer product prepared in example 8 of the present application.
FIG. 3 is a nuclear magnetic resonance hydrogen spectrum of the polymer product prepared in example 9 of the present application.
FIG. 4 is a nuclear magnetic resonance hydrogen spectrum of the polymer product prepared in example 10 of the present application.
Detailed Description
The alkaline electrolyzed water diaphragm plays an important role in ion conduction and isolation of hydrogen and oxygen generated by the cathode and the anode respectively in the alkaline electrolyzer. The performance indexes of the alkaline electrolyzed water membrane are mainly the bubble point of the membrane, the gas flux of the membrane and the surface resistance of the membrane. Wherein, the bubble point of the diaphragm and the gas flux of the diaphragm mainly influence the safety of the diaphragm; the surface resistance performance of the diaphragm is an index mainly affecting the conductivity of the diaphragm and thus the efficiency of water electrolysis.
Ion conduction in the diaphragm is mainly realized through pore channels in the diaphragm, and the larger the pore space of the diaphragm is, the better the ion conduction performance of the diaphragm is. However, the inventor finds that the larger the pores of the diaphragm, the better the air permeability of the diaphragm is often caused, and the effect of the diaphragm in blocking the hydrogen and the oxygen generated by the cathode and the anode respectively is further affected, so that the concentration of the hydrogen in the oxygen in the anode region of the electrolytic cell is increased, and potential safety hazards are easily caused.
To this end, the present application provides a composite membrane comprising: a porous support layer and a porous hydrophilic layer; the porous hydrophilic layer covers at least one surface of the porous supporting layer in the thickness direction, and the porous hydrophilic layer is filled in the pores of the porous supporting layer; wherein the first polymer is engineering plastic and the second polymer comprises at least one of an ionomer and a cross-linked product of the ionomer.
In the composite membrane provided by the application, the inorganic hydrophilic particles can endow the composite membrane with certain mechanical strength and hydrophilic performance, and the porous supporting layer can support the porous hydrophilic layer so as to improve the mechanical strength of the composite membrane; the first polymer, the second polymer and the inorganic hydrophilic particles form a porous hydrophilic layer together, the porous hydrophilic layer covers at least one surface of the porous supporting layer in the thickness direction, the porous hydrophilic layer is filled in the pores of the porous supporting layer, and the first polymer and the second polymer have synergistic effect, so that the composite membrane has lower surface resistance, lower gas flux and higher bubble point; the composite diaphragm provided by the application is used as an alkaline electrolyzed water composite diaphragm, so that the alkaline electrolyzed water composite diaphragm has higher safety and electrolysis water efficiency, and has good application prospect in the field of hydrogen production by alkaline electrolysis water.
In this application, cross-links of ionomers refer to: the ionomer is crosslinked to obtain the corresponding product; the present application is not limited to "the crosslinked structure of the ionomer", and the crosslinking agent used in the crosslinking of the ionomer may be a molecule containing two or more double bonds (for example, divinylbenzene), a molecule containing two or more amino groups (for example, tetramethyl ethylenediamine), or a molecule containing two or more halogen atoms.
In the present application, "the porous hydrophilic layer covers at least one surface in the thickness direction of the porous support layer" means: the porous hydrophilic layer may be coated on only one surface in the thickness direction of the porous support layer, or may be coated on opposite surfaces in the thickness direction of the porous support layer.
In some alternative embodiments of the present application, the backbone of the ionomer has salt units; or/and, the ionomer has salt units in the side chains. Wherein the salt unit comprises: a first anionic unit covalently attached to the ionomer and a first cationic unit electrostatically bound to the first anionic unit; alternatively, the salt unit includes: a second cationic unit covalently attached to the ionomer and a second anionic unit electrostatically bound to the second cationic unit. By the mode, the composite diaphragm has low surface resistance, low gas flux and high bubble point, and has good application prospect in the field of hydrogen production by alkaline water electrolysis.
Further, in some alternative embodiments of the present application, the first anionic unit comprises at least one of a sulfonic acid group anion and a carboxylic acid group anion; the first cation unit includes at least one of sodium ion, potassium ion, lithium ion, magnesium ion, and calcium ion.
It will be appreciated that the first anionic unit is not limited to the ions described above, as long as it is an anion capable of covalent attachment to the ionomer; the first cation unit is not limited to the above ion, and may be any cation capable of electrostatically binding to "anion covalently bonded to ionomer".
Further, in some alternative embodiments of the present application, the second cationic unit comprises at least one of a quaternary ammonium based cation, a protonated primary amino cation, a protonated secondary amino cation, and a protonated tertiary amino cation; the second anionic unit includes at least one of a halogen ion, a bicarbonate ion, a hydroxide ion, a trifluoromethanesulfonic acid anion, a para-trifluorobenzenesulfonic acid anion, a phosphorus hexafluoride anion, and a boron tetrafluoride anion.
It will be appreciated that the second cationic unit is not limited to the ions described above, as long as it is a cation capable of covalent attachment to the ionomer; the second anionic unit is not limited to the above ion, and may be any anion capable of electrostatically binding to "a cation covalently bonded to an ionomer".
In some alternative embodiments of the present application, the backbone of the ionomer has at least one of an aryl piperidine structure, a polyethylene structure, a polybenzimidazole structure, a polyphenylene ether structure, a polystyrene structure, a polyacrylic structure, an epoxy resin structure, a polyvinylpyridine structure, and a urea formaldehyde structure. By the mode, the composite diaphragm has low surface resistance, low gas flux and high bubble point, and has good application prospect in the field of hydrogen production by alkaline water electrolysis.
In this application, "the backbone of the ionomer has an aryl piperidine type structure" means: the backbone of the ionomer has "aryl groups linked to piperidinyl groups to form a repeating unit structure"; "the backbone of the ionomer has a polyethylene-based structure" means: ionomer backbone havingWherein R is an H atom or a substituent excluding a phenyl group; "the backbone of the ionomer has a polybenzimidazole type structure" means: the backbone of the ionomer has a repeating unit structure of "benzimidazolyl"; "the main chain of the ionomer has a polyphenylene ether structure" means: the backbone of the ionomer has "repeating units formed by the linkage of phenyl groups and ether linkages"; "the backbone of the ionomer has a polystyrene-based structure" means: ionomer backbone having- >Wherein R is an H atom or a substituent; "the backbone of the ionomer has a polystyrene-based structure" means: ionomer backbone having->Wherein R is an H atom or a substituent; "ReleaseThe ionomer corresponding to the backbone of the polymer having an epoxy resin-based structure "means: an ionomer which contains two or more epoxy groups, has an aliphatic, alicyclic or aromatic organic compound as a skeleton, and can be reacted with an epoxy group to form a useful heat-curable product; "the backbone of the ionomer has a polyvinyl pyridine structure" means: ionomer backbone with @>A repeating unit "formed by linking pyridyl groups, wherein R is an H atom or a substituent; the "ionomer having a urea-formaldehyde structure in its main chain" means an ionomer comprising: ionomers obtained by reacting urea with formaldehyde.
