CN109384944A - Cross-linking type block polymer anion-exchange membrane and its preparation and application - Google Patents
Cross-linking type block polymer anion-exchange membrane and its preparation and application Download PDFInfo
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Abstract
The present invention relates to cross-linking type block polymer anion-exchange membrane and its preparations and application.The block polymer of chloromethylation is carried out crosslinking and amination using one-step method in film-forming process by this method simultaneously, and further quaternized to film progress using tertiary amine after film forming, and cross-linking type anion-exchange membrane is obtained after alkalizing.This method is 1 using green low toxicity, 4- dichloro methyl butyl ether is that chloromethylation reagents carry out chloromethylation to polymer, the crosslinking and amination of polymer are carried out using tertiary amine in film forming procedure, tertiary amine amination again is used after film forming, further increases the quantity of quaternary ammonium group.Advantage of this approach is that crosslinking carries out simultaneously with quaternized in film forming procedure, the mechanical strength and dimensional stability of cross linking membrane are not only increased, and effectively increase quaternized efficiency.The cross-linking type anion-exchange membrane conductivity with higher that the present invention obtains has potential application prospect in alkaline anion-exchange membrane fuel cell.
Description
Technical field
The present invention relates to alkaline anion-exchange membrane fuel cell, specifically a kind of cross-linking type block polymer anion
The preparation method of exchange membrane.
Background technique
Alkaline membrane cell (AEMFC) has reduction kinetics of oxygen fast, and non-platinum catalyst, the requirement of material corrosion resistant can be used
It is small, the advantages that cost is few, so as the anion-exchange membrane of one of its critical material in terms of chemical property and stability and also
It is in urgent need to be improved.This is because current anion-exchange membrane is mainly made of different polymer backbone grafted cation groups,
Wherein cation group is then based on quaternary ammonium group.
The study found that between the ion exchange capacity and mechanical strength of this series anion-exchange membrane, there are a degree of lances
Shield, as when ion exchange capacity is excessive causes water content excessively high, film is easy embrittlement, when right ion exchange capacity is too small, although film
Mechanical strength have guarantee, but ionic conductivity is greatly reduced.In addition, quaternary ammonium polymer anion-exchange membrane is in highly basic
And it may be by OH under hot conditions-Nucleophillic attack, cause quaternary ammonium group be detached from skeleton, thus make film occur chemical degradation,
Conductivity and mechanical strength decline.In conclusion really to realize quaternary ammonium polymer anion-exchange membrane in a fuel cell
Application, need to propose a kind of effective solution method with reconcile film ion exchange capacity and mechanical strength between contradiction,
It is set to be provided simultaneously with ion exchange capacity height, conductivity height, high mechanical strength, thermal stability and chemical stability good etc. excellent
Point.
Studies have shown that can be obtained by the excellent polymer backbone of direct synthesizing new and to the chemical modification of existing polymer
Obtain ion exchange capacity height, the good anion-exchange membrane of mechanical strength.Wherein, the former be related to the design of molecular structure with it is excellent
Change, process is lengthy and tedious, and the period is long, and the latter is then easy to be quick, is easy to realize in a short time.The chemical modification for being referred from proton exchange membrane can
Know, be blended, adulterate, it is compound and crosslinking be used equally for improve film mechanical strength, wherein crosslinking have been demonstrated improve alkalinity
The ion exchange capacity of film and ionic conductivity are influenced while film mechanical strength smaller.Wuhan University's (Chinese patent " one
The preparation method of kind self-crosslinking polymer anion exchange membrane " number of patent application: 201010174360.5) discloses one kind certainly
The preparation method of cross-linked polymer anion-exchange membrane, they are added a little rudimentary secondary in the solution of chloromethylated polymer
Amine is passed through gaseous state trimethylamine under room temperature after mixing evenly and realizes quaternized, and rear casting film is concurrently born from cross-linking reaction, obtains
Anion-exchange membrane is much better than traditional polymer anion exchange in terms of mechanical performance, thermal stability and ion exchange capacity
Film.Unfortunately its preparation process is complex, and the rudimentary secondary amine used can not really realize the height between polymer backbone
Crosslinking, thus the raising space of membrane stability and little, while the chloromethyl of part is occupied after being crosslinked, continue it can not season
Ammonium thus reduces the quantity of quaternary ammonium group, ion exchange capacity is caused to become smaller.(China is specially for Dalian Chemical Physics Research Institute
Benefit: number of patent application: 201110427128.2) a kind of preparation method of crosslinking polymer anion-exchange membrane discloses poly-
The preparation method of aryl ether sulfone ketone cross linked anionic exchange membrane, this method makes crosslinking and quaternized synchronous progress, than in film forming
Quaternized preparation method afterwards, the anion-exchange membrane that the present invention obtains has higher ion exchange capacity, but it exists
Polymeric substrates contain the problems such as ehter bond etc. is easily degraded in alkaline environment.
