CN108841020A - A kind of microporous polymer membranes and preparation method and application with ion conduction property - Google Patents

A kind of microporous polymer membranes and preparation method and application with ion conduction property Download PDF

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CN108841020A
CN108841020A CN201810466843.9A CN201810466843A CN108841020A CN 108841020 A CN108841020 A CN 108841020A CN 201810466843 A CN201810466843 A CN 201810466843A CN 108841020 A CN108841020 A CN 108841020A
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film
microporous polymer
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CN108841020B (en
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赵云峰
李鹏丽
刘喜正
丁轶
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Tianjin University of Technology
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    • 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
    • C08J5/2287—After-treatment
    • 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
    • C08G67/00—Macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing oxygen or oxygen and carbon, not provided for in groups C08G2/00 - C08G65/00
    • 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
    • C08J5/2218—Synthetic macromolecular compounds
    • C08J5/2256—Synthetic macromolecular compounds based on macromolecular compounds obtained by reactions other than those involving carbon-to-carbon bonds, e.g. obtained by polycondensation
    • 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
    • C08J2373/00—Characterised by the use of macromolecular compounds obtained by reactions forming a linkage containing oxygen or oxygen and carbon in the main chain, not provided for in groups C08J2359/00 - C08J2371/00; Derivatives of such polymers

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Abstract

A kind of microporous polymer membranes and preparation method and application with ion conduction property, the film contain micropore and carboxylic acid/carboxylate/sulfonic acid group.The preparation of ion conductor function microporous polymer film includes：Microporous polymer is prepared with polyhydroxy and polyhalo monomer；Prepare microporous polymer membranes；It is the microporous polymer film that carboxylic salts obtain ion conductor function by the cyano in polymer/carboxylate group's hydrolysis；For containing methyl/aldehyde radical/sulfydryl polymer can by aoxidize by thin polymer film methyl or convert aldehyde groups be carboxyl/sulfonic group, obtain ion conductor function microporous polymer film；The microporous polymer film with proton/sodium/lithium/potassium ion and other specific ions is obtained by ion exchange；The test ion conductor function in water system and organic system electrolyte.Ion conductor microporous polymer film prepared by the present invention has many advantages, such as that preparation process is simple, ion is commutative, stability and safety are good, easy to use.

Description

A kind of microporous polymer membranes and preparation method and application with ion conduction property
Technical field
The present invention relates to a kind of polymer based ion conductor membranes, more particularly to skeleton are contained or carboxylic is contained in part Organic microporous polymer film of acid/carboxylate and sulfonic acid and sulfonate is applied to proton, lithium ion, sodium ion, potassium ion, zinc The selectively conducting field such as ion, aluminium ion, can be good at stopping various composition and the transmission of vapor in air, can be Respective metal-air cell (including the metals such as lithium, sodium, potassium, magnesium, zinc), lithium-sulfur cell, flow battery, lithium ion battery, sodium from Sub- battery, kalium ion battery, Magnesium ion battery, aluminium ion battery, fuel cell and electrolytic cell etc. are related to the device of ion conducting It is used in part as diaphragm or solid electrolyte material.
Background technique
In metal-air battery, (selectivity penetrates corresponding guest ions to film with specific ion conductor function, and has Effect stop oxygen, carbon dioxide and vapor transmission), (conducting lithium ions simultaneously effectively stop wearing for more sulphions to lithium-sulfur cell Shuttle), flow battery (proton or the conduction of corresponding guest ions and stop the shuttle of active constituent) fuel cell (proton conductor), lithium It is widely used, plays in ion battery (lithium ion conductor), sodium-ion battery (sodium ion conductor) and numerous energy storage devices The active material for effectively separating yin-yang the two poles of the earth, avoids quickly conducting guest ions while short circuit.
With the development of all-solid-state battery, inorganic ceramic ion conductor diaphragm is widely studied.But inorganic ceramic membrane There is at high cost, yield rate is low, unyielding disadvantage, which has limited its large-scale promotion, especially inoranic membrane is generally resistant to Soda acid performance is poor, and this severely limits its application fields.
Recently, with the fast development in the field of wearable flexible electronic, develop have ion conduction property excellent soft Property diaphragm have become the key technology of flexible energy storage device development.
Polytetrafluoroethylene (PTFE) and perfluor -3,6- diepoxy -4- methyl -7- decene-sulfuric acid copolymer, i.e.,Film, It is the ion conducting diaphragm extensively used at present, has the characteristics that flexible, machinability is high, but its diaphragm is with larger Duct, can not effectively obstruct the shuttle of solvent, while its preparation process is complicated, at high cost.
Chinese invention patent CN101891848A discloses a kind of list based on polyvinyl alcohol and prepares ionomer electrolysis Matter and preparation method improve the security performance of lithium ion battery, and cost is relatively low.
Chinese invention patent CN103236557A discloses a kind of polyparaphenylene's benzo dioxazole spy and polyphosphoric acids blend film, For high-temperature fuel cell.
Chinese invention patent CN106887622A discloses a kind of fluorine-containing single ion conductor polymer dielectric and its preparation side Method and application.
The filming performance and ionic conductivity of these organic polyelectrolytes are not met by battery requirements, most Polymer film with ion conductor function is hybrid films, and polymer only serves structural support effect, the reality of ion conductor function Now more depend on adulterates metal salt therein；And the ion conducting group of straight polymer film mainly grafts on side chain, synthesis step Rapid more, stability and mechanical performance are undesirable, since strand itself is without pore structure, need by the means system such as mutually separating Standby is nanofiltration or microfiltration membranes with large hole, and the molecules such as solvent can not be obstructed effectively, therefore high performance in order to obtain The polymer film needs with ionic conduction characteristic of solvent molecule can be stopped further to carry out from the structure of polymer Optimization design.
Summary of the invention
The purpose of the present invention is obtain the microporous polymer film with ion conduction property and be applied to all kinds of accumulators Part field, polymer molecular chain is due to that can form intrinsic micropore, the introducing energy of micropore when assembling film forming with space structure Enough effective ion transmission performances for improving thin polymer film；Meanwhile micropore can effectively obstruct water, various gases and organic molten Agent molecule cluster realizes conducting ion and obstructs the function of solvent.
It is a further object of the present invention to provide a kind of preparation method of organic porous polymer with ion conduction property, The preparation method simple process, process is short, is easy to amplify, and the membrane component of preparation can easily be accommodated, which has ion conduction Can and there is barrier action to water, organic solvent simultaneously, and demonstrate in all kinds of energy storage devices it and meanwhile be used as diaphragm and from The effect of sub- conductive membranes.
The technical solution adopted by the present invention is that：A kind of microporous polymer membranes with ion conduction property,
Wherein the chemical general formula of the polymer containing micropore is：
In formula, A1-A2 is that main polymer chain functional group also acts as other than guaranteeing the polymer molecule degree of polymerization and constructs sky Between micropore effect；B is the alkyl that carbon atom number is 1~10 or alkoxy or cyano nonionic conduction function group；C is carboxyl Or the group with ionic conduction performance of sulfonic group or imide or sulfimide base；M be proton or alkali metal metal from The tradable ion of son or alkaline-earth metal ions.
A kind of preparation method of the microporous polymer membranes with ion conduction property：
Preparation containing organic microporous polymer：To contain halogenated more cyano/carboxyl/carboxylate/methyl/aldehyde radical/sulfonic groups Benzene derivative and the structure containing spatial warping polyhydroxy benzene derivative be monomer, in alkali such as potassium carbonate/sodium carbonate/cesium carbonates Property under the conditions of high temperature polymerization can prepare the serial organic polymer containing more cyano, the molecular weight of polymer is 5000-300000, by The thin polymer film after film forming is caused to contain a large amount of micropore containing distorted-structure in monomer；
The preparation of organic microporous polymer film：Step 1 polymer obtained is dissolved in chloroform, tetrahydrofuran, two Chloromethanes, dichloroethanes, 1,2- dichloroethanes, N, N '-dimethyl formamide (DMF), N, N '-dimethyl acetamide (DMAC), One of N-Methyl pyrrolidone (NMP) solvent or in the mixed solvent, polymer are 0.5~30wt% in concentration range, can It as at film liquid, at film liquid after ultrasonic degassing, is poured on horizontal quartz/glass/polytetrafluoroethylene (PTFE) or metal plate, controls It is made 5-100 degrees Celsius of film temperature, can get uniform continuous film；It is controlled, be can get by the concentration and dosage of casting solution The porous polymer film not waited with a thickness of 3-100 microns of equal thickness；