Further, in some alternative embodiments of the present application, the backbone of the ionomer has at least one of an aryl piperidine type structure and a polystyrene type structure; the surface resistance and gas flux of the composite membrane are further reduced, and the bubble point and alkali stability of the composite membrane are further improved.
In some alternative embodiments of the present application, when the backbone of the ionomer has an aryl piperidine type structure, the ionomer includes at least one of a first species and a second species.
The structural formula of the first substance is as follows:
wherein m is 1 ＞0，n 1 ≥0；Ar 1 Ar, ar 2 Each independently selected from substituted or unsubstituted aryl; x is X 1 - Is an anion; r is R 1 R is as follows 2 Each independently is a substituted or unsubstituted alkyl group; r is R 3 Is a group containing fluorine atoms.
The structural formula of the second substance is as follows:
wherein m is 2 ＞0，n 2 ＞0；Ar 3 Ar, ar 4 Each independently selected from substituted or unsubstituted aryl; x is X 2 - Is an anion; p is 1-6; r is R 4 Is a group containing fluorine atoms.
The ionomer comprises at least one of the first substance and the second substance, is favorable for further reducing the surface resistance and the gas flux of the composite membrane, further improves the bubble point of the composite membrane, and has good application prospect in the field of hydrogen production by alkaline water electrolysis.
In some alternative embodiments of the present application, m in the first substance 1 And n 1 The ratio of (2) is greater than 1:1; the surface resistance of the composite diaphragm is further reduced.
Further, in the first substance, m 1 And n 1 The ratio of (2) to (1) is more than or equal to 2; the surface resistance of the composite diaphragm is further reduced. Still further, in the first substance, m 1 And n 1 The ratio (2-20) of (C) to (C) is 1.
As an example, m in the first substance 1 And n 1 The ratio of (2) to (1) may be any one point value or a range value between any two of 2:1, 3:1, 5:1, 8:1, 10:1, 12:1, 15:1, 17:1 and 20:1.
In some alternative embodiments of the present application, m in the first substance 1 And n 1 The ratio of the ratios (3-15) is 1; the surface resistance of the composite diaphragm is further reduced.
As an example, in the first substance, ar 1 Ar, ar 2 Each independently selected from a substituted or unsubstituted phenyl group, a substituted or unsubstituted naphthyl group, a substituted or unsubstituted fluorenyl group, a substituted or unsubstituted condensed ring aromatic compound, and the like.
In some alternative embodiments of the present application, ar in the first species 1 Ar, ar 2 Each independently selected from the group consisting of substituted or unsubstituted biphenyl, substituted or unsubstituted meta-terphenyl, substituted or unsubstituted para-terphenyl, substituted or unsubstituted tetrabiphenyl, substituted or unsubstituted pentabiphenyl, substituted or unsubstituted naphthalene, and substituted or unsubstituted fluorene.
Further, the method comprises the steps of,in the second substance, ar 1 Ar, ar 2 Each independently selected from substituted or unsubstituted biphenyl, substituted or unsubstituted meta-terphenyl, substituted or unsubstituted para-terphenyl, substituted or unsubstituted fluorene; the surface resistance of the composite diaphragm is further reduced.
As an example, in the first substance, ar 1 Ar, ar 2 The substituent on the above may be alkyl, alkenyl, alkynyl or fluoride, etc.
In some alternative embodiments of the present application, X 1 - At least one selected from the group consisting of a halogen ion, a bicarbonate ion, a hydroxide ion, a trifluoromethanesulfonic acid anion, a p-trifluorobenzenesulfonic acid anion, a phosphorus hexafluoride anion, and a boron tetrafluoride anion. Further, X 1 - Selected from halogen ions.
In some alternative embodiments of the present application, R 1 R is as follows 2 Each independently is at least one of a substituted or unsubstituted methyl group, a substituted or unsubstituted ethyl group, a substituted or unsubstituted propyl group, a substituted or unsubstituted butyl group, a substituted or unsubstituted pentyl group, and a substituted or unsubstituted hexyl group; illustratively, R is 1 R is as follows 2 The substituent in (b) may be a fluoride or the like.
In some alternative embodiments of the present application, R 3 Is trifluoromethyl.
In some alternative embodiments of the present application, m in the second substance 2 And n 2 The ratio of (2) is greater than 1:1; the surface resistance of the composite diaphragm is further reduced.
Further, in the second substance, m 2 And n 2 The ratio of (2) to (1) is more than or equal to 2; the surface resistance of the composite diaphragm is further reduced. Still further, in the first substance, m 2 And n 2 The ratio (2-20) of (C) to (C) is 1.
As an example, m in the second substance 2 And n 2 The ratio of (2) to (1) may be any one point value or a range value between any two of 2:1, 3:1, 5:1, 8:1, 10:1, 12:1, 15:1, 17:1 and 20:1.
In some alternative embodiments of the present application, m in the second substance 2 And n 2 The ratio of the ratios (3-15) is 1; the surface resistance of the composite diaphragm is further reduced.
As an example, in the second substance, ar 3 Ar, ar 4 Each independently selected from a substituted or unsubstituted phenyl group, a substituted or unsubstituted naphthyl group, a substituted or unsubstituted fluorenyl group, a substituted or unsubstituted condensed ring aromatic compound, and the like.
In some alternative embodiments of the present application, ar in the second substance 3 Ar, ar 4 Each independently selected from the group consisting of substituted or unsubstituted biphenyl, substituted or unsubstituted meta-terphenyl, substituted or unsubstituted para-terphenyl, substituted or unsubstituted tetrabiphenyl, substituted or unsubstituted pentabiphenyl, substituted or unsubstituted naphthalene, and substituted or unsubstituted fluorene.
Further, in the second substance, ar 3 Ar, ar 4 Each independently selected from substituted or unsubstituted biphenyl, substituted or unsubstituted meta-terphenyl, substituted or unsubstituted para-terphenyl, substituted or unsubstituted fluorene; the surface resistance of the composite diaphragm is further reduced.
As an example, in the second substance, ar 3 Ar, ar 4 The substituent on the above may be alkyl, alkenyl, alkynyl or fluoride, etc.
In some alternative embodiments of the present application, X 2 - At least one selected from the group consisting of a halogen ion, a bicarbonate ion, a hydroxide ion, a trifluoromethanesulfonic acid anion, a p-trifluorobenzenesulfonic acid anion, a phosphorus hexafluoride anion, and a boron tetrafluoride anion. Further, X 2 - Selected from halogen ions.
