CN104371128B - High-strength mechanical performance alkaline negative ion exchange composite film, preparation and application - Google Patents
High-strength mechanical performance alkaline negative ion exchange composite film, preparation and application Download PDFInfo
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- CN104371128B CN104371128B CN201410603355.XA CN201410603355A CN104371128B CN 104371128 B CN104371128 B CN 104371128B CN 201410603355 A CN201410603355 A CN 201410603355A CN 104371128 B CN104371128 B CN 104371128B
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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- 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
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Abstract
The present invention relates to a kind of preparation and its application of the alkaline negative ion exchange composite film with high-strength mechanical performance, its component includes：Low molecule amount oxygen-containing group water-soluble poval and the methyl 1H imidazoles of 1 vinyl of water-soluble chlorination 3 and the polymer of the pyrrolidones of 1 vinyl 2 containing quaternary ammonium group.Its preparation method is：By oxygen-containing group water-solubility PVA and contain quaternary ammonium group
Description
Technical field
The invention belongs to alkaline membrane and its preparation and application field, more particularly to a kind of alkali with high-strength mechanical performance
Property anion exchange composite membrane and its preparation and application.
Background technology
Polymer-membrane fuel battery (PEMFC), according to the difference of conductive ion, can be divided into PEM (PEM) fuel
Battery and alkaline anion-exchange membrane (AEM) fuel cell.PEM fuel cell has that disposal of pollutants is small, operating temperature is low, activation
Time is short, long lifespan, it is stable, be easy to large-scale production, the advantages of energy conversion efficiency is higher, it has also become 21 century is high
One of effect, environment-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.].For example, du pont company gives birth to
The PEM of productionIt is widely used with excellent electrical conductivity and chemistry, electrochemistry and mechanical stability.
However,Film production process is complicated, and its commercialized development is instability limit under expensive and high temperature
[V.Neburchilov, J.Martin, H.Wang, J.Zhang, A review of polymer
Electrolytemembranes for direct methanol fuel cells, Journal of Power Sources
169(2007)221]。
In recent years, AEM and its application in a fuel cell cause extensive concern.AEM fuel cells have faster
Kinetics, fuel leak and CO poisoning risk also greatly suppressed, further, it is also possible to be urged using non-platinum noble metals
Agent, can effectively reduce fuel cell cost.Alkaline negative ion exchange composite film (AEM) species is various, and its skeleton is from polyolefin
(PO), polysiloxanes (PSO), biphenyl polyether ketone (PPEK), poly (arylene ether) ether sulfone (PAES) wait until organic/inorganic composite material
[Y.J.Wang, 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.Power Sources 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, while in high concentration alkali
Under the conditions of liquid, particularly higher temperature (be more than 60 DEG C) it is unstable caused by film properties decline even membrane degradation, the mechanics of film
Intensity drastically declines therewith, therefore, develops and develop high-performance, high stability, with superior mechanical strength and easy preparation and valency
The cheap novel alkaline anion-exchange membrane of lattice is significant.
The content of the invention
The technical problem solved required for of the invention is to provide a kind of alkali anion with high-strength mechanical performance and handed over
Composite membrane and its preparation and application are changed, the film shows higher tensile resistance, there is certain elongation at break again, significantly
Reduction fuel cell cost, preparation method is simple, and cost is low, good film-forming property, is suitable for industrialized production.
In order to solve the above-mentioned technical problem, exchange compound the invention provides a kind of high-strength mechanical performance alkali anion
Film, it is characterised in that the oxygen-containing group water-soluble poval (PVA) including low molecule amount and the water-soluble poly containing quaternary ammonium group
Compound (Series polymer).
Preferably, the weight average molecular weight of the oxygen-containing group water-soluble ethylene alcohol of the low molecule amount is 89000 ＜ Mw＜
98000；The water-soluble polymer containing quaternary ammonium group be chlorination -1- vinyl -3- methyl isophthalic acid H- imidazoles and 1- vinyl -
The polymer of 2-Pyrrolidone.