For containing cyano/carboxylate group polymer, in-situ hydrolysis cyano/carboxylic acid group's preparation contains under alkaline condition Organic microporous polymer film of carboxylic acid；The cyano that polymer contains, in sodium hydroxide or potassium hydroxide or cesium hydroxide or four In water or water/alcohols mixed solution of the highly basic such as propyl ammonium hydroxide can in-situ hydrolysis hydrolyzed at carboxyl, or using acid condition, Film with a thickness of 1-500 microns, the concentration range of hydrolyzate is 1-50wt%, and hydrolysis temperature is room temperature to 100 degrees Celsius, or Person can be used up to 200 degrees Celsius under hydrothermal conditions；
For containing methyl/aldehyde radical/sulfydryl polymer, under oxidative conditions in-situ oxidation methyl/aldehyde radical/sulfydryl preparation Organic microporous polymer film carboxylic-containing acid；Methyl/aldehyde radical/sulfydryl that polymer contains is using potassium permanganate/persulfuric acid It can be by in-situ oxidation at carboxyl/sulfonic group in ammonium/iron chloride/hydrogen peroxide/oxygen strong oxidant solution；
Ion-exchange obtains organic microporous polymer film with all kinds of ions.Contain carboxylate/sulfonic acid after hydrolysis The thin polymer film of salt can be by carboxylic acid after any sort inorganic acid solution exchange in persalt, sulfuric acid, nitric acid, phosphoric acid, acetic acid Salt is changed into carboxylate radical/sulfonate radical, and carrying out ion exchange by all kinds of lithiums, sodium, sylvite or alkali can get containing corresponding ion Polymer film；
A kind of application of the microporous polymer membranes with ion conduction property, the ion conductor application of the microporous polymer membranes Range uses in water system, organic system and water system and organic system mixed electrolytic solution system.Application field includes metal-air Battery, lithium-sulfur cell, flow battery, lithium ion battery, sodium-ion battery, fuel cell, electro-catalysis, electrolysis etc. are related to ion and lead In the device of body thin film.
Ion conductor performance test.Thin polymer film is placed among metal electrode, to carry out exchange resistance under different temperatures Anti- test, according to formula σ=l/RS, (l is the thickness of polymer film, and R is the resistance for the polymer that AC impedance measures, and S is poly- The area of polymer electrolyte membrane) it calculates.
The advantages of the present invention are：
The molecular structure of the polymer film of the invention can easily be accommodated, and diversion of the ion conductor film is had excellent performance, can be with Commercialized inoranic membrane is compared, and film forming is easy, preparation process is simple, is suitble to expanding production.
Detailed description of the invention
Fig. 1 is cyano-containing/carboxyl/carboxylate/methyl/sulfonic group polyhalo monomer structure figure employed in the present invention.
Fig. 2 is the polyhydroxy monomer structure figure employed in the present invention containing stereoeffect.
Fig. 3 is the structural schematic diagram of representative polymer in the present invention.
Fig. 4 is the photo of the polymer film obtained in the present invention.
Fig. 5 is the infrared figure for the polymer film that the present invention obtains.
Fig. 6 is the ion conductor performance map for the polymer film that the present invention obtains.
Fig. 7 is in the present invention using polymer film as the lithium of diaphragm-flow battery structure chart.
Fig. 8 is in the present invention using polymer film as lithium-flow battery discharge curve of diaphragm.
In figure：1, proton conducting membranes；2, water based electrolyte；3, cathode；4, organic system electrolyte；5, anode.
Specific embodiment
The present invention is with attached shown in FIG. 1 containing halogenated more cyano/carboxyl/carboxylate/methyl/aldehyde radical/sulfonic benzene The polyhydroxy benzene derivative of derivative and the attached structure shown in Fig. 2 containing spatial warping is monomer, in potassium carbonate/sodium carbonate/carbon High temperature polymerization can prepare the serial organic polymer containing more cyano under the alkaline conditions such as sour caesium, and the molecular weight of polymer is 5000- 300000.Polymer is 0.5~30wt% in concentration range, can be used as into film liquid, at film liquid after ultrasonic degassing, is poured into On horizontal quartz/glass/polytetrafluoroethylene (PTFE) or metal plate, 5-100 degrees Celsius of film-forming temperature is controlled, can get uniform continuous Film.It is controlled by the concentration and dosage of casting solution, it is thin to can get the porous polymer not waited with a thickness of 3-100 microns of equal thickness Film, attached drawing 4 are the photo of the polymer film obtained in the present invention, and the infrared figure of the polymer film of acquisition is shown in attached drawing 5.Due to monomer In cause the thin polymer film after film forming to contain a large amount of micropore containing distorted-structure, attached drawing 3 show in invention representative poly- Close the structural schematic diagram of object.
