CN109988327A - A kind of non-fluorine ion exchange membrane and its preparation method and application - Google Patents
A kind of non-fluorine ion exchange membrane and its preparation method and application Download PDFInfo
- Publication number
- CN109988327A CN109988327A CN201711473747.9A CN201711473747A CN109988327A CN 109988327 A CN109988327 A CN 109988327A CN 201711473747 A CN201711473747 A CN 201711473747A CN 109988327 A CN109988327 A CN 109988327A
- Authority
- CN
- China
- Prior art keywords
- ion exchange
- exchange membrane
- phenolic compound
- fluorine ion
- solid
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- 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
- C08G8/00—Condensation polymers of aldehydes or ketones with phenols only
- C08G8/04—Condensation polymers of aldehydes or ketones with phenols only of aldehydes
- C08G8/08—Condensation polymers of aldehydes or ketones with phenols only of aldehydes of formaldehyde, e.g. of formaldehyde formed in situ
- C08G8/12—Condensation polymers of aldehydes or ketones with phenols only of aldehydes of formaldehyde, e.g. of formaldehyde formed in situ with monohydric phenols having only one hydrocarbon substituent ortho on para to the OH group, e.g. p-tert.-butyl phenol
-
- 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
- C08G8/00—Condensation polymers of aldehydes or ketones with phenols only
- C08G8/28—Chemically modified polycondensates
-
- 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
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/24—Crosslinking, e.g. vulcanising, of macromolecules
-
- 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
- C08J5/18—Manufacture of films or sheets
-
- 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
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/12—Chemical modification
-
- 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
- C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
- C08J7/12—Chemical modification
- C08J7/14—Chemical modification with acids, their salts or anhydrides
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/18—Regenerative fuel cells, e.g. redox flow batteries or secondary fuel cells
- H01M8/184—Regeneration by electrochemical means
- H01M8/188—Regeneration by electrochemical means by recharging of redox couples containing fluids; Redox flow type batteries
-
- 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
- C08J2361/00—Characterised by the use of condensation polymers of aldehydes or ketones; Derivatives of such polymers
- C08J2361/04—Condensation polymers of aldehydes or ketones with phenols only
- C08J2361/06—Condensation polymers of aldehydes or ketones with phenols only of aldehydes with phenols
- C08J2361/14—Modified phenol-aldehyde condensates
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- General Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Inorganic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Sustainable Development (AREA)
- Sustainable Energy (AREA)
- Electrochemistry (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
Abstract
The invention belongs to high molecular functional field of membrane material, and in particular to a kind of non-fluorine ion exchange membrane and its preparation method and application.The present invention is reacted using the phenolic compound containing carbon-carbon double bond or triple carbon-carbon bonds with formaldehyde, alkali metal hydroxide, then the amberplex obtained by sulfonating agent sulfonation has preferable mechanical performance, compared with high ion exchange volume and good battery efficiency.Method preparation condition provided by the invention is mild, technique is relatively easy, raw material sources are extensive, synthesis cost is cheap, is suitble to heavy industrialization application.
Description
Technical field
The invention belongs to high molecular functional field of membrane material, and in particular to flow battery amberplex and its preparation side
Method and application.
Background technique
Currently, the amberplex of non-fluorine type is increasingly becoming the hot spot of research due to its low raw-material cost, it is not of the same race
The non-fluorine ion exchange membrane of class, which is developed, to be prepared.Chinese patent CN 103515634B provides a kind of sulfonated poly aryl ether ketone
The synthesis preparation method of amberplex；Chinese patent CN 104804207B provides a kind of polyethers ether of side group containing imidazole salts
Sulfone anion-exchange membrane；Document (Electrochimica Acta 2014,150,114-122) provides a kind of sulfonated polyamide
The cation-exchange membrane of type；Document (Journal of Membrane Science 2009,342,215-220) provides one
Kind method of two steps radiation grafting on ETFE basement membrane obtains non-fluorine amphoteric ion exchange membrane.Although non-fluorine ion obtained above
Exchange membrane can preferably be applied to vanadium battery field, but very big ratio is still occupied in the overall cost of entire vanadium cell system
Example, and the amberplex raw material sources of above method preparation are narrow, also further limit the application in the field.Therefore exist
While guaranteeing that amberplex has preferable mechanical strength, ion exchange capacity and higher battery performance, exploitation one
The non-fluorine ion exchange membrane that kind raw material sources are wide, price is cheaper becomes research hotspot.
