CN110896150A - Method for preparing anion exchange membrane by polymerizing ionic liquid monomer - Google Patents
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- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
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- H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
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- H01M8/1041—Polymer electrolyte composites, mixtures or blends
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Abstract
A method for preparing an anion exchange membrane by polymerizing an ionic liquid monomer comprises the following steps: uniformly stirring chloromethyl styrene, an amine monomer and an initiator according to a certain proportion at low temperature to obtain a mixed solution of an ionic liquid and the initiator; after the porous matrix film is soaked in the mixed solution, placing the film in a polyester sheet for hot-pressing polymerization to prepare a chlorine type anion exchange membrane; and (3) performing alkali exchange on the chlorine type anion exchange membrane in strong base with a certain concentration to obtain the hydroxide type anion exchange membrane. The method has the advantages that the utilization rate is reduced in a low-temperature environment, the monomers containing the polymerization initiator are fully mixed in a liquid state, ionization and monomer polymerization are realized in one step through hot-pressing polymerization, chloromethylation and amination steps are omitted, highly carcinogenic chloromethyl ether and malodorous trimethylamine are not required, the method is environment-friendly and simple in step, the concentration of quaternary amine groups can be directly adjusted and the crosslinking degree can be controlled through the monomer adding proportion, and the prepared membrane has high ionic conductivity and good mechanical strength.
Description
Technical Field
The invention relates to a preparation method of an anion exchange membrane, belonging to the field of fuel cells.
Background
The anion exchange membrane has wide application in water treatment, purification, concentration and separation of substances, chlor-alkali industry, heavy metal recovery, alkaline anion exchange membrane fuel cells, liquid flow energy storage cells, novel supercapacitors and the like, and has important significance for developing anion exchange membranes in modern industry, environment and energy.
The polymer anion exchange membrane for fuel cells should have good chemical stability and mechanical properties in addition to high ionic conductivity. U.S. Pat. No. 4,024,043 discloses a basic anion exchange membrane prepared by immersing a polyethylene film as a substrate in a solution of styrene, divinylbenzene (cross-linking agent) and benzoyl peroxide (initiator), soaking at 70-90 deg.C for 10 minutes to 1 hour, taking out and clamping between two flat glasses, pressurizing, heating and polymerizing to obtain a base membrane, performing chloromethylation reaction in 2.5% of anhydrous stannic chloride chloromethyl ether, and performing quaternization reaction with 25% of trimethylamine acetone solution. The disadvantages of this method are: (1) chloromethyl ether used in the chloromethyl process is a carcinogen; (2) the method uses a trimethylamine solution with malodor to carry out quaternization, which seriously affects the environment; (3) the method comprises the steps of polymerization, chloromethylation and amination, and has more steps, and the reaction degree is not easy to accurately control.
Chinese patent application publication CN200910248539.8 discloses that polytetrafluoroethylene is used as a base film, immersed in a solution composed of chloromethylstyrene, divinylbenzene (cross-linking agent) and benzoyl peroxide (initiator), taken out and clamped between two flat glasses, thermally polymerized at 110-120 ℃ for 3-4 hours, and then quaternized with 33% trimethylamine aqueous solution or a mixed solution of trimethylamine and N, N' -tetramethylethylenediamine to obtain the basic anion exchange membrane. This method has similar disadvantages as described above.
At present, the reports of directly preparing the anion exchange membrane by polymerizing the ionic liquid monomer are less, mainly because the ionic liquid which is in a liquid state at room temperature is less, and the room-temperature ionic liquid which is suitable for polymerizing to form a membrane is less. When the organic substance containing chloromethyl group is mixed with amine substance, the reaction is exothermic, and the generated ionic compound is usually in solid state and can not be directly used as a film.
Disclosure of Invention
The method skillfully utilizes a low-temperature environment to reduce the reaction rate, fully mixes the monomers containing the polymerization initiator in a liquid state, realizes ionization and polymerization reaction in one step through hot pressing, has no chloromethylation and amination steps, does not need to use highly carcinogenic chloromethyl ether and stinky trimethylamine, is environment-friendly and simple in steps, can directly adjust the concentration of quaternary amine groups and control the crosslinking degree through the monomer adding proportion, and has higher ionic conductivity and good mechanical strength.
The invention provides a method for preparing an anion exchange membrane by polymerizing an ionic liquid monomer, which comprises the following steps:
(1) dissolving 1-40 parts by weight of initiator in 5-95 parts by weight of chloromethyl styrene, adding 5-95 parts by weight of amine monomer, and uniformly stirring at-60-10 ℃ to form an ionic liquid monomer mixed solution containing a polymerization initiator;
(2) dropwise adding the monomer mixed solution on the upper surface or the lower surface of the porous film, attaching release polyester sheets on the upper surface and the lower surface of the porous film, rolling the liquid uniformly, and placing the liquid between hot flat plates for hot-pressing polymerization; the polymerization temperature is 60-140 ℃, the polymerization time is 10 min-40 h, the pressure is 0.01-0.5MPa, and the dropping volume of the monomer mixed solution is 0.1-5 times of the volume of the porous film;
(3) taking out the polymerization product, and removing polyester chips to obtain a chlorine type anion exchange membrane;
(4) and soaking the chlorine type anion exchange membrane in a strong alkaline solution for alkali exchange to obtain the hydroxide type anion exchange membrane.
In the step (1), the chloromethyl styrene with the initiator dissolved therein is added to the amine monomer, or the speed of adding the amine monomer to the chloromethyl styrene with the initiator dissolved therein should be slow, and the mixture is stirred while being dripped, and the temperature of the mixed solution is controlled to be low, so that the mixed solution of the monomers is ensured to be liquid rather than solid.
Based on the above technical scheme, preferably, the initiator in the step (1) is at least one of tert-butyl hydroperoxide, benzoyl peroxide, methyl ethyl ketone peroxide, di-tert-amyl peroxide and tert-butyl 2-ethylhexanoate peroxide, and the amine monomer in the step (1) is at least one of triethylamine, tripropylamine, tetramethylethylenediamine, tetramethylhexanediamine, tetramethyldipropylenetriamine, pentamethyldiethylenetriamine or propanetriamine.
Based on the technical scheme, the stirring in the step (1) is preferably in an ice-water bath environment at 0 ℃.
Based on the technical scheme, preferably, the porous film in the step (2) is Polyethylene (PE) or polypropylene (PP), the pore diameter of the porous film is 0.01-1 μm, the thickness of the porous film is 5-100 μm, and the porosity of the porous film is 30% -90%.
The invention also provides an anion exchange membrane prepared by any one of the methods, the ion conductivity of the anion exchange membrane is 10-140 mS/cm, the breaking strength is not lower than 60MPa, the breaking elongation is not lower than 50%, and the power density of a full battery assembled by adopting the anion exchange membrane can reach 550mW/cm2The above.
Advantageous effects
Highly carcinogenic chloromethyl ether and foul trimethylamine are not used, the environment is friendly, the preparation method has simple steps, and chloromethyl styrene and amine monomer are mixed and subjected to ammoniation reaction when in liquid state, so that the product is uniform; the ratio of the quaternary amine functional group and the quaternary amine functional group can be easily adjusted, and the concentration of the quaternary amine functional group in the reaction product can be controlled, so that the contradiction between the ionic conductivity and the mechanical property can be balanced.
Drawings
FIG. 1 is an infrared spectrum of porous polyethylene and the composite anion exchange membrane prepared in example 1.
FIG. 2 is a graph of ion conductivity at different temperatures for the chlorine-type anion-exchange membrane prepared in example 1.
FIG. 3 is a graph of breaking strength versus elongation at break for the composite anion exchange membrane prepared in example 1.
FIG. 4 is a graph of full cell performance of the hydroxide-type composite anion exchange membrane prepared in example 1.
Detailed Description
The following examples further illustrate the preparation of the anion exchange membranes of the present invention.
Example 1
A100 ml beaker was placed in an ice-water mixture, 38.5 parts by weight of tetramethylethylenediamine was added to the beaker, and stirring was continued until the liquid temperature was lowered to 0 ℃. Taking another beaker, adding 6.5 parts by weight of Benzoyl Peroxide (BPO) monomer and 55 parts by weight of chloromethyl styrene (CMS), after dissolving BPO, dropwise adding tetramethylethylenediamine, stirring in an ice-water bath during the dropwise adding process, and keeping the temperature of the ionic liquid at 0 ℃.
Taking 10X 20cm2A Polyethylene (PE) porous film having a thickness of 10 μm was laid on a polyester sheet, and the mixture was dropped onto the surface of the PE porous film, and another polyester sheet was attached and sandwiched between stainless steel plates. The stainless steel plate was placed on a hot stage at 100 ℃ and thermally polymerized under a pressure of 0.1MPa for 10 hours.
And peeling the membrane from the polyester sheet to obtain the chlorine type anion exchange membrane. Basifying the membrane in 1M KOH solution to obtain the OH-type anion exchange membrane.
Water content and ion exchange capacity tests show that the water absorption rate and the ion exchange capacity of the chlorine-type anion exchange membrane are respectively 13.8 wt% and 1.67mmol/g-dry membrane.
FIG. 1 shows the FTIR spectrum of the film prepared in this example, with the abscissa being the wavenumberWavenumber(cm-1) And the ordinate is the transmittance. 2918 and 2848cm-1represents-CH2and-CH3Peak of telescopic vibration of 1380cm-1Represents a C-N group stretching vibration peak at 3400cm-1The left and right peaks are attributed to the stretching vibration peak of quaternary amine groups, which shows that the prepared membrane is a composite membrane containing quaternary amine groups.
FIG. 2 is a graph showing the ionic conductivity of the chlorine-type anion exchange membrane prepared in this example, and it can be seen that the ionic conductivity of the composite membrane is above 15mS/cm at each temperature, and the ionic conductivity increases with increasing temperature. The ionic conductivity was mutated around 60 ℃, which may be related to the basic group structure of the membrane.
FIG. 3 is a graph of the mechanical properties of the film prepared in this example, the elongation at break of the film being 65% and the strength at break being 80 MPa.
FIG. 4 shows the full cell performance of the membrane prepared in this example, where the cathode and anode catalysts are Pt/C and PtRu/C, respectively, the cell operating temperature is 50 deg.C, the reactant gases are hydrogen/oxygen, respectively, and the gas flow rates are all 1000 sccm.
Example 2
The same procedure as in example 1 was used. The difference from the example 1 is that the amine monomer is tetramethylhexanediamine, and the weight ratio of the chloromethyl styrene, the tetramethylhexanediamine and the benzoyl peroxide is 48:48:4 respectively.
The anion exchange membrane prepared in this example had an ion exchange capacity of 1.35mmol/g-dry membrane, an ionic conductivity of 10mS/cm (in deionized water at 25 ℃), an elongation at break of 120%, a breaking strength of 131MPa, example 3
The same procedure as in example 1 was used. The difference from example 1 is that the amine monomer is tetramethyl dipropylene triamine, the initiator is tert-butyl hydroperoxide, and the weight ratio of chloromethyl styrene, tetramethyl dipropylene triamine and tert-butyl hydroperoxide is 30:60: 10.
The anion exchange membrane prepared by this example had an ion exchange capacity of 1.85mmol/g-dry membrane, an ionic conductivity of 140mS/cm (in 80 ℃ deionized water), an elongation at break of 54%, and a breaking strength of 78 MPa.
The water content and ion exchange capacity were determined as follows:
the water content determination method comprises the following steps: immersing the prepared alkalized anion exchange membrane into deionized water at room temperature for 24h, taking out, rapidly adsorbing water on the surface of the membrane by using filter paper, and weighing to obtain WwetDrying the film sample in an oven at 60 ℃ for 24h, and weighing to obtain WdryAnd (3) solving the saturated water content according to the formula (1), namely testing the water content. Δ W (wt.%)
Ion exchange capacity measurement method: a piece of the prepared alkalized anion exchange membrane is put into 30ml of 0.01MHCl solution and kept for 48 hours at the temperature of 30 ℃. Phenolphthalein is used as an indicator, 0.01M NaOH is adopted to titrate HCl solution, and the ion exchange capacity can be obtained according to the formula (2).
Mo,HClAnd Me,HClThe amounts of material before and after the HCl solution titrated with NaOH, respectively, and m is the mass of the dry film.
Claims (7)
1. The method for preparing the anion exchange membrane is characterized by adopting ionic liquid monomer polymerization preparation, and specifically comprises the following steps:
(1) dissolving 1-40 parts by weight of initiator in 5-95 parts by weight of chloromethyl styrene, adding 5-95 parts by weight of amine monomer, and uniformly stirring at-60-10 ℃ to form an ionic liquid monomer mixed solution containing a polymerization initiator;
(2) dropwise adding the monomer mixed solution on the upper surface or the lower surface of the porous film, attaching release polyester sheets on the upper surface and the lower surface of the porous film, uniformly rolling the liquid, and placing the liquid between hot flat plates for hot-pressing polymerization to obtain a polymerization product; the hot-pressing polymerization temperature is 60-140 ℃, the time is 10 min-40 h, the pressure is 0.01-0.5MPa, and the dropping volume of the monomer mixed solution is 0.1-5 times of the volume of the porous film;
(3) taking out the polymerization product, and removing polyester sheets to obtain a chlorine type anion exchange membrane;
(4) and soaking the chlorine type anion exchange membrane in a strong alkali solution for alkali exchange to obtain the hydroxide type anion exchange membrane.
2. The method of preparing an anion exchange membrane of claim 1, wherein: the initiator in the step (1) is at least one of tert-butyl hydroperoxide, benzoyl peroxide, methyl ethyl ketone peroxide, di-tert-amyl peroxide and tert-butyl peroxy-2-ethylhexanoate.
3. The method of preparing an anion exchange membrane of claim 1, wherein: the amine monomer in the step (1) is at least one of triethylamine, tripropylamine, tetramethylethylenediamine, tetramethylhexanediamine, tetramethyldipropylenetriamine, pentamethyldiethylenetriamine or propylenetriamine.
4. The method of preparing an anion exchange membrane of claim 1, wherein: and (2) stirring in the step (1) to be in an ice-water bath environment at 0 ℃.
5. The method of preparing an anion exchange membrane of claim 1, wherein: the porous film in the step (2) is Polyethylene (PE) or polypropylene (PP), the aperture of the porous film is 0.01-1 mu m, the thickness of the porous film is 5-100 mu m, and the porosity of the porous film is 30% -90%.
6. An anion exchange membrane prepared by the method of any of claims 1 to 5.
7. The anion exchange membrane of claim 6 wherein: the ion conductivity of the anion exchange membrane is 10-140 mS/cm, the breaking strength is not lower than 60MPa, the breaking elongation is not lower than 50%, and the anion exchange membrane is adoptedThe power density of the full battery assembled by the film can reach 550mW/cm2The above.
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| CN112760991A (en) * | 2021-01-25 | 2021-05-07 | 福州大学 | Method for preparing anion exchange membrane in green manner |
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| CN102690392A (en) * | 2012-06-26 | 2012-09-26 | 苏州大学 | Anion exchange membrane based on ionic liquid crosslinking agent and preparation method of anion exchange membrane |
| CN103881132A (en) * | 2012-12-19 | 2014-06-25 | 中国科学院大连化学物理研究所 | Composite anion exchange membrane preparation method |
| CN104124463A (en) * | 2013-04-26 | 2014-10-29 | 中国科学院大连化学物理研究所 | Ionic liquid-polymer composite membrane for hydrogen chloride fuel cell and preparation and application thereof |
| CN104447560A (en) * | 2013-09-13 | 2015-03-25 | 中国科学院大连化学物理研究所 | Imidazolyl ionic liquid and application thereof in alkaline anion exchange membrane |
| JP2017097975A (en) * | 2015-11-18 | 2017-06-01 | Ｊｆｅエンジニアリング株式会社 | Processing method of ion exchange membrane for ionic liquid, and ion exchange membrane for ionic liquid |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102690392A (en) * | 2012-06-26 | 2012-09-26 | 苏州大学 | Anion exchange membrane based on ionic liquid crosslinking agent and preparation method of anion exchange membrane |
| CN103881132A (en) * | 2012-12-19 | 2014-06-25 | 中国科学院大连化学物理研究所 | Composite anion exchange membrane preparation method |
| CN104124463A (en) * | 2013-04-26 | 2014-10-29 | 中国科学院大连化学物理研究所 | Ionic liquid-polymer composite membrane for hydrogen chloride fuel cell and preparation and application thereof |
| CN104447560A (en) * | 2013-09-13 | 2015-03-25 | 中国科学院大连化学物理研究所 | Imidazolyl ionic liquid and application thereof in alkaline anion exchange membrane |
| JP2017097975A (en) * | 2015-11-18 | 2017-06-01 | Ｊｆｅエンジニアリング株式会社 | Processing method of ion exchange membrane for ionic liquid, and ion exchange membrane for ionic liquid |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112760991A (en) * | 2021-01-25 | 2021-05-07 | 福州大学 | Method for preparing anion exchange membrane in green manner |
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