The present invention has in the structural unit of the microporous polymer of ion conductor performance, makes containing stereoeffect unit Polymer chain in banking process can not close-packed arrays, increase its machinability and microcellular structure can be formed in turn, micropore is poly- It closes and contains carboxyl/sulfonic group and its salt in object chain, while the also groups such as cyano/methyl containing non-complete hydrolysis, polymer Main chain may be that fragrant chain, aliphatic chain or the two coexist, can also be with to improve polymer solubility or mechanical performance in main chain Purposeful to introduce the group with nonionic conduction property, synthetic method of the invention is only representative case, other to can be used for The reaction for synthesizing polymer with similar structure and condition are done specifically obviously there are also much below by embodiment It is bright.
Embodiment 1：
1) monomer A1 (5g) and B1 (3g) are taken, is added in solvent, 50-80 DEG C of holding 3-20min is heated to, to reactant Potassium carbonate catalytic polymerization is added in system to carry out, is warming up to 120-150 degrees Celsius, is kept for 10 minutes, it is sticky to obtain glassy yellow Liquid obtains polymer P -1；
2) it takes 300mgP-1 powder to be dissolved in tetrahydrofuran solution and obtains casting solution, after casting solution ultrasonic degassing, incline In on Flat bottom container or plate glass, the volatilization in 1-12 hours of control volatilization time is dry, obtains P-1 film；
3) P-1 film is placed in and fills 10wt% sodium hydroxide solution (solvent is that volume ratio is 1:9 water and ethyl alcohol) Container in, hydrolyze 5 hours or more at a certain temperature, the cyano in film be fully hydrolyzed as carboxylic acid group, P-1- is obtained Na；Sodium ion is replaced into proton and obtains P-1-H after persalt sufficiently exchanges；Further with 10wt% on the basis of P-1-H Lithium hydroxide solution carry out ion exchange, obtain P-1-Li；
4) the proton conducting membranes P-1-Li for obtaining step 3) is cut into the disk that diameter is 19mm, is loaded on button cell Middle progress ion conduction property test, the ion conductor performance obtained in 10wt% lithium hydroxide aqueous solution was as shown in fig. 6, should Detailed description of the invention：P-1-Li film has excellent water system ion conductor performance.
The ion conductor performance obtained in the lithium perchlorate organic electrolyte of 1M is as shown in fig. 6, the Detailed description of the invention：P-1- Li film also has excellent organic system ion conductor performance.
P-1-Li film is assembled as lithium metal-hydrogen peroxide flow battery, Fig. 7 is using polymer film as lithium-liquid stream of diaphragm The composed structure of battery structure figure, the battery is：Cathode is metal lithium sheet, and electrolyte is organic system Li salt；Just extremely hydrogen peroxide； Positive and negative polarities are separated with P-1-Li film.
By test, battery obtains stable discharge performance, and Fig. 8 is using polymer film as lithium-flow battery of diaphragm Discharge curve, the Detailed description of the invention：In the battery system, P-1-Li film can effectively stop the transmission of water and organic solvent, And it can effectively conduct Li ion.
