阅读说明：本技术 柔性陶瓷纤维膜增强的全氟质子交换膜及其制备方法 (Flexible ceramic fiber membrane reinforced perfluoro proton exchange membrane and preparation method thereof ) 是由 于洋洋 冯威 刘璐 袁超 赵玉会 张永明 于 2019-10-22 设计创作，主要内容包括：本发明属于燃料电池技术领域，具体的涉及一种柔性陶瓷纤维膜增强的全氟质子交换膜及其制备方法。由柔性陶瓷纤维膜与全氟磺酸树脂制备而成；其中柔性陶瓷纤维膜由改性的无机陶瓷纳米颗粒、可电纺聚合物、交联剂和弹性体材料通过静电纺丝法制备而成。本方法所述的柔性陶瓷纤维膜采用静电纺丝法制备，孔隙率高，纤维膜内部含有改性的无机陶瓷纳米颗粒，与磺酸树脂溶液复合浸润性好；加入的弹性体材料，使陶瓷纤维膜具有很好的柔性，且还保留着陶瓷纤维的强度及韧性。(The invention belongs to the technical field of fuel cells, and particularly relates to a flexible ceramic fiber membrane reinforced perfluorinated proton exchange membrane and a preparation method thereof. Is prepared from a flexible ceramic fiber membrane and perfluorinated sulfonic acid resin; the flexible ceramic fiber membrane is prepared from modified inorganic ceramic nanoparticles, an electrospinnable polymer, a cross-linking agent and an elastomer material by an electrostatic spinning method. The flexible ceramic fiber membrane is prepared by adopting an electrostatic spinning method, the porosity is high, and the interior of the fiber membrane contains modified inorganic ceramic nano-particles and has good composite wettability with a sulfonic acid resin solution; the added elastomer material ensures that the ceramic fiber membrane has good flexibility and also keeps the strength and the toughness of the ceramic fiber.)

1. A flexible ceramic fiber membrane reinforced perfluoro proton exchange membrane is characterized in that: is prepared from a flexible ceramic fiber membrane and perfluorinated sulfonic acid resin; the flexible ceramic fiber membrane is prepared from modified inorganic ceramic nanoparticles, an electrospinnable polymer, a cross-linking agent and an elastomer material by an electrostatic spinning method.

2. The flexible ceramic fiber membrane-reinforced perfluorinated proton exchange membrane according to claim 1, wherein: the elastomer material is one or more of ethylene-vinyl acetate copolymer, polyethylene octene co-elastomer, ethylene propylene rubber or ethylene octene copolymer.

3. The flexible ceramic fiber membrane-reinforced perfluorinated proton exchange membrane according to claim 1, wherein: the cross-linking agent is one or more of polymethacrylate, polymethyl acrylate, ethyl trisilicate or polyvinyl acetate.

4. The flexible ceramic fiber membrane-reinforced perfluorinated proton exchange membrane according to claim 1, wherein: the electrospinnable polymer is one of polyvinylpyrrolidone, polyvinylidene fluoride, polyvinyl butyral, polyacrylonitrile, polyvinyl alcohol or polyimide.

5. The flexible ceramic fiber membrane-reinforced perfluorinated proton exchange membrane according to claim 1, wherein: the modified inorganic ceramic nanoparticles are prepared by the following steps:

(1) performing ultrasonic hydrolysis on the coupling agent in an ethanol solution to obtain hydrolysate of the coupling agent;

(2) and then adding the inorganic ceramic nanoparticles into hydrolysate of the coupling agent, and stirring at normal temperature for reaction to obtain the coupling agent modified inorganic ceramic nanoparticles.

6. The flexible ceramic fiber membrane-reinforced perfluorinated proton exchange membrane according to claim 5, wherein: the inorganic ceramic nanoparticles are nano Al₂O₃Nano SiO₂Nano ZrO 2₂TiO 2 nanoparticles₂Nano CrO₂And one or more of nano MgO and nano ZnO.

7. The flexible ceramic fiber membrane-reinforced perfluorinated proton exchange membrane according to claim 5, wherein: the dosage of the coupling agent is 5-10% of the total mass of the coupling agent and the inorganic ceramic nano particles, and the dosage of the inorganic ceramic nano particles is 90-95% of the total mass of the coupling agent and the inorganic ceramic nano particles.

8. The flexible ceramic fiber membrane-reinforced perfluorinated proton exchange membrane according to claim 5, wherein: the coupling agent is one or more of silane coupling agent, aluminate coupling agent, titanate coupling agent or rare earth coupling agent in any ratio; the silane coupling agent is one or more of vinyltriethoxysilane, vinyltrimethoxysilane, aminopropyltriethoxysilane or methacrylic acid oxypropyltriethoxysilane.

9. A method of preparing a flexible ceramic fiber membrane reinforced perfluorinated proton exchange membrane according to claim 1, wherein the method comprises the following steps: prepared by the following steps:

(1) mixing and stirring the inorganic ceramic nanoparticle mixed solution modified by the coupling agent, the elastomer material and the crosslinking agent for 30-60 min at normal temperature to prepare a precursor solution;

(2) adding an electrospinnable polymer into the precursor solution prepared in the step (1), and magnetically stirring uniformly to obtain a spinning solution;

(3) performing electrostatic spinning on the spinning solution prepared in the step (2) to prepare a flexible ceramic fiber membrane;

(4) and (4) coating the flexible ceramic fiber membrane prepared in the step (3) on perfluorinated sulfonic acid resin to prepare the flexible ceramic fiber membrane reinforced perfluorinated proton exchange membrane.

10. The method of preparing a flexible ceramic fiber membrane reinforced perfluorinated proton exchange membrane according to claim 9, wherein the method comprises the following steps: the electrostatic spinning conditions in the step (3) are as follows: the accelerating voltage is 7-20kV, the spinning distance is 10-30cm, the spinning speed is 0.1-2ml/h, the spinning temperature is 20-25 ℃ and the spinning time is 1-6 h.

Technical Field

The invention belongs to the technical field of fuel cells, and particularly relates to a flexible ceramic fiber membrane reinforced perfluorinated proton exchange membrane and a preparation method thereof.

Background

From the technical point of view, the most core technology of the hydrogen fuel cell is the fuel cell membrane, which is used as the "chip" of the fuel cell, and plays the roles of conducting protons and blocking reaction gas during the operation of the PEMFC, directly influencing the performance and the service life of the fuel cell. Fuel cell membranes need to have high H + conductivity, strong mechanical strength and high dimensional stability. At present, the perfluor proton exchange membrane and the composite membrane are most widely applied, although the perfluor proton exchange membrane has the advantages of high conductivity, low hydrogen permeation and the like, the perfluor proton exchange membrane has the defects of low mechanical strength, poor stability and the like, and the perfluor proton exchange membrane mostly adopts polymer materials such as PTFE/PVDF and the like as reinforcing materials to reinforce the mechanical performance of the composite membrane, but has the problems of complex processing technology, poor solution wettability and the like, so that the finding of a novel material with high strength and good solution wettability to reinforce the performance of the perfluor proton exchange membrane has important significance.

Chinese patent application 201610556684.2 discloses a method for preparing a reinforced composite proton exchange membrane, wherein a Polytetrafluoroethylene (PTFE) porous membrane is introduced as a framework of a reinforced membrane to improve the strength during the preparation process, and a molecular sieve/acidified molecular sieve is added to improve the water retention capacity at high temperature. However, Polytetrafluoroethylene (PTFE) belongs to a hydrophobic material, a perfluorosulfonic acid resin solution is difficult to infiltrate the PTFE porous membrane, and although the strength of the composite proton exchange membrane is increased, the dimensional stability of the composite membrane is not improved.

Chinese patent application 201510011084.3 discloses a PVDF modified perfluorosulfonic acid proton exchange membrane and a preparation method thereof. According to the invention, PVDF is uniformly compounded into the perfluorosulfonic acid proton exchange membrane through ammonia water crosslinking, so that the prepared PVDF modified perfluorosulfonic acid proton exchange membrane has the advantages that the methanol permeability is reduced by times, and the mechanical stability, the size stability and the like of the composite proton exchange membrane are greatly improved. However, the addition of PVDF resin to the perfluorosulfonic acid resin solution affects the conductivity of the perfluorosulfonic acid resin, thereby reducing the electrical properties of the battery membrane.

Disclosure of Invention

The technical problem to be solved by the invention is as follows: overcomes the defects of the prior art and provides a flexible ceramic fiber membrane reinforced perfluorinated proton exchange membrane. The prepared flexible ceramic fiber membrane reinforced perfluorinated proton exchange membrane has high mechanical property and dimensional stability and long service life, and is suitable for popularization and application of fuel cells; the invention also provides a preparation method of the composition.

The flexible ceramic fiber membrane reinforced perfluorinated proton exchange membrane is prepared from a flexible ceramic fiber membrane and perfluorinated sulfonic acid resin; the flexible ceramic fiber membrane is prepared from modified inorganic ceramic nanoparticles, an electrospinnable polymer, a cross-linking agent and an elastomer material by an electrostatic spinning method.

Wherein:

the elastomer material is one or more of ethylene-vinyl acetate copolymer (EVA), polyethylene octene co-elastomer (POE), ethylene propylene rubber or ethylene-octene copolymer.

The cross-linking agent is one or more of polymethacrylate, polymethyl acrylate, ethyl trisilicate or polyvinyl acetate.

The electrospinnable polymer is one of polyvinylpyrrolidone (PVP), polyvinylidene fluoride (PVDF), polyvinyl butyral (PVB), Polyacrylonitrile (PAN), polyvinyl alcohol (PVA) or Polyimide (PI).

The modified inorganic ceramic nanoparticles are prepared by the following method:

(1) performing ultrasonic hydrolysis on the coupling agent in an ethanol solution to obtain hydrolysate of the coupling agent;

(2) and then adding the inorganic ceramic nanoparticles into hydrolysate of the coupling agent, and stirring at normal temperature for reaction to obtain the coupling agent modified inorganic ceramic nanoparticles.

Wherein:

the inorganic ceramic nanoparticles are nano Al₂O₃Nano SiO₂Nano ZrO 2₂TiO 2 nanoparticles₂Nano CrO₂And one or more of nano MgO and nano ZnO.

The dosage of the coupling agent is 5-10% of the total mass of the coupling agent and the inorganic ceramic nano particles, and the dosage of the inorganic ceramic nano particles is 90-95% of the total mass of the coupling agent and the inorganic ceramic nano particles.

The coupling agent is one or more of silane coupling agent, aluminate coupling agent, titanate coupling agent or rare earth coupling agent.

The silane coupling agent is one or more of vinyltriethoxysilane, vinyltrimethoxysilane, aminopropyltriethoxysilane (KH-550) or methoxypropyltriethoxysilane (KH-570) methacrylate.

The invention relates to a preparation method of a flexible ceramic fiber membrane reinforced perfluoro proton exchange membrane, which comprises the following steps:

(1) mixing and stirring the modified inorganic ceramic nanoparticle mixed solution, the elastomer material and the cross-linking agent for 30-60 min at normal temperature to prepare a uniform and stable precursor solution;

(2) adding an electrospinnable polymer into the precursor solution prepared in the step (1), and magnetically stirring uniformly to obtain a spinning solution;

(3) performing electrostatic spinning on the spinning solution prepared in the step (2) to prepare a flexible ceramic fiber membrane;

(4) and (4) coating the flexible ceramic fiber membrane prepared in the step (3) on perfluorinated sulfonic acid resin to prepare the flexible ceramic fiber membrane reinforced perfluorinated proton exchange membrane.

Wherein:

the electrostatic spinning in the step (3) is carried out in an electrostatic spinning propulsion device, and the electrostatic spinning conditions are as follows: the accelerating voltage is 7-20kV, the spinning distance is 10-30cm, the spinning speed is 0.1-2ml/h, the spinning temperature is 20-25 ℃ and the spinning time is 1-6 h.

Compared with the prior art, the invention has the following beneficial effects:

(1) the flexible ceramic fiber membrane is prepared by adopting an electrostatic spinning method, the porosity is high, and the interior of the fiber membrane contains modified inorganic ceramic nano-particles and has good composite wettability with a sulfonic acid resin solution; the added elastomer material ensures that the ceramic fiber membrane has good flexibility and also keeps the strength and the toughness of the ceramic fiber.

(2) The flexible ceramic fiber membrane reinforced perfluoro proton exchange membrane of the invention modifies inorganic ceramic material to prepare flexible fiber membrane as the middle reinforcing layer of the proton exchange membrane; the prepared perfluorinated proton exchange membrane has the advantages of high strength, long service life and the like, and is suitable for popularization and application of fuel cells.

Detailed Description

The present invention is further described below with reference to examples.