CN108448143A - A kind of hydrophobic silanization proton membrane and preparation method thereof - Google Patents
A kind of hydrophobic silanization proton membrane and preparation method thereof Download PDFInfo
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- CN108448143A CN108448143A CN201810181678.2A CN201810181678A CN108448143A CN 108448143 A CN108448143 A CN 108448143A CN 201810181678 A CN201810181678 A CN 201810181678A CN 108448143 A CN108448143 A CN 108448143A
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- 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
- H01M8/1018—Polymeric electrolyte materials
- H01M8/1041—Polymer electrolyte composites, mixtures or blends
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- 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
- H01M8/1018—Polymeric electrolyte materials
- H01M8/1041—Polymer electrolyte composites, mixtures or blends
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- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- 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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- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/1016—Fuel cells with solid electrolytes characterised by the electrolyte material
- H01M8/1018—Polymeric electrolyte materials
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Abstract
The invention discloses a kind of hydrophobic silanization proton membranes, it is made of the raw material of following weight parts：1H, 1H, 2H, 2H perfluoro decyls triethoxysilane 12, polyphenylene oxide 60 70, sym-closene 34, pentaerythrite 57, maleic anhydride 10 13, initiator 0.4 0.5,2 mercaptobenzimidazoles 0.7 1, nano silicon dioxide 69, catalyst 0.08 0.1, the present invention realizes the effective compatible of nano silicon dioxide and polyphenylene oxide, to improve the uniform and stable property and mechanical strength of finished product proton membrane, the present invention is modified by fluorine containing silane, the hydrophobic properties of the surface for effectively raising proton membrane improve the quality of finished film.
Description
Technical field
The invention belongs to proton membrane fields, and in particular to a kind of hydrophobic silanization proton membrane and preparation method thereof.
Background technology
Proton exchange membrane is the core component of PEMFC, and PEM has any different with the diaphragm used in general electrochmical power source.Proton
Clean materials of the substitution power source as PEM that exchange film fuel battery has become gasoline internal combustion mechanomotive force most competitiveness is answered
This meets the following conditions：The permeability that the electro-osmotic effects of good proton conductivity, hydrone in film are small, gas is in film
It is as small as possible, electrochemical stability is good, dry and wet conversion performance is good, with certain mechanical strength, machinability is good, price is suitable
When；
The clean substitution power source that Proton Exchange Membrane Fuel Cells has become gasoline internal combustion mechanomotive force most competitiveness is used as
The material of PEM should meet the following conditions:(1) good proton conductivity；(2) electro-osmotic effects of the hydrone in film are small；
(3) permeability of the gas in film is as small as possible；(4) electrochemical stability is good；(5) dry and wet conversion performance is good；(6) have certain
Mechanical strength；(7) machinability is good, price is appropriate.It is divided at this stage:Perfluorosulfonic acid type proton exchange membrane；Nafion double teemings
Film；Non-fluorinated polymer proton exchange membrane；New type proton exchange membrane etc.；
Wherein, how to reduce electro-osmotic effects of the hydrone in film is an important indicator of proton film quality, and carries
The hydrophobic properties of the surface of high proton film then can reduce electro-osmotic effects of the hydrone in film to a certain degree, for improving
The comprehensive quality of proton membrane, which has, to be promoted to be promoted well.
Invention content
In view of the defects and deficiencies of the prior art, the present invention intends to provide a kind of hydrophobic silanization proton membrane and its
Preparation method.
To achieve the above object, the present invention uses following technical scheme：
A kind of hydrophobic silanization proton membrane, it is made of the raw material of following weight parts：
1H, 1H, 2H, 2H- perfluoro decyl triethoxysilane 1-2, polyphenylene oxide 60-70, sym-closene 3-4, season penta
Tetrol 5-7, maleic anhydride 10-13, initiator 0.4-0.5,2-mercaptobenzimidazole 0.7-1, nano silicon dioxide 6-9, catalysis
Agent 0.08-0.1.
The initiator is one kind in ammonium persulfate, sodium peroxydisulfate.
The catalyst is p-methyl benzenesulfonic acid.
A kind of preparation method of hydrophobic silanization proton membrane, includes the following steps：
(1) 1H, 1H, 2H, 2H- perfluoro decyl triethoxysilanes is taken to be added in the chloroform of 10-14 times of its weight, stir
It mixes uniformly, obtains silane dispersion fluid；
(2) maleic anhydride is taken, is added in above-mentioned silane dispersion fluid, stirs evenly, be sent in reaction kettle, be passed through nitrogen
Gas, it is 55-60 DEG C to adjust temperature of reaction kettle, and initiator is added, and insulated and stirred 3-4 hours obtains polyanhydride dispersion liquid；
(3) sym-closene is taken, is added in the deionized water of 20-30 times of its weight, stirs evenly, 2- sulfydryls are added
Benzimidazole, it is 4-10 minutes ultrasonic, obtain aqueous dispersions；
(4) pentaerythrite, nano silicon dioxide mixing are taken, is added in the deionized water of 40-54 times of mixture weight, surpasses
Sound 15-20 minutes, obtains silica dispersions；
(5) above-mentioned aqueous dispersions, silica dispersions mixing are taken, is stirred evenly, it is 90-95 DEG C to increase temperature, is added
Catalyst, insulated and stirred 2-3 hours, obtains improved silica dispersion liquid；
(6) above-mentioned polyanhydride dispersion liquid, the mixing of improved silica dispersion liquid are taken, stirs evenly, chlorosulfonic acid is added, increase
Temperature is 55-60 DEG C, and insulated and stirred 1-2 hours obtains hydrophobically modified improved silica dispersion liquid；
(7) polyphenylene oxide is taken, is added in above-mentioned hydrophobically modified improved silica dispersion liquid, it is 2-3 hours ultrasonic, it filters,
Precipitation is washed, it is 40-50 minutes dry at 50-55 DEG C of vacuum, it is cooled to room temperature, obtains hydrophobically modified polyphenylene oxide；
(8) above-mentioned hydrophobically modified polyphenylene oxide is taken, is added in the dimethylformamide of 16-20 times of its weight, ultrasonic 1-2 is small
When, it pours into culture dish, is put into vacuum drying chamber, be dried in vacuo 20-30 hours at 70-85 DEG C, after film molding, is put into
95-105 DEG C of thermostatic drying chamber is handled 1-2 hours, takes off film, film water is washed, air drying is to get the hydrophobic silanization proton
Film.
Advantages of the present invention：
The present invention uses maleic anhydride for monomer, polymerize under initiator effect, 1H, 1H, 2H are added in the course of the polymerization process,
2H- perfluoro decyl triethoxysilanes obtain silanization polyacids anhydride solution, are then original with sym-closene, pentaerythrite
Material, is esterified, nano silicon dioxide is introduced in esterification process, under the action of catalyst by filling for nano-silica surface
It point organises, the effective compatible of nano silicon dioxide and polyphenylene oxide is realized, with polyphenylether blending to improve into quality again later
The uniform and stable property and mechanical strength, the present invention of sub- film are modified by fluorine containing silane, and the surface for effectively raising proton membrane is dredged
Aqueous energy, improves the quality of finished film.
Specific implementation mode
Embodiment 1
A kind of hydrophobic silanization proton membrane, it is made of the raw material of following weight parts：
1H, 1H, 2H, 2H- perfluoro decyl triethoxysilane 1, polyphenylene oxide 60, sym-closene 3, pentaerythrite 5, horse
Come acid anhydrides 10, initiator 0.4,2-mercaptobenzimidazole 0.7, nano silicon dioxide 6, catalyst 0.08.
The initiator is ammonium persulfate.
The catalyst is p-methyl benzenesulfonic acid.
A kind of preparation method of hydrophobic silanization proton membrane, includes the following steps：
(1) 1H, 1H, 2H, 2H- perfluoro decyl triethoxysilanes is taken to be added in the chloroform of 10 times of its weight, stirring is equal
It is even, obtain silane dispersion fluid；
(2) maleic anhydride is taken, is added in above-mentioned silane dispersion fluid, stirs evenly, be sent in reaction kettle, be passed through nitrogen
Gas, it is 55 DEG C to adjust temperature of reaction kettle, and initiator is added, and insulated and stirred 3 hours obtains polyanhydride dispersion liquid；
(3) sym-closene is taken, is added in the deionized water of 20 times of its weight, stirs evenly, 2- sulfydryl benzene is added
And imidazoles, ultrasound 4 minutes obtain aqueous dispersions；
(4) pentaerythrite, nano silicon dioxide mixing are taken, is added in the deionized water of 40-54 times of mixture weight, surpasses
Sound 15 minutes, obtains silica dispersions；
(5) above-mentioned aqueous dispersions, silica dispersions mixing are taken, is stirred evenly, it is 90 DEG C to increase temperature, and catalysis is added
Agent, insulated and stirred 2 hours, obtains improved silica dispersion liquid；
(6) above-mentioned polyanhydride dispersion liquid, the mixing of improved silica dispersion liquid are taken, stirs evenly, chlorosulfonic acid is added, increase
Temperature is 55 DEG C, and insulated and stirred 1 hour obtains hydrophobically modified improved silica dispersion liquid；
(7) polyphenylene oxide is taken, is added in above-mentioned hydrophobically modified improved silica dispersion liquid, ultrasound 2 hours filters, will
Precipitation is washed, 40 minutes dry at 50 DEG C of vacuum, is cooled to room temperature, is obtained hydrophobically modified polyphenylene oxide；
(8) above-mentioned hydrophobically modified polyphenylene oxide is taken, is added in the dimethylformamide of 16 times of its weight, ultrasound 1 hour,
Enter in culture dish, be put into vacuum drying chamber, be dried in vacuo 20 hours at 70 DEG C, after film molding, it is dry to be put into 95 DEG C of constant temperature
Dry case is handled 1 hour, takes off film, film water is washed, air drying is to get the hydrophobic silanization proton membrane.
Embodiment 2
A kind of hydrophobic silanization proton membrane, it is made of the raw material of following weight parts：
1H, 1H, 2H, 2H- perfluoro decyl triethoxysilane 2, polyphenylene oxide 70, sym-closene 4, pentaerythrite 7, horse
Come acid anhydrides 13, initiator 0.5,2-mercaptobenzimidazole 1, nanometer titanium dioxide -9, catalyst 0.1.
The initiator is sodium peroxydisulfate.
The catalyst is p-methyl benzenesulfonic acid.
A kind of preparation method of hydrophobic silanization proton membrane, includes the following steps：
(1) 1H, 1H, 2H, 2H- perfluoro decyl triethoxysilanes is taken to be added in the chloroform of 14 times of its weight, stirring is equal
It is even, obtain silane dispersion fluid；
(2) maleic anhydride is taken, is added in above-mentioned silane dispersion fluid, stirs evenly, be sent in reaction kettle, be passed through nitrogen
Gas, it is 60 DEG C to adjust temperature of reaction kettle, and initiator is added, and insulated and stirred 4 hours obtains polyanhydride dispersion liquid；
(3) sym-closene is taken, is added in the deionized water of 30 times of its weight, stirs evenly, 2- sulfydryl benzene is added
And imidazoles, ultrasound 10 minutes obtain aqueous dispersions；
(4) pentaerythrite, nano silicon dioxide mixing are taken, is added in the deionized water of 54 times of mixture weight, ultrasound
20 minutes, obtain silica dispersions；
(5) above-mentioned aqueous dispersions, silica dispersions mixing are taken, is stirred evenly, it is 90-95 DEG C to increase temperature, is added
Catalyst, insulated and stirred 3 hours, obtains improved silica dispersion liquid；
(6) above-mentioned polyanhydride dispersion liquid, the mixing of improved silica dispersion liquid are taken, stirs evenly, chlorosulfonic acid is added, increase
Temperature is 60 DEG C, and insulated and stirred 2 hours obtains hydrophobically modified improved silica dispersion liquid；
(7) polyphenylene oxide is taken, is added in above-mentioned hydrophobically modified improved silica dispersion liquid, ultrasound 3 hours filters, will
Precipitation is washed, 50 minutes dry at 55 DEG C of vacuum, is cooled to room temperature, is obtained hydrophobically modified polyphenylene oxide；
(8) above-mentioned hydrophobically modified polyphenylene oxide is taken, is added in the dimethylformamide of 20 times of its weight, ultrasound 2 hours,
Enter in culture dish, be put into vacuum drying chamber, be dried in vacuo 30 hours at 85 DEG C, after film molding, it is dry to be put into 105 DEG C of constant temperature
Dry case is handled 2 hours, takes off film, film water is washed, air drying is to get the hydrophobic silanization proton membrane.
Performance test：
Performance measurement is carried out to the proton membrane that embodiment 1-2 is prepared, heat resistance test is surveyed according to GB/T13464-92
Examination, film dynamic performance are tested according to GB4456-1996；
The proton conductivity of the proton exchange membrane of embodiment 1 is 3.01 × 10-2Scm-1, mechanical mechanics property 27.5Mpa,
Contact angle with water is 160 °；
The proton conductivity of the proton exchange membrane of embodiment 2 is 3.30 × 10-2Scm-1, mechanical mechanics property 26.6Mpa,
Contact angle with water is 161 °；
The proton conductivity of commercially available polyphenylene oxide proton exchange membrane is 2-2.5 × 10-2Scm-1, mechanical mechanics property 20-
25Mpa, 150 ° of the contact angle ＜ with water.
Claims (4)
1. a kind of hydrophobic silanization proton membrane, which is characterized in that it is made of the raw material of following weight parts：
1H, 1H, 2H, 2H- perfluoro decyl triethoxysilane 1-2, polyphenylene oxide 60-70, sym-closene 3-4, pentaerythrite
5-7, maleic anhydride 10-13, initiator 0.4-0.5,2-mercaptobenzimidazole 0.7-1, nano silicon dioxide 6-9, catalyst
0.08-0.1。
2. a kind of hydrophobic silanization proton membrane according to claim 1, which is characterized in that the initiator is persulfuric acid
One kind in ammonium, sodium peroxydisulfate.
3. a kind of hydrophobic silanization proton membrane according to claim 1, which is characterized in that the catalyst is to methyl
Benzene sulfonic acid.
4. a kind of preparation method of hydrophobic silanization proton membrane as described in claim 1, which is characterized in that including following step
Suddenly：
(1) 1H, 1H, 2H, 2H- perfluoro decyl triethoxysilanes is taken to be added in the chloroform of 10-14 times of its weight, stirring is equal
It is even, obtain silane dispersion fluid；
(2) maleic anhydride is taken, is added in above-mentioned silane dispersion fluid, stirs evenly, be sent in reaction kettle, is passed through nitrogen, is adjusted
It is 55-60 DEG C to save temperature of reaction kettle, and initiator is added, and insulated and stirred 3-4 hours obtains polyanhydride dispersion liquid；
(3) sym-closene is taken, is added in the deionized water of 20-30 times of its weight, stirs evenly, 2- sulfydryl benzos are added
Imidazoles, it is 4-10 minutes ultrasonic, obtain aqueous dispersions；
(4) pentaerythrite, nano silicon dioxide mixing are taken, is added in the deionized water of 40-54 times of mixture weight, ultrasound
15-20 minutes, obtain silica dispersions；
(5) above-mentioned aqueous dispersions, silica dispersions mixing are taken, is stirred evenly, it is 90-95 DEG C to increase temperature, and catalysis is added
Agent, insulated and stirred 2-3 hours, obtains improved silica dispersion liquid；
(6) above-mentioned polyanhydride dispersion liquid, the mixing of improved silica dispersion liquid are taken, stirs evenly, chlorosulfonic acid is added, increase temperature
It it is 55-60 DEG C, insulated and stirred 1-2 hours obtains hydrophobically modified improved silica dispersion liquid；
(7) polyphenylene oxide is taken, is added in above-mentioned hydrophobically modified improved silica dispersion liquid, it is 2-3 hours ultrasonic, it filters, will sink
It forms sediment and washes, it is 40-50 minutes dry at 50-55 DEG C of vacuum, it is cooled to room temperature, obtains hydrophobically modified polyphenylene oxide；
(8) above-mentioned hydrophobically modified polyphenylene oxide is taken, is added in the dimethylformamide of 16-20 times of its weight, it is 1-2 hours ultrasonic,
It pours into culture dish, is put into vacuum drying chamber, be dried in vacuo 20-30 hours at 70-85 DEG C, after film molding, be put into 95-
105 DEG C of thermostatic drying chamber is handled 1-2 hours, takes off film, film water is washed, air drying is to get the hydrophobic silanization proton membrane.
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| CN201810181678.2A CN108448143A (en) | 2018-03-06 | 2018-03-06 | A kind of hydrophobic silanization proton membrane and preparation method thereof |
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101220169A (en) * | 2007-09-14 | 2008-07-16 | 中国科学技术大学 | Production method for organic-inorganic hybridisation anion exchange membrane |
| CN102086265A (en) * | 2009-12-04 | 2011-06-08 | 现代自动车株式会社 | Sulfonated poly (arylene ether) copolymers and related polymer electrolyte membranes and fuel cells |
-
2018
- 2018-03-06 CN CN201810181678.2A patent/CN108448143A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101220169A (en) * | 2007-09-14 | 2008-07-16 | 中国科学技术大学 | Production method for organic-inorganic hybridisation anion exchange membrane |
| CN102086265A (en) * | 2009-12-04 | 2011-06-08 | 现代自动车株式会社 | Sulfonated poly (arylene ether) copolymers and related polymer electrolyte membranes and fuel cells |
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