CN103521276A - Carbon-nanotube-doped type basic anion exchange composite membrane, and preparation method and application thereof - Google Patents
Carbon-nanotube-doped type basic anion exchange composite membrane, and preparation method and application thereof Download PDFInfo
- Publication number
- CN103521276A CN103521276A CN201310476467.9A CN201310476467A CN103521276A CN 103521276 A CN103521276 A CN 103521276A CN 201310476467 A CN201310476467 A CN 201310476467A CN 103521276 A CN103521276 A CN 103521276A
- Authority
- CN
- China
- Prior art keywords
- carbon nano
- water
- doped type
- ion exchange
- negative ion
- 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
Images
Classifications
-
- 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
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
- Y02P70/50—Manufacturing or production processes characterised by the final manufactured product
Landscapes
- Fuel Cell (AREA)
Abstract
The invention relates to a carbon-nanotube-doped type basic anion exchange composite membrane, and a preparation method and application thereof. The composite membrane comprises: oxygen group-containing water-soluble polyvinyl alcohol PVA and a quaternary ammonium group-containing water-soluble polymer with a mass ratio of 1:0.5-1, and carbon nanotube accounting for 0.5-3 wt% of the above two components. The preparation method comprises: dissolving oxygen group-containing water-soluble polyvinyl alcohol in deionized water, heating to 90 DEG C and stirring into a transparent homogeneous solution; respectively dissolving the quaternary ammonium group-containing water-soluble polymer and carbon nanotube in deionized water, mixing the above three solutions to obtain a homogeneous solution, drying to form a membrane and further to obtain a polymer membrane; performing crosslinking processing on the polymer membrane, and finally performing ion exchange to obtain the composite membrane. The composite membrane is applicable to fuel cells, metal-air cells, chlor-alkali industry and wastewater processing. The composite membrane provided by the invention has relatively high hydroxide ion conductivity and excellent stability and endurance, is simple in production, good in membrane forming ability, low in cost, green and environment friendly.
Description
Technical field
The invention belongs to ion-exchange composite membranes and preparation thereof and application, particularly a kind of carbon nano tube-doped type alkaline negative ion exchange composite film and its preparation method and application.
Background technology
Polymer dielectric film fuel cell (PEMFCs) starts fast and the advantages such as quick response of load variations is become to study hotspot because of it, wherein amberplex is as a vitals of PEMFCs, and its electrical conductivity and stability play vital effect to the power generation performance of fuel cell.PEMFCs is of a great variety with amberplex, according to the difference of conducting ion, can be divided into PEM (PEMs) and alkaline anion-exchange membrane (AAEMs), the commercialization PEM of for example being produced by du pont company
, because its high conductivity and good chemistry, electrochemistry and mechanical stability are widely used in Proton Exchange Membrane Fuel Cells.Yet,
the manufacturing process of film complexity, fancy price and unstability at high temperature limited its in fuel cell technology field commercial applications [Q.Li, R.He, J.O.Jensen, N.J.Bierrum, Fuel cells, 4 (2004) 147 widely; K.D.Kreuer, J.Membr.Sci.185 (2001) 29].On the other hand, AAEMs is due to its alkaline operating environment, thereby the electrochemical reaction that makes fuel cell has kinetics faster, the poisoning risk of fuel leak and CO is also greatly suppressed, in addition, can also effectively use non-precious metal catalyst, thereby can effectively reduce the cost of manufacture of fuel cell, therefore be widely studied and be applied to [M.A.Abdel Rahim in alkaline anion-exchange membrane fuel cell (AEMFCs), R.M.Abdel Hameed, M.W.Khalil, J.Power Sources134(2004) 160].
In the last few years, various novel quaternary ammonium type polymer were in the news in succession, as PES-C, and PPESK, PEI, PVDF and FEP etc. [J.Wang, J.Wang, S.Li, S.Zhang, J.Membr.Sci.368 (2011) 246; L.Li, Y.Wang, J.Membr.Sci.262 (2005) 1; J.Fang, P.K.Shen, J.Membr.Sci.285 (2006) 317; G.Wang, Y.Weng, D.Chu; D.Xie, R.Chen, J.Membr.Sci.326 (2009) is 4.]; but these preparation of ammonia alkali base polymer often will be passed through chloromethylation, quaternary ammoniated three steps of alkalization that arrive again in season, complicated process of preparation is on the high side; particularly relate to toxicity very strong or even there is strong carcinogenesis chloromethyl methyl ether and Trimethylamine reagent; be unfavorable for environmental protection [J.F.Zhou, M.Unlu, J.A.Vega; P.A.Kohl, J.Power Sources190 (2009) 285; Y.Wu, C.Wu, J.R.Varcoec, S.D.Poyntonc, T.Xu, Y.Fu, J.Power Sources, 195 (2010) 3069; Y.Xiong, Q.L.Liu, Q.H.Zeng, J.Power Sources, 193 (2009) 541; G.Wang, Y.Weng, D.Chu, D.Xie, R.Chen, J.Membr.Sci, 326 (2009) 4].In high-temperature high concentration alkaline solution, easily there is nucleophilic attack or Hoffman simultaneously and eliminate reaction, cause membrane stability poor.
Summary of the invention
Technical problem to be solved by this invention is to provide a kind of carbon nano tube-doped type alkaline negative ion exchange composite film and its preparation method and application, preparation method of the present invention is simple, easily operation, cost are low, good film-forming property, and environmental protection, are applicable to suitability for industrialized production.
A kind of carbon nano tube-doped type alkaline negative ion exchange composite film of the present invention, its composition comprise mass ratio be 1:0.5～1 containing oxygen base water-soluble poval PVA and the water-soluble polymer that contains quaternary ammonium group and the CNT of both total amount 0.5～3wt%.
The described water-soluble polymer that contains quaternary ammonium group is that polydiene propyl-dimethyl ammonium chloride PDDA, polyacrylamide-co-diallyl ammonium chloride PAADDAC(are purchased from U.S. Aldrich company), quaternized ethoxylated hydroxyethylcellulose cellulose QHECE(is purchased from U.S. Aldrich company), poly dimethyl amine-co-chloropropylene oxide-co-ethylenediamine PDAECED(is purchased from U.S. Aldrich company), poly-[two (2-vinyl chloride) ether-alt-1,3-bis-[3-(dimethyl amine) propyl group] urea quaternary amine PBCEBDAP(is purchased from U.S. Aldrich company) in one or more.
Described CNT is one or more in without polishing multi-walled carbon nano-tubes MWCNTs, hydroxyl modified multi-walled carbon nano-tubes MWCNTs-OH, carboxyl modified multi-walled carbon nano-tubes MWCNTs-COOH.
The preparation method of a kind of carbon nano tube-doped type alkaline negative ion exchange composite film of the present invention, comprising:
(1) will be dissolved in deionized water containing oxygen base water-soluble poval PVA, at 90-100 ℃, heating is stirred to transparent uniform solution, and obtaining mass percentage concentration is the PVA solution of 5-15%;
(2) by PVA, be 1:0.5-1 with the mass ratio of the water-soluble polymer that contains quaternary ammonium group, the water-soluble polymer that contains quaternary ammonium group is soluble in water, prepare the water-soluble polymer solution that contains quaternary ammonium group;
(3) soluble in water with the CNT of the 0.5-3wt.% of the water-soluble polymer gross mass that contains quaternary ammonium group by PVA, prepare carbon nano-tube solution;
(4) above-mentioned PVA solution, the water-soluble polymer solution that contains quaternary ammonium group, carbon nano-tube solution are mixed, stir and obtain mixed solution, drying and forming-film, carry out crosslinking Treatment, finally carry out ion-exchange, clean, obtain carbon nano tube-doped type alkaline negative ion exchange composite film.
In described step (4) drying and forming-film mode be that nature dries, one or more in oven for drying, freeze drying, vacuum drying.
Crosslinking Treatment is placed in baking oven and heat-treats for film is peeled in described step (4), heat treatment temperature is 120-150 ℃, processing time is 0.5-1h, being dipped in percent by volume is the glutaraldehyde (GA that contains HCl of 3%-20% again, 25wt.%) film is taken out after stirring 1h in acetone (>=99.5wt.%) solution, be dipped in fully washing in deionized water, be then stored in deionized water, wherein the quality percentage composition of HCl is 0.2%-3%.
Described step (4) intermediate ion is exchanged for and in KOH solution, carries out ion-exchange.
