CN103540951A - Ion exchange membrane for electrolysis of oxygen cathode and preparation method thereof - Google Patents
Ion exchange membrane for electrolysis of oxygen cathode and preparation method thereof Download PDFInfo
- Publication number
- CN103540951A CN103540951A CN201310537577.1A CN201310537577A CN103540951A CN 103540951 A CN103540951 A CN 103540951A CN 201310537577 A CN201310537577 A CN 201310537577A CN 103540951 A CN103540951 A CN 103540951A
- Authority
- CN
- China
- Prior art keywords
- ion
- membrane
- resin
- perfluorinated
- exchange membrane
- 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.)
- Granted
Links
Landscapes
- Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
Abstract
The invention belongs to the technical field of polymer materials and specifically relates to an ion exchange membrane for electrolysis of an oxygen cathode and a preparation method thereof. The ion exchange membrane for electrolysis of the oxygen cathode is a multi-layer composite membrane comprising a perfluorosulfonic acid ion exchange resin layer, a perfluorocarboxylic acid ion exchange resin layer, a reinforcing mesh fabric, a hydrophilic coating and a multifunctional coating, wherein the thickness of the perfluorosulfonic acid resin layer is 80-150 mu m, the thickness of the perfluorocarboxylic acid resin layer is 8-15 mu m, the hydrophilic coating with the thickness of 3-12 mu m is coated on the surface on the anode side of the membrane, and the multifunctional coating with the thickness of 3-12 mu m is coated on the surface on the cathode side of the membrane. The preparation method comprises the following steps: spraying the carboxylic acid side of the ion membrane after transformation by using a dispersion solution containing perfluorosulfonic acid resin, a catalyst and a lower alcohol and drying to form the multifunctional coating. According to the preparation method provided by the invention, the surface of the ion membrane is endowed with a catalytic structure and the function, oxygen is in full contact with the surface of the ion membrane, and reaction is performed on the surface, so that the cell voltage is reduced and the catalytic efficiency is simultaneously improved.
Description
Technical field
The invention belongs to technical field of polymer materials, be specifically related to a kind of ion-exchange membrane for oxygen cathode electrolysis and preparation method thereof.
Background technology
Chlorine industry is produced caustic soda and chlorine by electrolysis brackish water, produces by product hydrogen simultaneously, is the basic chemical industry primary industry that occupies critical role in national economy.Current domestic soda processes is mainly ionic membrane method, and in production cost, power consumption cost accounts for 60%, therefore reduces power consumption and has very important significance for improving chlor-alkali industry economic benefit tool.Fundamentally, the huge current consumption of chlorine industry is to be determined by its chemical reaction itself.Therefore, fundamentally change the electrochemical reaction of electrolysis brackish water, thereby reduce theoretical decomposition voltage, can effectively realize the reduction of power consumption.
Electrode reaction and the electromotive force of the electrolysis of conventional ion film:
Anode: 2Cl
--2e → Cl
2↑
Negative electrode: 2H
2o+2e → H
2↑+2OH
- 
So traditional electrical solution theoretical decomposition voltage is poor is 1.36V-(0.83V)=2.19V.
As far back as the eighties in 20th century, U.S. EletechSystems company starts to utilize the principle of fuel cell gas diffusion electrode to prepare oxygen cathode type ion-exchange membrane electrolyzer.Its cathodic reaction is:
Negative electrode:
Therefore the theoretical decomposition voltage of oxygen cathode technique is poor, be 1.36V-0.40V=0.96V.
Theoretical decomposition voltage is poor: 2.19V-0.96V=1.23V, oxygen cathode technique can be energy-conservation more than 30% in theory, and (oxygen cathode technology has consumed oxygen certainly, and output H not
2).Ion film caustic soda film pole span technology ton alkali energy consumption is 2100kwh, and new oxygen cathode technology ton alkali energy consumption, lower than 1500kwh, receives the concern of chlor-alkali industry with the advantage of ton alkali economize on electricity 600kwh.Take that to produce 300000 tons of caustic soda projects per year be example, if all change oxygen cathode technology into, 1.8kwh every year can economize on electricity.World's chlor-alkali aggregated capacity has reached approximately 8,000 ten thousand tons, Chinese chlor-alkali aggregated capacity account for world's aggregated capacity near half, by this energy-saving effect, calculate, once this technology large-scale industrialization on market is promoted ，Jiang Dui world chlor-alkali general layout, produce great effect.
Current business-like for chlorine industry perfluorinated ion-exchange membrane (Membrane Used In Chlor-alkali Cell) be perfluorocarboxylic acid-perfluorinated sulfonic acid composite membrane, the anode side of film is that perfluorinated sulfonic acid layer, cathode side are perfluorocarboxylic acid layer.Sulphonic layer has higher ion and sees through ability, and is in 20%～30%, to have lower bath voltage at alkali concn, thereby can save significantly power consumption; And carboxylic layer can stop OH
-the infiltration migration of ion anode, guarantees higher current efficiency.
Yet, traditional Membrane Used In Chlor-alkali Cell is when for oxygen cathode chloralkali process, the defect that exists some to be difficult to overcome: oxygen can only react at catalysis electrode surface and the annex of electric groove, has increased to a certain extent reaction resistance, has improved bath voltage and has reduced catalytic efficiency simultaneously.
Summary of the invention
For solving the problems of the technologies described above, the present invention proposes a kind of have better catalytic performance and physical strength simultaneously, be applicable to perfluorinated ion-exchange membrane of oxygen cathode electrolysis process and preparation method thereof.
Technical scheme of the present invention is: for the ion-exchange membrane of oxygen cathode electrolysis, and the multilayer complex films that it is comprised of perfluorinated sulfonic acid resinbed, perfluorinated carboxylic acid ion-exchange resin's layer, enhancing screen cloth, hydrophilic coating and multi-functional coatings; Perfluorinated sulfonic resin bed thickness 80-150 micron wherein, perfluorinated carboxylic acid resin's layer is thick 8-15 micron, the hydrophilic coating of film anode side (sulfonic acid side) surface-coated 3-12 micron thick, the multi-functional coatings of film cathode side (carboxylic acid side) surface-coated 3-12 micron thick.
The basement membrane total thickness of described perfluorinated ion-exchange membrane between 90-189 micron, preferred 100-135 micron.
Described perfluorinated sulfonic acid resinbed, adopts current disclosed perfluorinated sulfonic resin material, preferably tetrafluoroethylene and perfluor sulfonyl base vinyl ether (as perfluor 3,6-dioxa-4-methyl-7-octene sulfonic acid fluoride, structural formula is: CF
2=CFOCF
2cF (CF
3) OCF
2cF
2sO
2f) perfluorinated sulfonic resin that copolymerization obtains, exchange capacity is 0.9-1.20mmo1/g.
Described perfluorinated carboxylic acid ion-exchange resin's layer, adopts current disclosed perfluorinated carboxylic acid resin's material, preferably tetrafluoroethylene and a small amount of perfluorocarboxylic acid ester vinyl ether (as perfluor 4,7-dioxa-5 methyl-8-nonenoic acid methyl esters, structural formula is: CF
2=CFOCF
2cF (CF
3) OCF
2cF
2cOOCH
3) polymkeric substance that copolymerization forms, loading capacity is 0.9-1.05mmol/g.
Described enhancing screen cloth comprises fortifying fibre, fortifying fibre is selected from: tetrafluoroethylene (PTFE) fiber, perfluoroethylene-propylene fiber, Ion Exchange Fiber (CN101003588), one or more in poly-perfluoro propyl vinyl ether fiber, tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer fibre fluorocarbon polymer fiber.
Described hydrophilic coating is by be coated in dry forming after ion exchange resin membrane surface containing nano inorganic oxide-lower alcohol dispersion liquid of perfluorinated sulfonic resin, preferably ethanol or propyl alcohol of lower alcohol wherein, and nano inorganic oxide is ZrO preferably
2.
Described multi-functional coatings is by be coated in dry forming after ion exchange resin membrane surface containing nano inorganic oxide-catalyzer-lower alcohol dispersion liquid of perfluorinated sulfonic resin, wherein catalyzer is redox catalyst, preferably the nano-silver powder of particle diameter 10-60nm or silver-colored line; Lower alcohol is ethanol or propyl alcohol preferably, and nano inorganic oxide is ZrO preferably
2.The effect of multi-functional coatings is: hydrophilic, air release and catalysis.