Summary of the invention
To make up the deficiencies in the prior art, it is extensive, at low cost, good mechanical property non-that the present invention provides a kind of raw material sources
The preparation method of fluorine ion exchange membrane.The amberplex is by the phenolic compound containing carbon-carbon double bond or triple carbon-carbon bonds, formaldehyde
Aqueous solution, thermal decomposition initiating and sulfonating agent are prepared.
Technical solution of the present invention is as follows, a kind of preparation method of non-fluorine ion exchange membrane, comprising the following steps:
(1) phenolic compound, formalin, alkali metal hydroxide are mixed, in atmosphere of inert gases, 90-120 DEG C
Under the conditions of reaction until obtain yellow gummy solid and generate foam, stop heating, after being cooled to 0-30 DEG C, take out solid system
At powder；
(2) sulfonating agent is added to powder obtained in (1), the abundant sulfonation at 40-60 DEG C will after being cooled to 0-30 DEG C
Above-mentioned reaction solution is added dropwise in precipitating reagent, and precipitating obtains solid, is filtered, washed, is dried, obtains solid powder；
(3) solid powder is dissolved in organic solvent, thermal decomposition initiating is added and carries out cross-linked polymeric, it is molten by what is obtained
Non- fluorine ion exchange membrane is made by being cast casting method in liquid；
The molar ratio of content of formaldehyde and phenolic compound is (1.2-2.0) in the formalin: 1, to ensure
The performance of film is best, preferably (1.5-1.7): 1；The molar ratio of the phenolic compound and alkali metal hydroxide is (1-
10): 1；The thermal decomposition initiating and the molar ratio of phenolic compound are (0.05-0.2): 1；Phenolic compound is to contain 8-12
The unsaturated phenol of a carbon atom, it is preferred that the phenolic compound has the structure as shown in formula I or formula II；
Wherein, R1To R6For H atom or the alkyl containing 1-4 carbon atom.
The thermal decomposition initiating is the mixing of one or more of azo-initiator, peroxide type initiators
Object；Such as azodiisobutyronitrile, azobisisoheptonitrile, benzoyl peroxide.The sulfonating agent is in the concentrated sulfuric acid or oleum
One kind.The alkali metal hydroxide is NaOH or KOH.The precipitating reagent is preferably without water-ice ether.
The step (1) further includes constantly isolating the moisture in system with oil water separator until producing in reaction process
The colloidal solid of raw yellow.
Need that excessive no water-ice ether is added in the step (2), that is, account for 5-20 times of reaction solution volume without water-ice ether.
Organic solvent is any polar high-boiling solvent in the step (3), such as dimethyl sulfoxide (DMSO), dimethyl
Formamide, metacresol, glycol monoethyl ether, N-Methyl pyrrolidone, 1,3-Dimethyl-2-imidazolidinone, preferably dimethyl are sub-
Sulfone.
The step (3) further includes being handled with 3% hydrogen peroxide and 0.5mol/L dilute sulfuric acid, is finally washed with distilled water to
Property, obtain non-fluorine ion exchange membrane.
Another object of the present invention is the non-fluorine ion exchange membrane that above method preparation is claimed.
Third purpose of the present invention is that the non-fluorine ion exchange membrane of above method preparation is claimed in flow battery
Using application especially in all-vanadium flow battery.
Compared with prior art, beneficial effects of the present invention are as follows:
(1) that the present invention provides a kind of preparation conditions is mild, technique is relatively easy, raw material sources are extensive, synthesis cost is low
It is honest and clean, it is suitble to the preparation method of the non-fluorine ion exchange membrane of heavy industrialization application；
(2) present invention is using the phenolic compound containing carbon-carbon double bond or triple carbon-carbon bonds and formaldehyde, alkali metal hydroxide
The amberplex that reaction obtains has preferable mechanical performance, compared with high ion exchange volume and good battery efficiency.
Specific embodiment
The present invention is described in detail below by specific embodiment, but is not limited the scope of the invention.Unless otherwise specified, originally
Experimental method used by inventing is conventional method, and experiment equipment used, material, reagent etc. can chemically company be bought.
The thickness of ionic membrane is tested by Fisher Thickness measuring instrument, and each sample surveys 50 values in different location and asks flat
Mean value；
The test reference standard GB/T 1040.3-2006 " plastic tensile of the tensile strength of ionic membrane, elongation at break
The measurement third portion of energy: the experimental condition of film and thin slice ", it is 10mm that film, which is cut into width, and the initial spacing of fixture is 50mm's
Strip is tested with the rate of extension of 200mm/min；
The all-vanadium liquid flow energy storage battery performance test conditions of ionic membrane: being 80mA/cm in current density2Under the conditions of filled
Discharge test charges to 1.55V, is discharged to 1.00V, is made using the graphite carbon felt that Beijing Jing Longte carbon Science and Technology Ltd. produces
For reaction electrode, the effective work area of electrode is 48cm2, positive and negative anodes electrolyte is respectively VO2+/VO2 +And V2+/V3+Sulfuric acid it is molten
Liquid, battery operating temperature are 37 DEG C.
The test method of the ion exchange capacity of intermediate ion exchange membrane of the present invention GB/T 20042.3- according to national standards
2009 " Proton Exchange Membrane Fuel Cells proton exchange membrane test methods " execute, and the reciprocal value of resulting ion-exchange equivalent is
Ion exchange capacity value.
Embodiment 1
By 120g 4-Vinyl phenol (1mol), 97.3g mass fraction be 37% formalin (formaldehyde 1.2mol),
40gNaOH powder is added in 500mL there-necked flask, installs oil water separator, is stirred continuously down in 110 DEG C of reaction 3h, during which not
Break and isolate moisture, until generating foam yellow colloidal solid in system, stops heating, cooling, taking-up yellow solid, dry,
It smashs to pieces.Then obtained solid powder is added in the concentrated sulfuric acid of 3 times of powder qualities, is stirred to react at 50 DEG C for 24 hours, it is cooling
To room temperature, above-mentioned reaction solution is added dropwise in excessive no water-ice ether, precipitating obtains solid, filters and more with ether
Secondary washing, it is dry, obtain solid powder；Above-mentioned powder is dissolved in dimethyl sulphoxide solution, obtaining mass fraction is
8.21g azodiisobutyronitrile is added in the solution of 15wt%, is stirred continuously at 80 DEG C and carries out further cross-linked polymeric.It is sufficiently anti-
Obtained solution (15wt%) is made by curtain coating casting method with a thickness of 50 ± 2 μm of amberplexes, reuses 3% by Ying Hou
After the processing of the dilute sulfuric acid of hydrogen peroxide and 0.5mol/L, vanadium cell of the present invention is obtained with non-fluorine ion exchange membrane.
In the present embodiment, the molar ratio of formaldehyde and 4-Vinyl phenol is 1.2:1, mole of 4-Vinyl phenol and NaOH
Than for 1:1, the molar ratio of thermal decomposition initiating azo-bis-isobutyl cyanide and 4-Vinyl phenol is 0.05:1.