Described KOH solution concentration is 2mol/L.
Described step (4) intermediate ion swap time is 12-24h.
The application of a kind of carbon nano tube-doped type alkaline negative ion exchange composite film of the present invention, composite membrane is applied to fuel cell, metal-air battery, chlorine industry and wastewater treatment.
Described fuel cell is H
2/ O
2fuel cell or the fuel liquid battery that methyl alcohol, ethanol, propyl alcohol, glycerine or dimethyl ether be fuel of take.
Beneficial effect
(1) a kind of carbon nano tube-doped type alkaline negative ion exchange composite film of the present invention is simultaneously with high hydroxide ion conductibility and good alkali stability, the significant cost that reduces fuel cell, and can be directly used in and take the fuel liquid battery that methyl alcohol, ethanol, propyl alcohol, glycerine and dimethyl ether etc. are fuel;
(2) preparation method of the present invention is simple, and easily operation, cost are low, good film-forming property and environmental protection, are suitable for suitability for industrialized production.
Accompanying drawing explanation
Fig. 1 is hydroxide ion electrical conductivity and the moisture content of the carbon nano tube-doped alkaline polymer film of variety classes; Film A:PVA/PDDA wherein; Film B:PVA/PDDA/MWCNTs; Film C:PVA/PDDA/MWCNTs-OH; Film D:PVA/PDDA/MWCNTs-COOH;
Fig. 2 is hydroxide ion electrical conductivity and the moisture content of the PVA/50%PDDA/MWCNTs-OH-of different carbon nano tube-doped content;
Fig. 3 is for to prepare membrane electrode with PVA/50%PDDA/MWCNTs-OH composite membrane, the monocell power generation performance that the Pt of take is respectively cathode and anode catalyst;
Fig. 4, for to prepare membrane electrode with PVA/50%PDDA/MWCNTs-OH composite membrane, be take Pt as anode catalyst, the heat treated carbon supported cobalt phthalocyanine of CoPc/C600(600oC) be the monocell power generation performance of cathod catalyst.
The specific embodiment
Below in conjunction with specific embodiment, further set forth the present invention.Should be understood that these embodiment are only not used in and limit the scope of the invention for the present invention is described.In addition should be understood that those skilled in the art can make various changes or modifications the present invention after having read the content of the present invention's instruction, these equivalent form of values fall within the application's appended claims limited range equally.
The PVA powder of 30g is dissolved in 300ml deionized water, and heating is stirred to transparent uniform solution at 90 ℃, prepares 10%PVA storing solution; By PVA and PDDA mass ratio=1:0.5, prepare PDDA uniform solution; By the 1wt% of PVA and PDDA total amount, stir respectively and ultrasonic, prepare respectively without polishing multi-walled carbon nano-tubes MWCNTs, hydroxyl modified multi-walled carbon nano-tubes MWCNTs-OH, carboxyl modified multi-walled carbon nano-tubes MWCNTs-COOH homogeneous mixed solution; Above solution mix and blend is obtained to homogeneous mixed solution for 24 hours, mixed liquor is molded in plastic disc, natural drying film forming.Film is peeled and is placed in baking oven 150 ℃ of heat treatment 1h respectively, be dipped in again 10%(percent by volume) the glutaraldehyde (GA that contains a small amount of (2% mass percent) HCl, 25wt.%) film is taken out after stirring 1h in acetone (>=99.5wt.%) solution, be dipped in fully washing in deionized water, be then stored in the quaternary ammonium salt anion composite membrane that obtains modification in deionized water.
In the 2M/L KOH solution that the film of preparing through said method is immersed in, carry out taking out after ion-exchange 24h, by deionized water, repeatedly clean the KOH of film adsorption to neutral, obtain alkaline negative ion exchange composite film, then film is stored in deionized water, utilize AC impedence method and dry weight in wet base method to measure respectively its electrical conductivity and moisture content, result as shown in Figure 1.