In some alternative embodiments of the present application, R 4 Is trifluoromethyl.
As an example, the first substance has the following structural formula:
illustratively, when the ionomer is the first material, the cross-linked structure of the ionomer is as follows:
wherein the sum of z1+q1 is m1, and s1 is more than or equal to 0.
In some alternative embodiments of the present application, when the backbone of the ionomer has a polystyrene-like structure, the ionomer comprises a third substance.
The structural formula of the third substance is as follows:wherein q is more than 0, r is more than or equal to 0, s is more than or equal to 0, and r and s are not simultaneously 0; r is R 4 + Is a positively charged cyclic amine group; x is X 3 - Is an anion; r is R 5 Selected from halogen substituted alkyl groups.
The ionomer comprises a third substance, is favorable for further reducing the surface resistance of the composite membrane, ensures that the composite membrane has better alkali stability, and has good application prospect in the field of alkaline water electrolysis hydrogen production.
In some alternative embodiments of the present application, the positively charged cyclic amine group in the third substance is selected from at least one of imidazolium, pyridinium, pyrazolium, pyrrolidinium, pyrimidinium, piperidinium, indolium, and triazinium.
Further, in the third substance, the positively charged cyclic amine group is selected from at least one of imidazolium and piperidinium; the surface resistance of the composite membrane is further reduced, and the composite membrane has better alkali stability.
Still further, in the third substance, the positively charged cyclic amine group is selected from at least one of tetramethylimidazolium and N-methylpiperidinium; the surface resistance of the composite membrane is further reduced, and the composite membrane has better alkali stability.
In some alternative embodiments of the present application, in the third substance, X 3 At least one selected from the group consisting of a hydroxyl group, a chlorine atom, a bromine atom, an iodine atom, a p-toluenesulfonyloxy group, a trifluoromethanesulfonic acid group and a methanesulfonyloxy group. Further, in the third substance, X 3 Selected from chlorine atoms.
In some alternative embodiments of the present application, in the third substance, R 5 At least one selected from chloromethyl, bromomethyl and iodomethyl.
In some alternative embodiments of the present application, the ratio of the sum of r and s to q in the third substance is (1:2) - (9:1); the surface resistance of the composite membrane is further reduced, and the composite membrane has better alkali stability.
As an example, the ratio of the sum of r and s to q may be any one of the point values or range values between any two of 1:2, 1:1.5, 1:1.25, 1:1.2, 1:1.1, 1.2:1, 1.25:1, 1.5:1, 1.7:1, 1.85:1, 2:1, 2.15:1, 2.25:1, 2.3:1, 2.35:1, 2.4:1, 2.5:1, 2.7:1, 3:1, 3.5:1, 4:1, 5:1, 7:1, and 9:1.
Illustratively, the third substance has the structural formula:
the ionomer may be selected from the first or second materials described above, which may result in a composite separator having better overall properties (including sheet resistance, gas flux, and bubble point) than the ionomer selected from the third material described above.
In some alternative embodiments of the present application, the first polymer is selected from at least one of polysulfone, polyethersulfone, and polyphenylsulfone; the composite diaphragm can have higher structural strength.
In some alternative embodiments of the present application, the first polymer is selected from at least one of polysulfone and polyethersulfone; is favorable for further improving the structural strength and alkali stability of the composite diaphragm.
In some alternative embodiments of the present application, the first polymer has a weight average molecular weight of 10000 to 500000.
As an example, the weight average molecular weight of the first polymer may be any one point value or a range value between any two of 10000, 20000, 50000, 75000, 100000, 200000, 250000, 300000, 400000, and 500000.
Further, the weight average molecular weight of the first polymer is 20000 to 250000; the composite membrane has higher structural strength, lower surface resistance, lower gas flux and higher bubble point.
In some alternative embodiments of the present application, the inorganic hydrophilic particles comprise at least one of zirconia, barium sulfate, hydrotalcite, titania, and magnesium hydroxide.
Further, the inorganic hydrophilic particles include at least one of zirconia and barium sulfate; wherein, zirconia is favorable for further reducing the surface resistance of the composite diaphragm; the cost of barium sulfate is low.
In some alternative embodiments of the present application, the inorganic hydrophilic particles have a particle size of 1nm to 1 μm.
As an example, the particle diameter of the inorganic hydrophilic particles may be any one point value or a range value between any two of 1nm, 5nm, 10nm, 50nm, 100nm, 200nm, 500nm, 750nm and 1 μm.
Further, the particle size of the inorganic hydrophilic particles is 5 nm-500 nm; the surface resistance of the composite diaphragm is further reduced.
Still further, the particle size of the inorganic hydrophilic particles is 5nm to 200nm; the surface resistance of the composite diaphragm is further reduced.
In some alternative embodiments of the present application, the mass fraction of the inorganic hydrophilic particles in the porous hydrophilic layer is 60% to 90%; the total mass of the first polymer and the second polymer accounts for 10% -40% of the mass of the porous hydrophilic layer, and the mass of the second polymer accounts for less than or equal to 70% of the total mass of the first polymer and the second polymer. By the mode, the composite diaphragm has low surface resistance, low gas flux and high bubble point, and has good application prospect in the field of hydrogen production by alkaline water electrolysis.
As an example, the mass fraction of inorganic hydrophilic particles in the porous hydrophilic layer may be any one point value or a range value between any two of 60%, 62%, 65%, 67%, 70%, 72%, 75%, 77%, 80%, 82%, 85%, 87%, and 90%; the percentage of the total mass of the first polymer and the second polymer to the mass of the porous, hydrophilic layer may be any one point value or a range value between any two of 10%, 13%, 15%, 18%, 20%, 23%, 25%, 27%, 30%, 33%, 35%, 37% and 40%; the mass of the second polymer may be 70%, 60%, 50%, 40%, 30%, 20%, 10%, 5%, 1%, 0.1% and 0.01% of the total mass of the first polymer and the second polymer by any one point value or a range value between any two.
Further, the mass fraction of the inorganic hydrophilic particles in the porous hydrophilic layer is 65-85%, and the total mass of the first polymer and the second polymer accounts for 15-35% of the mass of the porous hydrophilic layer; the composite membrane can have low surface resistance, low gas flux and high bubble point.
Further, the mass of the second polymer is 0.01% to 50% of the total mass of the first polymer and the second polymer; the composite membrane can have low surface resistance, low gas flux and high bubble point.
In some alternative embodiments of the present application, the porous support layer has a thickness of 30 μm to 500 μm.
As an example, the thickness of the porous support layer may be any one point value or a range value between any two of 30 μm, 50 μm, 80 μm, 100 μm, 150 μm, 200 μm, 250 μm, 300 μm, 350 μm, 400 μm, 450 μm, and 500 μm.