Embodiment 2
The present embodiment the difference from embodiment 1 is that, the dosage of formalin that mass fraction is 37% is changed to
121.8g is made at this point, the molar ratio of formaldehyde and 4-Vinyl phenol is 1.5:1 with a thickness of 50 ± 2 μm of amberplexes；
Embodiment 3
The present embodiment the difference from embodiment 1 is that, the dosage of formalin that mass fraction is 37% is changed to
130.0g is made at this point, the molar ratio of formaldehyde and 4-Vinyl phenol is 1.6:1 with a thickness of 50 ± 2 μm of amberplexes；
Embodiment 4
The present embodiment the difference from embodiment 1 is that, the dosage of formalin that mass fraction is 37% is changed to
138.0g is made at this point, the molar ratio of formaldehyde and 4-Vinyl phenol is 1.7:1 with a thickness of 50 ± 2 μm of amberplexes；
Embodiment 5
The present embodiment the difference from embodiment 1 is that, the dosage of formalin that mass fraction is 37% is changed to
162.2g is made at this point, the molar ratio of formaldehyde and 4-Vinyl phenol is 2:1 with a thickness of 50 ± 2 μm of amberplexes；
Embodiment 6
The present embodiment the difference from embodiment 1 is that, the quality of NaOH powder is changed to 8g, at this point, 4-Vinyl phenol
Molar ratio with NaOH is 5:1；It is made with a thickness of 50 ± 2 μm of amberplexes；
Embodiment 7
The present embodiment the difference from embodiment 1 is that, the quality of NaOH powder is changed to 4g, at this point, 4-Vinyl phenol
Molar ratio with NaOH is 10:1；It is made with a thickness of 50 ± 2 μm of amberplexes；
Embodiment 8
By 134g 4- isopropenyl phenol (1mol), formalin that 97.3g mass fraction is 37%, (content of formaldehyde is
1.2mol), 14g KOH powder is added in 500mL there-necked flask, installs oil water separator, is stirred continuously down and reacts at 115 DEG C
During which 5h constantly isolates moisture, until generating foam yellow colloidal solid in system, stop heating, cooling, and it is solid to take out yellow
Body, drying are smashed to pieces.Then obtained solid powder is added to the concentrated sulfuric acid of 3 times of powder qualities, be stirred to react at 50 DEG C
For 24 hours, after being cooled to room temperature, above-mentioned reaction solution is added dropwise in excessive no water-ice ether, precipitating obtains solid, and filtering is simultaneously
It is repeatedly washed with ether, it is dry, obtain solid powder；Above-mentioned powder is dissolved in dimethyl sulphoxide solution, quality point is obtained
Number is the solution of 15wt%, and 24.2g benzoyl peroxide is added, and is stirred continuously at 120 DEG C and carries out further cross-linked polymeric.It fills
After dividing reaction, obtained solution (15wt%) is made by curtain coating casting method with a thickness of 50 ± 2 μm of amberplexes, is reused
After the processing of the dilute sulfuric acid of 3% hydrogen peroxide and 0.5mol/L, vanadium cell of the present invention is obtained with non-fluorine ion exchange membrane.
In the present embodiment, the molar ratio of formaldehyde and 4- isopropenyl phenol is 1.2:1,4- isopropenyl phenol and KOH's
Molar ratio is 4:1, and the molar ratio of thermal decomposition initiating benzoyl peroxide and 4-Vinyl phenol is 0.1:1.
Embodiment 9
By 132g, to propinyl phenol (1mol), formalin that 97.3g mass fraction is 37%, (content of formaldehyde is
1.2mol), 56g KOH powder is added in 500mL there-necked flask, installs oil water separator, is stirred continuously down and reacts at 105 DEG C
During which 6h constantly isolates moisture, until generating foam yellow colloidal solid in system, stop heating, cooling, and it is solid to take out yellow
Body, drying are smashed to pieces.Then obtained solid powder is added to the concentrated sulfuric acid of 3 times of powder qualities, be stirred to react at 50 DEG C
For 24 hours, after being cooled to room temperature, above-mentioned reaction solution is added dropwise in excessive no water-ice ether, precipitating obtains solid, and filtering is simultaneously
It is repeatedly washed with ether, it is dry, obtain solid powder；Above-mentioned powder is dissolved in dimethyl sulphoxide solution, quality point is obtained
Number is the solution of 15wt%, and 49.6g azobisisoheptonitrile is added, and is stirred continuously at 70 DEG C and carries out further cross-linked polymeric.It fills
After dividing reaction, obtained solution (15wt%) is made by curtain coating casting method with a thickness of 50 ± 2 μm of amberplexes, is reused
After the processing of the dilute sulfuric acid of 3% hydrogen peroxide and 0.5mol/L, vanadium cell of the present invention is obtained with non-fluorine ion exchange membrane.