Present invention also offers the preparation method of above-mentioned high-strength mechanical performance alkaline negative ion exchange composite film, its feature
It is, comprises the following steps：
Step 1)：By oxygen-containing group water-soluble poval and chlorination -1- vinyl -3- methyl isophthalic acid H- imidazoles and 1- ethene
The polymer of base -2-Pyrrolidone is each configured to the aqueous solution, at room temperature by chlorination -1- vinyl -3- methyl isophthalic acid H- imidazoles with
The aqueous solutions of polymers of l-vinyl-2-pyrrolidone is slowly added in the oxygen-containing group water-soluble poval aqueous solution of stirring,
Continue to stir until obtaining forming homogeneous mixed solution, filtrate is poured into plastic culture dish, spontaneously dried into by vacuum filtration
Film, obtains polymer film；
Step 2)：By step 1) made from polymer film peeled off naturally from culture dish, thermally treated physical crosslinking, then pass through
Chemical crosslinking, finally leaching is placed in progress ion exchange in KOH solution and produced.
Preferably, the step 2) in heat treatment physical crosslinking crosslinking temperature be 130~190 DEG C；Crosslinking time is
30min~2h.
Further, the step 2) in heat treatment physical crosslinking crosslinking temperature be 170 DEG C；Crosslinking time is 1h.
Preferably, the step 2) in chemical crosslinking time be 1h.
Preferably, the step 2) in KOH solution molar concentration be 1-6mol/L.
It is applied to prepare alkalescence combustion present invention also offers a kind of high-strength mechanical performance alkaline negative ion exchange composite film
Expect cell membrane-electrode.
Preferably, the alkaline fuel cell membrane electrode is metal-air battery, CO2Electrochemical reduction and chlor-alkali work
Industry diaphragm material.
Compared with prior art, the beneficial effects of the present invention are：
(1) alkaline negative ion exchange composite film of the invention had both shown excellent tensile resistance, was physical crosslinking temperature
130 DEG C of condition Tensile strengths are up to 76.7Mpa；And have preferable fracture elongation, be physical crosslinking 170 DEG C of conditions of temperature
Under, elongation at break is 14.9%, with excellent mechanical stability；
(2) preparation method of the invention is simple, and with low cost, easy operation, good film-forming property is suitable for industrialized production；
(3) alkaline negative ion exchange composite film of the invention can be directly used for, with H2-air fuel cells, being also used as
Metal-air battery and CO2The diaphragm material of electrochemical reduction, significantly reduces the cost of manufacture of fuel cell.
Brief description of the drawings
Fig. 1 be PVA/Luviquat FC370 alkaline negative ion exchange composite films respectively at 130 DEG C, 150 DEG C, 170 DEG C and
Stress-strain diagram under 190 DEG C of physical crosslinking 1h again after being chemically crosslinked 1h；
Fig. 2 is the outward appearance photo pair of PVA/Luviquat FC370 alkaline anion-exchange membranes before and after 170 DEG C of physical crosslinkings
Than figure；
Fig. 3 is that PVA/Luviquat FC370 alkaline anion-exchange membranes are physical crosslinking at 170 DEG C after 1h, chemical crosslinking 1h
Oxidation stability；
Fig. 4 is PVA/Luviquat FC370 alkaline anion-exchange membranes respectively at 130 DEG C, 150 DEG C, 170 DEG C and 190 DEG C
Electrical conductivity and moisture content after 2M KOH solution ion exchanges are physical crosslinking under 1h, chemical crosslinking 1h；
Fig. 5 is PVA/Luviquat FC370 alkaline anion-exchange membranes respectively in 130 DEG C of (a), 150 DEG C of (b), (c) 170
DEG C, the outward appearance photo comparison figure that is impregnated in after 190 DEG C of (d) physical crosslinking 1h, chemical crosslinking 1h in 2M KOH solutions；
Fig. 6 is that PVA/Luviquat FC370 alkaline anion-exchange membranes are physical crosslinking at 130 DEG C after 1h, chemical crosslinking 1h
Prepare the monocell generating curve of membrane electrode (MEA) at normal temperatures and pressures.
Embodiment
To become apparent the present invention, hereby with preferred embodiment, and accompanying drawing is coordinated to be described in detail below.
Oxygen-containing group water-solubility PVA in embodiment 1-6 originates from Sigma-Aldrich (Shanghai) trade Co., Ltd；
Luviquat uses the FC370 that Sigma-Aldrich (Shanghai) trade Co., Ltd produces.
Embodiment 1
By 30g oxygen-containing group water-solubility PVA powder, (molecular weight is：89000-98000) it is dissolved in 300ml deionized waters,
Heating stirring prepares 10%PVA storing solutions to transparent uniform solution at 90 DEG C.By PVA withFC370 mass
Than=1: 1 by the above-mentioned PVA aqueous solution with(molecular weight is about FC370：400000) solution is mixed, and is stirred into homogeneous
After clear solution, mixed liquor is molded into plastic disc, film forming is spontaneously dried.Film is peeled off naturally, 130 DEG C are placed in baking oven
Be physical crosslinking 1h after, then by film be dipped in 15mL 10% containing a small amount of HCl glutaraldehyde (GA, 25wt%) acetone (>=
99.5wt%) in solution, taken the film out after carrying out chemical crosslink reaction 1h at room temperature, be dipped in deionized water and fully wash.Will
The PVA/ prepared through the above methodFC370 films, which are immersed in 2M KOH solutions, taken out after ion exchange 24h, uses
Deionized water cleans the KOH of film adsorption to neutrality repeatedly, that is, obtains PVA/FC370 alkali anions are exchanged
Composite membrane.
By H5K-S type Material Testing Machine (Britain Hounsfield) 20 DEG C of 60% relative humidity constant-temperature constant-humidity environment
It is lower to be tested.Speed of experiment is 5mm/min, and sample standard is 2cm × 1cm.As a result as shown in figure 1, being can be found that from figure
The film has very strong tensile resistance, and with maximum tensile strength, up to 76.7MPa, elongation at break is 11.8%, poplar
Family name's modulus is 958.5MPa.Under the conditions of same elongation at break 8%, the alkali anion through 130 DEG C of physical crosslinking Temperature Treatments
Exchange membrane has maximum tensile strength 67.2MPa.
Embodiment 2
By 30g PVA powder, (molecular weight is：89000-98000) it is dissolved in 300ml deionized waters, heating is stirred at 90 DEG C
Mix to transparent uniform solution, prepare 10%PVA storing solutions.By PVA withFC370 mass ratio=1: 1 will be above-mentioned
The PVA aqueous solution with(molecular weight is about FC370：400000) solution is mixed, and is stirred into after transparent and homogeneous solution, will
Mixed liquor is molded into plastic disc, spontaneously dries film forming.Film is peeled off naturally, is placed in baking oven after 150 DEG C of physical crosslinking 1h,
Film is dipped in 15mL 10% glutaraldehyde (GA, 25wt%) acetone (>=99.5wt%) solution containing a small amount of HCl again, room
Taken the film out after the lower progress chemical crosslink reaction 1h of temperature, be dipped in deionized water and fully wash.By what is prepared through the above method
PVA/FC370 films, which are immersed in 2M KOH solutions, taken out after ion exchange 24h, is cleaned repeatedly with deionized water
The KOH of film adsorption obtains PVA/ to neutralityFC370 alkaline negative ion exchange composite films.
By H5K-S type Material Testing Machine (Britain Hounsfield) 20 DEG C of 60% relative humidity constant-temperature constant-humidity environment
It is lower to be tested.Speed of experiment is 5mm/min, and sample standard is 2cm × 1cm.As a result as shown in figure 1, the film equally has very
Strong tensile resistance, tensile strength is 62.6MPa, and elongation at break is 14.1%, and Young's modulus is 791.7MPa.
Embodiment 3
By 30g PVA powder, (molecular weight is：89000-98000) it is dissolved in 300ml deionized waters, heating is stirred at 90 DEG C
Mix to transparent uniform solution, prepare 10%PVA storing solutions.By PVA withFC370 mass ratio=1: 1 will be upper
State the PVA aqueous solution with(molecular weight is about FC370：400000) solution is mixed, and is stirred into after transparent and homogeneous solution,
Mixed liquor is molded into plastic disc, film forming is spontaneously dried.Film is peeled and is placed in baking oven after 170 DEG C of physical crosslinking 1h, then
Film is dipped in 15mL 10% glutaraldehyde (GA, 25wt%) acetone (>=99.5wt%) solution containing a small amount of HCl, room temperature
Taken the film out after lower progress chemical crosslink reaction 1h, be dipped in deionized water and fully wash.The PVA/ that will be prepared through the above methodFC370 films, which are immersed in 2M KOH solutions, taken out after ion exchange 24h, cleans film table repeatedly with deionized water
The KOH of face absorption obtains PVA/ to neutralityFC370 alkaline negative ion exchange composite films.Fig. 2 is 170 DEG C of physics
The outward appearance photo comparison figure of PVA/Luviquat alkaline anion-exchange membranes before and after crosslinking, from Figure 2 it can be seen that 170 DEG C of physical crosslinkings
Front and rear PVA/Luviquat alkaline anion-exchange membranes are changed into yellow from colourless.
By H5K-S type Material Testing Machine (Britain Hounsfield) 20 DEG C of 60% relative humidity constant-temperature constant-humidity environment
It is lower to be tested.Speed of experiment is 5mm/min, and sample standard is 2cm × 1cm.As a result as shown in figure 1, tensile strength is
59.3MPa, elongation at break is 14.9%, and Young's modulus is 793.0MPa.It can be found that the film has maximum break from figure
Under the conditions of splitting elongation, same tensile strength 50MPa, the alkaline anion-exchange membrane through 170 DEG C of physical crosslinking Temperature Treatments
Elongation at break is maximum, up to 10.6%.
Embodiment 4
By 30g PVA powder, (molecular weight is：89000-98000) it is dissolved in 300ml deionized waters, heating is stirred at 90 DEG C
Mix to transparent uniform solution, prepare 10%PVA storing solutions.By PVA withFC370 mass ratio=1: 1 will be upper
State the PVA aqueous solution with(molecular weight is about FC370：400000) solution is mixed, and is stirred into after transparent and homogeneous solution,
Mixed liquor is molded into plastic disc, film forming is spontaneously dried.Film is peeled off naturally, 190 DEG C of physical crosslinking 1h in baking oven are placed in
Afterwards, then by film it is dipped in 15mL 10% glutaraldehyde (GA, 25wt%) acetone (>=99.5wt%) solution containing a small amount of HCl,
Taken the film out after carrying out chemical crosslink reaction 1h at room temperature, be dipped in deionized water and fully wash.By what is prepared through the above method
PVA/FC370 films, which are immersed in 2M KOH solutions, taken out after ion exchange 24h, is cleaned repeatedly with deionized water
The KOH of film adsorption obtains PVA/ to neutralityFC370 alkaline negative ion exchange composite films.
By H5K-S type Material Testing Machine (Britain Hounsfield) 20 DEG C of 60% relative humidity constant-temperature constant-humidity environment
It is lower to be tested.Speed of experiment is 5mm/min, and sample standard is 2cm × 1cm.As a result as shown in figure 1, tensile strength is
59.9MPa, elongation at break is 9.2%, and Young's modulus is 800.4MPa, as a result in error range.
Embodiment 5
By 30g PVA powder, (molecular weight is：89000-98000) it is dissolved in 300ml deionized waters, heating is stirred at 90 DEG C
Mix to transparent uniform solution, prepare 10%PVA storing solutions.By PVA withFC370 mass ratio=1: 1 will be upper
State the PVA aqueous solution with(molecular weight is about FC370：400000) solution is mixed, and is stirred into after transparent and homogeneous solution,
Mixed liquor is molded into plastic disc, film forming is spontaneously dried.Film is peeled off naturally, 170 DEG C of physical crosslinking 1h in baking oven are placed in
Afterwards, then by film it is dipped in 15mL 10% glutaraldehyde (GA, 25wt%) acetone (>=99.5wt%) solution containing a small amount of HCl,
Taken the film out after carrying out chemical crosslink reaction 1h at room temperature, be dipped in deionized water and fully wash, obtain modified quaternary ammonium salt cloudy
Ion composite membrane.The PVA/ that will be prepared through the above methodFC370 films, which are immersed in 2M KOH solutions, carries out ion exchange
Taken out after 24h, clean the KOH of film adsorption repeatedly with deionized water to neutrality, that is, obtain PVA/FC370 alkali
Property anion exchange composite membrane, film is stored in deionized water.
The PVA/Luviquat films prepared through the above method are immersed in H at room temperature2O2In (30wt%) solution, Mei Geyi
Their mass change of section timing.As a result as shown in figure 3, the film is demonstrated by excellent antioxidative stabilizer, in immersion H2O2
5% obvious mass loss is occurred in that in (30wt%) 96h, but in subsequent 240, almost stablizes the 93- in proper mass
94%.
Embodiment 6
By 30g PVA powder, (molecular weight is：89000-98000) it is dissolved in 300ml deionized waters, heating is stirred at 90 DEG C
Mix to transparent uniform solution, prepare 10%PVA storing solutions.By PVA withFC370 mass ratio=1: 1 will be upper
State the PVA aqueous solution with(molecular weight is about FC370：400000) solution is mixed, and is stirred into after transparent and homogeneous solution,
Mixed liquor is molded into plastic disc, film forming is spontaneously dried.Film is peeled off naturally, is placed in baking oven (130 under different temperatures
DEG C, 150 DEG C, 170 DEG C and 190 DEG C) after physical crosslinking 1h, then film is dipped in 15mL 10% glutaraldehyde containing a small amount of HCl
In (GA, 25wt%) acetone (>=99.5wt%) solution, taken the film out after carrying out chemical crosslink reaction 1h at room temperature, be dipped in from
Fully washed in sub- water.The PVA/ that will be prepared through the above methodFC370 films, which are immersed in 2M KOH solutions, carries out ion
Exchange and taken out after 24h, clean the KOH of film adsorption repeatedly with deionized water to neutrality, that is, obtain PVA/
Film, is then stored in deionized water by FC370 alkaline negative ion exchange composite films.
Its electrical conductivity and moisture content are determined respectively with AC impedence method and dry and wet weight method, as a result as shown in figure 4, electrical conductivity can
Up to 5.1 × 10-3S em-1, moisture content is 55% or so.Fig. 5 is PVA/Luviquat alkaline anion-exchange membranes 130 DEG C of (a)
(b) the outward appearance photo comparison in 2M KOH solutions is immersed in after 170 DEG C of 150 DEG C (c) (d) 190 DEG C of physical crosslinking 1h, chemical crosslinking 1h
Figure, as seen from Figure 5, temperature is higher, and the color of film is deeper.
Embodiment 7
By 30g PVA powder, (molecular weight is：89000-98000) it is dissolved in 300ml deionized waters, heating is stirred at 90 DEG C
Mix to transparent uniform solution, prepare 10%PVA storing solutions.By PVA withFC370 mass ratio=1: 1 (states
The PVA aqueous solution with(molecular weight is about FC370：400000) solution is mixed, and is stirred into after transparent and homogeneous solution, will
Mixed liquor is molded into plastic disc, spontaneously dries film forming.Film is peeled and is placed in baking oven after 130 DEG C of physical crosslinking 1h, then will
Film is dipped in 15mL 10% glutaraldehyde (GA, 25wt%) acetone (>=99.5wt%) solution containing a small amount of HCl, at room temperature
Taken the film out after carrying out chemical crosslink reaction 1h, be dipped in deionized water and fully wash, obtained modified quaternary ammonium salt anionic and answer
Close film.The PVA/ that will be prepared through the above methodFC370 films are immersed in 2M KOH solutions and carried out after ion exchange 24h
Take out, clean the KOH of film adsorption repeatedly with deionized water to neutrality, that is, obtain PVA/FC370 alkalescence it is cloudy from
Son exchanges composite membrane.
Fig. 6 is PVA/FC370 alkaline anion-exchange membranes are physical crosslinking 1h at 130 DEG C, chemical crosslinking 1h's
MEAH2/O2The room temperature generating curve of fuel cell, negative and positive the two poles of the earth use the 40%Pt/C of Johnson Matthey companies of the U.S.
Catalyst, carrying capacity is 0.5mg/cm2, effective area is 4cm2.At normal temperatures and pressures, hydrogen flowing quantity is 100mL/min, oxygen
Flow is 70mL/min, carries out monocell performance test.As seen from Figure 6, by PVA/FC370 alkalescence it is cloudy from
MEA open-circuit voltages (OCV) prepared by proton exchange reach 1.04V, suitable with the commercial alkaline film of Tokuyama companies of Japan,
Preliminary generated output is 11.40mW/cm2, maximum current density is 50.8mA/cm2, show in alkaline fuel cell field
Application potential.
Claims (8)
1. a kind of high-strength mechanical performance alkaline negative ion exchange composite film, it is characterised in that include the oxygen-containing group of low molecule amount
Water-soluble poval and the water-soluble polymer containing quaternary ammonium group；The oxygen-containing group water-soluble ethylene alcohol of the low molecule amount
Weight average molecular weight is 89000< Mw < 98000；The water-soluble polymer containing quaternary ammonium group be chlorination -1- vinyl -
The polymer of 3- methyl isophthalic acid H- imidazoles and l-vinyl-2-pyrrolidone.
2. a kind of preparation method of the high-strength mechanical performance alkaline negative ion exchange composite film described in claim 1, its feature
It is, comprises the following steps：
Step 1）：By oxygen-containing group water-soluble poval and chlorination -1- vinyl -3- methyl isophthalic acid H- imidazoles and 1- vinyl -2-
The polymer of pyrrolidones is each configured to the aqueous solution, at room temperature by chlorination -1- vinyl -3- methyl isophthalic acid H- imidazoles and 1- ethene
The aqueous solutions of polymers of base -2-Pyrrolidone is slowly added in the oxygen-containing group water-soluble poval aqueous solution of stirring, continues to stir
Mix until obtaining forming homogeneous mixed solution, vacuum filtration pours into filtrate in plastic culture dish, spontaneously dries film forming, obtains
Polymer film；
Step 2）：By step 1）Obtained polymer film is peeled off naturally from culture dish, thermally treated physical crosslinking, then through chemistry
Crosslinking, finally leaching is placed in progress ion exchange in KOH solution and produced.
3. the preparation method of high-strength mechanical performance alkaline negative ion exchange composite film as claimed in claim 2, its feature exists
In the step 2）In heat treatment physical crosslinking crosslinking temperature be 130 ~ 190 DEG C；Crosslinking time is 30min ~ 2h.
4. the preparation method of high-strength mechanical performance alkaline negative ion exchange composite film as claimed in claim 3, its feature exists
In the step 2）In heat treatment physical crosslinking crosslinking temperature be 170 DEG C；Crosslinking time is 1h.
5. the preparation side of the high-strength mechanical performance alkaline negative ion exchange composite film as described in any one in claim 2-4
Method, it is characterised in that the step 2）The time of middle chemical crosslinking is 1h.
6. the preparation method of high-strength mechanical performance alkaline negative ion exchange composite film as claimed in claim 2, its feature exists
In the step 2）The molar concentration of middle KOH solution is 1-6 mol/L.
7. the high-strength mechanical performance alkaline negative ion exchange composite film described in a kind of claim 1 is applied to prepare basic fuel
Cell membrane-electrode.
8. the application of high-strength mechanical performance alkaline negative ion exchange composite film as claimed in claim 7, it is characterised in that institute
Alkaline fuel cell membrane electrode is stated for metal-air battery, CO2Electrochemical reduction and chlorine industry diaphragm material.
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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 |
| CN105680055B (en) * | 2015-11-26 | 2018-05-04 | 杭州电子科技大学 | A kind of preparation method of alkaline anion-exchange membrane and its application in a fuel cell |
| CN111088504B (en) * | 2018-10-24 | 2021-04-02 | 武汉大学 | Practical carbon dioxide reduction membrane electrolyzer 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 |
| 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 |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN103384697A (en) * | 2011-02-23 | 2013-11-06 | 大日精化工业株式会社 | Aqueous liquid composition, aqueous coating, functional coating film, and composite material |
| CN103724644A (en) * | 2014-01-08 | 2014-04-16 | 山东大学 | Method for preparing PEI (Polyethyleneimine) and PVA (Polyvinyl Alcohol) based fuel cell composite proton conducting membrane |
-
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- 2014-10-30 CN CN201410603355.XA patent/CN104371128B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103384697A (en) * | 2011-02-23 | 2013-11-06 | 大日精化工业株式会社 | Aqueous liquid composition, aqueous coating, functional coating film, and composite material |
| 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 |
| CN103724644A (en) * | 2014-01-08 | 2014-04-16 | 山东大学 | Method for preparing PEI (Polyethyleneimine) and PVA (Polyvinyl Alcohol) based fuel cell composite proton conducting membrane |
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