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WO2016124052A1 - Membrane échangeuse de protons pour piles à combustible et son procédé de préparation - Google Patents

Membrane échangeuse de protons pour piles à combustible et son procédé de préparation Download PDF

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Publication number
WO2016124052A1
WO2016124052A1 PCT/CN2015/099738 CN2015099738W WO2016124052A1 WO 2016124052 A1 WO2016124052 A1 WO 2016124052A1 CN 2015099738 W CN2015099738 W CN 2015099738W WO 2016124052 A1 WO2016124052 A1 WO 2016124052A1
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WO
WIPO (PCT)
Prior art keywords
exchange membrane
proton exchange
heteropoly acid
proton
fuel cell
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.)
Ceased
Application number
PCT/CN2015/099738
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English (en)
Chinese (zh)
Inventor
陈庆
曾军堂
叶任海
陈兵
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.)
Chengdu New Keli Chemical Science Co Ltd
Original Assignee
Chengdu New Keli Chemical Science Co Ltd
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Filing date
Publication date
Application filed by Chengdu New Keli Chemical Science Co Ltd filed Critical Chengdu New Keli Chemical Science Co Ltd
Publication of WO2016124052A1 publication Critical patent/WO2016124052A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/20—Manufacture of shaped structures of ion-exchange resins
    • C08J5/22—Films, membranes or diaphragms
    • 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
    • H01M8/02—Details
    • 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
    • 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
    • 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
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Definitions

  • the present invention relates to the field of fuel cell proton exchange membranes, and in particular to a fuel cell proton exchange membrane and a method of preparing the same.
  • Proton exchange membrane is one of the key components in proton exchange membrane fuel cells (PEMFC). It is a dense proton-selective membrane that acts as a separator to separate fuel and oxidant from direct reaction. It also plays a role in conducting protons to electronic insulation. The performance of proton exchange membranes directly affects the performance of fuel cells, and is one of the key issues that restrict the large-scale commercial operation of fuel cells. With the in-depth study and development of proton exchange membranes, in order to improve the proton conductivity of proton exchange membranes, many methods have been proposed, such as: modification of proton conductive matrix resin to improve proton conductivity, and efficient addition. Proton conductivity materials, the development of new proton conductive materials, etc., have also made significant progress, but there are also many unresolved defects that limit their large-scale commercial operations and production.
  • PEMFC proton exchange membrane fuel cells
  • Adding a material having high proton conductivity to a matrix resin is one of the main means for solving the low proton conductivity of a proton exchange membrane, and the method can greatly improve the proton conductivity of a proton exchange membrane, and has broad application prospects and practicality. value.
  • the high proton conductivity materials currently added to the proton exchange membrane are mostly solid heteropolyacids, which have high proton conductivity and compatibility, and can be added to the matrix resin to greatly enhance the proton exchange membrane protons. Excellent conductivity and performance, but due to the water-soluble nature of heteropoly acid, it is easily lost in the fuel cell during use, which causes the proton exchange membrane to proton conductivity with the fuel cell. The rapid decline in use has seriously affected the service life of fuel cells, resulting in limited use of fuel cells.
  • Chinese Patent Publication No. CN1848504A discloses a composite proton exchange membrane for a high temperature proton exchange membrane fuel cell and a preparation method thereof, which comprises a mixture of heteropoly acid and zirconium hydrogen phosphate with polybenzimidazole (PBI) or sulfonate.
  • the polyaryloxyphosphazene was doped to prepare a composite proton exchange membrane material, and then formed into a film by a casting method.
  • the proton exchange membrane prepared by the method has wide application temperature and good alcohol resistance, but
  • the proton exchange membrane is obtained by physically mixing the heteropoly acid and zirconium hydrogen phosphate directly with polybenzimidazole (PBI) or sulfonated polyaryloxyphosphazene, and the heteropoly acid is easily lost with water in the fuel cell.
  • PBI polybenzimidazole
  • the proton conductivity of the proton exchange membrane is rapidly reduced, which seriously affects the discharge performance and service life of the fuel cell.
  • Chinese Patent Publication No. CN101034747A discloses a method for preparing an inorganic proton exchange membrane fuel cell membrane, which first physically mixes a heteropoly acid with an inorganic oxide to prepare a precursor solution, and then with an inorganic proton conductive powder, thermoplastic The resin binder is hot pressed to prepare an inorganic proton exchange membrane.
  • the membrane electrode prepared by the method has a high working temperature, but the proton exchange membrane is prepared by directly mixing the heteropoly acid, and the heteropoly acid is easily associated with water in the fuel cell. Loss and loss, the proton exchange membrane proton conductivity is rapidly reduced.
  • Chinese Patent Publication No. CN102376961A discloses a high-performance polymer high-temperature proton exchange membrane for a high-temperature proton exchange membrane fuel cell and a preparation method thereof.
  • the method treats the prepared homogeneous blend membrane with acidification (phosphoric acid or/and heteropolyacid) to have good high-temperature proton conductivity.
  • the exchange membrane has excellent chemical stability, thermal stability, mechanical properties and high-temperature proton conductivity, but the heteropoly acid in the same proton exchange membrane is easily lost with the loss of water in the fuel cell, proton exchange of proton exchange membrane Fast decrease in performance, short service life and low discharge efficiency.
  • the present invention provides a proton exchange membrane for a lignin fuel cell. Compared with other fuel cell proton exchange membranes, the present invention incorporates a modifier for modifying heteropolyacids and then adding them to proton conduction. In the matrix resin, the proton exchange conductivity of the heteropoly acid is maintained, and the proton exchange membrane is prevented from being lost together with water. The proton exchange membrane has the advantages of high proton conductivity and long service life. [0010] A further object of the present invention is to provide a method for preparing a proton exchange membrane for a fuel cell, which firstly modifies a heteropoly acid, and then dopes the heteropoly acid modified by the modification into a matrix resin.
  • the proton exchange membrane is obtained by the membrane forming process, and the obtained proton exchange membrane has the advantages of good proton conductivity and long service life, satisfies the application of the proton exchange membrane on the fuel cell, and can be mass-produced industrially, with stable quality and suitable for fuel. Promotion and application of battery pairs.
  • a fuel cell proton exchange membrane of the present invention is characterized by comprising a modified compound formed by an active group in a modifier and a metal ion of an amphoteric acid in a heteropoly acid under the action of hydrogen bonding and ionic bonding,
  • the composition of the raw materials is as follows:
  • the matrix resin is one or more of a sulfonated polyethersulfone, a sulfonated polyetheretherketone, a sulfonated polybenzimidazole, a sulfonated polysulfone, and a polyimide;
  • the heteropoly acid is one of H 5 GaW 12 0 40 , H 2 PtW u 0 36 , H 7As 2 W 18 0 62 , H 5 IW 6 0 24 , H 8 CeMo u 0 39 , H 6 TeMo 6 0 24 Or a plurality of;
  • the modifier is one or more of polyacrylamide, lauryl polyoxyethylene ether, diglycerin polypropylene glycol, N-methyl fatty acid amide, benzethonamide;
  • the fiber is one or more of barium sulfate fiber, fluorocarbon polymer fiber, and silicon carbide fiber.
  • a method for preparing a proton exchange membrane for a fuel cell the specific preparation steps are as follows:
  • the proton exchange membrane having a thickness of 0. 5-2 mm is obtained by a method of casting a film.
  • the organic solvent is one or more of dimethylamide, ethylenediamine, and isopropanol.
  • Heteropoly acid is a condensed oxo acid obtained by condensation of different oxoacids, is a protonic acid of uniform strength, has redox capability, has good proton conductivity, and is doped in proton conductive materials.
  • the preparation of a proton exchange membrane can greatly improve the proton conductivity of the proton exchange membrane.
  • the invention modifies the heteropoly acid, and uses the high-energy radiation of ultraviolet light, and the active group in the modifier and the metal ion of the amphoteric acid in the heteropoly acid form a new modification under the action of hydrogen bond and ionic bond.
  • a compound having a property of a heteropolyacid and a modifier a heteropolyacid moiety having hydrophilicity, capable of conducting protons, a modifier portion having water repellency, being insoluble in water, and preventing dissolution and loss of heteropoly acid, thereby It ensures that the conductivity of the proton exchange membrane will not decrease during the use of the fuel cell, and the service life and performance of the fuel cell are greatly improved, and the method is simple and convenient, low in cost, large-scale industrial production, stable in quality, suitable for fuel cells. Promotional application.
  • Table 1 Comparison of performance between the present invention and a proton exchange membrane of a conventional doped heteropoly acid fuel cell
  • the proton exchange membrane of the present invention contains a modified compound formed by a living group of a modifier and a metal ion of an amphoteric acid in a heteropoly acid under the action of a hydrogen bond and an ionic bond.
  • the present invention solves the problem that most of the proton exchange membranes doped with heteropolyacids are easily lost with the loss of water in the fuel cell, resulting in a rapid decrease in the proton conductivity of the proton exchange membrane. Short-lived defects.
  • the proton exchange membrane prepared by the invention has excellent proton conductivity and long service life, and can Large-scale industrial production, stable quality, suitable for the promotion and application of fuel cells.
  • the proton exchange membrane having a thickness of 0.5 mm is formed by a method of casting into a film.
  • the proton exchange membrane having a thickness of 0.5 mm is formed by a method of casting into a film.
  • the casting solution obtained in the step 2) is cast into a film to form a proton exchange membrane having a thickness of 1 mm.
  • the heteropoly acid-modified compound A obtained in the step 1) and the barium sulfate fiber in the weight part 10 are added and stirred uniformly. After obtaining a casting solution;
  • the proton exchange membrane having a thickness of 0.5 mm is formed by a method of casting into a film.
  • the present invention modifies the heteropoly acid and then adds it to the proton conductive matrix resin to maintain the proton conductivity of the heteropoly acid and prevent it from being lost together with water.
  • the proton exchange membrane has protons.
  • the utility model has the advantages of high electrical conductivity and long service life, and the method can be industrially produced on a large scale, and the quality is stable, and is suitable for the promotion and application of the fuel cell pair.

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  • Chemical & Material Sciences (AREA)
  • Manufacturing & Machinery (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • General Chemical & Material Sciences (AREA)
  • Electrochemistry (AREA)
  • Sustainable Energy (AREA)
  • Sustainable Development (AREA)
  • Health & Medical Sciences (AREA)
  • Organic Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Medicinal Chemistry (AREA)
  • Materials Engineering (AREA)
  • Fuel Cell (AREA)
  • Manufacture Of Macromolecular Shaped Articles (AREA)

Abstract

La présente invention concerne une membrane échangeuse de protons pour piles à combustible et un procédé de préparation. Dans la présente invention, un hétéropolyacide est modifié et ensuite ajouté à une résine de substrat conducteur de protons, héritant ainsi de la conductivité protonique de l'hétéropolyacide et empêchant l'hétéropolyacide d'être éliminé par lavage avec de l'eau. Cette membrane échangeuse de protons présente les avantages d'une conductivité protonique élevée et d'une longue durée de vie. De plus, le procédé peut être mis à l'échelle pour une production de manière industrielle avec une qualité stable, et est approprié pour une large application dans des piles à combustible.
PCT/CN2015/099738 2015-02-05 2015-12-30 Membrane échangeuse de protons pour piles à combustible et son procédé de préparation Ceased WO2016124052A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CN201510058803.7 2015-02-05
CN201510058803.7A CN104701560B (zh) 2015-02-05 2015-02-05 一种燃料电池质子交换膜及其制备方法

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WO2016124052A1 true WO2016124052A1 (fr) 2016-08-11

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Cited By (5)

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Publication number Priority date Publication date Assignee Title
CN114447383A (zh) * 2020-10-31 2022-05-06 中国石油化工股份有限公司 一种有机-无机复合质子交换膜及其制备方法
CN115051004A (zh) * 2022-06-10 2022-09-13 四川大学 燃料电池质子交换膜及其制备方法
CN115548398A (zh) * 2022-11-08 2022-12-30 安徽理工大学 磺化聚醚醚酮、硅钨酸和离子液体掺杂改性聚氯乙烯基质子交换膜的制备方法
CN116364995A (zh) * 2023-05-30 2023-06-30 河北工程大学 一种改性聚酰亚胺质子交换膜及其制备方法和应用
CN120127159A (zh) * 2025-03-20 2025-06-10 湖北工业大学 一种质子交换膜制备方法

Families Citing this family (7)

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Publication number Priority date Publication date Assignee Title
CN104701560B (zh) * 2015-02-05 2016-10-19 成都新柯力化工科技有限公司 一种燃料电池质子交换膜及其制备方法
WO2017151003A1 (fr) * 2016-03-02 2017-09-08 Общество С Ограниченной Ответственностью "Эй Ти Энерджи" Matériau composite pour des éléments combustibles basse température et procédé de fabrication
CN107658410A (zh) * 2017-09-30 2018-02-02 惠州佳合能新能源科技有限公司 一种动力电池组用组合桑蚕丝的隔离膜及其制备方法
CN109912928A (zh) * 2019-03-18 2019-06-21 山东星火科学技术研究院 磺化聚醚醚酮与磷钨酸复合膜的制备方法
CN112825359B (zh) * 2019-11-21 2022-07-26 重庆神华薄膜太阳能科技有限公司 一种复合离子交换膜及其制备方法和应用
CN112259771B (zh) * 2020-09-16 2022-02-18 深圳大学 一种具有宽运行温度的质子交换膜及其制备方法与应用
CN118878892B (zh) * 2024-09-29 2024-12-20 江苏源氢新能源科技股份有限公司 耐用型质子交换膜及其制备方法

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DE102004035309A1 (de) * 2004-07-21 2006-02-16 Pemeas Gmbh Membran-Elektrodeneinheiten und Brennstoffzellen mit erhöhter Lebensdauer
CN101728550B (zh) * 2009-12-10 2011-05-04 山东东岳神舟新材料有限公司 一种纤维增强掺杂稳定的质子交换膜

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CN102153827A (zh) * 2008-12-08 2011-08-17 于淑芳 一种纤维增强无机物掺杂全氟质子交换膜
CN101867050A (zh) * 2010-06-08 2010-10-20 南通大学 复合质子交换膜
CN101864163A (zh) * 2010-06-08 2010-10-20 南通大学 复合质子交换膜的制备方法
CN104701560A (zh) * 2015-02-05 2015-06-10 成都新柯力化工科技有限公司 一种燃料电池质子交换膜及其制备方法

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN114447383A (zh) * 2020-10-31 2022-05-06 中国石油化工股份有限公司 一种有机-无机复合质子交换膜及其制备方法
CN115051004A (zh) * 2022-06-10 2022-09-13 四川大学 燃料电池质子交换膜及其制备方法
CN115051004B (zh) * 2022-06-10 2023-09-08 四川大学 燃料电池质子交换膜及其制备方法
CN115548398A (zh) * 2022-11-08 2022-12-30 安徽理工大学 磺化聚醚醚酮、硅钨酸和离子液体掺杂改性聚氯乙烯基质子交换膜的制备方法
CN116364995A (zh) * 2023-05-30 2023-06-30 河北工程大学 一种改性聚酰亚胺质子交换膜及其制备方法和应用
CN116364995B (zh) * 2023-05-30 2023-12-22 河北工程大学 一种改性聚酰亚胺质子交换膜及其制备方法和应用
CN120127159A (zh) * 2025-03-20 2025-06-10 湖北工业大学 一种质子交换膜制备方法

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CN104701560A (zh) 2015-06-10

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