In the present embodiment, effective formaldehyde be 1.2:1 to the molar ratio of propinyl phenol, to propinyl phenol and KOH
Molar ratio is 1:1, and the molar ratio of thermal decomposition initiating benzoyl peroxide and 4-Vinyl phenol is 0.2:1.
Comparative example 1
Without using formaldehyde as crosslinking agent, other conditions are identical with embodiment 1, are made with a thickness of 50 ± 2 μm of ion exchanges
Film；Comparative example 2
Polymerization crosslinking reaction not being carried out under initiator effect, other conditions are identical with embodiment 1, be made with a thickness of 50 ±
2 μm of amberplexes；
The amberplex of non-fluorine ion exchange membrane, comparative example 1-2 preparation prepared by 1-9 of the embodiment of the present invention and the U.S.
The Nafion series membranes of E.I.Du Pont Company's exploitationIt is tested for the property by taking all-vanadium flow battery as an example, test result is such as
Shown in table 1.
The performance data of film prepared by table 1 embodiment 1-9 and comparative example 1-2
From table 1 it follows that non-fluorine ion exchange membrane obtained by the present invention has preferable tensile strength and fracture
Elongation, that is, have preferable mechanical performance, ion exchange capacity also above E.I.Du Pont Company's condition of equivalent thickness perfluorinated sulfonic acid from
Proton exchange, this illustrates that amberplex synthesized by the present invention has preferable ion-exchange capacity and ionic conductivity.
Charge-discharge test by the way that amberplex to be applied to all-vanadium liquid flow energy storage battery is tested, and is found same compared to E.I.Du Pont Company
ThicknessPerfluorinated ion-exchange membrane, the present invention prepared by amberplex energy efficiency with higher, coulomb effect
The experimental data of rate and voltage efficiency, comparative example and embodiment compares it is found that if lacking polymerization crosslinking and crosslinking agent friendship
Join any crosslinking method, all the mechanical performance of amberplex can be made to be greatly lowered, deterioration of cell properties.
The preferable specific embodiment of the above, only the invention, but the protection scope of the invention is not
It is confined to this, anyone skilled in the art is in the technical scope that the invention discloses, according to the present invention
The technical solution of creation and its inventive concept are subject to equivalent substitution or change, should all cover the invention protection scope it
It is interior.
Claims (13)
1. a kind of preparation method of non-fluorine ion exchange membrane, which comprises the following steps:
(1) phenolic compound, formalin, alkali metal hydroxide are mixed, in atmosphere of inert gases, 90-120 DEG C of condition
Until obtaining yellow gummy solid and generating foam, stopping heating after being cooled to 0-30 DEG C, takes out solid and powder is made for lower reaction
End；
(2) sulfonating agent is added to powder obtained in (1), the abundant sulfonation at 40-60 DEG C after being cooled to 0-30 DEG C, will react
Liquid is added dropwise in precipitating reagent, is precipitated, is filtered, washed, is dried, obtains solid powder；
(3) solid powder is dissolved in organic solvent, thermal decomposition initiating is added and carries out cross-linked polymeric, obtained solution is led to
It crosses curtain coating casting method and non-fluorine ion exchange membrane is made；
The molar ratio of the formaldehyde and phenolic compound is (1.2-2.0): 1；The phenolic compound and alkali metal hydroxide
Molar ratio be (1-10): 1；The thermal decomposition initiating and the molar ratio of phenolic compound are (0.05-0.2): 1；Phenol generalization
Conjunction object is the unsaturated phenol containing 8-12 carbon atom.
