CN104371128A - Alkaline anion-exchange composite membrane with high mechanical properties, and preparation and application thereof - Google Patents
Alkaline anion-exchange composite membrane with high mechanical properties, and preparation and application thereof Download PDFInfo
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Abstract
The invention relates to preparation and application of an alkaline anion-exchange composite membrane with high mechanical properties. The alkaline anion-exchange composite membrane with high mechanical properties comprises low-molecular-weight oxy water-soluble polyvinyl alcohol (PVA) and a polymer of quaternary-ammonium-group-containing water-soluble chlorinated-1-vinyl-3-methyl-1H-iminazole and 1-vinyl-2-pyrrolidone. The preparation method comprises the following steps: respectively dissolving oxy water-soluble PVA and quaternary-ammonium-group-containing Luviquat in deionized water to obtain a uniform mixed solution; carrying out vacuum filtration, pouring the filtrate into a plastic culture dish, and naturally drying to obtain a composite membrane; and carrying out thermophysical crosslinking on the composite membrane, carrying out chemical crosslinking, and finally, immersing in a KOH solution to carry out ion exchange. The preparation method has the advantages of accessible raw materials, low cost, no pollution, mild reaction conditions, short reaction time, simple and practical technique, high controllability and the like, and can easily implement large-scale production.
Description
Technical field
The invention belongs to alkaline membrane and Synthesis and applications field thereof, particularly a kind of alkaline negative ion exchange composite film and Synthesis and applications thereof with high-strength mechanical performance.
Background technology
Polymer-membrane fuel battery (PEMFC), according to the difference of conductive ion, can be divided into proton exchange membrane (PEM) fuel cell and alkaline anion-exchange membrane (AEM) fuel cell.PEM fuel cell has that disposal of pollutants is little, working temperature is low, activationary time is short, the life-span is long, stable, be easy to scale operation, effciency of energy transfer comparatively advantages of higher, become one of 21 century efficient, eco-friendly important energy source technology [M.A.J.Cropper, S.Geiger, D.M.Jollie, J.Power Sources 131 (2004) 57-61; J.R.Varcoe, R.C.T.Slade, E.Lam How Yee, S.D.Poynton, D.J.Driscoll, D.C.Apperley, Chem.Mater.19 (2007) 2686-2693.].Such as, the proton exchange membrane of du pont company's production
there is excellent specific conductivity and chemistry, electrochemistry and mechanical stability and be widely used.But,
film production process is complicated, its commercialized development [V.Neburchilov is instability limit under expensive and high temperature, J.Martin, H.Wang, J.Zhang, A review of polymerelectrolytemembranes for direct methanol fuel cells, Journal of Power Sources 169 (2007) 221].
In recent years, AEM and application in a fuel cell thereof cause and pay close attention to widely.AEM fuel cell has reaction kinetics faster, and fuel leak and the poisoning risk of CO are also greatly suppressed, and in addition, non-platinum noble metals can also be used to make catalyzer, can effectively reduce fuel cell cost.Alkaline negative ion exchange composite film (AEM) is of a great variety, its skeleton is from polyolefine (PO), polysiloxane (PSO), biphenyl polyether ketone (PPEK), poly (arylene ether) sulfone (PAES) organic/inorganic composite material [Y.J.Wang by the time, J.L.Qiao, R.Baker, J.J.Zhang, Chem.Soc.Rev.42 (2013) 5768; J.F.Zhou, M.
i.Anestis-Richard, P.A.Kohl, J.Membr.Sci.350 (2010) 286-292; M.A.Abdel Rahim, R.M.Abdel Hameed, M.W.Khalil, J.Power Sources 134 (2004) 160; S.M.A.Shibili, M.Noel, J.PowerSources 45 (1993) 139; S.Lu, J.Pan, A.Huang, L.Zhuang, J.Lu, Proc.Natl.Acad.Sci.USA 105 (2008) 20611-20614; J.Wang, J.Wang, S.Li, S.Zhang, J.Membr.Sci.368 (2011) 246-253].But these anion-exchange membrane preparation process are complicated, simultaneously in high-concentration alkali liquor, particularly unstable under comparatively high temps (being greater than 60 DEG C) condition and film properties that is that cause declines even membrane degradation, the mechanical strength of film sharply declines thereupon, therefore, Study and Development high-performance, high stability, have superior mechanical strength and easily preparation and cheap novel alkaline anion-exchange membrane significant.
Summary of the invention
The technical problem that will solve required for the present invention is to provide a kind of alkaline negative ion exchange composite film and the Synthesis and applications thereof with high-strength mechanical performance, this film shows higher stretch-proof performance, there is again certain elongation at break, the cost of significant reduction fuel cell, preparation method is simple, cost is low, good film-forming property, is suitable for suitability for industrialized production.
In order to solve the problems of the technologies described above, the invention provides a kind of high-strength mechanical performance alkaline negative ion exchange composite film, it is characterized in that, comprise low-molecular-weight containing oxygen base water-soluble poval (PVA) and containing quaternary ammonium group water-soluble polymers (
series polymer).
Preferably, the described low-molecular-weight weight-average molecular weight containing oxygen base water-soluble ethylene alcohol is 89000 < M
w< 98000; The described water-soluble polymers containing quaternary ammonium group is the polymkeric substance of chlorination-1-vinyl-3-methyl isophthalic acid H-imidazoles and l-vinyl-2-pyrrolidone.
Present invention also offers the preparation method of above-mentioned high-strength mechanical performance alkaline negative ion exchange composite film, it is characterized in that, comprise the following steps:
Step 1): the polymkeric substance containing oxygen base water-soluble poval and chlorination-1-vinyl-3-methyl isophthalic acid H-imidazoles and l-vinyl-2-pyrrolidone is configured to the aqueous solution respectively, under room temperature, the aqueous solutions of polymers of chlorination-1-vinyl-3-methyl isophthalic acid H-imidazoles and l-vinyl-2-pyrrolidone is slowly added stirring containing in the oxygen base water-soluble poval aqueous solution, continue to stir until obtain forming homogeneous mixing solutions, vacuum filtration, filtrate is poured in plastic culture dish, seasoning film forming, obtains polymeric film;
Step 2): by step 1) obtained polymeric film nature peels off from culture dish, through thermal treatment physical crosslinking, then through chemically crosslinked, finally leaching is placed in KOH solution and carries out ion-exchange and get final product.
Preferably, described step 2) in the crosslinking temperature of thermal treatment physical crosslinking be 130 ~ 190 DEG C; Crosslinking time is 30min ~ 2h.
Further, described step 2) in the crosslinking temperature of thermal treatment physical crosslinking be 170 DEG C; Crosslinking time is 1h.
Preferably, described step 2) in time of chemically crosslinked be 1h.
Preferably, described step 2) in the volumetric molar concentration of KOH solution be 1-6mol/L.
Present invention also offers a kind of high-strength mechanical performance alkaline negative ion exchange composite film to be applied to and to prepare alkaline fuel cell membrane electrode.
Preferably, described alkaline fuel cell membrane electrode is metal-air battery, CO
2electrochemical reduction and chlorine industry diaphragm material.
Compared with prior art, beneficial effect of the present invention is:
(1) alkaline negative ion exchange composite film of the present invention had both shown excellent stretch-proof performance, and physical crosslinking temperature 130 DEG C of condition Tensile strength can reach 76.7Mpa; And the good tension set of tool, under physical crosslinking temperature 170 DEG C of conditions, elongation at break is 14.9%, has excellent mechanical stability;
(2) preparation method of the present invention is simple, with low cost, easily operate, good film-forming property, is suitable for suitability for industrialized production;
(3) alkaline negative ion exchange composite film of the present invention can be directly used in H2-air fuel cell, also can be used as metal-air battery and CO
2the diaphragm material of electrochemical reduction, significantly reduces the cost of manufacture of fuel cell.
Accompanying drawing explanation
Fig. 1 is the stress-strain(ed) curve of PVA/Luviquat FC370 alkaline negative ion exchange composite film respectively under 130 DEG C, 150 DEG C, 170 DEG C and 190 DEG C of physical crosslinking 1h again after chemically crosslinked 1h;
Fig. 2 is the outward appearance photo comparison figure of PVA/Luviquat FC370 alkaline anion-exchange membrane before and after 170 DEG C of physical crosslinkings;
Fig. 3 be PVA/Luviquat FC370 alkaline anion-exchange membrane at 170 DEG C of physical crosslinking 1h, the oxidative stability after chemically crosslinked 1h;
Fig. 4 be PVA/Luviquat FC370 alkaline anion-exchange membrane respectively at 130 DEG C, 150 DEG C, 170 DEG C and 190 DEG C of physical crosslinking 1h, the specific conductivity under chemically crosslinked 1h after the ion-exchange of 2M KOH solution and water ratio;
Fig. 5 be PVA/Luviquat FC370 alkaline anion-exchange membrane respectively at (a) 130 DEG C, (b) 150 DEG C, (c) 170 DEG C, (d) 190 DEG C of physical crosslinking 1h, impregnated in after chemically crosslinked 1h in 2M KOH solution outward appearance photo comparison figure;
Fig. 6 be PVA/Luviquat FC370 alkaline anion-exchange membrane at 130 DEG C of physical crosslinking 1h, prepare after chemically crosslinked 1h membrane electrode (MEA) at normal temperatures and pressures monocell generating curve.
Embodiment
For making the present invention become apparent, hereby with preferred embodiment, and accompanying drawing is coordinated to be described in detail below.
The oxygen base water-solubility PVA that contains in embodiment 1-6 originates from Sigma-Aldrich (Shanghai) trade Co., Ltd; The FC370 that Luviquat adopts Sigma-Aldrich (Shanghai) trade Co., Ltd to produce.
Embodiment 1
Be dissolved in 300ml deionized water by the oxygen base water-solubility PVA powder (molecular weight is: 89000-98000) that contains of 30g, at 90 DEG C, heated and stirred is to transparent uniform solution, prepares 10%PVA storing solution.By PVA with
fC370 mass ratio=1: 1 by the above-mentioned PVA aqueous solution with
(molecular weight is about FC370: 400000) solution mixing, after stirring into transparent and homogeneous solution, is molded into mixed solution in plastic disc, seasoning film forming.Film is peeled off naturally, after being placed in baking oven 130 DEG C of physical crosslinking 1h, again film is dipped in the glutaraldehyde (GA containing a small amount of HCl of 15mL 10%, 25wt%) in acetone (>=99.5wt%) solution, after carrying out chemical crosslink reaction 1h under room temperature, film is taken out, be dipped in deionized water and fully wash.By the PVA/ prepared through aforesaid method
fC370 film takes out after being immersed in and carrying out ion-exchange 24h in 2M KOH solution, and the KOH repeatedly cleaning film surface adsorption with deionized water, to neutral, namely obtains PVA/
fC370 alkaline negative ion exchange composite film.
Tested under the constant-temperature constant-humidity environment of 20 DEG C of 60% relative humidity by H5K-S shaped material trier (Britain Hounsfield).Speed of experiment is 5mm/min, and sample standard is 2cm × 1cm.Result as shown in Figure 1, can find that from figure this film has very strong stretch-proof performance, have maximum tensile strength, and up to 76.7MPa, elongation at break is 11.8%, and Young's modulus is 958.5MPa.Under same elongation at break 8% condition, the alkaline anion-exchange membrane through 130 DEG C of physical crosslinking Temperature Treatment has maximum tensile strength 67.2MPa.
Embodiment 2
Be dissolved in 300ml deionized water by the PVA powder (molecular weight is: 89000-98000) of 30g, at 90 DEG C, heated and stirred is to transparent uniform solution, prepares 10%PVA storing solution.By PVA with
fC370 mass ratio=1: 1 by the above-mentioned PVA aqueous solution with
(molecular weight is about FC370: 400000) solution mixing, after stirring into transparent and homogeneous solution, is molded into mixed solution in plastic disc, seasoning film forming.Film is peeled off naturally, after being placed in baking oven 150 DEG C of physical crosslinking 1h, again film is dipped in the glutaraldehyde (GA containing a small amount of HCl of 15mL 10%, 25wt%) in acetone (>=99.5wt%) solution, after carrying out chemical crosslink reaction 1h under room temperature, film is taken out, be dipped in deionized water and fully wash.By the PVA/ prepared through aforesaid method
fC370 film takes out after being immersed in and carrying out ion-exchange 24h in 2M KOH solution, and the KOH repeatedly cleaning film surface adsorption with deionized water, to neutral, namely obtains PVA/
fC370 alkaline negative ion exchange composite film.
Tested under the constant-temperature constant-humidity environment of 20 DEG C of 60% relative humidity by H5K-S shaped material trier (Britain Hounsfield).Speed of experiment is 5mm/min, and sample standard is 2cm × 1cm.As shown in Figure 1, this film has very strong stretch-proof performance to result equally, and tensile strength is 62.6MPa, and elongation at break is 14.1%, and Young's modulus is 791.7MPa.
Embodiment 3
Be dissolved in 300ml deionized water by the PVA powder (molecular weight is: 89000-98000) of 30g, at 90 DEG C, heated and stirred is to transparent uniform solution, prepares 10%PVA storing solution.By PVA with
fC370 mass ratio=1: 1 by the above-mentioned PVA aqueous solution with
(molecular weight is about FC370: 400000) solution mixing, after stirring into transparent and homogeneous solution, is molded into mixed solution in plastic disc, seasoning film forming.Film is peeled after being placed in baking oven 170 DEG C of physical crosslinking 1h, again film is dipped in the glutaraldehyde (GA containing a small amount of HCl of 15mL 10%, 25wt%) in acetone (>=99.5wt%) solution, after carrying out chemical crosslink reaction 1h under room temperature, film is taken out, be dipped in deionized water and fully wash.By the PVA/ prepared through aforesaid method
fC370 film takes out after being immersed in and carrying out ion-exchange 24h in 2M KOH solution, and the KOH repeatedly cleaning film surface adsorption with deionized water, to neutral, namely obtains PVA/
fC370 alkaline negative ion exchange composite film.Fig. 2 is the outward appearance photo comparison figure of PVA/Luviquat alkaline anion-exchange membrane before and after 170 DEG C of physical crosslinkings, and as seen from Figure 2, before and after 170 DEG C of physical crosslinkings, PVA/Luviquat alkaline anion-exchange membrane becomes yellow from colourless.
Tested under the constant-temperature constant-humidity environment of 20 DEG C of 60% relative humidity by H5K-S shaped material trier (Britain Hounsfield).Speed of experiment is 5mm/min, and sample standard is 2cm × 1cm.As shown in Figure 1, tensile strength is 59.3MPa to result, and elongation at break is 14.9%, and Young's modulus is 793.0MPa.Can find that from figure this film has maximum elongation at break, under same tensile strength 50MPa condition, the elongation at break through the alkaline anion-exchange membrane of 170 DEG C of physical crosslinking Temperature Treatment is maximum, can reach 10.6%.
