CN108841020B - Microporous polymer membrane with ion conduction performance and preparation method and application thereof - Google Patents
Microporous polymer membrane with ion conduction performance and preparation method and application thereof Download PDFInfo
- Publication number
- CN108841020B CN108841020B CN201810466843.9A CN201810466843A CN108841020B CN 108841020 B CN108841020 B CN 108841020B CN 201810466843 A CN201810466843 A CN 201810466843A CN 108841020 B CN108841020 B CN 108841020B
- Authority
- CN
- China
- Prior art keywords
- ion
- polymer
- group
- microporous polymer
- film
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
Classifications
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Materials Engineering (AREA)
- Inorganic Chemistry (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
- Fuel Cell (AREA)
- Conductive Materials (AREA)
Abstract
A microporous polymer membrane with ion conducting property, its preparation method and application are disclosed, said membrane contains micropores and carboxylic acid/carboxylate/sulfonic acid group. The preparation of the ion conductor functional microporous polymer film comprises the following steps: preparing a microporous polymer from polyhydroxy and polyhalogenated monomers; preparing a microporous polymer membrane; hydrolyzing and converting cyano/carboxylic ester groups in the polymer into carboxyl salt to obtain the microporous polymer film with the function of the ion conductor; for a polymer containing methyl/aldehyde group/sulfhydryl group, converting the methyl or aldehyde group in the polymer film into carboxyl/sulfonic group through oxidation to obtain the ion conductor functional microporous polymer film; obtaining a microporous polymer film with proton/sodium/lithium/potassium ions and other specific ions through ion exchange; the ion conductor function was tested in aqueous and organic electrolytes. The ionic conductor microporous polymer film prepared by the invention has the advantages of simple preparation process, ion exchange, good stability and safety, easy use and the like.
Description
Technical Field
The invention relates to a polymer-based ion conductor diaphragm, in particular to an organic microporous polymer film with a skeleton containing or partially containing carboxylic acid/carboxylate, sulfonic acid and sulfonate, which is applied to the field of selective conduction of protons, lithium ions, sodium ions, potassium ions, zinc ions, aluminum ions and the like, can well block the permeation of various components and water vapor in air, and can be used as a diaphragm or a solid electrolyte material in devices related to ion conduction, such as corresponding metal-air batteries (including lithium, sodium, potassium, magnesium, zinc and other metals), lithium-sulfur batteries, flow batteries, lithium ion batteries, sodium ion batteries, potassium ion batteries, magnesium ion batteries, aluminum ion batteries, fuel batteries, electrolytic cells and the like.
Background
The film with the function of the specific ion conductor is widely used in metal air batteries (selectively permeating corresponding object ions and effectively blocking permeation of oxygen, carbon dioxide and water vapor), lithium sulfur batteries (conducting lithium ions and effectively blocking shuttle of polysulfide ions), flow batteries (proton or shuttle of corresponding object ions and blocking active ingredients), fuel batteries (proton conductors), lithium ion batteries (lithium ion conductors), sodium ion batteries (sodium ion conductors) and a plurality of energy storage devices, plays a role in effectively separating active substances at the positive pole and the negative pole, and can rapidly conduct the object ions while avoiding short circuit.
With the development of all-solid batteries, inorganic ceramic ion conductor separators have been widely studied. However, the inorganic ceramic membrane has the disadvantages of high cost, low yield and no bending, which limits the large-scale popularization of the inorganic ceramic membrane, and particularly, the inorganic membrane generally has poor acid-base resistance, which severely limits the application field of the inorganic membrane.
Recently, with the rapid development of the field of wearable flexible electronics, the development of a flexible membrane with excellent ion conduction performance has become a key technology for the development of flexible energy storage devices.
Copolymers of polytetrafluoroethylene and perfluoro-3, 6-diepoxy-4-methyl-7-decene-sulfuric acid, i.e.
The membrane is an ion conduction membrane widely used at present, has the characteristics of good flexibility and high processability, but has a larger pore passage, cannot effectively block shuttling of a solvent, and has complex preparation process and high cost.
Chinese patent CN101891848A discloses a polyvinyl alcohol-based single-component ionic polymer electrolyte and a preparation method thereof, which improve the safety performance of a lithium ion battery and have lower cost.
Chinese patent CN103236557A discloses a blend membrane of poly-p-phenylene benzobisoxazole and polyphosphoric acid, which is used for high-temperature fuel cells.