Ion-exchange membrane for oxygen cathode electrolysis of the present invention, its preparation methods steps is as follows:
A, described perfluorinated carboxylic acid resin, the perfluorinated sulfonic resin of employing, prepare perfluorinated ion exchange resin basement membrane by melting co-extrusion or the compound technique of multi hot press;
Enhancing screen cloth is inserted to ion exchange fluoro resin membrane surface for b, employing continous vacuum recombining process or inner formation strengthens ionic membrane;
C, the enhancing ionic membrane of step b gained is hydrolyzed to 6-12 hour in the KOH of the massfraction 25% of 90 ℃ (or NaOH) water-organic solvent solution makes the transition;
D, with containing massfraction 3-10% perfluorinated sulfonic resin, 5-15% nano inorganic oxide-lower alcohol dispersion liquid, the ionic membrane sulfonic acid side after to transition sprays, form hydrophilic coating after dry;
E, with containing nano inorganic oxide-catalyzer-lower alcohol dispersion liquid (mass ratio (3-12): (1-10): (88-96)) of perfluorinated sulfonic resin, the ionic membrane carboxylic acid side after to transition sprays, form multi-functional coatings after dry;
F, spray complete film and be immersed in massfraction 0.2%-2% aqueous sodium hydroxide solution, after standing aging 2-24 hour, obtain oxygen cathode electrolysis ion-exchange membrane of the present invention.
In above-mentioned steps c, organic solvent is a kind of in ethanol, Virahol or DMSO.
In above-mentioned steps d and e, the preferred ZrO of nano inorganic oxide
2, a kind of in lower alcohol preferred alcohol, propyl alcohol and Virahol.
In above-mentioned steps e, catalyzer is redox catalyst, and the nano-silver powder of preferable particle size 10-60nm or diameter are 15～300nm, length 10～200 μ m silver lines.
Ion-exchange membrane for oxygen cathode electrolysis prepared by the present invention, can the Membrane Used In Chlor-alkali Cell electrolyzer for oxygen cathode electrolysis process on.
Beneficial effect of the present invention is: by catalytic structure and function endowing ionic membrane surface, keep ion film strength and thickness simultaneously.Like this, both can keep film strength and conductivity, can give again ionic membrane surface with catalytic performance, fully adapt to oxygen cathode chloralkali process.Oxygen and ionic membrane surface fully contacts and in its surface reaction, has reduced bath voltage and has improved catalytic efficiency simultaneously.
Embodiment
Below in conjunction with embodiment, illustrate the present invention.
Embodiment 1:
(1) preparation of resin granular material
Perfluorinated sulfonic resin is tetrafluoroethylene and perfluor 3, and 6-dioxa-4-methyl-7-octene sulfonic acid fluoride carries out the powder that in-situ polymerization obtains, and loading capacity is 0.95mmol/g.Tetrafluoroethylene and perfluor 4, the powder that the methyl-8-nonenoic acid methyl esters copolymerization of 7-dioxa-5 obtains, loading capacity is 0.95mmol/g.Perfluorinated sulfonic resin powder and perfluorinated carboxylic acid resin's powder obtain pellet separately through melt extruding granulation respectively.
(2) preparation of film and enhancing
Adopt above-mentioned perfluorinated carboxylic acid resin's pellet, perfluorinated sulfonic resin pellet, by melting coextrusion processes, prepare perfluorinated ion exchange resin basement membrane; Then adopt continous vacuum recombining process that PTFE is strengthened to screen cloth and insert the inner enhancing ionic membrane that forms of perfluorinated ion exchange resin basement membrane;
(3) transition of film and surface treatment
Step (2) gained ionic membrane is hydrolyzed to 6 hours in the massfraction 25%NaOH-water-aqueous isopropanol of 90 ℃ to make the transition; With containing massfraction 5% perfluorinated sulfonic resin, 10% nano inorganic oxide-alcohol dispersion liquid, the dried ionic membrane sulfonic acid side that makes the transition being sprayed, the dry rear air release coating that forms; By the silver powder-alcohol dispersion liquid containing massfraction 5% perfluorinated sulfonic resin, 7% particle diameter 15nm, the dried ionic membrane carboxylic acid side that makes the transition is sprayed the dry rear multi-functional coatings that forms; Spray complete film and be immersed in massfraction 0.2% aqueous sodium hydroxide solution, after standing aging 24 hours, obtain oxygen cathode electrolysis ion-exchange membrane of the present invention.
The ionic membrane tensile strength of embodiment 1 preparation is 35MPa, can be for the ion-exchange membrane in ion-exchange membrane electrolyzer for chlor-alkali production, at 4.5kA/m
2the oxygen cathode condition of current density under, negative electrode NaOH solution quality specific concentration 32%, anode enter groove salt solution NaCl concentration 305g/L, go out under the condition of groove salt solution NaCl concentration 210g/L, 85～87 ℃ of groove temperature, activated cathode, 1mm pole span to test, bath voltage is 2.16-2.19V, current efficiency 97.5%.
Embodiment 2:
(1) preparation of resin granular material
Perfluorinated sulfonic resin is tetrafluoroethylene, R 1216 and perfluor 3, the powder that the copolymerization of 6-dioxa-4-methyl-7-octene sulfonic acid fluoride obtains, and loading capacity is 0.98mmol/g, resin powder is melt extruded to granulation and obtain the pellet containing perfluorinated sulfonic resin.Tetrafluoroethylene and perfluor 4, the powder that the methyl-8-nonenoic acid methyl esters copolymerization of 7-dioxa-5 obtains, loading capacity is 0.93mmol/g, obtains perfluorinated carboxylic acid resin's pellet through melt extruding granulation.
(2) preparation of film and enhancing
Adopt above-mentioned perfluorinated carboxylic acid resin's pellet, perfluorinated sulfonic resin pellet, by melt extruding, obtain respectively perfluorocarboxylic acid and perfluorinated sulfonic acid ion exchange resin membrane; Then adopt the compound screen cloth that again PTFE strengthened of multi hot press to insert the inner enhancing ionic membrane that forms of perfluorinated ion exchange resin basement membrane;
(3) transition of film and surface treatment
Step (2) gained enhancing ionic membrane is hydrolyzed to 12 hours in massfraction 25%KOH water-DMSO solution of 90 ℃ to make the transition; Respectively with contain massfraction 4% perfluorinated sulfonic resin, 8% nano inorganic oxide-alcohol dispersion liquid and make the transition dried ionic membrane sulfonic acid side and carboxylic acid side are sprayed, are dried containing long 10～25 μ m silver line-propanol dispersion liquors (mass ratio 6:8:86) of perfluorinated sulfonic resin-diameter 25nm simultaneously; Spray complete film and be immersed in 2% aqueous sodium hydroxide solution, after standing aging 4 hours, obtain oxygen cathode electrolysis ion-exchange membrane of the present invention.
The ionic membrane tensile strength of embodiment 2 preparations is 34MPa, can be for the ion-exchange membrane in ion-exchange membrane electrolyzer for chlor-alkali production, at 5.5kA/m
2the oxygen cathode condition of current density under, negative electrode NaOH solution quality specific concentration 32%, anode enter groove salt solution NaCl concentration 305g/L, go out groove salt solution NaCl concentration 205g/L, test under the condition of 85～87 ℃ of groove temperature, activated cathode, zero pole span, bath voltage is 2.26-2.32V, current efficiency 97.7%.
Embodiment 3:
Step (1), step (2) are identical with embodiment 1 with step (3), and the size distribution of different is nano-silver powder in step (1) is in 25-45 nanometer.
The ionic membrane tensile strength of embodiment 3 preparations is 33MPa, can be for the ion-exchange membrane in ion-exchange membrane electrolyzer for chlor-alkali production, at 5.5kA/m
2current density under, negative electrode NaOH solution quality specific concentration 32%, anode enter groove salt solution NaCl concentration 305g/L, go out under the condition of groove salt solution NaCl concentration 210g/L, 85～87 ℃ of groove temperature, activated cathode, 1mm pole span to test, bath voltage is 2.24-2.31V, current efficiency 96.7%.Embodiment 4:
Step (1), step (2) are identical with embodiment 1 with step (3), and different is in step (3), with containing massfraction 9% perfluorinated sulfonic resin, 8wt% nano inorganic oxide-alcohol dispersion liquid, the dried ionic membrane that makes the transition being carried out to double-face spray painting.
The ionic membrane tensile strength of embodiment 4 preparations is 32MPa, can be for the ion-exchange membrane in ion-exchange membrane electrolyzer for chlor-alkali production, at 5kA/m
2current density under, negative electrode NaOH liquid quality fraction 32%, anode enter groove salt solution NaCl concentration 305g/L, go out groove salt solution NaCl concentration 205g/L, test under the condition of 85～87 ℃ of groove temperature, activated cathode, zero pole span, bath voltage is 2.21-2.25V, current efficiency 96.8%.
Embodiment 5:
Step (1), step (2) are identical with embodiment 1 with step (3), and different is in step (1), and perfluorinated sulfonic resin loading capacity is that 1.15mmol/g, perfluorinated carboxylic acid resin's loading capacity are 0.99mmol/g.
The ionic membrane tensile strength of embodiment 5 preparations is 30MPa, can be for the ion-exchange membrane in ion-exchange membrane electrolyzer for chlor-alkali production, at 4.8kA/m
2current density under, negative electrode NaOH liquid quality fraction 32%, anode enter groove salt solution NaCl concentration 305g/L, go out groove salt solution NaCl concentration 210g/L, test under the condition of 86 ℃ of groove temperature, activated cathode, zero pole span, bath voltage is 2.18-2.21V, current efficiency 96.5%.
