CN108586781A - A kind of high intensity semi-annular jade pendant proton exchange membrane and preparation method thereof - Google Patents

A kind of high intensity semi-annular jade pendant proton exchange membrane and preparation method thereof Download PDF

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CN108586781A
CN108586781A CN201810395617.6A CN201810395617A CN108586781A CN 108586781 A CN108586781 A CN 108586781A CN 201810395617 A CN201810395617 A CN 201810395617A CN 108586781 A CN108586781 A CN 108586781A
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段国凡
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Wuhu Tian Ke Biological Technology Co Ltd
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    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/20Manufacture of shaped structures of ion-exchange resins
    • C08J5/22Films, membranes or diaphragms
    • C08J5/2206Films, membranes or diaphragms based on organic and/or inorganic macromolecular compounds
    • C08J5/2218Synthetic macromolecular compounds
    • C08J5/2256Synthetic macromolecular compounds based on macromolecular compounds obtained by reactions other than those involving carbon-to-carbon bonds, e.g. obtained by polycondensation
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00Fuel cells; Manufacture thereof
    • H01M8/10Fuel cells with solid electrolytes
    • H01M8/1016Fuel cells with solid electrolytes characterised by the electrolyte material
    • H01M8/1018Polymeric electrolyte materials
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00Fuel cells; Manufacture thereof
    • H01M8/10Fuel cells with solid electrolytes
    • H01M8/1016Fuel cells with solid electrolytes characterised by the electrolyte material
    • H01M8/1018Polymeric electrolyte materials
    • H01M8/102Polymeric electrolyte materials characterised by the chemical structure of the main chain of the ion-conducting polymer
    • H01M8/1025Polymeric electrolyte materials characterised by the chemical structure of the main chain of the ion-conducting polymer having only carbon and oxygen, e.g. polyethers, sulfonated polyetheretherketones [S-PEEK], sulfonated polysaccharides, sulfonated celluloses or sulfonated polyesters
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00Fuel cells; Manufacture thereof
    • H01M8/10Fuel cells with solid electrolytes
    • H01M8/1016Fuel cells with solid electrolytes characterised by the electrolyte material
    • H01M8/1018Polymeric electrolyte materials
    • H01M8/1041Polymer electrolyte composites, mixtures or blends
    • H01M8/1046Mixtures of at least one polymer and at least one additive
    • H01M8/1051Non-ion-conducting additives, e.g. stabilisers, SiO2 or ZrO2
    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01MPROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M8/00Fuel cells; Manufacture thereof
    • H01M8/10Fuel cells with solid electrolytes
    • H01M8/1016Fuel cells with solid electrolytes characterised by the electrolyte material
    • H01M8/1018Polymeric electrolyte materials
    • H01M8/1069Polymeric electrolyte materials characterised by the manufacturing processes
    • H01M8/1072Polymeric electrolyte materials characterised by the manufacturing processes by chemical reactions, e.g. insitu polymerisation or insitu crosslinking
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    • C08JWORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2371/00Characterised by the use of polyethers obtained by reactions forming an ether link in the main chain; Derivatives of such polymers
    • C08J2371/08Polyethers derived from hydroxy compounds or from their metallic derivatives
    • C08J2371/10Polyethers derived from hydroxy compounds or from their metallic derivatives from phenols
    • C08J2371/12Polyphenylene oxides
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00Use of inorganic substances as compounding ingredients
    • C08K3/34Silicon-containing compounds
    • C08K3/36Silica
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    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00Use of pretreated ingredients
    • C08K9/04Ingredients treated with organic substances
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30Hydrogen technology
    • Y02E60/50Fuel cells

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Abstract

The invention discloses a kind of high intensity semi-annular jade pendant proton exchange membrane, it is made of the raw material of following weight parts:Polyphenylene oxide 110 130, myristic acid soda soap 12, chlorosulfonic acid 10 13, palm wax 35, triethylamine 13, polyisoprene 58,8 oxyquinolines 0.1 0.2, fatty acid polyethylene glycol ester 12, nano silicon dioxide 23, the present invention handles 8 oxyquinolines using triethylamine, it is then added in alcoholic solution and nano silicon dioxide is disperseed, the effective surface-active for improving silica, to improve the mechanical stability of finished product exchange membrane, the exchange membrane conductive stability of the present invention is good, and comprehensive performance is superior.

Description

A kind of high intensity semi-annular jade pendant proton exchange membrane and preparation method thereof
Technical field
The invention belongs to exchange membrane fields, and in particular to a kind of high intensity semi-annular jade pendant proton exchange membrane and preparation method thereof.
Background technology
Fuel cell power system be it is a kind of without burning directly in a manner of electrochemical reaction by the chemical energy of fuel turn The power generator for becoming electric energy is of great significance to solving current " energy shortage " and " environmental pollution " two hang-up.Fuel Battery according to used electrolyte difference can be divided into alkaline fuel cell, phosphoric acid fuel cell, molten carbonate fuel cell, Solid oxide fuel cell, Proton Exchange Membrane Fuel Cells.Wherein, PEMFC is high, environmental-friendly with energy conversion efficiency, Can quickly it start in room temperature, electroless liquid stream is lost, water is easily discharged, long lifespan, specific power and the outstanding features such as higher than energy;
Proton exchange membrane is the core component in PEMFC, determines the performance of fuel cell.It is not only-kind of diaphragm material Material, and the transmission of proton can be completed as proton carrier again.Now widely used is the perfluor of DuPont Corporation's production The advantages that sulfonic acid Nafion membrane, this kind of perfluoro sulfonic acid membrane have proton conductive good, and corrosion resistance is strong, long lifespan.But it is high Price (800 U.S. dollars/m2), lower operating temperature (<100 DEG C), the ring that brings of higher methanol permeability and fluorine material Border problem etc. limits its business application.Therefore, searching is cheap, has high conductivity in wide temperature range, excellent Heat and chemical stability novel proton exchange membranes material be PEMFC important research direction.
Invention content
In view of the defects and deficiencies of the prior art, the present invention intends to provide a kind of high intensity semi-annular jade pendant proton exchange membrane And preparation method thereof.
To achieve the above object, the present invention uses following technical scheme:
A kind of high intensity semi-annular jade pendant proton exchange membrane, it is made of the raw material of following weight parts:
Polyphenylene oxide 110-130, myristic acid soda soap 1-2, chlorosulfonic acid 10-13, palm wax 3-5, triethylamine 1-3, poly- isoamyl Diene 5-8,8-hydroxyquinoline 0.1-0.2, fatty acid polyethylene glycol ester 1-2, nano silicon dioxide 2-3.
A kind of preparation method of high intensity semi-annular jade pendant proton exchange membrane, includes the following steps:
(1) 8-hydroxyquinoline is taken, is added in the absolute ethyl alcohol of 10-13 times of its weight, stirs evenly, increasing temperature is 60-65 DEG C, triethylamine is added, insulated and stirred 20-30 minutes obtains alkanolamine solution;
(2) myristic acid soda soap is taken, is added in the deionized water of 17-20 times of its weight, stirs evenly, obtains saponification dispersion Liquid;
(3) polyisoprene is taken, is added in the dimethylformamide of 40-60 times of its weight, stirs evenly, be sent to In 70-75 DEG C of water bath with thermostatic control, insulated and stirred 10-20 minutes, discharging cooling obtains amide dispersion liquid;
(4) palm wax, chlorosulfonic acid mixing are taken, is added in the chloroform of 7-10 times of its weight, is sent to 55-60 DEG C of constant temperature In water-bath, polyphenylene oxide is added, insulated and stirred 1-2 hours discharges, and filters, filter cake is dried in vacuo 2-3 hours at 50-55 DEG C, Obtain Noryl;
(5) above-mentioned alkanolamine solution, the mixing of saponification dispersion liquid are taken, stirs evenly, nano silicon dioxide is added, ultrasonic 1-2 is small When, precipitation is washed in filtering, and air drying obtains improved silica;
(6) above-mentioned improved silica, Noryl mixing are taken, is added in above-mentioned amide dispersion liquid, 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 high intensity semi-annular jade pendant proton Exchange membrane.
Advantages of the present invention:
The present invention handles 8-hydroxyquinoline using triethylamine, is then added in alcoholic solution and divides nano silicon dioxide It dissipates, the surface-active of silica is effectively improved, to improve the mechanical stability of finished product exchange membrane, friendship of the invention It is good to change film conductive stability, comprehensive performance is superior.
Specific implementation mode
Embodiment 1
A kind of high intensity semi-annular jade pendant proton exchange membrane, it is made of the raw material of following weight parts:
Polyphenylene oxide 110, myristic acid soda soap 1, chlorosulfonic acid 10-13, palm wax 3, triethylamine 1, polyisoprene 5,8- hydroxyls Base quinoline 0.1, fatty acid polyethylene glycol ester 1, nano silicon dioxide 2.
A kind of preparation method of high intensity semi-annular jade pendant proton exchange membrane, includes the following steps:
(1) 8-hydroxyquinoline is taken, is added in the absolute ethyl alcohol of 10 times of its weight, stirs evenly, it is 60 DEG C to increase temperature, Triethylamine is added, insulated and stirred 20 minutes obtains alkanolamine solution;
(2) myristic acid soda soap is taken, is added in the deionized water of 17 times of its weight, stirs evenly, obtain saponification dispersion liquid;
(3) polyisoprene is taken, is added in the dimethylformamide of 40 times of its weight, stirs evenly, be sent to 70 DEG C Water bath with thermostatic control in, insulated and stirred 10 minutes, discharging cooling, obtain amide dispersion liquid;
(4) palm wax, chlorosulfonic acid mixing are taken, is added in the chloroform of 7 times of its weight, is sent to 55 DEG C of water bath with thermostatic control In, polyphenylene oxide is added, insulated and stirred 1 hour discharges, and filters, filter cake is dried in vacuo 2 hours at 50 DEG C, obtains modified polyphenyl Ether;
(5) above-mentioned alkanolamine solution, the mixing of saponification dispersion liquid are taken, is stirred evenly, nano silicon dioxide is added, it is 1 hour ultrasonic, Filtering, precipitation is washed, and air drying obtains improved silica;
(6) above-mentioned improved silica, Noryl mixing are taken, is added in above-mentioned amide dispersion liquid, ultrasound 1 is small When, it pours into culture dish, is put into vacuum drying chamber, be dried in vacuo 20 hours at 70 DEG C, after film molding, be put into 95 DEG C of perseverance Warm drying box is handled 1 hour, takes off film, film water is washed, air drying is to get the high intensity semi-annular jade pendant proton exchange membrane.
Embodiment 2
A kind of high intensity semi-annular jade pendant proton exchange membrane, it is made of the raw material of following weight parts:
Polyphenylene oxide 130, myristic acid soda soap 2, chlorosulfonic acid 13, palm wax 5, triethylamine 3, polyisoprene 8,8- hydroxyl quinolines Quinoline 0.2, fatty acid polyethylene glycol ester 2, nano silicon dioxide 3.
A kind of preparation method of high intensity semi-annular jade pendant proton exchange membrane, includes the following steps:
(1) 8-hydroxyquinoline is taken, is added in the absolute ethyl alcohol of 13 times of its weight, stirs evenly, it is 65 DEG C to increase temperature, Triethylamine is added, insulated and stirred 30 minutes obtains alkanolamine solution;
(2) myristic acid soda soap is taken, is added in the deionized water of 20 times of its weight, stirs evenly, obtain saponification dispersion liquid;
(3) polyisoprene is taken, is added in the dimethylformamide of 60 times of its weight, stirs evenly, be sent to 75 DEG C Water bath with thermostatic control in, insulated and stirred 20 minutes, discharging cooling, obtain amide dispersion liquid;
(4) palm wax, chlorosulfonic acid mixing are taken, is added in the chloroform of 10 times of its weight, is sent to 60 DEG C of water bath with thermostatic control In, polyphenylene oxide is added, insulated and stirred 2 hours discharges, and filters, filter cake is dried in vacuo 3 hours at 55 DEG C, obtains modified polyphenyl Ether;
(5) above-mentioned alkanolamine solution, the mixing of saponification dispersion liquid are taken, is stirred evenly, nano silicon dioxide is added, it is 2 hours ultrasonic, Filtering, precipitation is washed, and air drying obtains improved silica;
(6) above-mentioned improved silica, Noryl mixing are taken, is added in above-mentioned amide dispersion liquid, ultrasound 2 is small When, it pours into culture dish, is put into vacuum drying chamber, be dried in vacuo 30 hours at 85 DEG C, after film molding, be put into 105 DEG C Thermostatic drying chamber is handled 2 hours, takes off film, film water is washed, air drying is to get the high intensity semi-annular jade pendant proton exchange membrane.
Performance test:
The proton conductivity of the high intensity semi-annular jade pendant proton exchange membrane of the present invention is 2.1-3.0 × 10-2Scm-1
Methanol permeability is 2.7-3 × 10-7cm2/S;
Mechanical mechanics property 26.8-30Mpa.

Claims (2)

1. a kind of high intensity semi-annular jade pendant proton exchange membrane, which is characterized in that it is made of the raw material of following weight parts:
Polyphenylene oxide 110-130, myristic acid soda soap 1-2, chlorosulfonic acid 10-13, palm wax 3-5, triethylamine 1-3, polyisoprene 5-8,8-hydroxyquinoline 0.1-0.2, fatty acid polyethylene glycol ester 1-2, nano silicon dioxide 2-3.
2. a kind of preparation method of high intensity semi-annular jade pendant proton exchange membrane as described in claim 1, which is characterized in that including following Step:
(1) 8-hydroxyquinoline is taken, is added in the absolute ethyl alcohol of 10-13 times of its weight, stirs evenly, raising temperature is 60-65 DEG C, triethylamine is added, insulated and stirred 20-30 minutes obtains alkanolamine solution;
(2) myristic acid soda soap is taken, is added in the deionized water of 17-20 times of its weight, stirs evenly, obtains saponification dispersion liquid;
(3) polyisoprene is taken, is added in the dimethylformamide of 40-60 times of its weight, stirs evenly, be sent to 70-75 DEG C water bath with thermostatic control in, insulated and stirred 10-20 minutes, discharging cooling, obtain amide dispersion liquid;
(4) palm wax, chlorosulfonic acid mixing are taken, is added in the chloroform of 7-10 times of its weight, is sent to 55-60 DEG C of water bath with thermostatic control In, polyphenylene oxide is added, insulated and stirred 1-2 hours discharges, and filters, filter cake is dried in vacuo 2-3 hours at 50-55 DEG C, must be changed Property polyphenylene oxide;
(5) above-mentioned alkanolamine solution, the mixing of saponification dispersion liquid are taken, stirs evenly, nano silicon dioxide, 1-2 hours ultrasonic, mistake is added Filter, precipitation is washed, and air drying obtains improved silica;
(6) above-mentioned improved silica, Noryl mixing are taken, is added in above-mentioned amide dispersion liquid, 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 handed over to get the high intensity semi-annular jade pendant proton Change film.
CN201810395617.6A 2018-04-27 2018-04-27 A kind of high intensity semi-annular jade pendant proton exchange membrane and preparation method thereof Pending CN108586781A (en)

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102329423A (en) * 2010-07-13 2012-01-25 现代自动车株式会社 Poly (arylene ether) copolymer with cation exchange group, preparation method and application thereof
CN104183859A (en) * 2014-09-03 2014-12-03 湖北工程学院 Proton exchange membrane and preparation method thereof
CN107936520A (en) * 2017-12-12 2018-04-20 安徽嘉美包装有限公司 A kind of nanometer fluorination Transparent plastic pack film and preparation method thereof

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102329423A (en) * 2010-07-13 2012-01-25 现代自动车株式会社 Poly (arylene ether) copolymer with cation exchange group, preparation method and application thereof
CN104183859A (en) * 2014-09-03 2014-12-03 湖北工程学院 Proton exchange membrane and preparation method thereof
CN107936520A (en) * 2017-12-12 2018-04-20 安徽嘉美包装有限公司 A kind of nanometer fluorination Transparent plastic pack film and preparation method thereof

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