The present invention is used as by tertiary amine using the aliphatic block polymer without containing ehter bond as polymeric substrates and is crosslinked examination
Agent forms a film with casting solution Hybrid Heating, the crosslinking of chloromethylated polymer basement membrane and primary quaternized is realized, relative to film forming
Quaternized method afterwards, carries out quaternized in film forming procedure, improves quaternized efficiency.Again using tertiary amine as season after film forming
Ammonium reagent carries out ammonium again, further increases the quantity of quaternary ammonium group on film.The cross-linking type anion that the present invention obtains
Exchange membrane shows apparent micron-scale phase separation structure, conductivity with higher, excellent dimensional stability and chemical stabilization
Property, there is potential application prospect in alkaline anion-exchange membrane fuel cell.
Summary of the invention
To overcome the conductivity of alkaline anion-exchange membrane existing in the prior art low, alkaline environment is degradable etc. is asked
Topic, the purpose of the present invention is to provide a kind of preparation method of environmental-friendly high-temperature resistance basic anion exchange membrane, make its
There is performance under preferable battery in alkaline anion-exchange membrane fuel cell.
To achieve the above object, the technical solution adopted by the present invention can be realized by the following method:
Cross-linking type block polymer anion-exchange membrane uses one-step method by the block after chloromethylation in film-forming process
Polymer carries out crosslinking and amination simultaneously, uses tertiary amine further quaternized after film forming, and the friendship of cross-linking type anion is obtained after alkalization
Film is changed, specifically includes the following steps:
1) configuration concentration is the chloromethylation block polymer organic solution of 0.5-5wt%, is stirred 12 hours at normal temperature
More than；
2) crosslinking agent will be added in chloromethylation block polymer organic solution, is stirred at room temperature 1-15 minutes, obtains mold
Liquid；
3) mold liquid is poured into flat plate mold, is put into 25-80 DEG C of drying box, kept for 12-48 hours, so that solvent steams
Hair, is crosslinked and quaternized Cl-Type polymer anion-exchange membrane；
4) by Cl-Type polymer anion-exchange membrane be immersed in ertiary amine solution further it is quaternized, impregnated at 25-60 DEG C
It is taken out after 24-48 hours, is rinsed for several times with deionized water, Cl is obtained after reaction-Type crosslinking polymer anion-exchange membrane；
5) Cl for obtaining step 4)-It is 0.01-10mol/L that type crosslinking polymer anion-exchange membrane, which is immersed in concentration,
Potassium hydroxide or sodium hydrate aqueous solution, soaking at room temperature takes out after 24-48 hours, rinsed with deionized water to flushing liquor pH value
It is 7, obtains cross-linking type block polymer anion-exchange membrane.
The solvent that the organic solution of configuration chloromethylation block polymer uses in step (1) of the present invention is dichloro
One of methane, chloroform or tetrahydrofuran or two kinds or more.