Further, the thickness of the porous support layer is 80 μm to 300 μm; the composite membrane can have low surface resistance, low gas flux and high bubble point.
In some alternative embodiments of the present application, the porous support layer has a mesh size of 20 mesh to 150 mesh.
As an example, the mesh number of the porous support layer may be any one of a point value or a range value between any two of 20 mesh, 25 mesh, 30 mesh, 50 mesh, 75 mesh, 100 mesh, 120 mesh, 130 mesh, 140 mesh, and 150 mesh.
Further, the mesh number of the porous supporting layer is 30-130 mesh; the composite membrane can have low surface resistance, low gas flux and high bubble point.
In some alternative embodiments of the present application, the porous support layer has a wire diameter of 30 μm to 180 μm.
In some optional embodiments of the present application, the material of the porous support layer includes at least one of a nonwoven fabric and a porous fabric.
In some optional embodiments of the present application, the material of the porous support layer includes at least one of polypropylene, polyethylene, polysulfone, polyphenylene sulfide, polyamide, polyethersulfone, polyphenylsulfone, polyethylene terephthalate, polyetheretherketone, sulfonated polyetheretherketone, chlorotrifluoroethylene, a copolymer of ethylene and tetrafluoroethylene, a copolymer of ethylene and chlorotrifluoroethylene, polyimide, polyetherimide, and meta-aramid.
As an example, the material of the porous support layer may be hydrophilically modified or sulphonated modified, which is not limited herein.
Further, in some optional embodiments of the present application, the porous support layer is made of a polyphenylene sulfide porous fabric; since polyphenylene sulfide is a semi-crystalline polymer with high melting point and high glass transition temperature, which is formed by alternately connecting benzene rings and sulfur atoms, the unique composition form of the polyphenylene sulfide endows the polyphenylene sulfide with excellent acid and alkali resistance, high mechanical strength and high flame retardance, and besides, the polyphenylene sulfide also has excellent creep resistance, wear resistance and the like.
In some alternative embodiments of the present application, the composite separator has a thickness of 200 μm to 800 μm.
As an example, the thickness of the composite separator may be any one point value or a range value between any two of 200 μm, 250 μm, 300 μm, 350 μm, 400 μm, 450 μm, 475 μm, 500 μm, 525 μm, 550 μm, 600 μm, 650 μm, 700 μm, 750 μm, and 800 μm.
The application also provides a preparation method of the composite membrane, which comprises the following steps: coating the slurry on the porous support layer so that part of the slurry is filled in the pores of the porous support layer and part of the slurry covers at least one surface of the porous support layer in the thickness direction; the coated system is placed in a coagulation bath for phase inversion treatment. Wherein the slurry comprises inorganic hydrophilic particles, a first polymer, a second polymer, and a pore-forming agent.
The preparation method of the composite membrane can enable the prepared composite membrane to have lower surface resistance, lower gas flux and higher bubble point; the composite diaphragm provided by the application is used as an alkaline electrolyzed water composite diaphragm, so that the alkaline electrolyzed water composite diaphragm has higher safety and electrolysis water efficiency, and has good application prospect in the field of hydrogen production by alkaline electrolysis water.
It will be appreciated that the porous support layer, the inorganic hydrophilic particles, the first polymer and the second polymer are selected and proportioned according to the above description, and will not be repeated here.
In some optional embodiments of the present application, the preparation method of the composite membrane provided herein includes the following steps:
s10, mixing the first polymer, the second polymer, the inorganic hydrophilic particles, the pore-forming agent and the organic solvent to obtain slurry.
It will be appreciated that the selection and proportioning of the first polymer, the second polymer and the inorganic hydrophilic particles are described above, and will not be repeated here.
The pore-forming agent may be largely removed in the subsequent phase inversion step as well as in the step of immersing in water, so that a porous structure is formed in the structure formed by the coating paste. In some alternative embodiments of the present application, the pore-forming agent is selected from at least one of polyvinylpyrrolidone, polyvinyl alcohol, polyvinyl acetate, polyethylene oxide, polyethylenimine, polyethylene glycol, methylcellulose, ethylcellulose, polyvinylidene fluoride, polyethylene oxide, polypropylene glycol, ethylene glycol, tripropylene glycol, glycerol, polyols, dibutyl phthalate, diethyl phthalate, di-undecyl phthalate, isononanoic acid or neodecanoic acid, polyvinylpyrrolidone, polyvinyl acetate, and polyacrylic acid or dextran.
Further, the pore-forming agent is at least one selected from polyvinylpyrrolidone, polyvinyl alcohol, glycerol and polyethylene glycol; the surface resistance of the composite diaphragm is further reduced.
In some alternative embodiments of the present application, the weight of the pore former is 20% or less of the total weight of the first polymer, the second polymer, the inorganic hydrophilic particles, and the pore former.
Further, the weight ratio of the pore-forming agent in the total weight of the first polymer, the second polymer, the inorganic hydrophilic particles and the pore-forming agent is less than or equal to 10 percent; the surface resistance of the composite diaphragm is further reduced.
Illustratively, the weight of the pore former is 0.1% to 10% of the total weight of the first polymer, the second polymer, the inorganic hydrophilic particles, and the pore former.
In some alternative embodiments of the present application, the organic solvent is selected from at least one of N, N-dimethylformamide, N-dimethylacetamide, dimethylsulfoxide, N-methylpyrrolidone, N-butylpyrrolidone, and N-ethylpyrrolidone.
In some alternative embodiments of the present application, the total mass of the first polymer, the second polymer, and the inorganic hydrophilic particles is present in the slurry at a mass ratio of 30% to 70%.
And S20, coating the slurry on the porous supporting layer so that part of the slurry is filled in the pores of the porous supporting layer, and part of the slurry covers at least one surface of the porous supporting layer in the thickness direction.
It will be appreciated that the porous support layer is selected from the above, and will not be described herein.
In some alternative embodiments of the present application, a portion of the slurry covers opposite surfaces of the porous support layer in a thickness direction, and the step of applying the slurry to the porous support layer includes: the slurry is coated on the substrate, then the porous support layer is placed on the slurry on the substrate, and then the slurry is coated on the porous support layer, so that the voids of the porous support layer are filled with the slurry (so that the porous support layer is located in the middle region of the slurry).
As an example, the coating paste may be a meyer rod or a doctor blade applicator, etc., which is not limited in this application; the substrate may be a glass substrate, which is not limited in this application.
S30, placing the coated system in a coagulating bath for phase inversion treatment.
And (3) placing the coated system in a coagulating bath for phase inversion treatment so that the slurry is solidified and the pore-forming agent in the slurry is removed, thereby forming a porous hydrophilic layer.
In some alternative embodiments of the present application, the coagulation bath comprises at least water; further, the coagulation bath further comprises at least one of N, N-dimethylformamide, N-dimethylacetamide, dimethylsulfoxide, N-methylpyrrolidone, N-butylpyrrolidone and N-ethylpyrrolidone.