Embodiment 2：
1) monomer A1 (5.106g) and B2 (3.003g) are taken, is added in solvent, 60 DEG C of holding 3-20min are heated to, to Potassium carbonate catalytic polymerization is added in reaction system to carry out, is warming up to 120-150 degrees Celsius, is kept for 10 minutes, obtained sticky Liquid obtains polymer P -2；
2) it takes 350mg P-2 powder to be dissolved in tetrahydrofuran solution and obtains casting solution, after casting solution ultrasonic degassing, incline In on Flat bottom container or plate glass, the volatilization in 1-12 hours of control volatilization time is dry, obtains P-2 film；
3) P-2 film is placed in the container for filling 10wt% sodium hydroxide solution, is hydrolyzed 5 hours at a certain temperature More than, the cyano in film is fully hydrolyzed as carboxylic acid group, acquisition P-2-Na；Sodium ion is set to after persalt sufficiently exchanges It is changed to proton and obtains P-2-H；Ion exchange is further carried out with the lithium hydroxide solution of 10wt% on the basis of P-2-H, is obtained P-2-Li；
4) proton conducting membranes for obtaining step 3) are cut into the disk that diameter is 19mm, loaded on carrying out in button cell The test of ion conduction property；
5) the more sulphions of the barrier for polymer film being used for lithium-sulfur cell, which shuttle, tests, and shows that P-2-Li film can effectively be grown Time prevents more sulphions from shuttling.
Embodiment 3：
1) monomer A1 (5.106g) and B4 (3.006g) are taken, is added in solvent, 80 DEG C of holding 3-20min are heated to, to Potassium carbonate catalytic polymerization is added in reaction system to carry out, is warming up to 120-150 degrees Celsius, is kept for 10 minutes, obtained bright orange Color thick liquid obtains polymer P -3；
2) it takes 300mgP-3 powder to be dissolved in tetrahydrofuran solution and obtains casting solution, after casting solution ultrasonic degassing, incline In on Flat bottom container or plate glass, the volatilization in 1-12 hours of control volatilization time is dry, obtains P-3 film；
3) P-3 film is placed in and fills 10wt% potassium hydroxide sodium solution (solvent is that volume ratio is 1:9 water and second Alcohol) container in, hydrolyze 5 hours or more at a certain temperature, the cyano in film be fully hydrolyzed as carboxylic acid group, P- is obtained 3-Na；Sodium ion is replaced into proton and obtains P-3-H after persalt is sufficiently delivered goods；On the basis of P-3-H further with The lithium hydroxide solution of 10wt% carries out ion exchange, obtains P-3-Li；
Embodiment 4：
1) monomer A10 (5.2g) and B5 (4.1g) are taken, is added in solvent, 70 DEG C of holding 3-20min are heated to, to reaction Potassium carbonate catalytic polymerization is added in system to carry out, is warming up to 120-150 degrees Celsius, is kept for 10 minutes, it is viscous to obtain glassy yellow Thick liquid obtains polymer P -4；
2) it takes 350mgP-4 powder to be dissolved in DMF solution and obtains casting solution, after casting solution ultrasonic degassing, be poured into flat On bottom container or plate glass, the volatilization in 1-12 hours of control volatilization time is dry, obtains P-4-H film；
3) P-4-H film is placed in and fills 10wt% sodium chloride solution, by sufficiently exchanging, obtain P-4-Na；In P- Ion exchange is further carried out with the zinc hydroxide solution of 10wt% on the basis of 4-H, obtains P-4-Zn；
Various embodiments provided by the invention can be combined with each other in any way as needed, be obtained by this combination Technical solution, it is also within the scope of the invention.
Obviously, in the case where not departing from theory and method of the invention, those skilled in the art can to the present invention into The various modification and variations of row.If being in claim and its equivalent program of the invention to these modification and variations of the invention In range, then the present invention also will include these modification and variations.

Claims (10)

1. a kind of microporous polymer membranes with ion conduction property,
Wherein the chemical general formula of the polymer containing micropore is：
In formula, A1-A2 is main polymer chain functional group；B be the alkyl that carbon atom number is 1~10 or alkoxy or cyano it is non-from Sub- conduction function group；C is the group with ionic conduction performance of carboxyl or sulfonic group or imide or sulfimide base； M is the tradable ion of proton or alkali metal metal ion or alkaline-earth metal ions.
2. the microporous polymer membranes according to claim 1 with ion conduction property, it is characterized in that：Point of the polymer Son amount is 5000-300000.
3. a kind of preparation method of the microporous polymer membranes with ion conduction property, it is characterized in that including the following steps：
Preparation containing organic microporous polymer：To contain halogenated more cyano/carboxyl/carboxylate/methyl/aldehyde radical/sulfonic benzene The polyhydroxy benzene derivative (attached drawing 2) of derivative (attached drawing 1) and the structure containing spatial warping be monomer, potassium carbonate/sodium carbonate/ High temperature polymerization can prepare the serial organic polymer containing more cyano under the alkaline conditions such as cesium carbonate；
The preparation of organic microporous polymer film：Step 1) polymer obtained is dissolved in chloroform, tetrahydrofuran, dichloromethane Alkane, dichloroethanes, 1,2- dichloroethanes, N, N '-dimethyl formamide (DMF), N, N '-dimethyl acetamide (DMAC), N- first One of base pyrrolidones (NMP) solvent or in the mixed solvent, polymer are 0.5~30wt% in concentration range, be can be used as At film liquid, at film liquid after ultrasonic degassing, be poured on horizontal quartz/glass/polytetrafluoroethylene (PTFE) or metal plate, control at 5-100 degrees Celsius of film temperature, it can get uniform continuous film；It is controlled by the concentration and dosage of casting solution, can get thickness The porous polymer film not waited for 3-100 microns of equal thickness.
4. the preparation method of the microporous polymer membranes according to claim 3 with ion conduction property, it is characterized in that：Institute The chemical general formula that organic microporous polymer must be contained is：
In formula, A1-A2 is main polymer chain functional group；B be the alkyl that carbon atom number is 1~10 or alkoxy or cyano it is non-from Sub- conduction function group；C is the group with ionic conduction performance of carboxyl or sulfonic group or imide or sulfimide base； M is the tradable ion of proton or alkali metal metal ion or alkaline-earth metal ions.
5. the preparation method of the microporous polymer membranes according to claim 4 with ion conduction property, it is characterized in that：It is poly- It closes and contains carboxyl/sulfonic group and its salt in object chain, while the also groups such as cyano/methyl containing non-complete hydrolysis, polymer Main chain may be that fragrant chain, aliphatic chain or the two coexist, can also be with to improve polymer solubility or mechanical performance in main chain It is purposeful to introduce the group with nonionic conduction property.
6. the preparation method of the microporous polymer membranes according to claim 3 with ion conduction property, it is characterized in that：It is right In the polymer containing cyano using the aqueous solution of sodium hydroxide or potassium hydroxide or cesium hydroxide or tetrapropylammonium hydroxide or By the cyan-hydrolysis in film in person's water/alcohol solution, or hydrolyzed using acid condition, film with a thickness of 1-500 microns, water The concentration range for solving liquid is 1wt-50wt%, is room temperature under hydrolysis temperature condition of normal pressure to 100 degrees Celsius, under hydrothermal conditions for Room temperature is hydrolyzed to 200 degrees Celsius.
7. the preparation method of the microporous polymer membranes according to claim 3 with ion conduction property, it is characterized in that：It is right In containing methyl/aldehyde radical/sulfydryl polymer, in-situ oxidation methyl/aldehyde radical/sulfydryl prepares and carboxylic-containing acid has under oxidative conditions Machine microporous polymer film；Methyl/aldehyde radical/sulfydryl that polymer contains uses potassium permanganate/ammonium persulfate/iron chloride/dioxygen Methyl/aldehyde radical/sulfhydryl oxidase in polymer is carboxyl/sulfonic group by water/oxygen oxidizer, original position.
8. the preparation method of the microporous polymer membranes according to claim 6 with ion conduction property, it is characterized in that：Water Containing carboxylate/sulfonate thin polymer film after solution, through any sort inorganic acid in persalt, sulfuric acid, nitric acid, phosphoric acid, acetic acid After solution exchange, carboxylate can be changed into carboxylate radical/sulfonate radical, carrying out ion exchange by all kinds of lithiums, sodium, sylvite or alkali can Obtain the polymer film for containing corresponding ion.
9. a kind of application of the microporous polymer membranes with ion conduction property, it is characterized in that：The ion of microporous polymer membranes is led Body application range is to use in water system, organic system and water system and organic system mixed electrolytic solution system.
10. the application of the microporous polymer membranes according to claim 9 with ion conduction property, it is characterized in that：Micropore The application field of polymer film include metal-air battery, lithium-sulfur cell, flow battery, lithium ion battery, sodium-ion battery, Fuel cell, is electrolysed in any device for being related to ion conductor film electro-catalysis.
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CN112768836A (en) * 2021-01-12 2021-05-07 东华大学 Zinc ion selective transmission diaphragm and preparation method thereof

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