The PVA powder of 30g is dissolved in 300ml deionized water, and heating is stirred to transparent uniform solution at 90 ℃, prepares 10%PVA storing solution; By PVA and PDDA mass ratio=1:0.5, prepare PDDA uniform solution; By 0wt.%, 0.5wt.%, 1wt.%, 2wt.%, the 3wt.% of PVA and PDDA total amount, stir respectively the also homogeneous mixed solution of the different hydroxyl modified multi-walled carbon nano-tubes of ultrasonic preparation MWCNTs-OH doping content; Above mixed solution is molded in plastic disc to natural drying film forming.Film is peeled and is placed in baking oven 150 ℃ of heat treatment 1h respectively, be dipped in again 5%(percent by volume) contain a small amount of HCl(0.2%, mass percent) glutaraldehyde (GA, 25wt.%) film is taken out after stirring 1h in acetone (>=99.5wt.%) solution, be dipped in fully washing in deionized water, be then stored in the quaternary ammonium salt anion composite membrane that obtains modification in deionized water.
In the 2M/L KOH solution that the film of preparing through said method is immersed in, carry out taking out after ion-exchange 24h, by deionized water, repeatedly clean the KOH of film adsorption to neutral, obtain alkaline negative ion exchange composite film, then film is stored in deionized water, utilize AC impedence method and dry weight in wet base method to measure respectively its electrical conductivity and moisture content, result as shown in Figure 2.
By prepared PVA/50%PDDA/MWCNTs-OH
-the power generation performance that composite membrane is prepared membrane electrode (MEA) carries out in GE/FC1-100 activation of fuel cell system.Negative electrode and anode are all used the business-like 40%Pt/C catalyst of Johnson Matthey, and Pt carrying capacity is 0.5mg/cm
2.The hot pressing condition of membrane electrode MEA is 6MPa-60 ℃-6min, and membrane electrode MEA effective active area is 4cm
2.Anode fuel is hydrogen, and flow is 100mL/min; Negative electrode is oxygen, and flow is 70mL/min, and respectively at the test of generating electricity at room temperature and 40 ℃, result as shown in Figure 3.
Embodiment 4
The power generation performance of PVA/50%PDDA/MWCNTs-OH-composite membrane carries out in GE/FC1-100 activation of fuel cell system.MEA electrode production process, the monocell evaluation of catalyst is identical with embodiment 3.Difference is that negative electrode is used CoPc/C600 catalyst, and carrying capacity is 3.0mg/cm
2, the hot pressing condition of membrane electrode MEA is 6MPa-60 ℃-6min, membrane electrode MEA effective active area is 4cm
2.Anode fuel is hydrogen, and flow is 100mL/min; Negative electrode is oxygen, and flow is 70mL/min, and respectively at the test of generating electricity at room temperature and 40 ℃, result as shown in Figure 4.
Claims (10)
1. a carbon nano tube-doped type alkaline negative ion exchange composite film, is characterized in that: its composition comprise mass ratio be 1:0.5～1 containing oxygen base water-soluble poval PVA and the water-soluble polymer that contains quaternary ammonium group and the CNT of both total amount 0.5～3wt%.
2. a kind of carbon nano tube-doped type alkaline negative ion exchange composite film according to claim 1, it is characterized in that: described in contain quaternary ammonium group water-soluble polymer be polydiene propyl-dimethyl ammonium chloride PDDA, polyacrylamide-co-diallyl ammonium chloride PAADDAC, quaternized ethoxylated hydroxyethylcellulose cellulose QHECE, poly dimethyl amine-co-chloropropylene oxide-co-ethylenediamine PDAECED, poly-[two (2-vinyl chloride) ether-alt-1, one or more in 3-bis-[3-(dimethyl amine) propyl group] urea quaternary amine PBCEBDAP.
3. a kind of carbon nano tube-doped type alkaline negative ion exchange composite film according to claim 1, is characterized in that: described CNT is one or more in without polishing multi-walled carbon nano-tubes MWCNTs, hydroxyl modified multi-walled carbon nano-tubes MWCNTs-OH, carboxyl modified multi-walled carbon nano-tubes MWCNTs-COOH.
4. a preparation method for the carbon nano tube-doped type alkaline negative ion exchange composite film as described in as arbitrary in claim 1-3, comprising:
(1) will be dissolved in deionized water containing oxygen base water-soluble poval PVA, at 90-100 ℃, heating is stirred to transparent uniform solution, and obtaining mass percentage concentration is the PVA solution of 5-15%;
(2) by PVA, be 1:0.5-1 with the mass ratio of the water-soluble polymer that contains quaternary ammonium group, the water-soluble polymer that contains quaternary ammonium group is soluble in water, prepare the water-soluble polymer solution that contains quaternary ammonium group;
(3) soluble in water with the CNT of the 0.5-3wt.% of the water-soluble polymer gross mass that contains quaternary ammonium group by PVA, prepare carbon nano-tube solution;
(4) above-mentioned PVA solution, the water-soluble polymer solution that contains quaternary ammonium group, carbon nano-tube solution are mixed, stir and obtain mixed solution, drying and forming-film, carry out crosslinking Treatment, finally carry out ion-exchange, clean, obtain carbon nano tube-doped type alkaline negative ion exchange composite film.
5. the preparation method of a kind of carbon nano tube-doped type alkaline negative ion exchange composite film according to claim 4, is characterized in that: in described step (4) drying and forming-film mode be that nature dries, one or more in oven for drying, freeze drying, vacuum drying.
6. the preparation method of a kind of carbon nano tube-doped type alkaline negative ion exchange composite film according to claim 4, it is characterized in that: crosslinking Treatment is placed in baking oven and heat-treats for film is peeled in described step (4), heat treatment temperature is 120-150 ℃, processing time is 0.5-1h, be dipped in again percent by volume and be after stirring 1h in the acetone soln of the glutaraldehyde that contains HCl of 3%-20% film is taken out, be dipped in fully washing in deionized water, be then stored in deionized water.
7. the preparation method of a kind of carbon nano tube-doped type alkaline negative ion exchange composite film according to claim 4, is characterized in that: described step (4) intermediate ion is exchanged for and in KOH solution, carries out ion-exchange; KOH solution concentration is 2mol/L.
8. the preparation method of a kind of carbon nano tube-doped type alkaline negative ion exchange composite film according to claim 4, is characterized in that: described step (4) intermediate ion swap time is 12-24h.
9. an application for the carbon nano tube-doped type alkaline negative ion exchange composite film as described in as arbitrary in claim 1-3, is characterized in that: composite membrane is applied to fuel cell, metal-air battery, chlorine industry and wastewater treatment.
10. the application of a kind of carbon nano tube-doped type alkaline negative ion exchange composite film according to claim 9, is characterized in that: described fuel cell is H
2/ O
2fuel cell or the fuel liquid battery that methyl alcohol, ethanol, propyl alcohol, glycerine or dimethyl ether be fuel of take.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310476467.9A CN103521276B (en) | 2013-10-12 | 2013-10-12 | A kind of carbon nano tube-doped type alkaline negative ion exchange composite film and its preparation method and application |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310476467.9A CN103521276B (en) | 2013-10-12 | 2013-10-12 | A kind of carbon nano tube-doped type alkaline negative ion exchange composite film and its preparation method and application |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103521276A true CN103521276A (en) | 2014-01-22 |
| CN103521276B CN103521276B (en) | 2016-01-20 |
Family
ID=49923837
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310476467.9A Expired - Fee Related CN103521276B (en) | 2013-10-12 | 2013-10-12 | A kind of carbon nano tube-doped type alkaline negative ion exchange composite film and its preparation method and application |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103521276B (en) |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105170122A (en) * | 2015-10-09 | 2015-12-23 | 辽宁石油化工大学 | Preparation method and application of full-interpenetrating membrane based on quaternized polyvinyl alcohols |
| CN105924865A (en) * | 2016-05-12 | 2016-09-07 | 盐城工学院 | Acid proton exchange membrane and preparing method thereof |
| CN106463740A (en) * | 2014-06-13 | 2017-02-22 | 日东电工株式会社 | Anion-exchange electrolyte membrane, membrane-electrode assembly for fuel cells provided with same, and fuel cell |
| CN107403941A (en) * | 2017-07-24 | 2017-11-28 | 湖北工程学院 | Compound alkaline polyelectrolyte film of hydrotalcite enveloped carbon nanometer tube and preparation method thereof |
| CN107413395A (en) * | 2017-08-30 | 2017-12-01 | 苏州明昊色谱技术有限公司 | A kind of agglomeration type high-hydrophilic strong anion exchanger, preparation method and its application in liquid chromatographic packing materials |
| CN108997599A (en) * | 2018-05-30 | 2018-12-14 | 东华大学 | High-intensitive binary is crosslinked alkaline negative ion exchange composite film, preparation method and application |
| CN110556559A (en) * | 2019-09-16 | 2019-12-10 | 东北大学 | Method for preparing low-temperature proton exchange membrane with layered structure based on vacuum-assisted flocculation technology |
| CN111952649A (en) * | 2020-07-30 | 2020-11-17 | 四川大学 | Polyvinyl alcohol/polyquaternium anion exchange membrane for anion exchange membrane fuel cell |
| CN111952651A (en) * | 2020-07-30 | 2020-11-17 | 四川大学 | Preparation method of polyvinyl alcohol/polyquaternium anion exchange membrane for anion exchange membrane fuel cell |
| CN112090299A (en) * | 2020-08-18 | 2020-12-18 | 赛福纳米科技(徐州)有限公司 | Homogeneous anion exchange membrane and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101497701A (en) * | 2009-03-02 | 2009-08-05 | 天津大学 | Preparation of multi-wall carbon nano-tube / dodecyl sodium sulfonate / polyvinyl alcohol compound film |
| CN102544547A (en) * | 2012-01-06 | 2012-07-04 | 东华大学 | Alkaline negative ion exchange composite film with alkali stability and preparation and application thereof |
-
2013
- 2013-10-12 CN CN201310476467.9A patent/CN103521276B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101497701A (en) * | 2009-03-02 | 2009-08-05 | 天津大学 | Preparation of multi-wall carbon nano-tube / dodecyl sodium sulfonate / polyvinyl alcohol compound film |
| CN102544547A (en) * | 2012-01-06 | 2012-07-04 | 东华大学 | Alkaline negative ion exchange composite film with alkali stability and preparation and application thereof |
Cited By (17)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106463740B (en) * | 2014-06-13 | 2019-07-30 | 日东电工株式会社 | Anion exchange dielectric film, have the dielectric film fuel cell film-electrode bond and fuel cell |
| CN106463740A (en) * | 2014-06-13 | 2017-02-22 | 日东电工株式会社 | Anion-exchange electrolyte membrane, membrane-electrode assembly for fuel cells provided with same, and fuel cell |
| CN105170122A (en) * | 2015-10-09 | 2015-12-23 | 辽宁石油化工大学 | Preparation method and application of full-interpenetrating membrane based on quaternized polyvinyl alcohols |
| CN105170122B (en) * | 2015-10-09 | 2018-07-06 | 辽宁石油化工大学 | A kind of preparation method and applications based on the full interpenetrating film of quaternized polyvinyl alcohol class |
| CN105924865A (en) * | 2016-05-12 | 2016-09-07 | 盐城工学院 | Acid proton exchange membrane and preparing method thereof |
| CN105924865B (en) * | 2016-05-12 | 2018-04-20 | 盐城工学院 | A kind of acidic proton exchange membrane and preparation method thereof |
| CN107403941A (en) * | 2017-07-24 | 2017-11-28 | 湖北工程学院 | Compound alkaline polyelectrolyte film of hydrotalcite enveloped carbon nanometer tube and preparation method thereof |
| CN107413395A (en) * | 2017-08-30 | 2017-12-01 | 苏州明昊色谱技术有限公司 | A kind of agglomeration type high-hydrophilic strong anion exchanger, preparation method and its application in liquid chromatographic packing materials |
| CN107413395B (en) * | 2017-08-30 | 2020-05-19 | 苏州明昊色谱技术有限公司 | Agglomeration type high-hydrophilicity strong anion exchanger, preparation method and application thereof in liquid chromatography column packing |
| CN108997599A (en) * | 2018-05-30 | 2018-12-14 | 东华大学 | High-intensitive binary is crosslinked alkaline negative ion exchange composite film, preparation method and application |
| CN110556559A (en) * | 2019-09-16 | 2019-12-10 | 东北大学 | Method for preparing low-temperature proton exchange membrane with layered structure based on vacuum-assisted flocculation technology |
| CN110556559B (en) * | 2019-09-16 | 2022-06-14 | 东北大学 | Method for preparing low-temperature proton exchange membrane with layered structure based on vacuum-assisted flocculation technology |