Embodiment 4
Be dissolved in 300ml deionized water by the PVA powder (molecular weight is: 89000-98000) of 30g, at 90 DEG C, heated and stirred is to transparent uniform solution, prepares 10%PVA storing solution.By PVA with
fC370 mass ratio=1: 1 by the above-mentioned PVA aqueous solution with
(molecular weight is about FC370: 400000) solution mixing, after stirring into transparent and homogeneous solution, is molded into mixed solution in plastic disc, seasoning film forming.Film is peeled off naturally, after being placed in baking oven 190 DEG C of physical crosslinking 1h, again film is dipped in the glutaraldehyde (GA containing a small amount of HCl of 15mL 10%, 25wt%) in acetone (>=99.5wt%) solution, after carrying out chemical crosslink reaction 1h under room temperature, film is taken out, be dipped in deionized water and fully wash.By the PVA/ prepared through aforesaid method
fC370 film takes out after being immersed in and carrying out ion-exchange 24h in 2M KOH solution, and the KOH repeatedly cleaning film surface adsorption with deionized water, to neutral, namely obtains PVA/
fC370 alkaline negative ion exchange composite film.
Tested under the constant-temperature constant-humidity environment of 20 DEG C of 60% relative humidity by H5K-S shaped material trier (Britain Hounsfield).Speed of experiment is 5mm/min, and sample standard is 2cm × 1cm.As shown in Figure 1, tensile strength is 59.9MPa to result, and elongation at break is 9.2%, and Young's modulus is 800.4MPa, and result is all in limit of error.
Embodiment 5
Be dissolved in 300ml deionized water by the PVA powder (molecular weight is: 89000-98000) of 30g, at 90 DEG C, heated and stirred is to transparent uniform solution, prepares 10%PVA storing solution.By PVA with
fC370 mass ratio=1: 1 by the above-mentioned PVA aqueous solution with
(molecular weight is about FC370: 400000) solution mixing, after stirring into transparent and homogeneous solution, is molded into mixed solution in plastic disc, seasoning film forming.Film is peeled off naturally, after being placed in baking oven 170 DEG C of physical crosslinking 1h, again film is dipped in the glutaraldehyde (GA containing a small amount of HCl of 15mL 10%, 25wt%) in acetone (>=99.5wt%) solution, after carrying out chemical crosslink reaction 1h under room temperature, film is taken out, be dipped in deionized water and fully wash, obtain the quaternary ammonium salt negatively charged ion composite membrane of modification.By the PVA/ prepared through aforesaid method
fC370 film takes out after being immersed in and carrying out ion-exchange 24h in 2M KOH solution, and the KOH repeatedly cleaning film surface adsorption with deionized water, to neutral, namely obtains PVA/
fC370 alkaline negative ion exchange composite film, is stored in film in deionized water.
The PVA/Luviquat film prepared through aforesaid method is immersed in H under room temperature
2o
2(30wt%), in solution, their quality change is measured at set intervals.As shown in Figure 3, this film has showed excellent antioxidative stabilizer to result, at immersion H
2o
2(30wt%) occurred the obvious mass loss of 5% in 96h, but in 240 subsequently, almost stable is at the 93-94% of proper mass.
Embodiment 6
Be dissolved in 300ml deionized water by the PVA powder (molecular weight is: 89000-98000) of 30g, at 90 DEG C, heated and stirred is to transparent uniform solution, prepares 10%PVA storing solution.By PVA with
fC370 mass ratio=1: 1 by the above-mentioned PVA aqueous solution with
(molecular weight is about FC370: 400000) solution mixing, after stirring into transparent and homogeneous solution, is molded into mixed solution in plastic disc, seasoning film forming.Film is peeled off naturally, under being placed in baking oven differing temps after (130 DEG C, 150 DEG C, 170 DEG C and 190 DEG C) physical crosslinking 1h, again film is dipped in the glutaraldehyde (GA containing a small amount of HCl of 15mL 10%, 25wt%) in acetone (>=99.5wt%) solution, after carrying out chemical crosslink reaction 1h under room temperature, film is taken out, be dipped in deionized water and fully wash.By the PVA/ prepared through aforesaid method
fC370 film takes out after being immersed in and carrying out ion-exchange 24h in 2M KOH solution, and the KOH repeatedly cleaning film surface adsorption with deionized water, to neutral, namely obtains PVA/
fC370 alkaline negative ion exchange composite film, is then stored in film in deionized water.
Measure its specific conductivity and water ratio respectively by AC impedence method and dry weight in wet base method, as shown in Figure 4, specific conductivity can reach 5.1 × 10 to result
-3s em
-1, water ratio is about 55%.Fig. 5 is that PVA/Luviquat alkaline anion-exchange membrane is at (a) 130 DEG C (b) 150 DEG C (c) 170 DEG C (d) 190 DEG C of physical crosslinking 1h, the outward appearance photo comparison figure in 2M KOH solution is immersed in after chemically crosslinked 1h, as seen from Figure 5, temperature is higher, and the color of film is darker.
Embodiment 7
Be dissolved in 300ml deionized water by the PVA powder (molecular weight is: 89000-98000) of 30g, at 90 DEG C, heated and stirred is to transparent uniform solution, prepares 10%PVA storing solution.By PVA with
fC370 mass ratio=1: 1 (state the PVA aqueous solution with
(molecular weight is about FC370: 400000) solution mixing, after stirring into transparent and homogeneous solution, is molded into mixed solution in plastic disc, seasoning film forming.Film is peeled after being placed in baking oven 130 DEG C of physical crosslinking 1h, again film is dipped in the glutaraldehyde (GA containing a small amount of HCl of 15mL 10%, 25wt%) in acetone (>=99.5wt%) solution, after carrying out chemical crosslink reaction 1h under room temperature, film is taken out, be dipped in deionized water and fully wash, obtain the quaternary ammonium salt negatively charged ion composite membrane of modification.By the PVA/ prepared through aforesaid method
fC370 film takes out after being immersed in and carrying out ion-exchange 24h in 2M KOH solution, and the KOH repeatedly cleaning film surface adsorption with deionized water, to neutral, namely obtains PVA/
fC370 alkaline negative ion exchange composite film.
Fig. 6 is PVA/
fC370 alkaline anion-exchange membrane is at 130 DEG C of physical crosslinking 1h, the MEAH of chemically crosslinked 1h
2/ O
2the room temperature generating curve of fuel cell, negative and positive the two poles of the earth all adopt the 40%Pt/C catalyzer of JohnsonMatthey company of the U.S., and carrying capacity is 0.5mg/cm
2, useful area is 4cm
2.At normal temperatures and pressures, hydrogen flowing quantity is 100mL/min, and oxygen flow is 70mL/min, carries out monocell performance test.As seen from Figure 6, by PVA/
mEA open circuit voltage (OCV) prepared by FC370 alkaline anion-exchange membrane reaches 1.04V, and the commercial alkaline film with Japanese Tokuyama company is suitable, and preliminary generated output is 11.40mW/cm
2, maximum current density is 50.8mA/cm
2, show the application potential in alkaline fuel cell field.
Claims (9)
1. a high-strength mechanical performance alkaline negative ion exchange composite film, is characterized in that, comprises low-molecular-weight containing oxygen base water-soluble poval and the water-soluble polymers containing quaternary ammonium group.
2. high-strength mechanical performance alkaline negative ion exchange composite film as claimed in claim 1, is characterized in that, the described low-molecular-weight weight-average molecular weight containing oxygen base water-soluble ethylene alcohol is 89000 < M
w< 98000; The described water-soluble polymers containing quaternary ammonium group is the polymkeric substance of chlorination-1-vinyl-3-methyl isophthalic acid H-imidazoles and l-vinyl-2-pyrrolidone.
3. a preparation method for high-strength mechanical performance alkaline negative ion exchange composite film according to claim 2, is characterized in that, comprise the following steps:
Step 1): the polymkeric substance containing oxygen base water-soluble poval and chlorination-1-vinyl-3-methyl isophthalic acid H-imidazoles and l-vinyl-2-pyrrolidone is configured to the aqueous solution respectively, under room temperature, the aqueous solutions of polymers of chlorination-1-vinyl-3-methyl isophthalic acid H-imidazoles and l-vinyl-2-pyrrolidone is slowly added stirring containing in the oxygen base water-soluble poval aqueous solution, continue to stir until obtain forming homogeneous mixing solutions, vacuum filtration, filtrate is poured in plastic culture dish, seasoning film forming, obtains polymeric film;
Step 2): by step 1) obtained polymeric film nature peels off from culture dish, through thermal treatment physical crosslinking, then through chemically crosslinked, finally leaching is placed in KOH solution and carries out ion-exchange and get final product.