The connection agent being added in step (2) of the present invention into the organic solution of chloromethylation block polymer, packet
Include N, N, N ', N '-tetramethyl methanediamine (TMMDA), N,N,N',N' tetramethylethylene diamine (TMEDA), N, N, N ', N '-tetramethyl
One of base -1,6- hexamethylene diamine (TMHDA), additional amount are 0.5-2 times of chloromethylated polymer molal quantity.
The quaternized ertiary amine solution used is trimethylamine, triethylamine, tripropyl amine (TPA), second two in step (4) of the present invention
The mixture of one or more of amine.
Block polymer used in step (1) of the present invention specifically includes that styrene-butylene block copolymer
(SBS), styrene-ethylene-butadiene block copolymer (SEBS), acrylonitrile-butadiene-styrene copolymer (ABS), propylene
Nitrile-ethylene-styrene copolymer (AES), acrylonitritrile-styrene resin (AS), acrylonitrile-styrene-acrylic ester copolymerization
One of object (ASA) or two kinds or more, wherein styrene block content is 10-57wt.%.Wherein, chloromethylation block is poly-
The chloromethylation process for closing object is as follows:
Block polymer substrate is dissolved in chloroform, Isosorbide-5-Nitrae-dichloro methyl butyl ether (BCMB) and catalysis is added
Agent is stirred to react 1-12 hours at 20-80 DEG C；After reaction by reaction mixture pour into ethyl alcohol or methanol separate, wash,
It is dry, obtain chloromethylated polymer；Wherein, block polymer and BCMB molar ratio are 1:1-1:10；The solvent used for
Every gram of polymer, solvent usage 5-100mL；The reaction temperature of polymer chloromethylation is -20-100 DEG C, preferably -10-
25 DEG C, the reaction time is 10min to 12h；It is anhydrous zinc chloride or anhydrous stannic chloride, catalyst and polymer that catalyst, which is added,
The ratio between the amount of substance be 10:1-1:1.
Cross-linking type block polymer anion-exchange membrane is obtained using the preparation method, may be used as basic fuel electricity
Cation-exchange membrane in cell system.
Compared with prior art, the present invention has the advantage that
1) film-forming process is environmental-friendly, and carcinogenic organic solvent is not used；
2) the 1,4- dichloro methyl butyl ether (BCMB) of green low toxicity is used to carry out chlorine to polymer for chloromethylation reagents
Methylation, reactivity are high and low in cost；
3) crosslinking of chloromethylated polymer basement membrane and quaternized while carrying out, preparation process simple and effective, institute is realized
The cross linking membrane dimensional stability and chemical stability of preparation are excellent, and conductivity is higher than 10mS/cm, can preferably be applied to alkaline membrane
Fuel cell.
Detailed description of the invention
Fig. 1 is the structural schematic diagram of cross linking membrane prepared by embodiment 1.
Fig. 2 is the nuclear magnetic spectrogram of cross linking membrane prepared by embodiment 1.
Fig. 3 is the conductivity versus temperature curve of cross linking membrane prepared by embodiment 1.
Fig. 4 is the polarization curve of crosslinking film battery prepared by embodiment 2.
Fig. 5 is the antioxidative stabilizer test chart of cross linking membrane prepared by embodiment 2.
Fig. 6 is cross linking membrane antioxidative stabilizer test front and back conductivity and mechanical performance situation of change prepared by embodiment 2.
Fig. 7 is the alkaline stability test chart of cross linking membrane prepared by embodiment 3.
Fig. 8 is that the swellbility of cross linking membrane prepared by embodiment 3 varies with temperature figure.
Specific embodiment
Embodiment 1:
By molecular weight Mn ≈ 130000, polystyrene-ethylene-butylene-styrene of 5g styrene block content 58wt.%
(SEBS) it is dissolved in 150mL organic reagent chloroform, is stirred 5 hours at 55 DEG C, 7mL SnCl is added4With 46mL BCMB, reaction
3h pours into the solution after reaction in anhydrous methanol, after polymer is precipitated, filters, is washed with deionized to neutrality, then exists
60 DEG C of drying, obtain chloromethylated polystyrene-ethylene-butylene, Styrene (CMSEBS) in vacuum drying oven.It is dissolved in again
In chloroformic solution, the solution of 5wt.% is formed, N, N, N ' are added thereto, N '-tetramethyl -1,6- hexamethylene diamine (TMHDA) rubs
Your number is 1 times of CMSEBS, is stirred at room temperature 60 seconds, is subsequently poured into instrument bezel, is put into baking oven at 60 DEG C, and heating for 24 hours, will
Solvent drying, is removed.
By film soaking at room temperature in trimethylamine aqueous solution, impregnates 24 and as a child took out, be crosslinked and secondary quaternized
Cl-Form polymer anion-exchange membrane finally makes film soaking at room temperature in 1mol/L KOH solution for 24 hours, it is embedding to obtain cross-linking type
Section polymer anion-exchange membrane.
Obtained cross linking membrane, preparation process and structure are as shown in Figure 1.Its knot of polymer can be confirmed by nuclear magnetic spectrogram
Structure, as shown in Figure 2.
Conductivity (not being humidified completely, see attached drawing 3) under cross linking membrane different temperatures is tested using AC impedence method (EIS).It surveys
The potential amplitude of amount is that the ion resistance of 10mV composite membrane is carried out using Solarton S11260&1287 electrochemical test system
Measurement, the potential amplitude of measurement are 10mV, and test frequency range is 1M Hz-100Hz.It is tied to reduce contact resistance to measurement
Error caused by fruit, the resistance of test are transverse direction (in-plane) resistance of membrane sample.Composite membrane, which is cut into size, in experiment is
40mm × 10mm is placed in fixture as illustrated, and fixture is put in a vacuum drying oven, keeps 1h at 25 DEG C.Test temperature
From 30 DEG C to 80 DEG C, every 10 DEG C of compound film resistances of test.Then it heats up, and keeps 2h or more, reduce error caused by temperature.
The ionic conductivity σ of sample is finally calculated according to formula:
In σ=l/ (wdR) formula, the length (cm) of l film between electrode, w is the width (cm) of film, and d is the thickness (μm) of film,
R is the film resistance (m Ω) measured.
It can be seen that obtained alkaline membrane room-temperature conductivity reaches 15mS/cm, as the temperature rises, conductivity is gradually
Increase, at 60 DEG C, conductivity reaches 23mS/cm.Show that film made from this method has application well in alkaline fuel cell
Prospect.
Embodiment 2:
By molecular weight Mn ≈ 130000, polystyrene-ethylene-butylene-benzene second of 10g styrene block content 42wt.%
Alkene (SEBS) is dissolved in 150mL organic reagent chloroform, is stirred 6 hours at 55 DEG C, and 13mL SnCl is added4With 88mL BCMB,
10h is reacted, the solution after reaction is poured into anhydrous methanol, after polymer is precipitated, filters, is washed with deionized to neutrality,
Then 60 DEG C of drying in vacuum drying oven, obtain chloromethylated polystyrene-ethylene-butylene, Styrene (CMSEBS).Again by it
It is dissolved in chloroformic solution, forms the solution of 3wt.%, N, N, N ', N '-tetramethyl -1,6- hexamethylene diamine are added thereto
(TMHDA), molal quantity is 1.5 times of CMSEBS, is stirred at room temperature 30 seconds, is subsequently poured into instrument bezel, is put into baking oven in 60
At DEG C, heating for 24 hours, solvent is dried, is removed.
By film soaking at room temperature in trimethylamine aqueous solution, impregnates 48 and as a child took out, be crosslinked and secondary quaternized
Cl-Form polymer anion-exchange membrane finally makes film soaking at room temperature 48h in 1mol/L KOH solution, it is embedding to obtain cross-linking type
Section polymer anion-exchange membrane.
Assembled battery, using self-control front three amine type SEBS resin as binder, cathod catalyst 70%Pt/C in electrode
Carrying capacity is 0.4mg cm-2, anode catalyst 60%PtRu/C carrying capacity is 0.4mg cm-2Catalyst and resin quality ratio are 7:3.
The battery performance under different temperatures is tested on monocell evaluating apparatus, performance curve is shown in attached drawing 4.Cell operating conditions are as follows:
Battery temperature is 60 DEG C, and hydrogen, oxygen gas flow rate are respectively 300,200ml min-1, gas humidification degree be 100wt%, pressure is
0.2MPa。
It can be seen that obtained alkaline membrane has good initial discharge performance, battery maximum power density reaches
416mW/cm2。
And test the antioxidative stabilizer of cross linking membrane, experimental procedure: serous coat is immersed in 40 DEG C of Fenton reagents, often
The quality of film was weighed every 24 hours, calculated residual mass.Fenton reagent concentration is as follows: 3wt%H2O2,4ppm Fe2+'s
Fenton.It is smaller that Fig. 5 can be seen that cross linking membrane mass loss in 40 DEG C of Fenton reagents, and it is more excellent to illustrate that film has
Antioxygenic property.In addition, the variation of cross linking membrane film character before and after Fenton reagent immersion for further test preparation, test
Impregnate the front and back conductivity of film and the situation of change of drawing mechanical performance, such as Fig. 6.The results show that conductance at 30 DEG C of cross linking membrane
Rate becomes 14.2mS/cm from original 14.9mS/cm；And ultimate tensile strength becomes 32MPa from original 35MPa.It can see
Out, for cross linking membrane after Fenton oxidation, conductivity and the mechanical performance variation of film are smaller, further illustrate friendship prepared by the present invention
Joining film has preferable antioxidative stabilizer.
Embodiment 3:
By molecular weight Mn ≈ 80000, polystyrene-ethylene-butylene-benzene second of 10g styrene block content 3.7wt.%
Alkene (SEBS) is dissolved in 300mL organic reagent chloroform, is stirred 5 hours at 60 DEG C, and 15mL SnCl is added4With 95mL BCMB,
10h is reacted, the solution after reaction is poured into anhydrous methanol, after polymer is precipitated, filters, is washed with deionized to neutrality,
Then 60 DEG C of drying in vacuum drying oven, obtain chloromethylated polystyrene-ethylene-butylene, Styrene (CMSEBS).Again by it
It is dissolved in chloroformic solution, forms the solution of 5wt.%, N, N, N ', N '-tetramethyl -1,6- hexamethylene diamine are added thereto
(TMHDA), molal quantity is 0.5 times of CMSEBS, is stirred at room temperature 60 seconds, is subsequently poured into instrument bezel, is put into baking oven in 60
At DEG C, heating for 24 hours, solvent is dried, is removed.
By film soaking at room temperature in trimethylamine aqueous solution, impregnates 24 and as a child took out, be crosslinked and secondary quaternized
Cl-Form polymer anion-exchange membrane finally makes film soaking at room temperature in 1mol/L KOH solution for 24 hours, it is embedding to obtain cross-linking type
Section polymer anion-exchange membrane.
The stability for being test film in alkaline environment, we test after film impregnates in 1M KOH, conductivity with
The situation of change of time.When test, film is immersed in 1M KOH, at regular intervals, is rinsed after taking-up with deionized water, is soaked
Conductivity of the test film in 60 DEG C of deionized waters after bubble.
Comparative example 3: as a comparison, we are prepared for front three amine type SEBS type alkaline anion-exchange membrane as a comparison, mark
It is denoted as: comparative example 3.It is specific the preparation method is as follows: the SEBS after chloromethylation is dissolved in chloroform, after being stirred at room temperature tiling with
In casting film plate, taken off after drying at room temperature.After being immersed in trimethylamine solution for 24 hours, carry out basification, after rushed with deionized water
It washes.Fig. 6 can be seen that prepared by the present embodiment that SEBS/TMHDA cross-linking type alkaline anion-exchange membrane is after 480h, conductance
Rate remains at 14mS/cm or more, and cross-linked structure improves the alkaline stability of film.
The swellbility stability of different temperatures lower film is shown in Fig. 7, uncrosslinked front three amine type SEBS film is compared, after crosslinking
SEBS/TMHDA alkali anion permutoid swelling degree is substantially reduced, and is not increased with the growth of temperature, illustrates the present invention
The film of preparation has excellent in dimension stability.
Embodiment 4:
By molecular weight Mn ≈ 80000, polystyrene-ethylene-butylene-benzene second of 10g styrene block content 4.8wt.%
Alkene (SEBS) is dissolved in 100mL organic reagent chloroform, is stirred 5 hours at 60 DEG C, and 15mL SnCl is added4With 95mL BCMB,
12h is reacted, the solution after reaction is poured into anhydrous methanol, after polymer is precipitated, filters, is washed with deionized to neutrality,
Then 60 DEG C of drying in vacuum drying oven, obtain chloromethylated polystyrene-ethylene-butylene, Styrene (CMSEBS).Again by it
It is dissolved in chloroformic solution, forms the solution of 5wt.%, N, N, N ', N '-tetramethyl -1,6- hexamethylene diamine are added thereto
(TMHDA), molal quantity is 1.8 times of CMSEBS, is stirred at room temperature 60 seconds, is subsequently poured into instrument bezel, is put into baking oven in 60
At DEG C, heating for 24 hours, solvent is dried, is removed.
By film soaking at room temperature in trimethylamine aqueous solution, impregnates 24 and as a child took out, be crosslinked and secondary quaternized
Cl-Form polymer anion-exchange membrane finally makes film soaking at room temperature 48h in 1mol/L KOH solution, it is embedding to obtain cross-linking type
Section polymer anion-exchange membrane.
Comparative example 4: as a comparison, we are prepared for front three amine type SEBS type alkaline anion-exchange membrane as a comparison, system
Preparation Method is same as Example 4, and crosslinking agent TMHDA is not added.Label are as follows: comparative example 4.
Claims (7)
1. cross-linking type block polymer anion-exchange membrane and its preparation and application, it is characterised in that the preparation method includes
Following steps:
1) configuration concentration is the chloromethylation block polymer organic solution of 0.5-5wt%, stir 12 hours at normal temperature or more；
2) crosslinking agent will be added in chloromethylation block polymer organic solution, is stirred at room temperature 1-15 minutes, obtains mold liquid；
3) mold liquid is poured into flat plate mold, is put into 25-80 DEG C of drying box, kept for 12-48 hours, so that solvent evaporates,
It is crosslinked and quaternized Cl-Type polymer anion-exchange membrane；
4) by Cl-Type polymer anion-exchange membrane be immersed in ertiary amine solution further it is quaternized, impregnate 24-48 at 25-60 DEG C
It is taken out after hour, with deionized water flushing 2 times or more, Cl is obtained after reaction-Type crosslinking polymer anion-exchange membrane；
5) Cl for obtaining step 4)-Type crosslinking polymer anion-exchange membrane is immersed in the hydrogen that concentration is 0.01-10mol/L
Potassium oxide and/or sodium hydrate aqueous solution, soaking at room temperature are taken out after 24-48 hours, are rinsed with deionized water to flushing liquor pH value
It is 7, obtains cross-linking type block polymer anion-exchange membrane.
2. preparation method described in accordance with the claim 1, it is characterised in that: configuration chloromethylation block polymer organic solution makes
Organic solvent is one of methylene chloride, chloroform or tetrahydrofuran or two kinds or more.
3. preparation method described in accordance with the claim 1, it is characterised in that: into the organic solution of chloromethylation block polymer
The crosslinking agent of addition comprising N, N, N ', N '-tetramethyl methanediamine (TMMDA), n,N,N',N'-tetramethylethylenediamine
(TMEDA), N, N, N ', one of N '-tetramethyl -1,6- hexamethylene diamine (TMHDA) or two kinds or more, additional amount are chloromethyl
0.5-2 times of fluidized polymer molal quantity.
4. preparation method described in accordance with the claim 1, it is characterised in that: the quaternized ertiary amine solution used is three in step 4)
The mixture of one or more of methylamine, triethylamine, tripropyl amine (TPA), ethylenediamine.
5. preparation method described in accordance with the claim 1, it is characterised in that: the block polymer used specifically includes that styrene-
Butene block copolymer (SBS), styrene-ethylene-butadiene block copolymer (SEBS), acrylonitrile-butadiene-styrene (ABS) copolymerization
Object (ABS), acrylonitrile ethylene styrene copolymer (AES), acrylonitritrile-styrene resin (AS), acrylonitrile-styrene-
One of acrylate copolymer (ASA) or two kinds or more, wherein styrene block content is 10-57wt.%；
Wherein, the chloromethylation process of chloromethylation block polymer is as follows:
Block polymer is dissolved in chloroform, addition Isosorbide-5-Nitrae-dichloro methyl butyl ether (BCMB) and catalyst, 20-80 DEG C
Under be stirred to react 1-12 hours；Reaction mixture is poured into ethyl alcohol and/or methanol after reaction and separates, wash, is dry, is obtained
To chloromethylated polymer；Wherein, block polymer and BCMB molar ratio are 1:1-1:10；The solvent used polymerize every gram
Object, solvent usage 5-100mL；The reaction temperature of polymer chloromethylation be -20-100 DEG C, preferably -10-25 DEG C, instead
It is 10min to 12h between seasonable；It is anhydrous zinc chloride or anhydrous stannic chloride that catalyst, which is added, catalyst and block polymer
The ratio between amount of substance is 10:1-1:1.
6. obtaining cross-linking type block polymer anion-exchange membrane using any preparation method of claim 1 to 5.
7. cross-linking type polybenzimidazoles alkaline anion-exchange membrane answering in alkaline membrane cell described in a kind of claim 6
With.
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Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109280199A (en) * | 2018-09-06 | 2019-01-29 | 大连理工大学 | A kind of crystal type anion-exchange membrane and preparation method with micro phase separation structure |
| CN111276723A (en) * | 2020-02-19 | 2020-06-12 | 北京化工大学 | Comb-structured alkaline anion exchange membrane and preparation method thereof |
| CN111944188A (en) * | 2020-08-10 | 2020-11-17 | 哈尔滨工程大学 | Cationic hyperbranched cross-linked membrane and preparation method thereof |
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| CN115028956A (en) * | 2022-07-08 | 2022-09-09 | 北京化工大学 | Anion exchange membrane, preparation method thereof, and preparation and application of alkaline anion exchange membrane |
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103159974A (en) * | 2011-12-19 | 2013-06-19 | 中国科学院大连化学物理研究所 | Preparation method of crosslinking type polymer anion exchange membrane |
| CN106328958A (en) * | 2015-07-06 | 2017-01-11 | 中国科学院大连化学物理研究所 | Preparation method for membrane electrode of alkali anion exchange membrane fuel cell |
-
2017
- 2017-08-02 CN CN201710651962.7A patent/CN109384944A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103159974A (en) * | 2011-12-19 | 2013-06-19 | 中国科学院大连化学物理研究所 | Preparation method of crosslinking type polymer anion exchange membrane |
| CN106328958A (en) * | 2015-07-06 | 2017-01-11 | 中国科学院大连化学物理研究所 | Preparation method for membrane electrode of alkali anion exchange membrane fuel cell |
Non-Patent Citations (3)
| Title |
|---|
| WANGTING LU等: "Preparation of anion exchange membranes by an efficient chloromethylation method and homogeneous quaternization/crosslinking strategy", 《SOLID STATE IONICS》 * |
| 陈荣等: "自交联型季铵化聚醚砜阴离子交换膜的制备与性能", 《高分子学报》 * |
| 高学强等: "用于碱性膜燃料电池的SEBS基阴离子交换树脂", 《电源技术》 * |
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