| CN111952649A (en) * | 2020-07-30 | 2020-11-17 | 四川大学 | Polyvinyl alcohol/polyquaternium anion exchange membrane for anion exchange membrane fuel cell |
| CN111952651A (en) * | 2020-07-30 | 2020-11-17 | 四川大学 | Preparation method of polyvinyl alcohol/polyquaternium anion exchange membrane for anion exchange membrane fuel cell |
| CN111952651B (en) * | 2020-07-30 | 2021-09-10 | 四川大学 | Preparation method of polyvinyl alcohol/polyquaternium anion exchange membrane for anion exchange membrane fuel cell |
| CN111952649B (en) * | 2020-07-30 | 2023-03-10 | 四川大学 | Polyvinyl alcohol/polyquaternium anion exchange membrane for anion exchange membrane fuel cell |
| CN112090299A (en) * | 2020-08-18 | 2020-12-18 | 赛福纳米科技(徐州)有限公司 | Homogeneous anion exchange membrane and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103521276B (en) | 2016-01-20 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103521276B (en) | A kind of carbon nano tube-doped type alkaline negative ion exchange composite film and its preparation method and application | |
| Vilela et al. | Nanocellulose-based materials as components of polymer electrolyte fuel cells | |
| Qiu et al. | Alkaline imidazolium-and quaternary ammonium-functionalized anion exchange membranes for alkaline fuel cell applications | |
| Zhao et al. | Quaternary ammonia polysulfone-PTFE composite alkaline anion exchange membrane for fuel cells application | |
| Choudhury et al. | High performance and eco-friendly chitosan hydrogel membrane electrolytes for direct borohydride fuel cells | |
| WO2017088732A1 (en) | Preparation method for alkaline anion exchange membrane and use thereof in fuel cell | |
| CN105295079A (en) | Graphene oxide-doped chitosan-based alkaline anion exchange composite membrane and preparation method therefor and application thereof | |
| CN102544547A (en) | Alkaline negative ion exchange composite film with alkali stability and preparation and application thereof | |
| Meenakshi et al. | Chitosan‐polyvinyl alcohol‐sulfonated polyethersulfone mixed‐matrix membranes as methanol‐barrier electrolytes for DMFCs | |
| Zakaria et al. | Evaluation of Quaternized polyvinyl alcohol/graphene oxide‐based membrane towards improving the performance of air‐breathing passive direct methanol fuel cell s | |
| Choudhury et al. | High performance polymer chemical hydrogel-based electrode binder materials for direct borohydride fuel cells | |
| Choudhury et al. | Chitosan chemical hydrogel electrode binder for direct borohydride fuel cells | |
| Hou et al. | Synthesis and characterization of a new anion exchange membrane by a green and facile route | |
| Samsudin et al. | Poly (vinyl alcohol)-Based Anion Exchange Membranes for Alkaline Direct Ethanol Fuel Cells. | |
| CN101853947B (en) | Compound crosslinking alkaline polymer film for fuel cell, preparation method and application | |
| JP2011514915A (en) | Composition with high proton conductivity | |
| Gupta et al. | A study on synthesis of chemical crosslinked polyvinyl alcohol-based alkaline membrane for the use in low-temperature alkaline direct ethanol fuel cell | |
| US10985381B2 (en) | Nanostructured electrode for polymer electrolyte membrane fuel cell, and manufacturing method therefor | |
| CN104130433B (en) | A kind of preparation method of cross-linking type polyphenylene oxide compound proton exchange membrane | |
| CN102945968A (en) | Composite polyepoxy chloropropane alkaline polymer membrane electrode and preparation method thereof | |
| Osifo et al. | The influence of chitosan membrane properties for direct methanol fuel cell applications | |
| CN104371041B (en) | Efficient chitosan-based alkaline negative ion exchange composite film and its preparation and application | |
| Üçtuğ et al. | Effect of polymer sulfonation on the proton conductivity and fuel cell performance of polyvinylalcohol‐mordenite direct methanol fuel cell membranes | |
| CN106784949A (en) | A kind of preparation method of the full interpenetrating type anion-exchange membranes of crosslinking QCS CM Guanidine | |
| CN103865231B (en) | Sulfonated polyether-ether-ketone-original position phosphorylation titania hybrid film and Synthesis and applications |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20160120 Termination date: 20201012 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |