阅读说明：本技术 Pbi纤维膜增强的耐高温复合质子交换膜及其制备方法 (PBI fiber membrane reinforced high-temperature-resistant composite 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PBI纤维膜增强的耐高温复合质子交换膜及其制备方法。由聚苯并咪唑维膜与全氟磺酸树脂制备而成。本发明所述的PBI多孔纤维膜增强的耐高温复合质子交换膜,通过采用静电纺丝工艺制备的PBI多孔纤维膜,孔径及纤维直径大小可调,孔隙率高,全氟磺酸树脂溶液浸润性好；制备的高温质子交换膜具有高的机械性能及优良的离子传导性能,同时在高温下亦能保持较好的性能。(The invention belongs to the technical field of fuel cells, and particularly relates to a high-temperature-resistant composite proton exchange membrane reinforced by PBI fiber membranes and a preparation method thereof.)

The high temperature resistant composite proton exchange membrane reinforced by kinds of PBI fiber membrane is characterized in that the membrane is prepared by polybenzimidazole porous fiber membrane and perfluorosulfonic acid resin.

2. The PBI fiber membrane-reinforced high temperature resistant composite proton exchange membrane of claim 1, wherein: the structural formula of polybenzimidazole is:

3. the PBI fiber membrane-reinforced high temperature resistant composite proton exchange membrane of claim 1, wherein: the polybenzimidazole porous fiber membrane layer is positioned in the middle of the composite proton exchange membrane, and the perfluorosulfonic acid resin is completely filled in micropores of the polybenzimidazole porous fiber membrane.

4, A preparation method of the PBI fiber membrane reinforced high temperature resistant composite proton exchange membrane of claim 1, which is characterized by comprising the following steps:

(1) preparation of PBI porous fiber membrane

Adding PBI into a polar solvent to obtain an electrostatic spinning solution, and then preparing a PBI porous fiber membrane by adopting a solution electrostatic spinning process;

(2) preparation of PBI porous fiber membrane reinforced composite proton exchange membrane

And (3) uniformly spraying the perfluorinated sulfonic acid resin solution on the PBI porous fiber membrane material in a spraying or coating mode, and drying at the temperature of 40-170 ℃ to obtain the PBI enhanced high-temperature resistant composite proton exchange membrane.

5. The preparation method of the PBI fiber membrane reinforced high-temperature-resistant composite proton exchange membrane according to claim 4, which is characterized in that: the mass concentration of the PBI in the polar solvent in the step (1) is 1-50%.

6. The preparation method of the PBI fiber membrane reinforced high-temperature-resistant composite proton exchange membrane according to claim 4, which is characterized in that: the thickness of the high-temperature resistant composite proton exchange membrane in the step (2) is 5-100 μm.

7. The preparation method of the PBI fiber membrane reinforced high-temperature-resistant composite proton exchange membrane according to claim 4, which is characterized in that: the preparation method of the PBI porous fiber membrane comprises the following steps:

① preparation of Electrostatic spinning solution

Gradually adding PBI powder into a polar solvent, stirring for 6-12h at 60 ℃ until the PBI powder is completely dissolved, and standing for 8-12h to prepare an electrostatic spinning solution;

② preparation of PBI porous fiber membrane

And (3) placing the PBI solution in an electrostatic spinning propulsion device, setting electrostatic spinning process parameters for electrostatic spinning, and then carrying out vacuum drying at 50-100 ℃ to prepare the PBI porous fiber membrane.

8. The method of claim 7, wherein the polar solvent used in step ① is selected from the group consisting of N, N-dimethylformamide, N-dimethylacetamide, N-methylpyrrolidone, dimethylsulfoxide, acetone, and butanone .

9. The method for preparing the PBI fiber membrane-reinforced high-temperature-resistant composite proton exchange membrane according to claim 7, wherein the electrostatic spinning process parameters in the step ② are that the electrostatic spinning voltage is 5-30KV, the injector propulsion speed is 0.01-5mm/min, the spinning distance is 05-25cm, and the temperature is 20-25 ℃.

10. The method for preparing the PBI fiber membrane-reinforced high-temperature-resistant composite proton exchange membrane according to claim 7, wherein the thickness of the PBI porous fiber membrane prepared in the step ② is 6-15 μm.

Technical Field

The invention belongs to the technical field of fuel cells, and particularly relates to an PBI fiber membrane reinforced high-temperature-resistant composite proton exchange membrane and a preparation method thereof.

Background

Fuel cells are electric generators for directly converting chemical energy stored in fuel and catalyst into electric energy, and research and development of fuel cells have been greatly progressed so far, and are green energy technologies which are gradually mature, can solve two major problems of energy saving and environmental protection, and are called final new energy forms.

The proton exchange membrane of the traditional PEMFC is formed by perfluorinated sulfonic acid resin, the proton conduction performance of the membrane depends on liquid water seriously, works at 60-90 ℃ as usual, the PEM is dehydrated due to overhigh temperature, the proton conduction rate is reduced sharply, and the performance of the cell is attenuated seriously, therefore, the development of the high-temperature resistant PEMFC is effective to solve the problems of poor environmental tolerance, performance attenuation and the like of the traditional PEMFC such as . in practice, considers that the PEMFC with the working temperature over 100 ℃ can be called as a high-temperature PEMFC, while the high-temperature PEMFC is the core part of the PEMFC and is the key point for realizing high-temperature operation.

Chinese patent application No. 2017113 0.5 discloses high-temperature-resistant composite proton exchange membranes, which are prepared by compounding polybenzimidazole and aromatic polymers with benzyl halogens on side chains to form composite cross-linked membranes and then soaking phosphoric acid, and the prepared composite proton exchange membranes have higher phosphoric acid doping level and good mechanical property.

Disclosure of Invention

The invention aims to solve the technical problems that the defects of the prior art are overcome, kinds of PBI fiber membrane reinforced high-temperature resistant composite proton exchange membranes are provided, the prepared high-temperature resistant composite proton exchange membranes have high mechanical properties and excellent ion conduction properties, and can keep better properties at high temperature, and the invention also provides a preparation method of the high-temperature resistant composite proton exchange membranes.

The invention relates to a PBI fiber membrane reinforced high-temperature-resistant composite proton exchange membrane which is prepared from a Polybenzimidazole (PBI) porous fiber membrane and perfluorosulfonic acid resin.

Wherein:

the polybenzimidazole porous fiber membrane layer is positioned in the middle of the composite proton exchange membrane, and the perfluorosulfonic acid resin is completely filled in micropores of the polybenzimidazole porous fiber membrane.

The structural formula of the polybenzimidazole is as follows:

the preparation method of the PBI fiber membrane reinforced high-temperature-resistant composite proton exchange membrane comprises the following steps:

(1) preparation of PBI porous fiber membrane

Adding PBI into a polar solvent to obtain an electrostatic spinning solution, and then preparing the PBI porous fiber membrane by adopting a solution electrostatic spinning process.

(2) Preparation of PBI porous fiber membrane reinforced composite proton exchange membrane

And (3) uniformly spraying the perfluorinated sulfonic acid resin solution on the PBI porous fiber membrane material in a spraying or coating mode, and drying at the temperature of 40-170 ℃ to obtain the PBI enhanced high-temperature resistant composite proton exchange membrane.

Wherein:

the mass concentration of the PBI in the polar solvent in the step (1) is 1-50%.

The thickness of the high-temperature resistant composite proton exchange membrane in the step (2) is 5-100 μm.

Preferably, the preparation method of the PBI porous fiber membrane comprises the following steps:

① preparation of Electrostatic spinning solution

Gradually adding PBI powder into a polar solvent, stirring for 6-12h at 60 ℃ until the PBI powder is completely dissolved, and standing for 8-12h to prepare an electrostatic spinning solution;

② preparation of PBI porous fiber membrane

And (3) placing the PBI solution in an electrostatic spinning propulsion device, setting electrostatic spinning process parameters for electrostatic spinning, and then placing the PBI solution at 50-100 ℃ for vacuum drying to prepare the PBI porous fiber membrane.

Wherein:

the polar solvent used in step ① is or more selected from N, N-dimethylformamide, N-dimethylacetamide, N-methylpyrrolidone, dimethylsulfoxide, acetone, and butanone.

The electrostatic spinning process parameters in the step ② are that the electrostatic spinning voltage is 5-30KV, the injector propulsion speed is 0.01-5mm/min, the spinning distance (the distance between the needle head and the flat plate receiver) is 05-25cm, and the temperature is 20-25 ℃.

The thickness of the PBI porous fiber membrane prepared in the step ② is 6-15 μm.

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

(1) the high-temperature-resistant composite proton exchange membrane reinforced by the PBI fiber membrane is characterized in that the high-strength PBI porous fiber membrane is compounded with a perfluorinated sulfonic acid resin solution, the prepared high-temperature-resistant composite proton exchange membrane not only keeps the high conductivity of the perfluorinated sulfonic acid resin solution, but also can improve the mechanical property of the composite membrane at high temperature by taking the PBI porous fiber membrane as a reinforcing material.

(2) The PBI fiber membrane reinforced high-temperature-resistant composite proton exchange membrane has the advantages that the PBI porous fiber membrane has high strength and uniform pore diameter, and the prepared high-temperature proton exchange membrane has high mechanical property and excellent ion conduction property and can keep better performance at high temperature.

(3) The PBI porous fiber membrane prepared by the electrostatic spinning process has adjustable pore diameter and fiber diameter, high porosity and good infiltration of perfluorinated sulfonic acid resin solution; the mechanical strength and stability at high temperature are improved, and the conductivity is also improved.

Drawings

FIG. 1 SEM image of PBI fiber membrane of example 1.

Detailed Description

The invention is further described with reference to the following examples.