As an example, the coagulation bath may be a 10wt% aqueous solution of N-methylpyrrolidone.
In some alternative embodiments of the present application, the temperature of the phase inversion is between 0 ℃ and 80 ℃ and the time of the phase inversion is between 0h and 2h.
S40, soaking the system after phase conversion in water.
Immersing the phase-converted system in water to remove residual solvent, etc.
The application also provides an application of the composite membrane in preparing a hydrogen production device by electrolyzing water; the composite membrane is the composite membrane provided by the above, or the composite membrane is the composite membrane prepared by the preparation method of the composite membrane provided by the above.
Illustratively, the water electrolysis hydrogen-producing device is an alkaline water electrolysis hydrogen-producing device.
The composite separator and the composite separator manufactured by the manufacturing method of the composite separator can be applied to other fields, for example, as a battery separator in a secondary battery; as an example, the secondary battery includes at least one of a lithium battery and a sodium battery.
In order to make the objects, technical solutions and advantages of the embodiments of the present application more clear, the technical solutions in the embodiments of the present application will be clearly and completely described below. The specific conditions are not noted in the examples and are carried out according to conventional conditions or conditions recommended by the manufacturer. The reagents or apparatus used were conventional products commercially available without the manufacturer's attention.
Example 1
The embodiment provides a composite membrane, comprising the following steps:
(1) And (3) reacting tetramethylimidazole and p-chloromethyl styrene with a molar ratio of 1:1.2 by taking acetonitrile as a solvent at 80 ℃ for 36 hours, centrifuging, pulping and purifying the solid to obtain a first monomer.
Wherein, the structural formula of the first monomer is as follows:
(2) Styrene, the first monomer obtained in step (1), and azobisisobutyronitrile were dissolved in a mixed solvent containing 400 μl of toluene and 400 μl of ethanol, reacted at 80 ℃ for 8 hours to obtain a copolymer dispersed in the mixed solvent, and reprecipitated with ethyl acetate to obtain a solid product (i.e. ionomer). Wherein the molar ratio of the styrene to the first monomer is 2:1, the mass of the first monomer is 400mg, the molar amount of the azodiisobutyronitrile is 1% of the total molar amount of the styrene and the first monomer, and the ionomer has the following structural formula:
1.5g of the obtained solid product, 30mg of Divinylbenzene (DVB), 0.45mg of azobisisobutyronitrile, 2.55g of absolute ethanol and 1.874g of absolute toluene were mixed, reacted under nitrogen atmosphere at 78℃for 1 hour, then cooled to 55℃for 20 hours, and then reprecipitated by methanol solution to obtain a crosslinked ionomer (denoted as polymer product).
(3) 10g of Polysulfone (PSU) powder particles, 1g of the polymer product obtained in step (2), 39g of ZrO having an average particle size of 30nm were mixed 2 The powder, 1g of polyvinylpyrrolidone and 50g of N-methylpyrrolidone were mixed to form a slurry, which was then dried under vacuum at 25℃to remove the bubbles.
The method comprises the steps of uniformly coating the slurry on a glass substrate by using a Meyer rod, covering a layer of porous polyphenylene sulfide fabric on the slurry on the glass substrate, coating a layer of slurry with the thickness of 600 mu m on the porous polyphenylene sulfide fabric, and filling the slurry into the pores of the porous polyphenylene sulfide fabric. The system on the glass substrate is quickly immersed in a coagulating bath of 10wt% of N-methyl pyrrolidone aqueous solution, is immersed for 60min at 25 ℃ for phase inversion, and is then immersed in water after being taken out of the coagulating bath, so that the composite diaphragm is prepared.
Wherein the thickness of the porous polyphenylene sulfide fabric is 280 mu m, and the mesh number is 40 mesh.
Example 2
This embodiment provides a composite separator, which differs from embodiment 1 only in that: in step (3), the mass of Polysulfone (PSU) powder particles was 8.25g and the mass of the polymer product was 2.75g.
Example 3
This embodiment provides a composite separator, which differs from embodiment 1 only in that: in step (3), the mass of Polysulfone (PSU) powder particles was 5.5g and the mass of polymer product was 5.5g.
Example 4
This embodiment provides a composite separator, which differs from embodiment 1 only in that: in step (3), polysulfone (P)SU) powder particles 13.64g, polymer product 1.36g, zro 2 The mass of the powder was 35g.
Example 5
This embodiment provides a composite separator, which differs from embodiment 1 only in that: the difference of the step (2); step (2) of this embodiment is as follows:
styrene, p-chloromethyl styrene, the first monomer obtained in step (1) and azobisisobutyronitrile were dissolved in a mixed solvent containing 400. Mu.L of toluene and 400. Mu.L of ethanol, reacted at 80℃for 8 hours to obtain a copolymer dispersed in the mixed solvent, and reprecipitated with ethyl acetate to obtain a solid product (i.e., ionomer). Wherein the molar ratio of the styrene to the first monomer is 2:1, the mass of the first monomer is 400mg, the molar ratio of the p-chloromethyl styrene to the styrene is 1:20, the molar amount of the azobisisobutyronitrile is 1% of the total molar amount of the styrene and the first monomer, and the ionomer has the following structural formula:
1.5g of the obtained solid product, 30mg of Divinylbenzene (DVB), 0.45mg of azobisisobutyronitrile, 2.55g of absolute ethanol and 1.874g of absolute toluene were mixed, reacted under nitrogen atmosphere at 78℃for 1 hour, then cooled to 55℃for 20 hours, and then reprecipitated by methanol solution to obtain a crosslinked ionomer (denoted as polymer product).
Example 6
This embodiment provides a composite separator, which differs from embodiment 1 only in that: step (2) of the present embodiment is different from step (2) as follows:
styrene, the first monomer obtained in step (1), p-chloromethylstyrene and azobisisobutyronitrile were dissolved in a mixed solvent containing 400. Mu.L of toluene and 400. Mu.L of ethanol, reacted at 80℃for 8 hours to obtain a copolymer dispersed in the mixed solvent, and reprecipitated with ethyl acetate to obtain a solid product (i.e., ionomer). Wherein the molar ratio of the styrene to the first monomer is 2:1, the mass of the first monomer is 400mg, the molar ratio of the p-chloromethyl styrene to the styrene is 1:20, the molar amount of the azobisisobutyronitrile is 1% of the total molar amount of the styrene and the first monomer, and the ionomer has the following structural formula:
1.5g of the obtained solid product, 25mg of tetramethyl ethylenediamine, 2.55g of absolute ethanol and 1.874g of absolute toluene were mixed, reacted at 78℃for 1 hour under a nitrogen atmosphere, then cooled to 55℃for 20 hours, and then reprecipitated by a methanol solution to obtain a crosslinked ionomer (denoted as a polymer product).