Chinese patent CN106887622A discloses a fluorine-containing single-ion conductor polymer electrolyte and a preparation method and application thereof.
The film-forming property and ionic conductivity of the organic polymer electrolytes can not meet the requirements of batteries, most of polymer films with the function of ionic conductors are mixed films, polymers only play a role in structural support, and the realization of the function of ionic conductors depends on metal salts doped in the polymer films; the ion conducting groups of the pure polymer membrane are mainly grafted to side chains, so that the synthesis steps are multiple, the stability and the mechanical property are not ideal, the molecular chains do not have porous structures, the molecular chains need to be prepared into nanofiltration or microfiltration membranes with larger pores by means of phase separation and the like, molecules such as solvents and the like cannot be effectively blocked, and therefore further optimization design needs to be carried out on the structure of the polymer in order to obtain the high-performance polymer membrane with the ion conducting property and capable of blocking the solvent molecules.
Disclosure of Invention
The invention aims to obtain a microporous polymer film with ion conduction performance and apply the microporous polymer film to the field of various energy storage devices, an intrinsic micropore can be formed when a polymer molecular chain is integrated into a film due to the spatial structure, and the introduction of the micropore can effectively improve the ion transmission performance of the polymer film; meanwhile, the micropores can effectively block water, various gases and organic solvent molecular clusters, and realize the functions of conducting ions and blocking solvents.
The invention also aims to provide a preparation method of the organic porous polymer with ion conduction performance, the preparation method has simple process, short flow and easy amplification, the prepared membrane component is easy to adjust, the membrane has ion conduction performance and has barrier effect on water and organic solvent, and the membrane can be used as a diaphragm and an ion conduction membrane in various energy storage devices.
The technical scheme adopted by the invention is as follows: a microporous polymer membrane having ion-conducting properties,
wherein the chemical formula of the polymer containing micropores is:
in the formula, A1-A2 is a polymer main chain functional group, which not only ensures the polymerization degree of polymer molecules, but also plays a role in constructing space micropores; b is an alkyl or alkoxy or cyano nonionic conducting functional group with 1-10 carbon atoms; c is a carboxyl group or a sulfonic group or an imide group or a sulfonimide group which has ion-conducting property; m is a proton or an exchangeable ion of an alkali metal ion or an alkaline earth metal ion.
A method for preparing a microporous polymer membrane with ion conduction performance comprises the following steps:
preparation of organic microporous containing polymer: benzene derivatives containing halogenated polycyano/carboxyl/carboxylate/methyl/aldehyde/sulfonic acid group and polyhydroxy benzene derivatives containing space twist structure are taken as monomers, and high-temperature polymerization is carried out under the alkaline conditions of potassium carbonate/sodium carbonate/cesium carbonate and the like to prepare a series of organic polymers containing polycyano, wherein the molecular weight of the polymers is 5000-300000, and the polymer film after film formation contains a large number of micropores due to the twist structure contained in the monomers;
preparation of organic microporous polymer film: dissolving the polymer obtained in the step 1 in one or a mixed solvent of chloroform, tetrahydrofuran, dichloromethane, dichloroethane, 1, 2-dichloroethane, N '-Dimethylformamide (DMF), N' -Dimethylacetamide (DMAC) and N-methylpyrrolidone (NMP), wherein the concentration of the polymer is 0.5-30 wt%, the polymer can be used as a film forming solution, the film forming solution is subjected to ultrasonic degassing and poured onto a horizontal quartz/glass/polytetrafluoroethylene or metal plate, and the film forming temperature is controlled to be 5-100 ℃ to obtain a uniform and continuous film; the porous polymer film with the thickness of 3-100 microns and the like can be obtained by controlling the concentration and the dosage of the casting solution;
for polymers containing cyano/carboxylate groups, hydrolyzing the cyano/carboxylic acid groups in situ under alkaline conditions to prepare carboxylic acid-containing organic microporous polymer films; the cyano group contained in the polymer can be hydrolyzed into carboxyl in situ in water or water/alcohol mixed solution of strong base such as sodium hydroxide, potassium hydroxide, cesium hydroxide or tetrapropylammonium hydroxide and the like, or the hydrolysis is carried out under acidic condition, the thickness of the film is 1-500 micrometers, the concentration range of the hydrolysis solution is 1-50 wt%, the hydrolysis temperature is room temperature to 100 ℃, or the hydrolysis temperature can be up to 200 ℃ under hydrothermal condition;
for a polymer containing methyl/aldehyde group/sulfhydryl group, oxidizing the methyl/aldehyde group/sulfhydryl group in situ under an oxidizing condition to prepare a carboxylic acid-containing organic microporous polymer film; the methyl/aldehyde group/sulfydryl contained in the polymer can be oxidized into carboxyl/sulfonic group in situ in a solution using potassium permanganate/ammonium persulfate/ferric chloride/hydrogen peroxide/oxygen strong oxidizer;
and (3) carrying out an ion exchange method to obtain the organic microporous polymer film with various ions. After hydrolysis, the polymer film containing carboxylate/sulfonate is exchanged by any inorganic acid solution of hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid and acetic acid, the carboxylate can be converted into carboxylate/sulfonate, and the polymer film containing corresponding ions can be obtained by ion exchange of various lithium, sodium, potassium salts or alkali;
the application of microporous polymer film with ion conducting performance is in water system, organic system and mixed electrolyte system. The application fields include metal-air batteries, lithium-sulfur batteries, flow batteries, lithium ion batteries, sodium ion batteries, fuel cells, electrocatalysis, electrolysis and other devices relating to ion conductor films.
And (5) testing the performance of the ion conductor. The polymer film was placed between metal electrodes, and ac impedance test was performed at different temperatures, calculated according to the formula σ ═ l/RS (l is the thickness of the polymer film, R is the resistance of the polymer measured by ac impedance, and S is the area of the polymer electrolyte film).
The invention has the advantages and beneficial effects that:
the molecular structure of the polymer film is easy to adjust, the ion conducting performance of the ion conductor film is excellent, and compared with a commercialized inorganic film, the polymer film is easy to form, simple in preparation process and suitable for expanded production.
Drawings
FIG. 1 is a structural view of a cyano group-containing/carboxyl group/carboxylate/methyl group/sulfonic group-containing polyhalogenated monomer used in the present invention.
FIG. 2 is a structural view of a steric structure-containing polyhydroxy monomer employed in the present invention.
FIG. 3 is a schematic representation of the structure of a representative polymer of the present invention.
Fig. 4 is a photograph of the polymer film obtained in the present invention.
Fig. 5 is an infrared image of a polymer film obtained according to the present invention.
FIG. 6 is a graph showing the ion conductor performance of the polymer membrane obtained in the present invention.
Fig. 7 is a structural diagram of a lithium-flow battery using a polymer membrane as a separator according to the present invention.
Fig. 8 is a discharge curve of a lithium-flow battery using a polymer membrane as a separator according to the present invention.
In the figure: 1. a proton conductor membrane; 2. a water-based electrolyte; 3. a cathode; 4. an organic electrolyte; 5. and an anode.
Detailed Description
The invention takes benzene derivatives containing halogenated polycyano/carboxyl/carboxylate/methyl/aldehyde group/sulfonic group shown in figure 1 and polyhydroxy benzene derivatives containing space twist structure shown in figure 2 as monomers, and can prepare a series of organic polymers containing polycyano by high-temperature polymerization under the alkaline conditions of potassium carbonate/sodium carbonate/cesium carbonate and the like, wherein the molecular weight of the polymers is 5000-300000. The polymer with the concentration range of 0.5-30 wt% can be used as a film forming solution, the film forming solution is poured on a horizontal quartz/glass/polytetrafluoroethylene or metal plate after being subjected to ultrasonic degassing, and the film forming temperature is controlled to be 5-100 ℃, so that a uniform and continuous film can be obtained. The porous polymer film with the thickness of 3-100 micrometers and the like can be obtained by controlling the concentration and the dosage of the casting solution, the attached figure 4 is a photo of the polymer film obtained in the invention, and the infrared image of the obtained polymer film is shown in the attached figure 5. The polymer film after film formation contains a large number of micropores due to the twisted structure contained in the monomer, and fig. 3 is a schematic structural diagram of a representative polymer in the invention.
The structural unit of the microporous polymer with ion conductor performance of the present invention contains a spatial stereo structural unit, so that polymer chains can not be closely arranged in a stacking process, the processability is increased, and a microporous structure can be further formed, the microporous polymer chain contains carboxyl/sulfonic acid group and salt thereof, and also contains incompletely hydrolyzed cyano/methyl group, etc., the main chain of the polymer may be an aromatic chain, an aliphatic chain or the coexistence of the aromatic chain and the aliphatic chain, and a group with non-ionic conduction performance can be purposefully introduced into the main chain for improving the solubility or the mechanical performance of the polymer.
Example 1:
1) adding monomers A1(5g) and B1(3g) into a solvent, heating to 50-80 ℃, keeping for 3-20min, adding potassium carbonate into a reaction system for catalytic polymerization, heating to 120-150 ℃, keeping for 10 min, and obtaining bright yellow viscous liquid to obtain a polymer P-1;
2) dissolving 300mgP-1 powder in a tetrahydrofuran solution to obtain a casting solution, ultrasonically degassing the casting solution, pouring the casting solution on a flat-bottom container or flat glass, and controlling the volatilization time to volatilize within 1-12 hours to obtain a P-1 film;
3) placing the P-1 film in a container containing 10 wt% of sodium hydroxide solution (the solvent is water and ethanol with the volume ratio of 1: 9), hydrolyzing for more than 5 hours at a certain temperature, and fully hydrolyzing cyano groups in the film into carboxylic acid groups to obtain P-1-Na; after full exchange of hydrochloric acid, sodium ions are replaced by protons to obtain P-1-H; carrying out ion exchange by using 10 wt% of lithium hydroxide solution on the basis of the P-1-H to obtain P-1-Li;
4) cutting the proton conductor membrane P-1-Li obtained in the step 3) into a wafer with the diameter of 19mm, placing the wafer in a button cell for ion conduction performance test, wherein the ion conductor performance obtained in a10 wt% lithium hydroxide aqueous solution is shown in figure 6, and the figure shows that: the P-1-Li film has excellent aqueous ion conductor performance.
The ion conductor performance obtained in a 1M lithium perchlorate organic electrolyte is shown in fig. 6, which illustrates: the P-1-Li film also has excellent organic ion conductor properties.
Assembling the P-1-Li film into a lithium-double oxygen water flow battery, and taking the polymer film as a diaphragm, wherein the structure of the lithium-flow battery is as follows: the negative electrode is a metal lithium sheet, and the electrolyte is organic Li salt; the positive electrode is hydrogen peroxide; the positive and negative poles are separated by a P-1-Li film.
The battery obtained smooth discharge performance through the test, fig. 8 is a discharge curve of the lithium-flow battery using the polymer film as the diaphragm, and the figure illustrates that: in the battery system, the P-1-Li film can effectively block the permeation of water and organic solvents and can effectively conduct Li ions.
Example 2:
1) adding monomers A1(5.106g) and B2(3.003g) into a solvent, heating to 60 ℃ and keeping for 3-20min, adding potassium carbonate into a reaction system for catalytic polymerization, heating to 120-150 ℃ and keeping for 10 min to obtain viscous liquid to obtain a polymer P-2;
2) dissolving 350mg of P-2 powder in a tetrahydrofuran solution to obtain a casting solution, ultrasonically degassing the casting solution, pouring the casting solution on a flat-bottomed container or flat glass, and controlling the volatilization time to volatilize within 1-12 hours to obtain a P-2 film;
3) placing the P-2 film in a container containing 10 wt% of sodium hydroxide solution, hydrolyzing for more than 5 hours at a certain temperature, and fully hydrolyzing cyano groups in the film into carboxylic acid groups to obtain P-2-Na; after full exchange of hydrochloric acid, sodium ions are replaced by protons to obtain P-2-H; carrying out ion exchange by using 10 wt% of lithium hydroxide solution on the basis of the P-2-H to obtain P-2-Li;
4) cutting the proton conductor membrane obtained in the step 3) into a wafer with the diameter of 19mm, and placing the wafer in a button cell for ion conduction performance test;
5) the polymer film is used for preventing the shuttle experiment of polysulfide ions of a lithium-sulfur battery, and the P-2-Li film can effectively prevent the shuttle experiment of the polysulfide ions for a long time.
Example 3:
1) adding monomers A1(5.106g) and B4(3.006g) into a solvent, heating to 80 ℃ for 3-20min, adding potassium carbonate into a reaction system for catalytic polymerization, heating to 120-150 ℃, and keeping for 10 min to obtain a bright yellow viscous liquid to obtain a polymer P-3;
2) dissolving 300mgP-3 powder in a tetrahydrofuran solution to obtain a casting solution, ultrasonically degassing the casting solution, pouring the casting solution on a flat-bottomed container or flat glass, and controlling the volatilization time to volatilize within 1-12 hours to obtain a P-3 film;
3) placing the P-3 film in a container containing 10 wt% of sodium potassium hydroxide solution (the solvent is water and ethanol with the volume ratio of 1: 9), hydrolyzing for more than 5 hours at a certain temperature, and fully hydrolyzing cyano groups in the film into carboxylic acid groups to obtain P-3-Na; after hydrochloric acid is fully delivered, sodium ions are replaced by protons to obtain P-3-H; carrying out ion exchange by using 10 wt% of lithium hydroxide solution on the basis of the P-3-H to obtain P-3-Li;
example 4:
1) adding monomers A10(5.2g) and B5(4.1g) into a solvent, heating to 70 ℃ and keeping for 3-20min, adding potassium carbonate into a reaction system for catalytic polymerization, heating to 120-150 ℃ and keeping for 10 min to obtain a bright yellow viscous liquid, and thus obtaining a polymer P-4;
2) dissolving 350mgP-4 powder in a DMF (dimethyl formamide) solution to obtain a casting solution, ultrasonically degassing the casting solution, pouring the casting solution on a flat-bottom container or flat glass, and controlling the volatilization time to volatilize within 1-12 hours to obtain a P-4-H film;
3) putting the P-4-H film in 10 wt% sodium chloride solution, and fully exchanging to obtain P-4-Na; carrying out ion exchange by using 10 wt% of zinc hydroxide solution on the basis of the P-4-H to obtain P-4-Zn;
the various embodiments provided by the invention can be combined with each other in any way according to the needs, and the technical solution obtained by the combination is also within the scope of the invention.
It is apparent that those skilled in the art can make various modifications and variations to the present invention without departing from the concept and method of the present invention. It is intended that the present invention cover the modifications and variations of this invention provided they come within the scope of the appended claims and their equivalents.
Claims (10)
1. A microporous polymer membrane having ion-conducting properties,
wherein the chemical formula of the polymer containing micropores is:
wherein A1-A2 is a polymer backbone functional group; b is a nonionic conductive functional group of alkyl or alkoxy or cyano with 1-10 carbon atoms; c is a carboxyl group or a sulfonic group or an imide group or a sulfonimide group which has ion-conducting property; m is a proton or an exchangeable ion of an alkali metal ion or an alkaline earth metal ion.
2. A microporous polymer membrane with ion conducting properties according to claim 1, wherein: the molecular weight of the polymer is 5000-300000.
3. A preparation method of a microporous polymer membrane with ion conduction performance is characterized by comprising the following steps:
preparation of organic microporous containing polymer: benzene derivatives (figure 1) containing halogenated polycyano/carboxyl/carboxylate/methyl/aldehyde/sulfonic acid group and polyhydroxy benzene derivatives (figure 2) containing space twist structure are taken as monomers, and high-temperature polymerization is carried out under the alkaline conditions of potassium carbonate/sodium carbonate/cesium carbonate and the like to prepare a series of organic polymers containing polycyano;
preparation of organic microporous polymer film: dissolving the polymer obtained in the step 1) in one or a mixed solvent of chloroform, tetrahydrofuran, dichloromethane, dichloroethane, 1, 2-dichloroethane, N '-Dimethylformamide (DMF), N' -Dimethylacetamide (DMAC) and N-methylpyrrolidone (NMP), wherein the concentration of the polymer is 0.5-30 wt%, the polymer can be used as a film forming solution, the film forming solution is subjected to ultrasonic degassing and poured onto a horizontal quartz/glass/polytetrafluoroethylene or metal plate, and the film forming temperature is controlled to be 5-100 ℃ to obtain a uniform and continuous film; the porous polymer film with thickness of 3-100 microns and different thicknesses can be obtained by controlling the concentration and the dosage of the casting solution.
4. A method of preparing a microporous polymer membrane with ion conducting properties according to claim 3, wherein: the chemical formula of the obtained organic micropore-containing polymer is as follows:
wherein A1-A2 is a polymer backbone functional group; b is a nonionic conductive functional group of alkyl or alkoxy or cyano with 1-10 carbon atoms; c is a carboxyl group or a sulfonic group or an imide group or a sulfonimide group which has ion-conducting property; m is a proton or an exchangeable ion of an alkali metal ion or an alkaline earth metal ion.
5. The method of claim 4, wherein the microporous polymer membrane with ion conducting properties comprises: the polymer chain contains carboxyl/sulfonic acid group and salt thereof, and also contains incompletely hydrolyzed cyano/methyl group and other groups, the main chain of the polymer can be an aromatic chain, an aliphatic chain or the coexistence of the aromatic chain and the aliphatic chain, and groups with non-ionic conduction performance can be purposefully introduced into the main chain for improving the solubility or the mechanical performance of the polymer.
6. A method of preparing a microporous polymer membrane with ion conducting properties according to claim 3, wherein: for the polymer containing the cyano groups, the cyano groups in the film are hydrolyzed by adopting aqueous solution or water/alcohol solution of sodium hydroxide or potassium hydroxide or cesium hydroxide or tetrapropylammonium hydroxide, or hydrolyzed by adopting acidic condition, the thickness of the film is 1-500 micrometers, the concentration range of the hydrolyzed solution is 1-50 wt%, the hydrolysis temperature is room temperature to 100 ℃ under normal pressure condition, and the hydrolysis is carried out under hydrothermal condition at room temperature to 200 ℃.
7. A method of preparing a microporous polymer membrane with ion conducting properties according to claim 3, wherein: for a polymer containing methyl/aldehyde group/sulfhydryl group, oxidizing the methyl/aldehyde group/sulfhydryl group in situ under an oxidizing condition to prepare a carboxylic acid-containing organic microporous polymer film; the methyl/aldehyde group/sulfydryl contained in the polymer is oxidized into carboxyl/sulfonic group in situ by using potassium permanganate/ammonium persulfate/ferric chloride/hydrogen peroxide/oxygen oxidant.
8. The method of claim 6, wherein the microporous polymer membrane with ion conducting properties comprises: after hydrolysis, the polymer film containing carboxylate/sulfonate is exchanged by any inorganic acid solution of hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid and acetic acid, the carboxylate can be converted into carboxylate/sulfonate, and the polymer film containing corresponding ions can be obtained by ion exchange by various lithium, sodium, potassium salts or alkali.
9. Use of a microporous polymer membrane with ion-conducting properties according to claim 1 or 2, characterized in that: the microporous polymer membrane has applications in aqueous, organic, and mixed aqueous and organic electrolyte systems.
10. Use of a microporous polymer membrane with ion-conducting properties according to claim 9, characterized in that: the application fields of the microporous polymer membrane comprise any one of metal-air batteries, lithium-sulfur batteries, flow batteries, lithium ion batteries, sodium ion batteries, fuel cells, electrocatalysis and electrolysis devices relating to an ion conductor thin film.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810466843.9A CN108841020B (en) | 2018-05-16 | 2018-05-16 | Microporous polymer membrane with ion conduction performance and preparation method and application thereof |
| PCT/CN2018/103768 WO2019218542A1 (en) | 2018-05-16 | 2018-09-03 | Microporous polymer film with ion conductivity and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810466843.9A CN108841020B (en) | 2018-05-16 | 2018-05-16 | Microporous polymer membrane with ion conduction performance and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN108841020A CN108841020A (en) | 2018-11-20 |
| CN108841020B true CN108841020B (en) | 2020-05-19 |
Family
ID=64213068
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810466843.9A Active CN108841020B (en) | 2018-05-16 | 2018-05-16 | Microporous polymer membrane with ion conduction performance and preparation method and application thereof |
Country Status (2)
| Country | Link |
|---|---|
| CN (1) | CN108841020B (en) |
| WO (1) | WO2019218542A1 (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109880032A (en) * | 2019-01-16 | 2019-06-14 | 大连理工大学 | Rich nitrogen micropore organic polymer containing functional group and preparation method thereof |
| CN112768836B (en) * | 2021-01-12 | 2022-12-20 | 东华大学 | Zinc ion selective transmission diaphragm and preparation method thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1697852A (en) * | 2002-06-27 | 2005-11-16 | 佩密斯股份有限公司 | Proton-conducting membrane and the use thereof |
| CN102299351A (en) * | 2010-06-25 | 2011-12-28 | 中国科学院大连化学物理研究所 | Polybenzimidazole polymer ion exchange membrane, and preparation and application thereof |
| CN103094643A (en) * | 2011-10-27 | 2013-05-08 | 三星电子株式会社 | Electrolyte for lithium air battery and lithium air battery including the same |
| CN103367780A (en) * | 2012-04-03 | 2013-10-23 | 通用汽车环球科技运作有限责任公司 | Rubber crack mitigants in polyelectrolyte membranes |
-
2018
- 2018-05-16 CN CN201810466843.9A patent/CN108841020B/en active Active
- 2018-09-03 WO PCT/CN2018/103768 patent/WO2019218542A1/en active Application Filing
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1697852A (en) * | 2002-06-27 | 2005-11-16 | 佩密斯股份有限公司 | Proton-conducting membrane and the use thereof |
| CN102299351A (en) * | 2010-06-25 | 2011-12-28 | 中国科学院大连化学物理研究所 | Polybenzimidazole polymer ion exchange membrane, and preparation and application thereof |
| CN103094643A (en) * | 2011-10-27 | 2013-05-08 | 三星电子株式会社 | Electrolyte for lithium air battery and lithium air battery including the same |
| CN103367780A (en) * | 2012-04-03 | 2013-10-23 | 通用汽车环球科技运作有限责任公司 | Rubber crack mitigants in polyelectrolyte membranes |
Also Published As
| Publication number | Publication date |
|---|---|
| WO2019218542A1 (en) | 2019-11-21 |
| CN108841020A (en) | 2018-11-20 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108565384B (en) | Preparation method and application of sulfonated polyether-ether-ketone lithium polymer electrolyte membrane | |
| Lee et al. | Electrospun polyetherimide nanofiber mat-reinforced, permselective polyvinyl alcohol composite separator membranes: A membrane-driven step closer toward rechargeable zinc–air batteries | |
| CN109273647B (en) | Porous single-ion conductive polymer electrolyte diaphragm and preparation method and application thereof | |
| KR102390373B1 (en) | Lithium air battery and preparing method thereof | |
| US11069940B2 (en) | Ionically conductive material for electrochemical generator and production methods | |
| JP2014503946A (en) | Application of porous membrane and its composite membrane in redox flow battery | |
| CN101475699B (en) | Preparation of proton conduction membrane | |
| TW200825121A (en) | Polymer electrolyte, production process thereof and electrochemical device | |
| CN111261932B (en) | Ionic plastic crystal-polymer-inorganic composite electrolyte membrane, and preparation method and application thereof | |
| CN109193027B (en) | Lithium ion polymer electrolyte membrane and preparation method and application thereof | |
| CN102569702B (en) | Ion selective membrane used by non-solid-state electrode and preparation method thereof | |
| CN108841020B (en) | Microporous polymer membrane with ion conduction performance and preparation method and application thereof | |
| WO2018214843A1 (en) | Crosslinked porous membrane resulting from hydrolysis of ester group side chain and preparation method therefor | |
| CN103123958B (en) | Solid nano porous membrane with temperature sensitive response characteristics and preparation method thereof | |
| CN101613481A (en) | A kind of method for preparing interpenetrating network type conducting film of poly ion liquid | |
| CN106229445A (en) | A kind of lithium ion battery separator and preparation method thereof and lithium ion battery | |
| CN111748096B (en) | Preparation and application of polybenzimidazole based single-ion polymer gel electrolyte | |
| KR20200044701A (en) | Dispersant for separator of non-aqueous electrolyte battery comprising 2-cyanoethyl group-containing polymer, separator of non-aqueous electrolyte battery, and non-aqueous electrolyte battery | |
| CN111969184A (en) | Polymer composite pole piece and preparation method and application thereof | |
| CN102190839B (en) | Gel polymer lithium ion battery, porous composite electrode and porous membrane composition | |
| CN105552276A (en) | Preparation method of temperature responsive composite microporous membrane | |
| KR100843569B1 (en) | Proton conductive composite triblock polymer electrolyte membrane and preparation method thereof | |
| CN105017171A (en) | Preparation methods and applications for diaminebenzoxazole and copolyamide electrolyte of diaminebenzoxazole | |
| KR100947781B1 (en) | Electrolyte membranes comprising soluble polymers and crosslinkable multi-block copolymers | |
| CN111525187A (en) | Sulfonated polyvinyl alcohol solid polymer electrolyte membrane for lithium battery and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |