CN116103694A - Modified glass fiber cloth reinforced composite proton exchange membrane and preparation method thereof - Google Patents

Modified glass fiber cloth reinforced composite proton exchange membrane and preparation method thereof Download PDF

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CN116103694A
CN116103694A CN202310065990.6A CN202310065990A CN116103694A CN 116103694 A CN116103694 A CN 116103694A CN 202310065990 A CN202310065990 A CN 202310065990A CN 116103694 A CN116103694 A CN 116103694A
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glass fiber
fiber cloth
silicon dioxide
ion exchange
resin
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程义
董欣
郑和成
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Hunan Zhongchi Hydrogen Energy Technology Co ltd
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    • C25B13/00—Diaphragms; Spacing elements
    • C25B13/04—Diaphragms; Spacing elements characterised by the material
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Abstract

The invention belongs to the technical field of hydrogen energy, and discloses a preparation method of a modified glass fiber cloth reinforced composite proton exchange membrane. The preparation method comprises the following steps: coating a silicon dioxide layer on the surface of the glass fiber cloth; sulfonation treatment of glass fiber cloth coated with a silicon dioxide layer on the surface; preparing a mixed solution of ion exchange resin and sulfonated silicon dioxide; and (3) soaking the mixed solution or coating the mixed solution on the two sides of the glass fiber cloth after sulfonation treatment, and drying to obtain the modified glass fiber cloth reinforced composite proton exchange membrane. The preparation method is relatively simple, and the prepared modified glass fiber cloth reinforced composite proton exchange membrane has good proton conductivity and stability, high mechanical strength and low cost.

Description

Modified glass fiber cloth reinforced composite proton exchange membrane and preparation method thereof
Technical Field
The invention belongs to the technical field of hydrogen energy, and particularly relates to a proton exchange membrane and a preparation method thereof.
Background
The non-renewable nature of fossil energy and environmental pollution from long-term use have motivated the development and use of hydrogen energy technology worldwide. Hydrogen production, hydrogen storage and conversion of hydrogen energy into electrical energy are one of the solutions for future energy sources. The proton exchange membrane is a core component in the electrolysis of water to produce hydrogen and the proton exchange membrane fuel cell, and plays roles in conducting hydrogen ions, isolating fuel and oxidant and blocking electrons.
The ideal proton exchange membrane has the characteristics of high proton conductivity, good chemical and thermal stability, high mechanical strength, low fuel permeability and low cost. The most commercialized state of the art is perfluorosulfonic acid proton exchange membranes, typified by Nafion, but high temperature dehydration results in reduced proton conductivity, reduced mechanical properties, increased fuel permeability, and high cost, which has prompted researchers to study composite PEM and fluorine-free PEM.
The structure of the composite PEM is mainly that of a perfluorinated nonionic microporous medium combined with perfluorinated ion exchange resin, such as a porous polytetrafluoroethylene substrate developed by Gore company combined with Nafion resin. The Nafion resin is poured on the porous polytetrafluoroethylene substrate, so that the properties of the original membrane are improved, the mechanical strength and the dimensional stability are improved, and the cost of the membrane is reduced. The ion exchange resin filled in the pores transports charge carriers and acts as a separator between the electrodes. However, the proton conductivity of the pore-filling membrane substrate is low, the composite PEM can conduct proton only by means of ion exchange resin in the pores, which requires that the substrate has good control on the porosity and the pores, the ion exchange resin can be uniformly and completely filled in the pores, and the substrate and the resin have good interfacial compatibility, so that the preparation process of the proton exchange membrane has high requirements.
The fluorine-free PEM is mainly a sulfonated polyaromatic proton exchange membrane and has the advantages of high mechanical strength, strong physical and chemical stability, low price, better modification space and the like. However, because the sulfonated aromatic hydrocarbon polymer does not have a unique hydrophilic-hydrophobic microscopic phase separation structure of the Nafion membrane, the proton conductivity of the sulfonated polyaromatic hydrocarbon proton exchange membrane often depends on high Ion Exchange Capacity (IEC), but the excessive Ion Exchange Capacity (IEC) is easy to cause excessive water absorption swelling of the membrane, and even completely loses mechanical strength.
Disclosure of Invention
Aiming at the problems existing in the prior art, the invention aims to provide a preparation method of a modified glass fiber cloth reinforced composite proton exchange membrane, which improves the proton conductivity, the proton stability and the mechanical strength of the proton exchange membrane and reduces the cost of the membrane.
In order to achieve the above object, the present invention provides the following specific technical solutions.
A preparation method of a modified glass fiber cloth reinforced composite proton exchange membrane comprises the following steps:
step S1, coating a silicon dioxide layer on the surface of glass fiber cloth;
step S2, sulfonating glass fiber cloth coated with a silicon dioxide layer on the surface;
s3, preparing a mixed solution of ion exchange resin and sulfonated silicon dioxide;
and S4, soaking the mixed solution or coating the glass fiber cloth subjected to sulfonation treatment in the step S2 on two sides, and drying to obtain the modified glass fiber cloth reinforced composite proton exchange membrane.
Further, in some preferred embodiments of the present invention, the glass fiber cloth is one of an electronic glass fiber cloth, an alkali-free glass fiber cloth, and a high silica glass fiber cloth.
Further preferably, the glass fiber cloth has a thickness of 3 to 30 μm and a pore diameter of 40 to 140 μm.
Further, in some preferred embodiments of the present invention, the specific implementation manner of step S1 is: adding tetraethyl orthosilicate into water, and stirring to form gel; and soaking the glass fiber cloth in the gel for a period of time, and then taking out and drying.
It is further preferable that tetraethyl orthosilicate is added to water and stirred under ice-water bath conditions.
Further preferably, the glass fiber cloth is soaked in the gel for 1-5 hours.
Further preferably, the thickness of the silica layer is 20nm to 1 μm.
Further, in some preferred embodiments of the present invention, the specific implementation manner of step S2 is: soaking the glass fiber cloth with the surface coated with the silicon dioxide layer in concentrated sulfuric acid, and then taking out, cleaning and drying.
Further preferably, the concentration of the concentrated sulfuric acid is 12.9-18.4 mol/L.
Further preferably, the time for soaking the glass fiber cloth coated with the silicon dioxide layer on the surface by the concentrated sulfuric acid is 4-48 hours.
Further preferably, the temperature of the glass fiber cloth with the silica layer coated on the surface soaked by the concentrated sulfuric acid is 20-40 ℃.
Further, in a part of the preferred embodiments of the present invention, the ion exchange resin is one of perfluorosulfonic acid ion exchange resin and fluorine-free sulfonated polyaromatic resin.
Further preferably, the perfluorosulfonic acid ion exchange resin is at least one of Nafion series membrane produced by DuPont, perfluorosulfonic acid ion exchange resin produced by Shandong Dongyue group of China, and perfluorosulfonic acid ion exchange resin produced by Suzhou Kouzu materials Co., ltd.
Further, when the ion exchange resin is a fluorine-free sulfonated polyaromatic resin, a coupling agent is added in step S3. Preferably, the fluorine-free sulfonated polyaromatic resin is at least one of sulfonated polyether ether ketone, sulfonated polyether sulfone, sulfonated polyphenylene oxide and sulfonated polyimide. Preferably, the coupling agent is a silane coupling agent or a titanate coupling agent.
More preferably, the amount of the sulfonated silica added is 0.1 to 15wt% based on the ion exchange resin.
Further, in a part of the preferred embodiments of the present invention, the double-sided coating method is selected from one of flat coating and roll-to-roll coating.
More preferably, the flat coating method is one of blade coating, four-sided film former coating, extrusion coating, and wire bar coating.
Based on the same inventive concept, the invention provides a modified glass fiber cloth reinforced composite proton exchange membrane which is a sandwich structure formed by sulfonic acid resin, modified glass fiber cloth and sulfonic acid resin; wherein the surface of the modified glass fiber cloth is coated with silicon dioxide and then is subjected to sulfonation treatment.
Further, the modified glass fiber cloth reinforced composite proton exchange membrane is prepared by the preparation method.
According to the invention, the surface of the glass fiber cloth with uniform porosity is modified, a layer of sulfonated silicon dioxide is attached to the surface of the glass fiber cloth, and then the ion exchange resin is wrapped, so that the modified glass fiber cloth reinforced composite proton exchange membrane is prepared. The whole preparation process is relatively simple, and the prepared modified glass fiber cloth reinforced composite proton exchange membrane has good proton conductivity and stability, high mechanical strength and low cost.
Drawings
FIG. 1 shows the electrolytic water polarization curves of the films prepared in example 1, comparative example 1 and comparative example 2, as well as Nafion raw film and Nafion212 film at 30 ℃.
FIG. 2 shows the electrolytic water polarization curves of the films prepared in example 1, comparative example 1 and comparative example 2, as well as Nafion raw film and Nafion212 film at 80 ℃.
FIG. 3 is an electrolytic water polarization curve at 30℃for the films prepared in example 2, comparative example 3, comparative example 4, and SPEEK films.
FIG. 4 is an electrolytic water polarization curve at 80℃for the films prepared in example 2, comparative example 3, comparative example 4, and SPEEK films.
Detailed Description
The present invention will be described more fully hereinafter with reference to the accompanying drawings, in which preferred embodiments are shown, for the purpose of illustrating the invention, but the scope of the invention is not limited to the specific embodiments shown.
Unless defined otherwise, all technical and scientific terms used hereinafter have the same meaning as commonly understood by one of ordinary skill in the art. The terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the scope of the present invention.
Unless otherwise specifically indicated, the various raw materials, reagents, instruments, equipment and the like used in the present invention are commercially available or may be prepared by existing methods.
The invention provides a modified glass fiber cloth reinforced composite proton exchange membrane and a preparation method thereof.
The preparation method of the modified glass fiber cloth reinforced composite proton exchange membrane provided by the invention comprises the following steps:
step S1, coating a silicon dioxide layer on the surface of glass fiber cloth;
step S2, sulfonating glass fiber cloth coated with a silicon dioxide layer on the surface;
s3, preparing a mixed solution of ion exchange resin and sulfonated silicon dioxide;
and S4, soaking the mixed solution or coating the glass fiber cloth subjected to sulfonation treatment in the step S2 on two sides, and drying to obtain the modified glass fiber cloth reinforced composite proton exchange membrane.
In a specific embodiment, the glass fiber cloth is one of an electronic glass fiber cloth, an alkali-free glass fiber cloth and a high silica glass fiber cloth.
In a specific embodiment, the glass fiber cloth preferably has a thickness of 3 to 30 μm and a pore diameter of 40 to 140 μm.
(1) For step S1, coating a silica layer on the surface of the glass fiber cloth:
the method is realized by the following specific embodiments:
adding tetraethyl orthosilicate into water, and stirring to form gel; the glass fiber cloth is soaked in the gel for a period of time and then taken out.
Preferably, the tetraethyl orthosilicate is added to water and stirred under ice-water bath conditions.
Preferably, the soaking time of the glass fiber cloth in the gel is 1-5 hours.
(2) For step S2, sulfonating the glass fiber cloth coated with the silica layer on the surface:
the method is realized by the following specific embodiments: soaking the glass fiber cloth with the surface coated with the silicon dioxide layer in concentrated sulfuric acid, and then taking out, cleaning and drying.
Preferably, the concentration of the concentrated sulfuric acid is 12.9-18.4 mol/L; further preferably 18.4mol/L.
Preferably, the time for soaking the glass fiber cloth coated with the silicon dioxide layer on the surface by the concentrated sulfuric acid is 4-48 hours.
Preferably, the temperature of the glass fiber cloth with the silica layer coated on the surface immersed by the concentrated sulfuric acid is 20-40 ℃.
After the surface of the glass fiber cloth is coated with the silicon dioxide layer, sulfonation treatment is further carried out, and the surface of the obtained glass fiber cloth is provided with sulfonic acid groups, so that strong interaction is carried out between the sulfonic acid groups of the ion exchange resin, and good interface compatibility is ensured. On the basis, even after repeated swelling and drying, the glass fiber cloth does not generate internal detachment due to inconsistent swelling degree, water absorption and ion exchange resin.
In addition, the glass fiber cloth has good acid resistance and mechanical stability, and has excellent proton conductivity after sulfonation modification.
(3) For step S3, a mixed solution of ion exchange resin and sulfonated silica is prepared.
The method is realized by the following specific embodiments: adding ion exchange resin and sulfonated silicon dioxide into a solvent, stirring for 6 hours at room temperature to prepare ion exchange resin mixed solution, and performing bubble removal treatment. The solvent is preferably N, N-dimethylacetamide.
Preferably, the addition amount of the sulfonated silica is 0.1-15 wt% of the ion exchange resin. The addition and amount of the sulfonated silica can avoid the agglomeration of the inorganic nanoparticles, thereby causing the reduction of proton conductivity.
Preferably, the mass concentration of the ion exchange resin in the mixed solution is 5% -22%, and the thickness uniformity of the coating film or the casting film is ensured.
(4) For the step S4, the mixed solution is soaked or the glass fiber cloth after the sulfonation treatment of the step S2 is coated on both sides, and the glass fiber cloth is dried:
in a specific embodiment, the ion exchange resin is one of perfluorosulfonic acid ion exchange resin and fluorine-free sulfonated polyaromatic resin.
In a specific embodiment, when the ion exchange resin is a fluorine-free sulfonated polyaromatic resin, a coupling agent is added in step S3. Further preferably, the fluorine-free sulfonated polyaromatic resin is at least one of sulfonated polyether ether ketone, sulfonated polyether sulfone, sulfonated polyphenylene oxide and sulfonated polyimide. Preferably, the coupling agent is a silane coupling agent or a titanate coupling agent.
The interface between the organic polymer and the inorganic modified glass fiber cloth can be further enhanced by adding the coupling agent, the swelling rate of the polymer is reduced, and the glass fiber cloth is prevented from being separated from the polymer during swelling.
In a specific embodiment, the perfluorosulfonic acid ion exchange resin is at least one of Nafion series membrane produced by dupont, perfluorosulfonic acid ion exchange resin produced by eastern group of shandong, china, perfluorosulfonic acid ion exchange resin produced by su zhou materials, inc.
In a specific embodiment, the double-sided coating mode is selected from one of flat coating and roll-to-roll coating.
In a specific embodiment, the flat coating mode is one of doctor blade coating, four-sided film maker coating, extrusion coating and wire rod coating.
Through the preparation method, the proton exchange membrane with the sandwich structure formed by the sulfonic acid resin, the modified glass fiber cloth and the sulfonic acid resin can be prepared, wherein the surface of the modified glass fiber cloth is coated with the silicon dioxide layer and then is further subjected to sulfonation treatment.
Further description will be given below by way of specific examples.
In specific examples, the properties of the films produced were tested as follows.
The procedure for the water absorption test was as follows:
the sample is dried in an oven at 80+/-2 ℃ for 24 hours, and after being cooled to room temperature in a dryer, the initial mass of the sample is weighed by an analytical balance
Figure SMS_1
。
The water absorption test method at 30 ℃ and 80 ℃ is as follows: a) Water absorption test at 30 ℃): placing the sample into a constant-temperature water bath at 30+/-2 ℃ for at least 2 hours; the sample was removed from the thermostatic water bath, the surface was blotted dry with filter paper and its mass was measured within 30 seconds. b) Placing the sample into distilled water at 80+/-2 ℃ for soaking for 1h, quickly transferring the sample into distilled water at room temperature for cooling for 15+/-1 min, taking the sample out of a constant-temperature water bath, sucking the surface of the sample to dryness by using filter paper, and measuring the mass of the sample within 30 s.
The water absorption calculation formula is:
Figure SMS_2
in the method, in the process of the invention,
Figure SMS_3
is the water absorption rate; />
Figure SMS_4
The mass of the sample after being soaked in the constant-temperature water bath is given in grams (g); />
Figure SMS_5
The initial mass of the sample is given in grams (g).
The average value was calculated as the test result by taking 3 samples as a group.
The Ion Exchange Capacity (IEC) test procedure was as follows:
ion exchange capacity refers to the amount of ions that can be exchanged per unit volume or mass of ion exchange material. The ion exchange capacity is generally proportional to the number of active groups per unit volume or mass, representing the acid concentration within the proton exchange membrane. The procedure for measuring the ion exchange capacity by acid-base titration was as follows:
cutting 0.1. 0.1 g film sample, soaking in 1 mol/L hydrochloric acid solution for 72 h, taking out, washing with deionized water for several times to neutrality, cutting, drying in vacuum oven at 80deg.C for 3h, rapidly taking out, weighing, and recording as M dry The method comprises the steps of carrying out a first treatment on the surface of the The film sample was placed in a conical flask containing 15% sodium chloride solution and shaken on a shaker 72H (H was added + Completely replaced); titration with 0.2 mol/L NaOH solution using phenolphthalein as indicator, recording the disappearance of color after the phenolphthalein solution turns red and does not fade within half a minuteThe volume of sodium hydroxide consumed, designated V NaOH . The calculation formula of IEC is:
Figure SMS_6
wherein IEC is ion exchange capacity, and the unit is mmol/g; c (C) NaOH The concentration of NaOH solution is in mol/L; v (V) NaOH The volume of NaOH consumed for titration is in mL; m is M dry The dry weight of the sample is measured in grams (g).
The proton conductivity test steps were as follows:
preparation before testing: all samples were immersed in a 5% strength hydrogen peroxide solution at 80 ℃ for 1h or more, rinsed with deionized water, activated in a 1M sulfuric acid solution at 80 ℃ for 1h or more, and rinsed with deionized water to remove residual sulfuric acid. Soaking in deionized water at 80deg.C for more than 1 hr.
The proton conductivity of the polymer membrane was evaluated using an electrochemical workstation. The method is carried out under 100% relative humidity by a four-electrode alternating current impedance method, the test frequency is 1 Hz-1 MHz, the amplitude is 10mV, the test temperature is 20-100 ℃, and the sample size is not less than 2cm x 2cm. The proton conductivity of the membrane material was calculated by the following formula:
Figure SMS_7
wherein R is the surface resistance (omega) of the film. For planar proton conductivity measurements, L is the distance (cm) between the two electrodes, A is the cross-sectional area of the membrane (cm 2 ) The method comprises the steps of carrying out a first treatment on the surface of the For the measurement of the section proton conductivity, L is the thickness (cm) of the membrane, A is the overlap area (cm) of the two electrodes 2 ）。
The mechanical property test steps are as follows:
cutting a film sample to be tested into a length and width of 3cm multiplied by 1 cm, and testing the elongation at break and the tensile strength of the film by a universal tensile machine, wherein the tensile rate is 5mm min -1 Each group of film samples was tested 3 times to average.
The electrolytic water performance test process is as follows:
a Membrane Electrode Assembly (MEA) (2×2 cm) with iridium oxide as a catalyst was prepared using a catalyst coating membrane process (CCM). The gas diffusion layer of the MEA is a carbon plate and a titanium felt. The MEA and fluororubber gaskets (10 cm x 10 cm) were covered by stainless steel flow field plates. To control the temperature, heating elements and thermocouples were mounted on the stainless steel flow field plates. Copper plates are stacked at two ends of the stainless steel flow field plate to serve as cathode and anode electrodes. The power source for the electrode connection is a commercial battery test equipment (TDC 1000, shenzhen Towao technology Co., ltd.). The electrochemical clamp is clamped at 0.45A/cm before testing 2 And (80 ℃) activating for 40-90 min. During the test, the flow rate of the electrolyte was controlled at 50 mL/min. The polarization curve of MEA was measured at 30℃and 80℃in a constant pressure mode of 1.42V to 2V.
Example 1
60g of tetraethyl orthosilicate is added dropwise into 20ml of deionized water, and the mixture is magnetically stirred under the condition of ice-water bath for 3 hours to form miscible gel. 5X 5cm glass fiber cloth was soaked in the gel for 2 hours, then taken out, and dried at 100℃for 24 hours. And (3) soaking the dried glass fiber cloth in concentrated sulfuric acid with the concentration of 18.4mol/L for 36 hours, then washing with a large amount of deionized water, and drying to obtain the modified glass fiber cloth.
Nafion resin and 2wt% sulfonated silica of Nafion resin are added into N, N-dimethylacetamide, stirred for 6 hours at room temperature, and ultrasonically mixed for 1 hour to prepare a mixed solution of Nafion resin with the concentration of 7 wt%.
Soaking and pouring the modified glass fiber cloth in a culture dish by using a mixed solution, removing bubbles in vacuum for 1h, then drying at 60 ℃ for 6h, and drying at 120 ℃ for 4h to obtain the composite membrane with the sandwich structure of the perfluorinated sulfonic acid resin-modified glass fiber cloth-perfluorinated sulfonic acid resin.
Comparative example 1
The difference between this comparative example and example 1 is that: the glass fiber cloth is not modified.
The method comprises the following specific steps:
nafion resin and 2wt% sulfonated silica of Nafion resin are added into N, N-dimethylacetamide, stirred for 6 hours at room temperature, and ultrasonically mixed for 1 hour to prepare a mixed solution with the concentration of Nafion resin of 7 wt%.
And (3) soaking and pouring the glass fiber cloth in a culture dish by using the mixed solution, removing bubbles in vacuum for 1h, then drying at 60 ℃ for 6h, and drying at 120 ℃ for 4h to obtain the composite membrane with the sandwich structure of the perfluorinated sulfonic acid resin-glass fiber cloth-perfluorinated sulfonic acid resin.
Comparative example 2
The difference between this comparative example and example 1 is that: no sulfonated silica was added to the Nafion resin substrate.
The method comprises the following specific steps:
60g of tetraethyl orthosilicate is added dropwise into 20ml of deionized water, and the mixture is magnetically stirred under the condition of ice-water bath for 3 hours to form miscible gel. 5X 5cm glass fiber cloth was soaked in the gel for 2 hours, then taken out, and dried at 100℃for 24 hours. And (3) soaking the dried glass fiber cloth in concentrated sulfuric acid with the concentration of 18.4mol/L for 36 hours, then washing with a large amount of deionized water, and drying to obtain the modified glass fiber cloth.
And (3) impregnating and pouring the modified glass fiber cloth into a culture dish by using Nafion resin, removing bubbles in vacuum for 1h, drying at 60 ℃ for 6h, and drying at 120 ℃ for 4h to obtain the perfluorinated sulfonic acid resin-modified glass fiber cloth-perfluorinated sulfonic acid resin sandwich structure composite membrane.
The composite membranes obtained in example 1, comparative example 2, and Nafion raw membranes (from DuPont, USA) and Nafion212 membranes (from DuPont, USA) were subjected to water absorption test, ion exchange capacity (ICE) test, proton conductivity test, and mechanical property test using a 20wt% concentration Nafion dispersion casting. The test results are shown in Table 1.
Table 1 test results
Figure SMS_8
FIGS. 1 and 2 show the polarization curves of electrolyzed water at 30℃and 80℃of the membranes prepared in example 1, comparative example 1 and comparative example 2, and the Nafion raw membrane and Nafion212 membrane, and it can be seen from the figures that the proton exchange membrane obtained in example 1 has higher electrolyzed water efficiency than other membranes under the same conditions.
Example 2
Firstly, stirring polyether-ether-ketone (PEEK) at normal temperature to dissolve the PEEK in concentrated sulfuric acid, and continuing the process for 24 hours; then heating to 50 ℃, and continuously reacting for 30min to obtain sulfonated polyether-ether-ketone with the sulfonation degree of 55%;
60g of tetraethyl orthosilicate is added dropwise into 20ml of deionized water, and the mixture is magnetically stirred under the condition of ice-water bath for 3 hours to form miscible gel. And soaking the glass fiber cloth with the length of 5 multiplied by 5cm in gel for 2-5 hours, taking out, and drying at 100 ℃ for 24 hours. And (3) soaking the dried glass fiber cloth in concentrated sulfuric acid with the concentration of 18.4M for 36 hours, then washing with a large amount of deionized water, and drying to obtain the modified glass fiber cloth.
Sulfonated polyether ether ketone (SPEEK), titanate coupling agent (HY 311W) and sulfonated silica accounting for 2wt% of the sulfonated polyether ether ketone are added into solvent N, N-methyl formamide, stirred for 6 hours at room temperature, prepared into mixed solution with the concentration (solid content) of the sulfonated polyether ether ketone of 3wt%, and subjected to bubble removal treatment.
And (3) soaking and pouring the modified glass fiber cloth in a culture dish by using a mixed solution, removing bubbles in vacuum for 1h, then drying at 60 ℃ for 6-8 h, and drying at 120 ℃ for 4h to obtain the SPEEK-modified glass fiber cloth-SPEEK sandwich structure composite film.
Comparative example 3
The difference between this comparative example and example 2 is that: the glass fiber cloth is not modified.
The method comprises the following specific steps:
firstly, stirring PEEK at normal temperature to dissolve in concentrated sulfuric acid, and continuing the process for 24 hours; then heating to 50 ℃, and continuously reacting for 30min to obtain sulfonated polyether-ether-ketone with the sulfonation degree of 55%;
sulfonated polyether-ether-ketone (SPEEK), titanate coupling agent (HY 311W) and sulfonated silicon dioxide accounting for 2wt% of the sulfonated polyether-ether-ketone are added into solvent N, N-dimethylformamide, stirred for 6 hours at room temperature, so as to prepare a mixed solution with the polyether-ether-ketone concentration (solid content) of 3wt%, and bubble removal treatment is carried out.
And (3) soaking and pouring the glass fiber cloth in a culture dish by using the mixed solution, removing bubbles in vacuum for 1h, drying at 60 ℃ for 6-8 h, and drying at 120 ℃ for 4h to obtain the composite membrane with the sandwich structure of SPEEK-glass fiber cloth-SPEEK.
Comparative example 4
The difference between this comparative example and example 2 is that: no sulfonated silica was added to the SPEEK substrate.
The method comprises the following specific steps:
firstly, stirring PEEK at normal temperature to dissolve in concentrated sulfuric acid, and continuing the process for 24 hours; then heating to 50 ℃, and continuously reacting for 30min to obtain sulfonated polyether-ether-ketone with the sulfonation degree of 55%;
60g of tetraethyl orthosilicate is added dropwise into 20ml of deionized water, and the mixture is magnetically stirred under the condition of ice-water bath for 3 hours to form miscible gel. And soaking the glass fiber cloth with the length of 5 multiplied by 5cm in gel for 2-5 hours, taking out, and drying at 100 ℃ for 24 hours. And (3) soaking the dried glass fiber cloth in concentrated sulfuric acid with the concentration of 18.4M for 36 hours, then washing with a large amount of deionized water, and drying to obtain the modified glass fiber cloth.
Adding sulfonated polyether-ether-ketone (SPEEK) and titanate coupling agent (HY 311W) into solvent N, N-dimethylformamide, stirring for 6 hours at room temperature, preparing a mixed solution with the concentration (solid content) of the sulfonated polyether-ether-ketone being 3wt%, and carrying out bubble removal treatment.
And (3) soaking and pouring the modified glass fiber cloth in a culture dish by using a mixed solution, removing bubbles in vacuum for 1h, then drying at 60 ℃ for 6-8 h, and drying at 120 ℃ for 4h to obtain the SPEEK-modified glass fiber cloth-SPEEK sandwich structure composite film.
The composite membranes obtained in example 2, comparative example 3, comparative example 4, and SPEEK pure membranes were subjected to water absorption test, ion exchange capacity (ICE) test, proton conductivity test, and mechanical property test. The results are shown in Table 2.
Table 2 test results
Figure SMS_9
FIGS. 3 and 4 are respectively polarization curves of electrolyzed water at 30℃and 60℃for example 2, comparative example 3, comparative example 4, and SPEEK membranes, and it can be seen that the proton exchange membrane obtained in example 2 has higher electrolyzed water efficiency than other membranes under the same conditions.
The foregoing is merely a preferred embodiment of the present invention and it should be noted that modifications and adaptations to those skilled in the art may be made without departing from the principles of the present invention, which are intended to be comprehended within the scope of the present invention.

Claims (10)

1. The preparation method of the modified glass fiber cloth reinforced composite proton exchange membrane is characterized by comprising the following steps of:
step S1, coating a silicon dioxide layer on the surface of glass fiber cloth;
step S2, sulfonating glass fiber cloth coated with a silicon dioxide layer on the surface;
s3, preparing a mixed solution of ion exchange resin and sulfonated silicon dioxide;
and S4, soaking the mixed solution or coating the glass fiber cloth subjected to sulfonation treatment in the step S2 on two sides, and drying to obtain the modified glass fiber cloth reinforced composite proton exchange membrane.
2. The preparation method according to claim 1, wherein the specific implementation manner of step S1 is as follows: adding tetraethyl orthosilicate into water, and stirring to form gel; and soaking the glass fiber cloth in the gel for a period of time, and then taking out and drying.
3. The method of claim 1, wherein the silicon dioxide layer has a thickness of 20nm to 1 μm.
4. The preparation method according to claim 1, wherein the specific implementation manner of step S2 is as follows: soaking the glass fiber cloth with the surface coated with the silicon dioxide layer in concentrated sulfuric acid, and then taking out, cleaning and drying.
5. The method of claim 1, wherein the ion exchange resin is one of a perfluorosulfonic acid ion exchange resin and a fluorine-free sulfonated polyaromatic resin.
6. The method according to claim 5, wherein a coupling agent is added in step S3 when the ion exchange resin is a fluorine-free sulfonated polyaromatic resin.
7. The method of claim 1 or 5, wherein the sulfonated silica is added in an amount of 0.1 to 15wt% of the ion exchange resin.
8. The method of claim 1, wherein the double-sided coating is selected from one of flat coating and roll-to-roll coating.
9. The modified glass fiber cloth reinforced composite proton exchange membrane is characterized by being of a sandwich structure formed by sulfonic acid resin, modified glass fiber cloth and sulfonic acid resin; wherein the surface of the modified glass fiber cloth is coated with silicon dioxide and then is subjected to sulfonation treatment.
10. The modified glass fiber cloth reinforced composite proton exchange membrane according to claim 9, which is prepared by the preparation method according to any one of claims 1 to 8.
CN202310065990.6A 2023-02-06 2023-02-06 Modified glass fiber cloth reinforced composite proton exchange membrane and preparation method thereof Pending CN116103694A (en)

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