Example 7
This embodiment provides a composite separator, which differs from embodiment 1 only in that: step (2) of the present embodiment is different from step (2) as follows:
styrene, the first monomer obtained in step (1), p-chloromethylstyrene and azobisisobutyronitrile were dissolved in a mixed solvent containing 400. Mu.L of toluene and 400. Mu.L of ethanol, reacted at 80℃for 8 hours to obtain a copolymer dispersed in the mixed solvent, and reprecipitated with ethyl acetate to obtain a solid product (i.e., ionomer). Wherein the molar ratio of the styrene to the first monomer is 2:1, the mass of the first monomer is 400mg, the molar ratio of the p-chloromethyl styrene to the styrene is 1:20, the molar amount of the azobisisobutyronitrile is 1% of the total molar amount of the styrene and the first monomer, and the ionomer has the following structural formula:
1.5g of the obtained solid product, 0.45mg of azobisisobutyronitrile, 2.55g of absolute ethanol and 1.874g of absolute toluene were mixed, reacted under nitrogen atmosphere at 78℃for 1 hour, then cooled to 55℃for 20 hours, and then reprecipitated by methanol solution to obtain a crosslinked ionomer (noted as a polymer product).
Example 8
This embodiment provides a composite separator, which differs from embodiment 1 only in that: different polymer products, in this example, the polymer products were prepared as follows:
2.06g of terphenyl, 0.86g of N-methyl-4-piperidone and 0.23g of trifluoroacetophenone were dissolved in 7.5mL of methylene chloride, and 7.5mL of trifluoromethanesulfonic acid and 0.6mL of trifluoroacetic acid were slowly added under ice-bath conditions. And (3) carrying out ice bath reaction for 24 hours to obtain a viscous solution, and slowly dripping the viscous solution into ethanol to precipitate white fibrous solid. Adding 1M aqueous solution of potassium carbonate into white fibrous solid, reacting for 12 hours at 50 ℃, filtering and drying, taking 1g of solid, adding 20mL of DMSO, adding 1mL of methyl iodide, reacting for 16 hours at 25 ℃, dripping the obtained liquid phase into ethyl acetate to obtain a solid product, and drying at 60 ℃ to obtain a polymer product; wherein the structural formula of the polymer product is as follows:
example 9
This embodiment provides a composite separator, which differs from embodiment 1 only in that: different polymer products, in this example, the polymer products were prepared as follows:
1.38g of biphenyl, 1.01g of N-methyl-4-piperidone were dissolved in 7.5mL of methylene chloride, and 7.5mL of trifluoromethanesulfonic acid and 0.6mL of trifluoroacetic acid were slowly added under ice-bath conditions. And (3) carrying out ice bath reaction for 24 hours to obtain a viscous solution, and slowly dripping the viscous solution into ethanol to precipitate white fibrous solid. Adding 1M aqueous solution of potassium carbonate into white fibrous solid, reacting for 12 hours at 50 ℃, filtering and drying, taking 1g of solid, adding 20mL of DMSO, adding 1mL of methyl iodide, reacting for 16 hours at 25 ℃, dripping the obtained liquid phase into ethyl acetate to obtain a solid product, and drying at 60 ℃ to obtain a polymer product; wherein the structural formula of the polymer product is as follows:
Example 10
This embodiment provides a composite separator, which differs from embodiment 1 only in that: different polymer products, in this example, the polymer products were prepared as follows:
1.49g of 9,9' -dimethylfluorene and 1.01g of N-methyl-4-piperidone were dissolved in 7.5mL of methylene chloride, and 7.5mL of trifluoromethanesulfonic acid and 0.6mL of trifluoroacetic acid were slowly added under ice-bath conditions. And (3) carrying out ice bath reaction for 24 hours to obtain a viscous solution, and slowly dripping the viscous solution into ethanol to precipitate white fibrous solid. Adding 1M aqueous solution of potassium carbonate into white fibrous solid, reacting for 12 hours at 50 ℃, filtering and drying, taking 1g of solid, adding 20mL of DMSO, adding 1mL of methyl iodide, reacting for 16 hours at 25 ℃, dripping the obtained liquid phase into ethyl acetate to obtain a solid product, and drying at 60 ℃ to obtain a polymer product; wherein the structural formula of the polymer product is as follows:
example 11
This embodiment provides a composite separator, which differs from embodiment 1 only in that: different polymer products, in this example, the polymer products were prepared as follows:
2.06g of terphenyl, 0.86g of N-methyl-4-piperidone and 0.23g of trifluoroacetophenone were dissolved in 7.5mL of methylene chloride, and 7.5mL of trifluoromethanesulfonic acid and 0.6mL of trifluoroacetic acid were slowly added under ice-bath conditions. And (3) carrying out ice bath reaction for 24 hours to obtain a viscous solution, and slowly dripping the viscous solution into ethanol to precipitate white fibrous solid. Adding 1M aqueous solution of potassium carbonate into white fibrous solid, reacting for 12 hours at 50 ℃, filtering and drying, taking 1g of solid, adding 20mL of DMSO, firstly adding 0.026g of dibromobutane, reacting for 2 hours at 60 ℃, then cooling to 25 ℃, then adding 1mL of methyl iodide, reacting for 16 hours at 25 ℃, dripping the obtained liquid phase into ethyl acetate to obtain a solid product, and drying at 60 ℃ to obtain a polymer product; wherein the structural formula of the polymer product is as follows:
Example 12
This embodiment provides a composite separator, which differs from embodiment 1 only in that: different polymer products, in this example, the polymer products were prepared as follows:
2.06g of terphenyl, 0.86g of N-methyl-4-piperidone and 0.23g of trifluoroacetophenone were dissolved in 7.5mL of methylene chloride, and 7.5mL of trifluoromethanesulfonic acid and 0.6mL of trifluoroacetic acid were slowly added under ice-bath conditions. And (3) carrying out ice bath reaction for 24 hours to obtain a viscous solution, and slowly dripping the viscous solution into ethanol to precipitate white fibrous solid. Adding 1M aqueous solution of potassium carbonate into white fibrous solid, reacting for 12 hours at 50 ℃, filtering and drying, taking 1g of solid, adding 20mL of DMSO, firstly adding 0.018g of p-chloromethyl styrene, reacting for 2 hours at 80 ℃, adding 0.5g of azobisisobutyronitrile, reacting for 8 hours at 80 ℃, reducing the temperature to 25 ℃, then adding 1mL of methyl iodide, reacting for 16 hours at 25 ℃, dripping the obtained liquid phase into ethyl acetate to obtain a solid product, and drying at 60 ℃ to obtain a polymer product; wherein the structural formula of the polymer product is as follows:
example 13
This embodiment provides a composite separator, which differs from embodiment 1 only in that: zrO in example 1 2 The powder is replaced by barium sulfate powder.