4. the preparation method of high-strength mechanical performance alkaline negative ion exchange composite film as claimed in claim 3, is characterized in that, described step 2) in the crosslinking temperature of thermal treatment physical crosslinking be 130 ~ 190 DEG C; Crosslinking time is 30min ~ 2h.
5. the preparation method of high-strength mechanical performance alkaline negative ion exchange composite film as claimed in claim 4, is characterized in that, described step 2) in the crosslinking temperature of thermal treatment physical crosslinking be 170 DEG C; Crosslinking time is 1h.
6. as the preparation method with high-strength mechanical performance alkaline negative ion exchange composite film in claim 3-5 as described in any one, it is characterized in that, described step 2) in time of chemically crosslinked be 1h.
7. there is the preparation method of high-strength mechanical performance alkaline negative ion exchange composite film as claimed in claim 3, it is characterized in that, described step 2) in the volumetric molar concentration of KOH solution be 1-6mol/L.
8. a high-strength mechanical performance alkaline negative ion exchange composite film is applied to and prepares alkaline fuel cell membrane electrode.
9. the application of high-strength mechanical performance alkaline negative ion exchange composite film as claimed in claim 8, it is characterized in that, described alkaline fuel cell membrane electrode is metal-air battery, CO
2electrochemical reduction and chlorine industry diaphragm material.
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| CN112510235A (en) * | 2020-12-03 | 2021-03-16 | 东华大学 | Polyvinyl alcohol-bacterial cellulose trimmings structure type alkaline anion exchange membrane, preparation and application |
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| CN107108928A (en) * | 2014-12-19 | 2017-08-29 | 通用电气公司 | The amberplex prepared using cross-linking ion exchange polymer constituent |
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| US20200099078A1 (en) * | 2015-11-26 | 2020-03-26 | Hangzhou Dianzi University | Preparation Method for Alkaline Anion Exchange Membrane and Use Thereof in Fuel Cell |
| US10797333B2 (en) * | 2015-11-26 | 2020-10-06 | Hangzhou Dianzi University | Preparation method for alkaline anion exchange membrane and use thereof in fuel cell |
| CN111088504A (en) * | 2018-10-24 | 2020-05-01 | 武汉大学 | Practical carbon dioxide reduction membrane electrolyzer and preparation method thereof |
| CN110444792A (en) * | 2019-07-12 | 2019-11-12 | 大连理工大学 | A kind of long-chain polyfunctional group Polyvinyl alcohol anion-exchange membrane and preparation method thereof |
| CN110444792B (en) * | 2019-07-12 | 2022-04-12 | 大连理工大学 | Long-chain polyfunctional group polyvinyl alcohol anion exchange membrane and preparation method thereof |
| CN110534682A (en) * | 2019-08-05 | 2019-12-03 | 长沙理工大学 | A kind of preparation method of alkaline oxygenated reduction flow battery amberplex |
| CN112510235A (en) * | 2020-12-03 | 2021-03-16 | 东华大学 | Polyvinyl alcohol-bacterial cellulose trimmings structure type alkaline anion exchange membrane, preparation and application |
| CN114292425A (en) * | 2021-12-21 | 2022-04-08 | 盐城工学院 | Polymer @ metal-MOF @ ionic liquid composite alkaline anion exchange membrane and preparation method thereof |
| CN114292425B (en) * | 2021-12-21 | 2023-11-17 | 盐城工学院 | Polymer @ metal-MOF@ ionic liquid composite alkaline anion exchange membrane and preparation method thereof |
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