2. the method according to claim 1, wherein the phenolic compound has as shown in formula I or formula II
Structure；
Wherein, R1To R6For H atom or the alkyl containing 1-4 carbon atom.
3. method according to claim 1 or 2, which is characterized in that the molar ratio of formaldehyde and phenolic compound is (1.5-
1.7): 1.
4. method according to claim 1 or 2, which is characterized in that the sulfonating agent is in the concentrated sulfuric acid or oleum
It is a kind of.
5. method according to claim 1 or 2, which is characterized in that the alkali metal hydroxide is NaOH or KOH.
6. method according to claim 1 or 2, which is characterized in that the thermal decomposition initiating is azo-initiator, mistake
One of oxide-based initiator or more than one.
7. method according to claim 1 or 2, which is characterized in that the precipitating reagent is no water-ice ether.
8. the method according to the description of claim 7 is characterized in that accounting for reaction solution volume without water-ice ether in the step (2)
5-20 times.
9. method according to claim 1 or 2, which is characterized in that organic solvent is dimethyl sulfoxide, dimethyl formyl
It is amine, metacresol, glycol monoethyl ether, N-Methyl pyrrolidone, one or more kinds of in 1,3- dimethyl-2-imidazolinone.
10. according to the method described in claim 9, it is characterized in that, organic solvent is dimethyl sulfoxide.
11. method according to claim 1 or 2, which is characterized in that the step (1) specifically: by phenolic compound plus
Enter in NaOH the or KOH alkaline aqueous solution dissolved with formaldehyde, in atmosphere of inert gases, reacts, reacted under the conditions of 90-120 DEG C
Cheng Zhong constantly isolates the moisture in system, until obtaining the colloidal solid of yellow and generating foam, stops heating, cooling
To room temperature, takes out wherein solid and smash to pieces to obtain powder.
12. the non-fluorine ion exchange membrane of any method preparation of claim 1-11.
13. application of the non-fluorine ion exchange membrane of any method preparation of claim 1-11 in flow battery.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711473747.9A CN109988327A (en) | 2017-12-29 | 2017-12-29 | A kind of non-fluorine ion exchange membrane and its preparation method and application |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711473747.9A CN109988327A (en) | 2017-12-29 | 2017-12-29 | A kind of non-fluorine ion exchange membrane and its preparation method and application |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN109988327A true CN109988327A (en) | 2019-07-09 |
Family
ID=67109557
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201711473747.9A Pending CN109988327A (en) | 2017-12-29 | 2017-12-29 | A kind of non-fluorine ion exchange membrane and its preparation method and application |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109988327A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111013669A (en) * | 2019-12-04 | 2020-04-17 | 大连融科储能技术发展有限公司 | Cation exchange membrane and preparation method and application thereof |
| CN112909277A (en) * | 2020-12-31 | 2021-06-04 | 大连融科储能技术发展有限公司 | Ion exchange membrane and preparation method and application thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105932317A (en) * | 2016-04-22 | 2016-09-07 | 宁波高新区夏远科技有限公司 | Preparation method of ion exchange membrane used in vanadium battery |
| CN107394240A (en) * | 2017-06-02 | 2017-11-24 | 南京工业大学 | Preparation method and application of sulfonated polyaryletherketone ion exchange membrane |
-
2017
- 2017-12-29 CN CN201711473747.9A patent/CN109988327A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105932317A (en) * | 2016-04-22 | 2016-09-07 | 宁波高新区夏远科技有限公司 | Preparation method of ion exchange membrane used in vanadium battery |
| CN107394240A (en) * | 2017-06-02 | 2017-11-24 | 南京工业大学 | Preparation method and application of sulfonated polyaryletherketone ion exchange membrane |
Non-Patent Citations (2)
| Title |
|---|
| 李文友等: "《有机化学》", 31 July 2017, 中国农业大学出版社 * |
| 龚志宇等: "《新型燃料电池用质子交换膜的合成和性能研究》", 31 December 2011, 吉林大学出版社 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111013669A (en) * | 2019-12-04 | 2020-04-17 | 大连融科储能技术发展有限公司 | Cation exchange membrane and preparation method and application thereof |
| CN111013669B (en) * | 2019-12-04 | 2022-09-06 | 大连融科储能技术发展有限公司 | Cation exchange membrane and preparation method and application thereof |
| CN112909277A (en) * | 2020-12-31 | 2021-06-04 | 大连融科储能技术发展有限公司 | Ion exchange membrane and preparation method and application thereof |
| CN112909277B (en) * | 2020-12-31 | 2022-02-11 | 大连融科储能技术发展有限公司 | Ion exchange membrane and preparation method and application thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN110336052B (en) | Mixed matrix type cation exchange membrane and preparation method thereof | |
| AU2009324261B2 (en) | Polymer blend proton exchange membrane and method for manufacturing the same | |
| CN110903449A (en) | Isatin arene copolymer, preparation method and application | |
| JPH1045913A (en) | High-molecular electrolyte, its production and fuel cell made by using the same | |
| CN109096473B (en) | Aromatic piperidine amphoteric ion exchange membrane without aryl ether bond and preparation method thereof | |
| CN108899566B (en) | Tertiary amino amphoteric ion exchange membrane and preparation method thereof | |
| JPH11116679A (en) | Polymer electrode, polymer electrode membrane, and fuel battery | |
| JPH1021943A (en) | Polymer electrolytic substance for fuel cell, and fuel cell | |
| WO2016095237A1 (en) | N1-substituted imidazole compound, and alkaline anion exchange membrane and preparation | |
| Khataee et al. | Poly (arylene alkylene) s functionalized with perfluorosulfonic acid groups as proton exchange membranes for vanadium redox flow batteries | |
| Zhang et al. | High proton-conducting polymer electrolytes based on pendent poly (arylene ether ketone) with H-bond for proton exchange membranes | |
| CN107383404A (en) | A kind of preparation method of fluorine-containing branched sulphonated polyimides proton conductive membrane | |
| CN109988327A (en) | A kind of non-fluorine ion exchange membrane and its preparation method and application | |
| CN103319741B (en) | Preparation method of sulfonated polyimide/titanium dioxide composite proton conductive membrane | |
| CN110437438A (en) | A kind of intensive sulfonated fluoropolymers polyarylether proton exchange membrane and preparation method thereof for all-vanadium flow battery | |
| CN103709379B (en) | aromatic sulfonated polyketone and preparation method thereof | |
| CN115477720B (en) | Heterocyclic quaternary ammonium salt functionalized perfluorinated anion exchange resin, preparation method thereof and ion exchange membrane with heterocyclic quaternary ammonium salt functionalized perfluorinated anion exchange resin | |
| CN115368492B (en) | Long side chain perfluorinated anion exchange resin, preparation method thereof and ion exchange membrane containing same | |
| CN112820921A (en) | Nafion/g-C3N4Composite membrane and preparation method and application thereof | |
| KR101372071B1 (en) | Polysulfone-based polymer, electrolyte membrane comprising the same, and method for preparing the polymer | |
| CN108929407A (en) | A kind of cation-exchange membrane and its preparation method and application based on beta-cyclodextrin cross-linked polymer | |
| Shen et al. | Modifying microphase separation of PVA based membranes for improving proton/methanol selectivity | |
| CN108912362A (en) | A kind of polyamine functional polybenzimidazoles cross linking membrane and preparation method | |
| JP6028963B2 (en) | Method for producing polymer electrolyte | |
| Fang et al. | Low methanol permeable sulfonated poly (phthalazinone ether sulfone) membranes for DMFCs |
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 | ||
| WD01 | Invention patent application deemed withdrawn after publication | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20190709 |