Embodiment 6:
Step (1), step (2) are identical with embodiment 2 with step (3), and different is in step (1), and perfluorinated sulfonic resin loading capacity is that 0.94mmol/g, perfluorinated carboxylic acid resin's loading capacity are 1.05mmol/g.
The ionic membrane tensile strength of embodiment 6 preparations is 32MPa, can be for the ion-exchange membrane in ion-exchange membrane electrolyzer for chlor-alkali production, at 5kA/m
2current density under, negative electrode NaOH solution quality specific concentration 32%, anode enter groove salt solution NaCl concentration 305g/L, go out groove salt solution NaCl concentration 205g/L, test under the condition of 85～87 ℃ of groove temperature, activated cathode, zero pole span, bath voltage is 2.19-2.24V, current efficiency 97.4%.
Embodiment 7:
Step (1), step (2) are identical with embodiment 2 with step (3), and different is in step (1), nano-silver thread diameter 55nm, long 30～180 μ m).
The ionic membrane tensile strength of embodiment 7 preparations is 35MPa, can be for the ion-exchange membrane in ion-exchange membrane electrolyzer for chlor-alkali production, at 4.5kA/m
2current density under, negative electrode NaOH solution quality specific concentration 32%, anode enter groove salt solution NaCl concentration 305g/L, go out groove salt solution NaCl concentration 205g/L, test under the condition of 85～87 ℃ of groove temperature, activated cathode, zero pole span, bath voltage is 2.12-2.14V, current efficiency 97.5%.Embodiment 8:
Step (1), step (2) are identical with embodiment 2 with step (3), and different is in step (3), and nano-silver thread is changed to particle diameter 30nm nano-silver powder and nano-silver thread (diameter 25nm, long 10～25 μ m) mixture (mass ratio 1:1).
The ionic membrane tensile strength of embodiment 8 preparations is 34MPa, can be for the ion-exchange membrane in ion-exchange membrane electrolyzer for chlor-alkali production, at 4.5kA/m
2current density under, negative electrode NaOH solution quality specific concentration 32%, anode enter groove salt solution NaCl concentration 305g/L, go out groove salt solution NaCl concentration 205g/L, test under the condition of 85～87 ℃ of groove temperature, activated cathode, zero pole span, bath voltage is 2.10-2.12V, current efficiency 97.6%.
Claims (10)
1. for an ion-exchange membrane for oxygen cathode electrolysis, it is characterized in that the multilayer complex films that it is comprised of perfluorinated sulfonic acid resinbed, perfluorinated carboxylic acid ion-exchange resin's layer, enhancing screen cloth, hydrophilic coating and multi-functional coatings; The basement membrane total thickness of wherein said perfluorinated ion-exchange membrane is between 90-189 micron, perfluorinated sulfonic resin bed thickness 80-150 micron, perfluorinated carboxylic acid resin's layer is thick 8-15 micron, film anode-side surface applies the hydrophilic coating of 3-12 micron thick, and film cathode-side surface applies the multi-functional coatings of 3-12 micron thick.
2. the ion-exchange membrane for oxygen cathode electrolysis according to claim 1; it is characterized in that; described perfluorinated sulfonic acid resinbed is the perfluorinated sulfonic resin that tetrafluoroethylene and the copolymerization of perfluor sulfonyl base vinyl ether obtain, and exchange capacity is 0.9-1.20mmo1/g.
3. the ion-exchange membrane for oxygen cathode electrolysis according to claim 1, it is characterized in that, described perfluorinated carboxylic acid ion-exchange resin's layer is the polymkeric substance that tetrafluoroethylene and the copolymerization of perfluorocarboxylic acid ester vinyl ether form, and loading capacity is 0.9-1.05mmol/g.
4. the ion-exchange membrane for oxygen cathode electrolysis according to claim 1, it is characterized in that, described hydrophilic coating is by be coated in dry forming after ion exchange resin membrane surface containing nano inorganic oxide-lower alcohol dispersion liquid of perfluorinated sulfonic resin, wherein lower alcohol is ethanol or propyl alcohol, and nano inorganic oxide is ZrO
2.
5. the ion-exchange membrane for oxygen cathode electrolysis according to claim 1, it is characterized in that, described multi-functional coatings is by be coated in dry forming after ion exchange resin membrane surface containing nano inorganic oxide-catalyzer-lower alcohol dispersion liquid of perfluorinated sulfonic resin.
6. the ion-exchange membrane for oxygen cathode electrolysis according to claim 5, it is characterized in that, the described mass ratio containing three kinds of materials in nano inorganic oxide-catalyzer-lower alcohol dispersion liquid of perfluorinated sulfonic resin is: the nano inorganic oxide that contains perfluorinated sulfonic resin: catalyzer; Lower alcohol=(3-12): (1-10): (88-96).
7. the ion-exchange membrane for oxygen cathode electrolysis according to claim 5, is characterized in that, described catalyzer is redox catalyst, and the nano-silver powder of 10-60nm or diameter are 15～300nm, length 10～200 μ m silver lines; Lower alcohol is ethanol or propyl alcohol, and nano inorganic oxide is ZrO
2.
8. according to the ion-exchange membrane for oxygen cathode electrolysis described in claim 1-7 any one, its preparation method is: a, described perfluorinated carboxylic acid resin, the perfluorinated sulfonic resin of employing, by melting co-extrusion or the compound technique of multi hot press, prepare perfluorinated ion exchange resin basement membrane;
Enhancing screen cloth is inserted to ion exchange fluoro resin membrane surface for b, employing continous vacuum recombining process or inner formation strengthens ionic membrane;
C, the enhancing ionic membrane of step b gained is hydrolyzed to 6-12 hour in the KOH of the massfraction 25% of 90 ℃ (or NaOH) water-organic solvent solution makes the transition;
D, with containing massfraction 3-10% perfluorinated sulfonic resin, 5-15% nano inorganic oxide-lower alcohol dispersion liquid, the ionic membrane sulfonic acid side after to transition sprays, form hydrophilic coating after dry;
E, with containing nano inorganic oxide-catalyzer-lower alcohol dispersion liquid of perfluorinated sulfonic resin, the ionic membrane carboxylic acid side after to transition sprays, form multi-functional coatings after dry;
F, spray complete film and be immersed in massfraction 0.2%-2% aqueous sodium hydroxide solution, after standing aging 2-24 hour, obtain oxygen cathode electrolysis ion-exchange membrane of the present invention.
9. the preparation method of the ion-exchange membrane for oxygen cathode electrolysis according to claim 8, is characterized in that: in described step c, organic solvent is a kind of in ethanol, Virahol or DMSO.
10. the preparation method of the ion-exchange membrane for oxygen cathode electrolysis according to claim 8, it is characterized in that: in described step e, the mass ratio that contains three kinds of materials in nano inorganic oxide-catalyzer-lower alcohol dispersion liquid of perfluorinated sulfonic resin is: the nano inorganic oxide that contains perfluorinated sulfonic resin: catalyzer; Lower alcohol=(3-12): (1-10): (88-96).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310537577.1A CN103540951B (en) | 2013-11-04 | 2013-11-04 | A kind of ion exchange membrane for oxygen cathode electrolysis and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310537577.1A CN103540951B (en) | 2013-11-04 | 2013-11-04 | A kind of ion exchange membrane for oxygen cathode electrolysis and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103540951A true CN103540951A (en) | 2014-01-29 |
| CN103540951B CN103540951B (en) | 2016-08-17 |
Family
ID=49964785
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310537577.1A Active CN103540951B (en) | 2013-11-04 | 2013-11-04 | A kind of ion exchange membrane for oxygen cathode electrolysis and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103540951B (en) |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2015184570A1 (en) * | 2014-06-06 | 2015-12-10 | 山东东岳高分子材料有限公司 | Zero pole distance ion exchange membrane and preparation method therefor |
| WO2015184572A1 (en) * | 2014-06-06 | 2015-12-10 | 山东东岳高分子材料有限公司 | Novel ion-conducting membrane used in chlor-alkali industry and preparation method therefor |
| WO2015184571A1 (en) * | 2014-06-06 | 2015-12-10 | 山东东岳高分子材料有限公司 | Ion-conducting membrane and preparation method therefor |
| WO2015184568A1 (en) * | 2014-06-06 | 2015-12-10 | 山东东岳高分子材料有限公司 | Novel ion-conducting membrane and preparation method therefor |
| CN108321417A (en) * | 2018-04-27 | 2018-07-24 | 奇瑞汽车股份有限公司 | A kind of amberplex and preparation method thereof |
| CN111118542A (en) * | 2019-12-31 | 2020-05-08 | 山东东岳未来氢能材料有限公司 | Ultrathin perfluorocarboxylic acid ion exchange membrane with rough coating and preparation method thereof |
| CN111378988A (en) * | 2020-03-31 | 2020-07-07 | 山东东岳高分子材料有限公司 | Preparation method of pre-swelling perfluorinated ion exchange membrane |
| CN112481657A (en) * | 2020-11-16 | 2021-03-12 | 山东东岳高分子材料有限公司 | Fluoride ion exchange membrane for alkali chloride electrolysis having impurity tolerance |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20060199059A1 (en) * | 2005-03-01 | 2006-09-07 | Xu Helen X | Ion conductive polymer electrolyte and its membrane electrode assembly |
| US20100009165A1 (en) * | 2008-07-10 | 2010-01-14 | Zyvex Performance Materials, Llc | Multifunctional Nanomaterial-Containing Composites and Methods for the Production Thereof |
| CN101773788A (en) * | 2009-12-07 | 2010-07-14 | 山东东岳高分子材料有限公司 | Fluorine-containing ion exchange membrane with reinforced sacrificial fiber mesh cloth |
| CN101971394A (en) * | 2008-02-12 | 2011-02-09 | 科学与工业研究委员会 | Composition with enhanced proton conductivity |
| CN102336043A (en) * | 2011-05-27 | 2012-02-01 | 山东东岳高分子材料有限公司 | Ion exchange membrane with high current efficiency, and preparation method and application thereof |
| CN102978654A (en) * | 2012-12-14 | 2013-03-20 | 山东东岳高分子材料有限公司 | Low-resistance and high-strength ion exchange membrane for chlor-alkali industry and preparation method of low-resistance and high-strength ion exchange membrane |
| CN103014757A (en) * | 2012-12-14 | 2013-04-03 | 山东东岳高分子材料有限公司 | Hole-containing fiber reinforced ion exchange membrane for chlor-alkali industry and preparation method thereof |
| CN103031566A (en) * | 2012-12-14 | 2013-04-10 | 山东东岳高分子材料有限公司 | Fiber-reinforced perfluorinated ion exchange membrane containing non-continuous nano-pore canal and preparation method thereof |
-
2013
- 2013-11-04 CN CN201310537577.1A patent/CN103540951B/en active Active
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20060199059A1 (en) * | 2005-03-01 | 2006-09-07 | Xu Helen X | Ion conductive polymer electrolyte and its membrane electrode assembly |
| CN101971394A (en) * | 2008-02-12 | 2011-02-09 | 科学与工业研究委员会 | Composition with enhanced proton conductivity |
| US20100009165A1 (en) * | 2008-07-10 | 2010-01-14 | Zyvex Performance Materials, Llc | Multifunctional Nanomaterial-Containing Composites and Methods for the Production Thereof |
| CN101773788A (en) * | 2009-12-07 | 2010-07-14 | 山东东岳高分子材料有限公司 | Fluorine-containing ion exchange membrane with reinforced sacrificial fiber mesh cloth |
| CN102336043A (en) * | 2011-05-27 | 2012-02-01 | 山东东岳高分子材料有限公司 | Ion exchange membrane with high current efficiency, and preparation method and application thereof |
| CN102978654A (en) * | 2012-12-14 | 2013-03-20 | 山东东岳高分子材料有限公司 | Low-resistance and high-strength ion exchange membrane for chlor-alkali industry and preparation method of low-resistance and high-strength ion exchange membrane |
| CN103014757A (en) * | 2012-12-14 | 2013-04-03 | 山东东岳高分子材料有限公司 | Hole-containing fiber reinforced ion exchange membrane for chlor-alkali industry and preparation method thereof |
| CN103031566A (en) * | 2012-12-14 | 2013-04-10 | 山东东岳高分子材料有限公司 | Fiber-reinforced perfluorinated ion exchange membrane containing non-continuous nano-pore canal and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| 王学军: "全氟磺酸树脂在氯碱膜中的作用机理探析", 《化学世界》 * |
| 董建华: "Ag在质子交换膜燃料电池催化层中富氧作用的研究", 《大连交通大学硕士学位论文》 * |
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2015184570A1 (en) * | 2014-06-06 | 2015-12-10 | 山东东岳高分子材料有限公司 | Zero pole distance ion exchange membrane and preparation method therefor |
| WO2015184572A1 (en) * | 2014-06-06 | 2015-12-10 | 山东东岳高分子材料有限公司 | Novel ion-conducting membrane used in chlor-alkali industry and preparation method therefor |
| WO2015184571A1 (en) * | 2014-06-06 | 2015-12-10 | 山东东岳高分子材料有限公司 | Ion-conducting membrane and preparation method therefor |
| WO2015184568A1 (en) * | 2014-06-06 | 2015-12-10 | 山东东岳高分子材料有限公司 | Novel ion-conducting membrane and preparation method therefor |
| CN108321417A (en) * | 2018-04-27 | 2018-07-24 | 奇瑞汽车股份有限公司 | A kind of amberplex and preparation method thereof |
| CN111118542A (en) * | 2019-12-31 | 2020-05-08 | 山东东岳未来氢能材料有限公司 | Ultrathin perfluorocarboxylic acid ion exchange membrane with rough coating and preparation method thereof |
| CN111118542B (en) * | 2019-12-31 | 2021-07-09 | 山东东岳高分子材料有限公司 | Ultrathin perfluorocarboxylic acid ion exchange membrane with rough coating and preparation method thereof |
| CN111378988A (en) * | 2020-03-31 | 2020-07-07 | 山东东岳高分子材料有限公司 | Preparation method of pre-swelling perfluorinated ion exchange membrane |
| CN111378988B (en) * | 2020-03-31 | 2021-10-22 | 山东东岳高分子材料有限公司 | Preparation method of pre-swelling perfluorinated ion exchange membrane |
| CN112481657A (en) * | 2020-11-16 | 2021-03-12 | 山东东岳高分子材料有限公司 | Fluoride ion exchange membrane for alkali chloride electrolysis having impurity tolerance |
| CN112481657B (en) * | 2020-11-16 | 2021-10-26 | 山东东岳高分子材料有限公司 | Fluoride ion exchange membrane for alkali chloride electrolysis having impurity tolerance |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103540951B (en) | 2016-08-17 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103540951B (en) | A kind of ion exchange membrane for oxygen cathode electrolysis and preparation method thereof | |
| CN102978654B (en) | Low-resistance and high-strength ion exchange membrane for chlor-alkali industry and preparation method of low-resistance and high-strength ion exchange membrane | |
| CN103031566B (en) | Fiber-reinforced perfluorinated ion exchange membrane containing non-continuous nano-pore canal and preparation method thereof | |
| CN103556178B (en) | For the ion-exchange membrane and preparation method thereof of superhigh-current-density oxygen cathode electrolysis | |
| CN103014757B (en) | Hole-containing fiber reinforced ion exchange membrane for chlor-alkali industry and preparation method thereof | |
| CN103556179B (en) | High current density perfluorinated ion-exchange membrane of carbon nano-tube modification and preparation method thereof | |
| Wang et al. | The influence of Ferric ion contamination on the solid polymer electrolyte water electrolysis performance | |
| CN101768758B (en) | Cation permeation composite membrane for electrolysis | |
| WO2017193896A1 (en) | Three-electrode system-based two-step chlorine-alkali electrolytic method and device adopting dual electrolytic cells | |
| EP3527697B1 (en) | Diaphragm for electrolyzing alkaline water, and device for electrolyzing alkaline water | |
| EP3348674A1 (en) | Production method for ion exchange membrane for alkali chloride electrolysis and production method for alkali chloride electrolysis device | |
| CN104388978A (en) | Micro-nano pore-containing chlorine-alkali ion membrane preparation method | |
| WO2015184572A1 (en) | Novel ion-conducting membrane used in chlor-alkali industry and preparation method therefor | |
| CN107075703A (en) | Ion-exchange membrane for alkali chloride electrolysis and alkali chloride electrolysis device | |
| CN1865509A (en) | Novel dipolar membrane and use thereof in electrolysis preparation of ferrate | |
| CN110791773A (en) | Method and device for producing hydrogen by electrolyzing water | |
| Kumar et al. | Heterogeneous–homogeneous composite bipolar membrane for the conversion of salt of homologous carboxylates into their corresponding acids and bases | |
| CN102336043B (en) | Ion exchange membrane with high current efficiency, and preparation method and application thereof | |
| Lei et al. | Multi-length-scale heterogeneous structured ion exchange membranes for cost-effective electrolysis and hydrogen production | |
| CN110042452B (en) | Photo-anode composite film, preparation method and application thereof | |
| Bin et al. | High-pressure proton exchange membrane water electrolysis: Current status and challenges in hydrogen production | |
| Kirner et al. | Exploring electrochemical flow-cell designs and parameters for CO2 reduction to formate under industrially relevant conditions | |
| CN106531468A (en) | Preparation method for sulfonated graphene oxide/stannic dioxide/polypyrrole composite material | |
| Floner et al. | Homogeneous coating of graphite felt by nickel electrodeposition to achieve light nickel felts with high surface area | |
| Pu et al. | Surface coating combined with in situ cyclic voltammetry to enhance the stability of gas diffusion electrodes for electrochemical CO2 reduction |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |