CN109273747A - A kind of polypyrrole enhancing proton exchange membrane and preparation method thereof - Google Patents

A kind of polypyrrole enhancing proton exchange membrane and preparation method thereof Download PDF

Info

Publication number
CN109273747A
CN109273747A CN201811071525.9A CN201811071525A CN109273747A CN 109273747 A CN109273747 A CN 109273747A CN 201811071525 A CN201811071525 A CN 201811071525A CN 109273747 A CN109273747 A CN 109273747A
Authority
CN
China
Prior art keywords
added
ketone
ether
exchange membrane
taken
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
CN201811071525.9A
Other languages
Chinese (zh)
Inventor
汪青霞
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Individual
Original Assignee
Individual
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Individual filed Critical Individual
Priority to CN201811071525.9A priority Critical patent/CN109273747A/en
Publication of CN109273747A publication Critical patent/CN109273747A/en
Withdrawn legal-status Critical Current

Links

Classifications

    • 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
    • H01M8/1044—Mixtures of polymers, of which at least one is ionically conductive
    • 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
    • H01M8/1039—Polymeric electrolyte materials halogenated, e.g. sulfonated polyvinylidene fluorides
    • 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
    • H01M8/1069—Polymeric electrolyte materials characterised by the manufacturing processes
    • H01M8/1072—Polymeric electrolyte materials characterised by the manufacturing processes by chemical reactions, e.g. insitu polymerisation or insitu crosslinking
    • 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
    • H01M8/1069—Polymeric electrolyte materials characterised by the manufacturing processes
    • H01M8/1086—After-treatment of the membrane other than by polymerisation
    • H01M8/1088—Chemical modification, e.g. sulfonation
    • 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
    • H01M2008/1095—Fuel cells with polymeric electrolytes
    • 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
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells

Landscapes

  • Chemical & Material Sciences (AREA)
  • General Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Sustainable Development (AREA)
  • Sustainable Energy (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Composite Materials (AREA)
  • Manufacture Of Macromolecular Shaped Articles (AREA)
  • Fuel Cell (AREA)

Abstract

The invention discloses a kind of polypyrrole enhancing proton exchange membrane and preparation method thereof, the exchange membrane is made of the raw material of following weight parts: p-methyl benzenesulfonic acid 1-3, butyl methacrylate 20-30, pyrroles 10-15, initiator 0.3-0.4, sulfonated polyether-ether-ketone 130-150, ethylene bis stearamide 1-2,1,2- methylimidazole 0.3-1, aminopropyl triethoxysilane 2-4.The present invention is by by modified polyether ether ketone and modified polymer blending reaction, so as to improve dispersion compatibility of each raw material in dimethyl sulfoxide, to improve the mechanics conductive stability of finished product exchange membrane.

Description

A kind of polypyrrole enhancing proton exchange membrane and preparation method thereof
Technical field
The invention belongs to Material Fields, and in particular to a kind of polypyrrole enhancing proton exchange membrane and preparation method thereof.
Background technique
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 transmitting 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, and the service life is long.But it is high Price (800 U.S. dollars/m2), lower operating temperature (< 100 DEG C), higher methanol permeability and fluorine material bring ring 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；However proton membrane exists at present The defects of proton conductivity is low, and film mechanicalness is poor.
Summary of the invention
In view of the defects and deficiencies of the prior art, the present invention intends to provide a kind of polypyrroles to enhance proton exchange membrane And preparation method thereof.
To achieve the above object, the invention adopts the following technical scheme:
A kind of polypyrrole enhancing proton exchange membrane, it is composed of the following raw materials by weight:
P-methyl benzenesulfonic acid 1-3, butyl methacrylate 20-30, pyrroles 10-15, initiator 0.3-0.4, sulfonated polyether Ether ketone 130-150, ethylene bis stearamide 1-2, DMIZ 1,2 dimethylimidazole 0.3-1, aminopropyl triethoxysilane 2-4.
The initiator is one of ammonium persulfate, potassium peroxydisulfate.
A kind of preparation method of the polypyrrole enhancing proton exchange membrane, comprising the following steps:
(1) initiator is taken, is added in the deionized water of 20-30 times of its weight, stirs evenly；
(2) p-methyl benzenesulfonic acid is taken, is added in the chloroform of 7-9 times of its weight, stirs evenly, raising temperature is 50-60 DEG C, pyrroles is added, insulated and stirred 1-2 hours, chloroform is distilled off, obtains modified pyrroles；
(3) butyl methacrylate is taken, is mixed with modified pyrroles, is added to the deionized water of 10-20 times of mixture weight In, it stirs evenly, above-mentioned initiator solution is added, be passed through nitrogen, adjusting temperature of reaction kettle is 60-70 DEG C, insulated and stirred 4-7 Hour, discharging cooling obtains polymer solution；
(4) 1,2- methylimidazole is taken, is added in the dehydrated alcohol of 60-74 times of its weight, stirs evenly, ammonia third is added Ethyl triethoxy silicane alkane, increasing temperature is 50-60 DEG C, and sulfonated polyether-ether-ketone is added, 1-2 hours ultrasonic, and ethyl alcohol is distilled off, obtains Modified polyether ether ketone；
(5) above-mentioned modified polyether ether ketone is taken, is added in polymer solution, increasing temperature is 70-75 DEG C, insulated and stirred 2- It 4 hours, filters, filter cake is washed, air drying, obtain polymer modification polyether-ether-ketone；
(6) above-mentioned polymer modification polyether-ether-ketone is taken, is mixed with ethylene bis stearamide, mixture weight 17- is added to In 20 times of dimethyl sulfoxide, ultrasound 10-20 hours at 80-100 DEG C, casting film-forming enhances proton to get the polypyrrole Exchange membrane.
Advantages of the present invention:
Processing pyrroles is blended using p-methyl benzenesulfonic acid, chloroform in the present invention, modified pyrroles is obtained, later by itself and methyl Butyl acrylate mixing polymerize under initiator effect, obtains polypyrrole/butyl methacrylate；Three second of aminopropyl is used again Oxysilane handles sulfonated polyether-ether-ketone, obtains the sulfonated polyether-ether-ketone of surface amination, later by by modified polyether ether ketone With modified polymer blending reaction, so as to improve dispersion compatibility of each raw material in dimethyl sulfoxide, to improve The mechanics conductive stability of finished product exchange membrane.
Specific embodiment
Embodiment 1
A kind of polypyrrole enhancing proton exchange membrane, it is composed of the following raw materials by weight:
P-methyl benzenesulfonic acid 3, butyl methacrylate 30, pyrroles 15, initiator 0.4, sulfonated polyether-ether-ketone 150, ethylene Bis-stearamides 2, DMIZ 1,2 dimethylimidazole 1, aminopropyl triethoxysilane 4.
The initiator is one of ammonium persulfate, potassium peroxydisulfate.
A kind of preparation method of the polypyrrole enhancing proton exchange membrane, comprising the following steps:
(1) initiator is taken, is added in the deionized water of 30 times of its weight, stirs evenly；
(2) p-methyl benzenesulfonic acid is taken, is added in the chloroform of 9 times of its weight, stirs evenly, increasing temperature is 60 DEG C, is added Enter pyrroles, insulated and stirred 2 hours, chloroform is distilled off, obtains modified pyrroles；
(3) butyl methacrylate is taken, is mixed with modified pyrroles, is added to the deionized water of 10-20 times of mixture weight In, it stirs evenly, above-mentioned initiator solution is added, be passed through nitrogen, adjusting temperature of reaction kettle is 70 DEG C, insulated and stirred 7 hours, Discharging cooling, obtains polymer solution；
(4) 1,2- methylimidazole is taken, is added in the dehydrated alcohol of 74 times of its weight, stirs evenly, aminopropyl is added Triethoxysilane, increasing temperature is 60 DEG C, and sulfonated polyether-ether-ketone is added, and ethyl alcohol is distilled off in ultrasound 2 hours, must be modified poly- Ether ether ketone；
(5) above-mentioned modified polyether ether ketone is taken, is added in polymer solution, increasing temperature is 75 DEG C, and insulated and stirred 4 is small When, it filters, filter cake is washed, air drying, obtain polymer modification polyether-ether-ketone；
(6) above-mentioned polymer modification polyether-ether-ketone is taken, is mixed with ethylene bis stearamide, is added to 20 times of mixture weight Dimethyl sulfoxide in, at 100 DEG C ultrasound 20 hours, casting film-forming to get the polypyrrole enhance proton exchange membrane.
Embodiment 2
A kind of polypyrrole enhancing proton exchange membrane, it is composed of the following raw materials by weight:
P-methyl benzenesulfonic acid 1, butyl methacrylate 20, pyrroles 10, initiator 0.3, sulfonated polyether-ether-ketone 130, ethylene Bis-stearamides 1, DMIZ 1,2 dimethylimidazole 0.3, aminopropyl triethoxysilane 2.
The initiator is one of ammonium persulfate, potassium peroxydisulfate.
A kind of preparation method of the polypyrrole enhancing proton exchange membrane, comprising the following steps:
(1) initiator is taken, is added in the deionized water of 20 times of its weight, stirs evenly；
(2) p-methyl benzenesulfonic acid is taken, is added in the chloroform of 7 times of its weight, stirs evenly, increasing temperature is 50 DEG C, is added Enter pyrroles, insulated and stirred 1 hour, chloroform is distilled off, obtains modified pyrroles；
(3) butyl methacrylate is taken, is mixed with modified pyrroles, is added to the deionized water of 10-20 times of mixture weight In, it stirs evenly, above-mentioned initiator solution is added, be passed through nitrogen, adjusting temperature of reaction kettle is 60 DEG C, insulated and stirred 4 hours, Discharging cooling, obtains polymer solution；
(4) 1,2- methylimidazole is taken, is added in the dehydrated alcohol of 60 times of its weight, stirs evenly, aminopropyl is added Triethoxysilane, increasing temperature is 50 DEG C, and sulfonated polyether-ether-ketone is added, and ethyl alcohol is distilled off in ultrasound 1 hour, must be modified poly- Ether ether ketone；
(5) above-mentioned modified polyether ether ketone is taken, is added in polymer solution, increasing temperature is 70 DEG C, and insulated and stirred 2 is small When, it filters, filter cake is washed, air drying, obtain polymer modification polyether-ether-ketone；
(6) above-mentioned polymer modification polyether-ether-ketone is taken, is mixed with ethylene bis stearamide, is added to 17 times of mixture weight Dimethyl sulfoxide in, at 80 DEG C ultrasound 10 hours, casting film-forming to get the polypyrrole enhance proton exchange membrane.
Performance test:
The polypyrrole of the embodiment of the present invention 1 enhances proton exchange membrane:
Proton conductivity is 3.55 × 10‐2Scm‐1, mechanical mechanics property 38.7MPa；
The polypyrrole of embodiment 2 enhances proton exchange membrane:
Proton conductivity is 3.70 × 10‐2Scm‐1, mechanical mechanics property 39.1MPa；
Commercially available polyether-ether-ketone proton membrane:
Proton conductivity is 2.0-3.0 × 10‐2Scm‐1, mechanical mechanics property 20-30MPa.

Claims (3)

1. a kind of polypyrrole enhances proton exchange membrane, which is characterized in that it is composed of the following raw materials by weight:
P-methyl benzenesulfonic acid 1-3, butyl methacrylate 20-30, pyrroles 10-15, initiator 0.3-0.4, sulfonated polyether-ether-ketone 130-150, ethylene bis stearamide 1-2, DMIZ 1,2 dimethylimidazole 0.3-1, aminopropyl triethoxysilane 2-4.
2. a kind of polypyrrole according to claim 1 enhances proton exchange membrane, which is characterized in that the initiator was One of ammonium sulfate, potassium peroxydisulfate.
3. a kind of a kind of preparation method of polypyrrole enhancing proton exchange membrane as described in claim 1, which is characterized in that including Following steps:
(1) initiator is taken, is added in the deionized water of 20-30 times of its weight, stirs evenly；
(2) p-methyl benzenesulfonic acid is taken, is added in the chloroform of 7-9 times of its weight, stirs evenly, increasing temperature is 50-60 DEG C, is added Enter pyrroles, insulated and stirred 1-2 hours, chloroform is distilled off, obtains modified pyrroles；
(3) butyl methacrylate is taken, is mixed with modified pyrroles, is added in the deionized water of 10-20 times of mixture weight, stirs It mixes uniformly, above-mentioned initiator solution is added, be passed through nitrogen, adjusting temperature of reaction kettle is 60-70 DEG C, insulated and stirred 4-7 hours, Discharging cooling, obtains polymer solution；
(4) 1,2- methylimidazole is taken, is added in the dehydrated alcohol of 60-74 times of its weight, stirs evenly, aminopropyl three is added Ethoxysilane, increasing temperature is 50-60 DEG C, and sulfonated polyether-ether-ketone is added, 1-2 hours ultrasonic, and ethyl alcohol is distilled off, obtains modification Polyether-ether-ketone；
(5) above-mentioned modified polyether ether ketone is taken, is added in polymer solution, increasing temperature is 70-75 DEG C, and insulated and stirred 2-4 is small When, it filters, filter cake is washed, air drying, obtain polymer modification polyether-ether-ketone；
(6) above-mentioned polymer modification polyether-ether-ketone is taken, is mixed with ethylene bis stearamide, 17-20 times of mixture weight is added to Dimethyl sulfoxide in, ultrasound 10-20 hours at 80-100 DEG C, casting film-forming to get the polypyrrole enhance proton exchange Film.
CN201811071525.9A 2018-09-14 2018-09-14 A kind of polypyrrole enhancing proton exchange membrane and preparation method thereof Withdrawn CN109273747A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201811071525.9A CN109273747A (en) 2018-09-14 2018-09-14 A kind of polypyrrole enhancing proton exchange membrane and preparation method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201811071525.9A CN109273747A (en) 2018-09-14 2018-09-14 A kind of polypyrrole enhancing proton exchange membrane and preparation method thereof

Publications (1)

Publication Number Publication Date
CN109273747A true CN109273747A (en) 2019-01-25

Family

ID=65189437

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201811071525.9A Withdrawn CN109273747A (en) 2018-09-14 2018-09-14 A kind of polypyrrole enhancing proton exchange membrane and preparation method thereof

Country Status (1)

Country Link
CN (1) CN109273747A (en)

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101188301A (en) * 2007-12-10 2008-05-28 华南理工大学 A proton exchange film for direct carbinol fuel battery and its making method
US7867667B2 (en) * 2005-06-28 2011-01-11 Samsung Sdi Co., Ltd. Polymer electrolyte for a fuel cell, a method of producing the same, and a fuel cell system comprising the same
JP2011138782A (en) * 2002-03-06 2011-07-14 Basf Fuel Cell Gmbh Forming method of proton conductive polymer membrane
CN108306036A (en) * 2018-02-11 2018-07-20 温州市赢创新材料技术有限公司 A kind of polyalcohol intercalation basic zirconium phosphate proton exchange membrane and preparation method thereof

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2011138782A (en) * 2002-03-06 2011-07-14 Basf Fuel Cell Gmbh Forming method of proton conductive polymer membrane
US7867667B2 (en) * 2005-06-28 2011-01-11 Samsung Sdi Co., Ltd. Polymer electrolyte for a fuel cell, a method of producing the same, and a fuel cell system comprising the same
CN101188301A (en) * 2007-12-10 2008-05-28 华南理工大学 A proton exchange film for direct carbinol fuel battery and its making method
CN108306036A (en) * 2018-02-11 2018-07-20 温州市赢创新材料技术有限公司 A kind of polyalcohol intercalation basic zirconium phosphate proton exchange membrane and preparation method thereof

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
孟宪辉 等: "等离子体诱导下导电高分子复合膜的研究与应用", 《化学工程师》 *

Similar Documents

Publication Publication Date Title
CN110336052B (en) Mixed matrix type cation exchange membrane and preparation method thereof
CN107394242B (en) A kind of preparation method of amination graphene oxide/sulfonate polybenzimidazole proton exchange composite membrane resistant to high temperature
CN106252696B (en) Fuel cell inorganic-organic hybrid type proton exchange membrane and preparation method thereof
CN107308824B (en) Preparation method of sulfonic acid type cation exchange membrane
CN108493468A (en) A kind of epoxy polyphenylene oxide proton membrane and preparation method thereof
CN109535457A (en) A kind of preparation method of novel sulfonated polyether-ether-ketone/sulfoxidation graphene compound proton exchange membrane
CN101891899A (en) Ionic liquid doped heterocyclic polyarylether or sulfonate thereof for high-temperature and low-humidity ionic membrane and preparation method thereof
CN105949367B (en) A kind of hydrophilic/hydrophobic inierpeneirating network structure polymer dielectric film and preparation method thereof
CN111403785A (en) Sulfonated polyaryletherketone sulfone composite membrane and preparation method thereof
CN112940323A (en) Preparation of proton exchange membrane by anchoring metal organic framework on sulfonated polyaryletherketone sulfone in chemical bonding mode
CN104277216B (en) A kind of sulfonated perfluorocarbon cyclobutyl polyarylether polymer and its preparation method and application
CN106832278A (en) One class high transparency copoly type fluorine-containing polyimide film material and preparation method thereof
CN109830724A (en) A kind of compound proton exchange membrane and preparation method thereof of protonation carbonitride enhancing
CN110041480A (en) A kind of polymer and preparation method thereof and the purposes in pem fuel electrode catalyst layer
CN106751839A (en) Fuel cell polymer microsphere/sulfonated poly aryl ether ketone sulfone proton exchange membrane material, preparation method and applications containing amino
CN104250383A (en) Amphoteric ion exchange membrane and preparation method thereof
CN103709379A (en) Aromatic sulfonated poly ketone and preparation method thereof
CN109273747A (en) A kind of polypyrrole enhancing proton exchange membrane and preparation method thereof
CN107805302A (en) A kind of fluorine-containing sulfonated polyether compound of long side chain type based on bisphenol S and preparation method thereof
CN104987509A (en) Polymer containing ester group and amino group, preparation method, polymer containing carboxyl group and amino group, preparation method, and proton exchange membrane
CN102911494B (en) Organic-inorganic ternary hybrid sulfonated poly aryl ether ketone proton exchange membrane and preparation method thereof
CN113150248B (en) Ether-bond-free aryl sulfonated non-fluorine ionomer and preparation method and application thereof
CN111944259B (en) Conductive film material and preparation method thereof
CN108276596A (en) A kind of acid doped polyaniline proton exchange membrane
CN108264752A (en) A kind of heat-proof polyimide composite proton membrane and preparation method thereof

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
WW01 Invention patent application withdrawn after publication
WW01 Invention patent application withdrawn after publication

Application publication date: 20190125