Comparative example
This comparative example provides a composite separator comprising the steps of:
11g of Polysulfone (PSU) powder particles, 39g of ZrO having an average particle size of 30nm were mixed 2 The powder, 1g of polyvinylpyrrolidone and 50g of N-methylpyrrolidone are mixed to form a slurry, and then at 25 DEG CAnd (5) vacuum drying and defoaming.
The method comprises the steps of uniformly coating the slurry on a glass substrate by using a Meyer rod, covering a layer of porous polyphenylene sulfide fabric on the slurry on the glass substrate, coating a layer of slurry with the thickness of 600 mu m on the porous polyphenylene sulfide fabric, and filling the slurry into the pores of the porous polyphenylene sulfide fabric. The system on the glass substrate is quickly immersed in a coagulating bath of 10wt% of N-methyl pyrrolidone aqueous solution, is immersed for 60min at 25 ℃ for phase inversion, and is then immersed in water after being taken out of the coagulating bath, so that the composite diaphragm is prepared.
Wherein the thickness of the porous polyphenylene sulfide fabric is 280 mu m, and the mesh number is 40 mesh.
Experimental example 1
The first monomer obtained in step (1) of example 1, the polymer product obtained in example 8, the polymer product obtained in example 9 and the polymer product obtained in example 10 were each subjected to structural characterization, and nuclear magnetic resonance hydrogen spectra are shown in fig. 1 to 4.
As can be seen from fig. 1, the nuclear magnetic hydrogen spectrum of the first monomer prepared in step (1) of example 1 is consistent with the expected structure. 1 H NMR(500MHz,DMSO)δ7.52-7.47(m,2H),7.14(d,J＝8.1Hz,2H),6.74(dd,J＝17.7,10.9Hz,1H),5.85(d,J＝17.7Hz,1H),5.43(s,2H),5.29(d,J＝11.0Hz,1H),3.66(s,3H),3.42(s,2H),3.17(s,1H),2.63(s,3H),2.24(s,3H),2.13(s,3H)。
As can be seen from FIG. 2, the nuclear magnetic hydrogen spectrum of the polymer product obtained in example 8 is consistent with the expected structure. In the nuclear magnetic resonance hydrogen spectrum, the displacement of 7.33-7.79ppm is the signal of aromatic hydrogen on terphenyl, the displacement of 7.21-7.44ppm is the signal of aromatic hydrogen on trifluoroacetophenone, and the displacement of 2.89-3.41ppm is the hydrocarbon signal on piperidane structure.
As can be seen from FIG. 3, the nuclear magnetic hydrogen spectrum of the polymer product obtained in example 9 is consistent with the expected structure. In the nuclear magnetic resonance hydrogen spectrum, the displacement of 7.53-7.60ppm is the signal of aromatic hydrogen on the diphenyl, and the displacement of 2.71-3.45ppm is the hydrocarbon signal on the piperidane structure.
As can be seen from fig. 4, the nuclear magnetic hydrogen spectrum of the polymer product obtained in example 10 is consistent with the expected structure. In the nuclear magnetic resonance hydrogen spectrum, 7.34-7.79ppm is displaced to be the signal of aromatic hydrogen on fluorene, 1.39-3.36ppm is displaced to be the signal of methyl hydrogen on fluorene, and 2.86-3.36ppm is displaced to be the signal of hydrocarbon on piperidane structure.
Experimental example 2
The composite separators prepared in examples 1 to 13 and comparative example were subjected to the tests of surface resistance, gas flux and bubble point, and the test results are shown in table 1.
The surface resistance test method comprises the following steps: immersing the composite diaphragm in 30wt% potassium hydroxide aqueous solution for 12h, and testing by an electrochemical workstation through an alternating current impedance spectroscopy (EIS) method to obtain the resistance R (unit: omega) and the surface resistance (unit: omega cm) of the composite diaphragm 2 ) =r×s, where S is the surface area of the composite separator (unit: cm 2 )。
The gas flux and bubble point test steps were as follows: the composite membranes prepared in examples 1 to 13 and comparative example were immersed in ethanol, and then tested for gas flux and bubble point using a gas permeation rate meter.
TABLE 1
As can be seen from table 1, the composite separator of examples 1 to 13 can have a lower sheet resistance, a lower gas flux, and a higher bubble point than the composite separator of the comparative example.
In summary, in the composite membrane provided in the present application, the first polymer, the second polymer and the inorganic hydrophilic particles together form a porous hydrophilic layer, the porous hydrophilic layer covers at least one surface of the porous support layer in the thickness direction, and the porous hydrophilic layer is filled in the pores of the porous support layer, so that the first polymer and the second polymer have a synergistic effect, so that the composite membrane has a lower surface resistance, a lower gas flux and a higher bubble point; the composite diaphragm provided by the application is used as an alkaline electrolyzed water composite diaphragm, so that the alkaline electrolyzed water composite diaphragm has higher safety and electrolysis water efficiency, and has good application prospect in the field of hydrogen production by alkaline electrolysis water.
The embodiments described above are some, but not all, of the embodiments of the present application. The detailed description of the embodiments of the present application is not intended to limit the scope of the application, as claimed, but is merely representative of selected embodiments of the application. All other embodiments, which can be made by one of ordinary skill in the art without undue burden from the present disclosure, are within the scope of the present disclosure.

Claims (10)

1. A composite separator, the composite separator comprising: a porous support layer and a porous hydrophilic layer;
the porous hydrophilic layer covers at least one surface in the thickness direction of the porous support layer, and the porous hydrophilic layer is filled in the pores of the porous support layer;
wherein the porous hydrophilic layer comprises inorganic hydrophilic particles, a first polymer and a second polymer; the first polymer is engineering plastic, and the second polymer comprises at least one of an ionomer and a cross-linked product of the ionomer.
2. The composite separator of claim 1 wherein the ionomer has a backbone with salt units; or/and, the ionomer has salt units in the side chains;
Wherein the salt unit comprises: a first anionic unit covalently attached to the ionomer and a first cationic unit electrostatically bound to the first anionic unit; or, the salt unit includes: a second cationic unit covalently attached to the ionomer and a second anionic unit electrostatically bound to the second cationic unit;
optionally, the first anionic unit comprises at least one of a sulfonic acid group anion and a carboxylic acid group anion; the first cation unit comprises at least one of sodium ion, potassium ion, lithium ion, magnesium ion and calcium ion;
optionally, the second cationic unit comprises at least one of a quaternary ammonium based cation, a protonated primary amino cation, a protonated secondary amino cation, and a protonated tertiary amino cation; the second anionic unit includes at least one of a halogen ion, a bicarbonate ion, a hydroxide ion, a trifluoromethanesulfonic acid anion, a p-trifluorobenzenesulfonic acid anion, a phosphorus hexafluoride anion, and a boron tetrafluoride anion.
3. The composite separator according to claim 1, wherein the ionomer has a main chain having at least one of an aryl piperidine structure, a polyethylene structure, a polybenzimidazole structure, a polyphenylene ether structure, a polystyrene structure, a polyacrylic structure, an epoxy resin structure, a polyvinylpyridine structure, and a urea formaldehyde structure;
Optionally, the backbone of the ionomer has at least one of an aryl piperidine type structure and a polystyrene type structure.
4. The composite membrane of claim 3 wherein the ionomer comprises at least one of a first substance and a second substance;
the structural formula of the first substance is as follows:
wherein m is 1 ＞0，n 1 ≥0；
Ar 1 Ar, ar 2 Each independently selected from substituted or unsubstituted aryl;
X 1 - is an anion;
R 1 r is as follows 2 Each independently is a substituted or unsubstituted alkyl group;
R 3 is a group containing a fluorine atom;
the structural formula of the second substance is as follows:
wherein m is 2 ＞0，n 2 ＞0；
Ar 3 Ar, ar 4 Each independently selected from substituted or unsubstituted aryl;
X 2 - is an anion;
p is 1-6;
R 4 is a group containing a fluorine atom;
alternatively, m 1 And n 1 Ratio of m 2 And n 2 The ratio of (2) is greater than 1:1;
alternatively, m 1 And n 1 Ratio of m 2 And n 2 The ratio of (2) to (20): 1;
alternatively, ar 1 、Ar 2 、Ar 3 Ar, ar 4 Each independently selected from the group consisting of substituted or unsubstituted biphenyl, substituted or unsubstituted meta-terphenyl, substituted or unsubstituted para-terphenyl, substituted or unsubstituted tetrabiphenyl, substituted or unsubstituted pentabiphenyl, substituted or unsubstituted naphthalene, substituted or unsubstituted fluorene;
Alternatively, X 1 - X is as follows 2 - Each independently selected from at least one of a halogen ion, a bicarbonate ion, a hydroxide ion, a trifluoromethanesulfonic acid anion, a p-trifluorobenzenesulfonic acid anion, a phosphorus hexafluoride anion, and a boron tetrafluoride anion;
alternatively, R 3 R is as follows 4 Are trifluoromethyl;
optionally, the alkyl group is selected from at least one of methyl, ethyl, propyl, butyl, pentyl and hexyl.
5. The composite separator of claim 3 wherein the ionomer comprises a third substance having the formula:
wherein q is more than 0, r is more than or equal to 0, s is more than or equal to 0, and r and s are not simultaneously 0;
R 4 + is a positively charged cyclic amine group;
X 3 - is an anion;
R 5 selected from halogen substituted alkyl;
optionally, the positively charged cyclic amine group is selected from at least one of imidazolium, pyridinium, pyrazolium, pyrrolidinium, pyrimidinium, piperidinium, indolium, and triazinium;
optionally, the positively charged cyclic amine group is selected from at least one of imidazolium and piperidinium;
optionally, the positively charged cyclic amine group is selected from at least one of tetramethylimidazolium and N-methylpiperidinium;
Alternatively, X 3 At least one selected from the group consisting of a hydroxyl group, a chlorine atom, a bromine atom, an iodine atom, a p-toluenesulfonyloxy group, a trifluoromethanesulfonic acid group, and a methanesulfonyloxy group;
alternatively, X 3 Selected from chlorine atoms;
alternatively, R 5 At least one selected from chloromethyl, bromomethyl and iodomethyl;
alternatively, the ratio of the sum of r and s to q is (1:2) - (9:1).
6. The composite separator according to any one of claims 1 to 5, wherein the first polymer is selected from at least one of polysulfone, polyethersulfone, and polyphenylsulfone;
or/and the weight average molecular weight of the first polymer is 10000-500000;
or/and, the inorganic hydrophilic particles comprise at least one of zirconia, barium sulfate, hydrotalcite, titanium dioxide and magnesium hydroxide;
or/and the particle size of the inorganic hydrophilic particles is 1 nm-1 mu m;
optionally, the first polymer is selected from at least one of polysulfone and polyethersulfone;
optionally, the inorganic hydrophilic particles comprise at least one of zirconia and barium sulfate.
7. The composite separator according to any one of claims 1 to 5, wherein the mass fraction of the inorganic hydrophilic particles in the porous hydrophilic layer is 60% to 90%;
The total mass of the first polymer and the second polymer accounts for 10-40% of the mass of the porous hydrophilic layer, and the mass of the second polymer accounts for less than or equal to 70% of the total mass of the first polymer and the second polymer;
optionally, the mass fraction of the inorganic hydrophilic particles in the porous hydrophilic layer is 65% -85%, and the total mass of the first polymer and the second polymer accounts for 15% -35% of the mass of the porous hydrophilic layer;
optionally, the mass of the second polymer is 0.01% to 50% of the total mass of the first polymer and the second polymer.
8. The composite separator according to any one of claims 1 to 5, wherein the porous support layer has a thickness of 30 μιη to 500 μιη;
or/and the mesh number of the porous supporting layer is 20-150 meshes;
or/and the porous supporting layer is made of at least one of non-woven fabrics and porous fabrics;
or/and the thickness of the composite diaphragm is 200-800 mu m;
optionally, the material of the porous supporting layer includes at least one of polypropylene, polyethylene, polysulfone, polyphenylene sulfide, polyamide, polyethersulfone, polyphenylsulfone, polyethylene terephthalate, polyetheretherketone, sulfonated polyetheretherketone, chlorotrifluoroethylene, copolymer of ethylene and tetrafluoroethylene, copolymer of ethylene and chlorotrifluoroethylene, polyimide, polyetherimide and meta-aramid.
9. A method of producing the composite separator according to any one of claims 1 to 8, comprising: coating slurry on the porous support layer so that part of the slurry is filled in pores of the porous support layer and part of the slurry covers at least one surface of the porous support layer in the thickness direction;
placing the coated system in a coagulation bath for phase inversion treatment;
wherein the slurry comprises the inorganic hydrophilic particles, the first polymer, the second polymer, and a pore former.
10. The application of the composite diaphragm in preparing hydrogen production devices by electrolyzing water and secondary batteries;
wherein the composite membrane is the composite membrane according to any one of claims 1 to 8, or the composite membrane is a composite membrane produced by the production method of the composite membrane according to claim 9;
the secondary battery includes at least one of a lithium battery and a sodium battery.
CN202311804740.6A 2023-12-25 2023-12-25 Composite diaphragm and preparation method and application thereof Pending CN117802532A (en)

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