CN107394240B - Preparation method and application of sulfonated polyaryletherketone ion exchange membrane - Google Patents
Preparation method and application of sulfonated polyaryletherketone ion exchange membrane Download PDFInfo
- Publication number
- CN107394240B CN107394240B CN201710407864.9A CN201710407864A CN107394240B CN 107394240 B CN107394240 B CN 107394240B CN 201710407864 A CN201710407864 A CN 201710407864A CN 107394240 B CN107394240 B CN 107394240B
- Authority
- CN
- China
- Prior art keywords
- ion exchange
- sulfonated
- exchange membrane
- membrane
- solid
- 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.)
- Active
Links
Images
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
-
- 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
- H01M8/1067—Polymeric electrolyte materials characterised by their physical properties, e.g. porosity, ionic conductivity or thickness
-
- 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
-
- 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
- H01M8/18—Regenerative fuel cells, e.g. redox flow batteries or secondary fuel cells
- H01M8/184—Regeneration by electrochemical means
- H01M8/188—Regeneration by electrochemical means by recharging of redox couples containing fluids; Redox flow type batteries
-
- 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
Abstract
The invention discloses a preparation method based on a sulfonated polyaryletherketone ion exchange membrane and application thereof in an all-vanadium redox flow battery, and relates to the field of ion exchange membrane materials, wherein the sulfonated polyaryletherketone (SFPAEK) ion exchange membrane can be prepared by blending and compounding a sulfonic polymer and a reinforcing material, and inorganic nano sheets are uniformly dispersed in a matrix of cation exchange resin to form a vanadium ion barrier layer in the film preparation process through processes such as a tape casting wet method, a hot pressing dry method, an extrusion blow molding dry method, film stretching orientation and the like, so that the shuttle effect of vanadium ions accompanying the charge and discharge process of the all-vanadium redox flow battery is effectively inhibited; the method has the advantages of simple process, environmental protection and low cost, and the membrane is not damaged in the implementation process, so that the formed membrane has better mechanical strength, and the conductivity and the swelling degree of the membrane are ensured.
Description
Technical Field
The invention relates to the field of separation membranes of flow energy storage batteries and ion exchange membrane materials for fuel cells, in particular to a preparation method and application of a sulfonated polyaryletherketone (SFPAEK) ion exchange membrane.
Background
The all-Vanadium Redox Flow Battery (VRFB) realizes mutual conversion of electric energy and chemical energy through electrochemical reaction of vanadium ions with different valence states. The energy storage device has the advantages of long service life (more than 15 years), deep charge and discharge, high safety and stability (charge and discharge cycle is more than 16000 times), high energy efficiency and the like, and becomes one of the most potential energy storage devices for large-scale energy storage.
In the all-vanadium redox flow battery, the most key core material is a diaphragm in a galvanic pile, and the diaphragm is an ion exchange membrane and is responsible for separating positive and negative electrolytes, so that the self-discharge caused by mutual diffusion of the positive and negative electrolytes is avoided, and protons or sulfate radical or hydrogen sulfate radical anions are conducted to form the circuit in the battery. The method has the advantages that the transmission rate of ions is improved, the internal resistance of the battery is reduced, and the method is one of the keys for improving the performance of the flow battery. The ion exchange membrane applied to the all-vanadium redox flow battery has the following characteristics: 1. high ion conductivity; the surface resistance of the film is low, the voltage loss of the battery is reduced, and the charging and discharging efficiency of the battery is improved; 2. high ion selectivity; the selectivity of the membrane determines the coulombic efficiency of the galvanic pile, and the high ion selectivity can greatly avoid the mutual permeation of positive and negative electrolytes, thereby reducing the capacity loss of the battery; 3. the low water migration amount and the irreversible migration of water in the electrolyte can cause the concentration change of the solution in the electrolyte storage tank, and the stability of the galvanic pile can be influenced. 4. The all-vanadium redox flow battery has excellent electrochemical corrosion resistance, the operating environment of the all-vanadium redox flow battery is an acid medium, namely sulfuric acid, and high-oxygen V can be generated in the charging process of the battery5+Ion and ion exchange membranes must have excellent corrosion resistance to ensure stable operation of the galvanic pile.
Currently, most of ion exchange membranes used in flow energy storage batteries are perfluorosulfonic acid membranes (Nafion) of dupont, usa. The Nafion series membrane has excellent ionic conductivity and excellent electrochemical stability, but the membrane preparation process is complicated and expensive. The method is directly applied to the all-vanadium redox flow battery, and the reversed micelle formed by the sulfonic acid group of Nafion in the electrolyte is more beneficial to the shuttle of vanadium ions, so that the self-discharge of the battery is caused, and the battery capacity is reduced. How to reduce the shuttle effect of vanadium ions and develop an ion exchange membrane with low cost, high conductivity and high selectivity is one of the keys for solving the all-vanadium redox flow battery.
Disclosure of Invention
The invention aims to provide a composite proton exchange membrane with high ion selectivity and high ion conductivity, a preparation method and application in an all-vanadium redox flow battery.
In order to solve the problems, the invention adopts the following technical scheme:
the invention provides a preparation method of a sulfonated polyaryletherketone ion exchange membrane, which comprises the following specific steps:
(1) sulfonated 4, 4' -difluorobenzophenone: adding one part of 4, 4' -difluorobenzophenone with mass into a 250ml two-neck round-bottom flask with a reflux condenser, adding one part of fuming sulfuric acid with the volume of 20% of analytical pure grade, magnetically stirring, and heating to 110 ℃ for reaction; after the reaction is finished, cooling to room temperature, slowly pouring the product into an ice-water mixture with the volume of 5 parts, stirring and adding 5 parts by mass of sodium chloride until white solid is separated out, performing suction filtration and drying the solid; dissolving the dried solid in 1-2 parts by volume of deionized water, slowly adding sodium hydroxide, adjusting the solution to be neutral, adding sodium chloride to form a supersaturated solution, separating out a white solid, performing suction filtration, and drying; heating and dissolving the dried solid with dimethyl sulfoxide, filtering insoluble impurities while the solid is hot, distilling the filtrate under reduced pressure to obtain a product, washing the product with acetone, washing with absolute ethyl alcohol, performing suction filtration to obtain a white powdery solid, and performing vacuum drying at 80 ℃ for one day to obtain 3,5 '-sodium disulfonate-4, 4' -difluorobenzophenone;
(2) preparation of polymer sulfonated polyaryletherketone: adding 3,5 ' -sodium disulfonate-4, 4 ' -difluorobenzophenone, 4,4 ' -difluorobenzophenone and bisphenol AF into a 100ml three-neck round-bottom flask which is provided with a mechanical stirrer, a water separator and nitrogen gas guide according to a certain molar ratio, and adding 0.2 part by volume of anhydrous dimethylacetamide (DMAc) and 0.5-0.75 part by volume of redistilled toluene; heating to 130 ℃ firstly, keeping the temperature for 3-4 hours, pouring the liquid flowing into the water separator, slowly heating to 190 ℃ and keeping the temperature for 20-24 hours; introducing the product into 15 parts by volume of methanol solution, continuously stirring, carrying out suction filtration on the precipitated fibrous solid, washing the fibrous solid to be neutral by using deionized water, and carrying out vacuum drying at 80 ℃ for one day to obtain the polymer; the mass of one part is preferably 5g, and the volume of one part is preferably 20 ml;
(3) preparing porous boron nitride nanosheets: adding diboron trioxide and guanidine hydrochloride into a proper amount of methanol according to the molar ratio of 1:5, quickly stirring to form a colorless transparent solution, quickly stirring for one day to form a white solid, pouring the white solid into a quartz crucible, heating the quartz crucible to 1100 ℃ in a tubular furnace, keeping the temperature at 1100 ℃ for 10 ℃/min, keeping the temperature for 2 hours, and introducing a mixed gas of 15% hydrogen/85% nitrogen gas of nitrogen and hydrogen in the heating process to obtain a white solid powder porous boron nitride nanosheet;
(4) preparation of sulfonated porous boron nitride: adding 0.04 part by mass of white powder porous boron nitride nanosheets, 2 parts by volume of toluene and 0.08 part by mass of propane sultone into a two-neck round-bottom flask provided with a reflux condenser tube, magnetically stirring, heating to 110 ℃, keeping the temperature at 110 ℃, reacting for 24 hours, cooling to room temperature after the reaction is finished, centrifuging at 8000rpm for 5 minutes, pouring out liquid, washing with ethanol, centrifuging again, repeating the ethanol washing and centrifuging processes for 3 times, then centrifuging after the deionization washing, repeating the deionization washing and centrifuging processes for 3 times, finally obtaining yellow solid, and freeze-drying to obtain sulfonated porous boron nitride;
(5) preparing a sulfonated polyaryletherketone ion exchange membrane: the sulfonated polyaryletherketone ion exchange membrane is prepared by the processes of a casting wet method, a hot pressing dry method, an extrusion casting dry method, an extrusion calendaring dry method, an extrusion blow molding dry method, film stretching orientation and the like. For example of the casting wet process: preparing a sulfonated polyaryletherketone ion exchange membrane: the preparation of the sulfonated polyaryletherketone ion exchange membrane by the tape casting wet method comprises the following specific steps: preparing a 10% membrane solution from a polymer of sulfonated polyaryletherketone, wherein the solid content of the polymer is 10wt%, sequentially adding 1%, 3%, 5%, 7% and 10% of sulfonated porous boron nitride by mass fraction, wherein the mass fraction is the mass fraction of the sulfonated porous boron nitride relative to the sulfonated polyaryletherketone ion exchange membrane, performing ultrasonic treatment for 1-5 hours, then rapidly stirring for 12 hours, pouring the membrane solution on a piece of clean glass, drying for 12 hours at 60-80 ℃ in a vacuum drying oven, and performing vacuum drying for 12 hours at 80 ℃. The dried membrane was immersed in a 1M hydrochloric acid solution for one day, washed with deionized water to neutrality, and stored in deionized water.
As another preferable scheme of the invention, the sulfonated polyaryletherketone polymer film can also be prepared by adopting a hot pressing dry method, an extrusion casting dry method, an extrusion calendaring dry method, an extrusion blow molding dry method and a film stretching orientation process.
As another preferred embodiment of the present invention, the steps (3) to (5) can be further replaced by the following steps:
film formation of polymer sulfonated polyaryletherketone: preparing a polymer sulfonated polyaryletherketone film by adopting a tape casting wet method, and specifically comprising the following steps: adding a certain amount of the polymer obtained in the step (2) into dimethylacetamide (DMAc) to prepare a 10-12% membrane solution, pouring the membrane solution onto a piece of clean glass, drying the membrane solution in a vacuum drying oven at 60-80 ℃ for 12 hours, drying the membrane solution in vacuum at 80 ℃ for 12 hours, soaking the dried membrane in 1M hydrochloric acid solution for one day, washing the membrane to be neutral by using deionized water, and storing the membrane in the deionized water.
As another preferable embodiment of the present invention, the step (4) may further include: adding 0.08 part by mass of 60% sodium hydride into a three-neck round-bottom flask provided with a nitrogen gas guide tube and a drying tube, pouring 5 parts by volume of dimethyl sulfoxide into the flask under the protection of nitrogen, heating the flask to 75 ℃ for 1 hour, cooling the flask to 40 ℃, adding 0.04 part by mass of white powder porous boron nitride nanosheet into the flask, stirring the flask for 12 hours, then adding 0.08 part by mass of 1, 3-propane sultone into the flask to react at 40 ℃ for 24 hours, cooling the flask to room temperature after the reaction is finished, centrifuging the flask at 8000rpm for 5 minutes, pouring out liquid, washing the flask with ethanol, centrifuging the flask again, repeating the ethanol washing and centrifuging processes for 3 times, then centrifuging the flask after the deionization, repeating the centrifuging process after the deionization and the centrifuging processes for 3 times, and finally obtaining yellow solid, and freeze-drying the yellow solid.
As still another preferred embodiment of the present invention, in the step (2), the molar ratio of the sodium 3,5 ' -disulfonate-4, 4 ' -difluorobenzophenone, the 4,4 ' -difluorobenzophenone and the bisphenol AF is 4: 6: 10 or 5: 5: 10 or 6: 4: 10 or 7: 3: 10.
the invention also provides application of the preparation method of the sulfonated polyaryletherketone ion exchange membrane in an all-vanadium redox flow battery and a fuel cell thereof, wherein the synthesized sulfonated polyaryletherketone ion exchange membrane is used as a diaphragm of the all-vanadium redox flow battery.
Compared with the prior art, the invention has the beneficial effects that:
the invention synthesizes the polymer by synthesizing the sulfonated monomer by sulfonation and then carrying out polycondensation, thus being capable of more accurately controlling the sulfonation degree of the synthesized polymer product and conveniently regulating and controlling the balance of the swelling degree and the proton conductivity of the polymer membrane. Thereby obtaining the polymer proton exchange membrane which has high proton conductivity, lower sheet resistance and good ion selectivity. When the membrane is used in an all-vanadium flow battery, the performance of coulombic efficiency and energy efficiency higher than that of commercial Nafion 117 can be obtained.
According to the invention, 1-10% of porous sulfonated boron nitride inorganic nanosheets are added into the proton exchange membrane, so that the vanadium resistance of the membrane is further improved, the battery has better coulombic efficiency, and the voltage efficiency and the energy efficiency are higher than those of undoped membranes and commercial Nafion 117 membranes. And the capacity fade of its cells was also lower than that of commercial Nafion 117 membranes. Because of its wide raw material source and simple preparation process, the cost of the membrane is far lower than that of the commercial Nafion series perfluorosulfonic acid membrane.
The composite membrane can be applied to all-vanadium redox flow batteries and fuel batteries. The added sulfonated boron nitride nanosheet has excellent heat conduction performance, the aperture of the porous boron nitride nanosheet is regulated and controlled to realize good selectivity of ions, and the sulfonated boron nitride nanosheet has beneficial contribution to the heat management and the water management of the fuel cell.
Drawings
FIG. 1 is a molecular formula of a sulfonated polyaryletherketone ion exchange membrane in example 1 of the present invention;
FIG. 2 is a Fourier infrared spectrum of a sulfonated polyaryletherketone ion exchange membrane of example 1 in accordance with the present invention;
FIG. 3 is a graph showing proton conductivity comparison of sulfonated polyaryletherketone ion exchange membranes of different degrees of sulfonation in example 1 of the present invention. S4 represents a sulfonated polyaryletherketone component (molar ratio/sodium disulfonate difluorobenzophenone: bisphenol AF = 4: 6: 10), water absorption of 15.0%, swelling ratio of 4.5%, ion exchange capacity of 1.58 mmol/g; s5 represents a sulfonated polyaryletherketone component (molar ratio/sodium disulfonate difluorobenzophenone: bisphenol AF = 5: 5: 10), water absorption of 16.8%, swelling ratio of 5.8%, ion exchange capacity of 1.87 mmol/g; s6 represents a sulfonated polyaryletherketone component (molar ratio/sodium disulfonate difluorobenzophenone: bisphenol AF = 6: 4: 10), water absorption of 30.5%, swelling ratio of 7.1%, ion exchange capacity of 2.21 mmol/g; s7 represents a sulfonated polyaryletherketone component (molar ratio/sodium disulfonate difluorobenzophenone: bisphenol AF = 7: 3: 10), water absorption of 58.1%, swelling of 14.0%, ion exchange capacity of 2.40 mmol/g.
FIG. 4 is a schematic view of boron nitride in example 2 of the present invention;
FIG. 5 is an X-ray diffraction chart of boron nitride in example 2 of the present invention;
FIG. 6 is a transmission electron microscope photograph of porous boron nitride in example 2;
FIG. 7 is a composite sulfonated polyaryletherketone ion exchange membrane of example 2 of the present invention, an undoped sulfonated polyaryletherketone ion exchange membrane of example 1 and commercial Nafion 117 at 80mA/cm2A graph comparing coulombic efficiency, voltage efficiency and energy efficiency at current density;
FIG. 8 is a composite sulfonated polyaryletherketone ion exchange membrane of example 2, an undoped sulfonated polyaryletherketone ion exchange membrane of example 1 and commercial Nafion 117 at 80mA/cm2A charge-discharge curve graph under current density;
FIG. 9 shows the ion exchange membrane of sulfonated polyaryletherketone compounded in example 2 at 80mA/cm2(ii) coulombic efficiency, voltage efficiency and energy efficiency at 100 cycles at current density of;
FIG. 10 is a graph comparing the discharge capacity decay with cycle number for the composite sulfonated polyaryletherketone ion exchange membrane of example 2 of the present invention and a commercial Nafion 117 membrane.
Detailed Description
The present invention will be described in further detail with reference to specific examples, but the embodiments of the present invention are not limited thereto.
Example 1
The embodiment provides a preparation method of a sulfonated polyaryletherketone ion exchange membrane, which comprises the following specific steps:
1) sulfonated 4, 4' -difluorobenzophenone: adding 5g of 4, 4' -difluorobenzophenone into a 250ml two-neck round-bottom flask with a reflux condenser, adding 20ml of 20% fuming sulfuric acid of analytical pure grade, magnetically stirring, and heating to 110 ℃ for reaction; after the reaction is finished, cooling to room temperature, slowly pouring the product into 100ml of ice-water mixture, stirring and adding 25g of sodium chloride until white solid is separated out, filtering and drying the solid; dissolving the dried solid in 20-40ml of deionized water, slowly adding sodium hydroxide, adjusting the solution to be neutral, adding sodium chloride to form a supersaturated solution, precipitating a white solid, performing suction filtration, and drying; heating and dissolving the dried solid with dimethyl sulfoxide, filtering insoluble impurities while the solid is hot, distilling the filtrate under reduced pressure to obtain a product, washing the product with acetone, washing with absolute ethyl alcohol, performing suction filtration to obtain a white powdery solid, and performing vacuum drying at 80 ℃ for one day to obtain 3,5 '-sodium disulfonate-4, 4' -difluorobenzophenone;
2) preparation of polymer sulfonated polyaryletherketone: 3,5 ' -sodium disulfonate-4, 4 ' -difluorobenzophenone, 4,4 ' -difluorobenzophenone and bisphenol AF are mixed according to a molar ratio of 6: 4: 10 into a 100ml three-necked round bottom flask equipped with mechanical stirring, a water separator and nitrogen gas introduction, 0.2 part by volume of anhydrous DMAc and 10-15ml of redistilled toluene are added; heating to 130 ℃ firstly, keeping the temperature for 3-4 hours, pouring the liquid flowing into the water separator, slowly heating to 190 ℃ and keeping the temperature for 20-24 hours; introducing the product into 300ml of methanol solution and continuously stirring, carrying out suction filtration on the precipitated fibrous solid, washing the fibrous solid to be neutral by using deionized water, and carrying out vacuum drying at 80 ℃ for one day to obtain the polymer;
3) film formation of polymer sulfonated polyaryletherketone: the sulfonated polyaryletherketone ion exchange composite membrane is prepared by casting wet method, hot pressing dry method, extrusion casting dry method, extrusion calendaring dry method, extrusion blow molding dry method, film stretching orientation and other processes. For example of the casting wet process: adding DMAc into a certain amount of the polymer obtained in the step 2) to prepare a 10-12% membrane solution, pouring the membrane solution onto a piece of clean glass, drying the glass in a vacuum drying oven at 60-80 ℃ for 12 hours, drying the glass in vacuum at 80 ℃ for 12 hours, immersing the dried membrane in 1M hydrochloric acid solution for one day, washing the membrane to be neutral by using deionized water, and storing the membrane in the deionized water.
In this example, the undoped sulfonated polyaryletherketone ion exchange membrane described above was used as the membrane of an all vanadium flow battery.
Example 2
The embodiment provides a preparation method of a sulfonated polyaryletherketone ion exchange membrane, which comprises the following specific steps:
1) sulfonated 4, 4' -difluorobenzophenone: adding 5g of 4, 4' -difluorobenzophenone into a 250ml two-neck round-bottom flask with a reflux condenser, adding 20ml of 20% fuming sulfuric acid of analytical pure grade, magnetically stirring, and heating to 110 ℃ for reaction; after the reaction is finished, cooling to room temperature, slowly pouring the product into 100ml of ice-water mixture, stirring and adding 25g of sodium chloride until white solid is separated out, filtering and drying the solid; dissolving the dried solid in 20-40ml of deionized water, slowly adding sodium hydroxide, adjusting the solution to be neutral, adding sodium chloride to form a supersaturated solution, precipitating a white solid, performing suction filtration, and drying; heating and dissolving the dried solid with dimethyl sulfoxide, filtering insoluble impurities while the solid is hot, distilling the filtrate under reduced pressure to obtain a product, washing the product with acetone, washing with absolute ethyl alcohol, performing suction filtration to obtain a white powdery solid, and performing vacuum drying at 80 ℃ for one day to obtain 3,5 '-sodium disulfonate-4, 4' -difluorobenzophenone;
2) preparation of polymer sulfonated polyaryletherketone: 3,5 ' -sodium disulfonate-4, 4 ' -difluorobenzophenone, 4,4 ' -difluorobenzophenone and bisphenol AF are mixed according to a molar ratio of 6: 4: 10 into a 100ml three-neck round-bottom flask equipped with mechanical stirring, a water separator and nitrogen gas introduction, 20% by volume of anhydrous DMAc and 10-15ml of redistilled toluene are added; heating to 130 ℃ firstly, keeping the temperature for 3-4 hours, pouring the liquid flowing into the water separator, slowly heating to 190 ℃ and keeping the temperature for 20-24 hours; introducing the product into 300ml of methanol solution and continuously stirring, carrying out suction filtration on the precipitated fibrous solid, washing the fibrous solid to be neutral by using deionized water, and carrying out vacuum drying at 80 ℃ for one day to obtain the polymer;
3) preparing porous boron nitride nanosheets: adding diboron trioxide and guanidine hydrochloride into a proper amount of methanol according to the molar ratio of 1:5, quickly stirring to form a colorless transparent solution, quickly stirring for one day to form a white solid, pouring the white solid into a quartz crucible, heating the quartz crucible to 1100 ℃ in a tubular furnace, keeping the temperature at 1100 ℃ for 10 ℃/min, keeping the temperature for 2 hours, and introducing a mixed gas of 15% hydrogen/85% nitrogen gas of nitrogen and hydrogen in the heating process to obtain a white solid powder porous boron nitride nanosheet;
4) preparation of sulfonated porous boron nitride: adding 0.2g of white powder porous boron nitride nanosheets, 40ml of toluene and 0.4g of propane sultone into a two-neck round-bottom flask provided with a reflux condenser tube, magnetically stirring, heating to 110 ℃, keeping the temperature at 110 ℃, reacting for 24 hours, cooling to room temperature after the reaction is finished, centrifuging at 8000rpm for 5 minutes, pouring out liquid, washing with ethanol, centrifuging again, repeating the ethanol washing and centrifuging processes for 3 times, then centrifuging after the deionization washing, repeating the deionization washing and centrifuging processes for 3 times, finally obtaining yellow solid, and freeze-drying to obtain sulfonated porous boron nitride;
5) preparing a sulfonated polyaryletherketone ion exchange membrane: the sulfonated polyaryletherketone ion exchange composite membrane is prepared by casting wet method, hot pressing dry method, extrusion casting dry method, extrusion calendaring dry method, extrusion blow molding dry method, film stretching orientation and other processes. For example of the casting wet process: preparing a sulfonated polyaryletherketone ion exchange composite membrane: the preparation of the sulfonated polyaryletherketone ion exchange composite membrane by the tape casting wet method specifically comprises the following steps: preparing a 10% membrane solution from a polymer of sulfonated polyaryletherketone, wherein the solid content of the polymer is 10wt%, sequentially adding 1%, 3%, 5%, 7% and 10% of sulfonated porous boron nitride by mass fraction, wherein the mass fraction is the mass fraction of the sulfonated porous boron nitride relative to the sulfonated polyaryletherketone ion exchange membrane, performing ultrasonic treatment for 1-5 hours, then rapidly stirring for 12 hours, pouring the membrane solution on a piece of clean glass, drying for 12 hours at 60-80 ℃ in a vacuum drying oven, and performing vacuum drying for 12 hours at 80 ℃. The dried membrane was immersed in a 1M hydrochloric acid solution for one day, washed with deionized water to neutrality, and stored in deionized water.
In this example, the composite sulfonated polyaryletherketone ion exchange membrane described above was used as the separator of an all vanadium flow battery.
Based on the above, as shown in fig. 1, the molecular formula of the sulfonated polyaryletherketone ion exchange membrane in example 1; FIG. 2 shows a Fourier infrared spectrum of the ion-exchange membrane of sulfonated polyaryletherketone of example 1; as shown in FIG. 3, the proton conductivity of the ion-exchange membranes of sulfonated polyaryletherketones of example 1 with different degrees of sulfonation is plotted in comparison. FIG. 4 is a schematic view of porous boron nitride in example 2; as shown in FIG. 5, the X-ray diffraction pattern of the porous boron nitride in example 2; FIG. 6 is a transmission electron micrograph of porous boron nitride in example 2; FIG. 7 shows the coulombic, voltage and energy efficiencies of the composite sulfonated polyaryletherketone ion exchange membrane of example 2, the undoped sulfonated polyaryletherketone ion exchange membrane of example 1 and commercial Nafion 117; as shown in FIG. 8, the ion exchange membrane of sulfonated poly (aryl ether ketone) compounded in example 2, the ion exchange membrane of undoped sulfonated poly (aryl ether ketone) in example 1 and commercial Nafion 117 were at 80mA/cm2A charge-discharge curve graph under current density; as shown in FIG. 9, the ion exchange membrane of sulfonated poly (aryl ether ketone) compounded in example 2 was 80mA/cm2A graph of coulombic efficiency, voltage efficiency and energy efficiency cycled for 100 cycles at current density; as shown in FIG. 10, the comparative graph of the discharge capacity of the sulfonated polyaryletherketone composite ion exchange membrane of example 2 and the commercial Nafion 117 membrane with cycle number decay is shown. As can be seen from the figure, the coulombic efficiency, the voltage efficiency and the energy efficiency of the sulfonated polyaryletherketone ion exchange membrane prepared by the invention are all higher than those of Nafion series membranes adopted in the prior art, and the sulfonated polyaryletherketone ion exchange membrane compounded by the invention is optimal.
It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, which are described in the specification and illustrated only to illustrate the principle of the present invention, but that various changes and modifications may be made therein without departing from the spirit and scope of the present invention, which fall within the scope of the invention as claimed. The scope of the invention is defined by the appended claims and equivalents thereof.
Claims (3)
1. A preparation method of a sulfonated polyaryletherketone ion exchange membrane is characterized by comprising the following specific steps:
(1) preparation of sulfonated 4, 4' -difluorobenzophenone: adding one part of 4, 4' -difluorobenzophenone with mass into a 250ml two-neck round-bottom flask with a reflux condenser, adding one part of fuming sulfuric acid with the volume of 20% of analytical pure grade, magnetically stirring, and heating to 110 ℃ for reaction; after the reaction is finished, cooling to room temperature, slowly pouring the product into an ice-water mixture with the volume of 5 parts, stirring and adding 5 parts by mass of sodium chloride until white solid is separated out, performing suction filtration and drying the solid; dissolving the dried solid in 1-2 parts by volume of deionized water, slowly adding sodium hydroxide, adjusting the solution to be neutral, adding sodium chloride to form a supersaturated solution, separating out a white solid, performing suction filtration, and drying; heating and dissolving the dried solid with dimethyl sulfoxide, filtering insoluble impurities while the solid is hot, distilling the filtrate under reduced pressure to obtain a product, washing the product with acetone, washing with absolute ethyl alcohol, performing suction filtration to obtain a white powdery solid, and performing vacuum drying at 80 ℃ for one day to obtain 3,5 '-sodium disulfonate-4, 4' -difluorobenzophenone; the mass of one part is 5g, and the volume of one part is 20 ml;
(2) preparation of polymer sulfonated polyaryletherketone: adding 3,5 ' -sodium disulfonate-4, 4 ' -difluorobenzophenone, 4,4 ' -difluorobenzophenone and bisphenol AF into a 100ml three-neck round-bottom flask which is provided with a mechanical stirrer, a water separator and a nitrogen gas guide tube according to a certain molar ratio, and adding 0.2 part by volume of anhydrous dimethylacetamide and 0.5-0.75 part by volume of redistilled toluene; heating to 130 ℃ and keeping for 3-4 hours, pouring out the liquid flowing into the water separator, slowly heating to 160 ℃ and 190 ℃, and keeping for 20-24 hours; introducing the product into 15 parts by volume of methanol solution, continuously stirring, carrying out suction filtration on the precipitated fibrous solid, washing the fibrous solid to be neutral by using deionized water, and carrying out vacuum drying at 80 ℃ for one day to obtain the polymer; the molar ratio of the 3,5 ' -sodium disulfonate-4, 4 ' -difluorobenzophenone, the 4,4 ' -difluorobenzophenone and the bisphenol AF is 4: 6: 10 or 5: 5: 10 or 6: 4: 10 or 7: 3: 10;
(3) preparing porous boron nitride nanosheets: adding diboron trioxide and guanidine hydrochloride into a proper amount of methanol according to the molar ratio of 1:5, quickly stirring to form a colorless transparent solution, quickly stirring for one day to form a white solid, pouring the white solid into a quartz crucible, heating the quartz crucible to 1100 ℃ in a tubular furnace, keeping the temperature at 1100 ℃ for 10 ℃/min, keeping the temperature for 2 hours, and introducing a mixed gas of 15% hydrogen/85% nitrogen gas of nitrogen and hydrogen in the heating process to obtain a white solid powder porous boron nitride nanosheet;
(4) preparation of sulfonated porous boron nitride: adding 0.04 part by mass of white powder porous boron nitride nanosheets, 2 parts by volume of toluene and 0.08 part by mass of propane sultone into a two-neck round-bottom flask provided with a reflux condenser tube, magnetically stirring, heating to 110 ℃, keeping the temperature at 110 ℃, reacting for 24 hours, cooling to room temperature after the reaction is finished, centrifuging at 8000rpm for 5 minutes, pouring out liquid, washing with ethanol, centrifuging again, repeating the ethanol washing and centrifuging processes for 3 times, then centrifuging after the deionization washing, repeating the deionization washing and centrifuging processes for 3 times, finally obtaining yellow solid, and freeze-drying to obtain sulfonated porous boron nitride;
preparing a sulfonated polyaryletherketone ion exchange membrane: the preparation of the sulfonated polyaryletherketone ion exchange membrane by the tape casting wet method comprises the following specific steps: preparing a 10% membrane solution from a polymer of sulfonated polyaryletherketone, wherein the solid content of the polymer is 10wt%, sequentially adding 1%, 3%, 5%, 7% and 10% of sulfonated porous boron nitride by mass fraction, wherein the mass fraction is the mass fraction of the sulfonated porous boron nitride relative to a sulfonated polyaryletherketone ion exchange membrane, performing ultrasonic treatment for 1-5 hours, then rapidly stirring for 12 hours, pouring the membrane solution on a piece of clean glass, drying for 12 hours at 60-80 ℃ in a vacuum drying oven, and performing vacuum drying for 12 hours at 80 ℃; the dried membrane was immersed in a 1M hydrochloric acid solution for one day, washed with deionized water to neutrality, and stored in deionized water.
2. The method for preparing the sulfonated polyaryletherketone ion exchange membrane according to claim 1, wherein the sulfonated polyaryletherketone polymer film is prepared by a hot pressing dry method, an extrusion casting dry method, an extrusion calendering dry method, an extrusion blow molding dry method and a film stretching orientation process.
3. The application of the preparation method of the sulfonated polyaryletherketone ion exchange membrane of claim 1 in an all-vanadium flow battery, which is characterized in that the synthesized sulfonated polyaryletherketone ion exchange membrane is used as a diaphragm of the all-vanadium flow battery.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710407864.9A CN107394240B (en) | 2017-06-02 | 2017-06-02 | Preparation method and application of sulfonated polyaryletherketone ion exchange membrane |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710407864.9A CN107394240B (en) | 2017-06-02 | 2017-06-02 | Preparation method and application of sulfonated polyaryletherketone ion exchange membrane |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN107394240A CN107394240A (en) | 2017-11-24 |
| CN107394240B true CN107394240B (en) | 2020-05-26 |
Family
ID=60331962
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710407864.9A Active CN107394240B (en) | 2017-06-02 | 2017-06-02 | Preparation method and application of sulfonated polyaryletherketone ion exchange membrane |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107394240B (en) |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109988327A (en) * | 2017-12-29 | 2019-07-09 | 大连融科储能技术发展有限公司 | A kind of non-fluorine ion exchange membrane and its preparation method and application |
| CN109385752A (en) * | 2018-10-29 | 2019-02-26 | 厦门大学 | A kind of sulfonated poly aryl ether ketone positive particles adsorbed film and its electro spinning method for preparing |
| CN112080010B (en) * | 2019-06-14 | 2022-02-08 | 南京工业大学 | Preparation method and application of proton conductive material based on amino organic supermolecule nanosheet derivative |
| CN110534682A (en) * | 2019-08-05 | 2019-12-03 | 长沙理工大学 | A kind of preparation method of alkaline oxygenated reduction flow battery amberplex |
| CN111916628A (en) * | 2020-07-14 | 2020-11-10 | 盐山万兴新能源有限公司 | Lithium ion battery diaphragm and preparation method thereof |
| CN114220983B (en) * | 2021-12-15 | 2024-01-30 | 南京工业大学 | Modified membrane based on hollow carbon spheres and preparation method and application thereof |
| CN114864978B (en) * | 2022-06-16 | 2023-05-05 | 电子科技大学 | Hollow fiber membrane material of high-humidification hydrogen fuel cell humidifier, and preparation method and application thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1556100A (en) * | 2003-12-30 | 2004-12-22 | 吉林大学 | Sulfonated monomer, polymer and its synthesis method |
| CN102120874A (en) * | 2010-12-10 | 2011-07-13 | 中国科学院大连化学物理研究所 | Sulfonated polyarylether polymer ion exchange membrane containing crosslinking groups and application thereof |
-
2017
- 2017-06-02 CN CN201710407864.9A patent/CN107394240B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1556100A (en) * | 2003-12-30 | 2004-12-22 | 吉林大学 | Sulfonated monomer, polymer and its synthesis method |
| CN102120874A (en) * | 2010-12-10 | 2011-07-13 | 中国科学院大连化学物理研究所 | Sulfonated polyarylether polymer ion exchange membrane containing crosslinking groups and application thereof |
Non-Patent Citations (4)
| Title |
|---|
| "Enhanced Durability of Polymer Electrolyte Membrane Fuel Cells by Functionalized 2D Boron Nitride Nanoflakes";Keun-Hwan Oh，et al.;《ACS Appl. Mater. Interfaces》;20140407;第6卷(第10期);第7751-7758页 * |
| "Nano Hexagonal Boron Nitride–Nafion Composite Membranes for Proton Exchange Membrane Fuel Cells";Mert Akel,et al.;《POLYMER COMPOSITES》;20140825;第422-428页 * |
| "Porous boron nitride nanosheets for effective water cleaning";Weiwei Lei，et al.;《nature communications》;20130430;第1777(1-7)页 * |
| "Synthesis and characterization of polymer (sulfonated poly-ether-ether-ketone) based nanocomposite (h-boron nitride) membrane for hydrogen storage";R. Naresh Muthu，et al.;《international journal of hydrogen energy》;20141227;第1836-1845页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN107394240A (en) | 2017-11-24 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107394240B (en) | Preparation method and application of sulfonated polyaryletherketone ion exchange membrane | |
| Zuo et al. | Sulfonated microporous polymer membranes with fast and selective ion transport for electrochemical energy conversion and storage | |
| US9975995B2 (en) | Ion conducting polymer comprising partially branched block copolymer and use thereof | |
| Wang et al. | Novel sulfonated poly (ether ether ketone)/oxidized g-C3N4 composite membrane for vanadium redox flow battery applications | |
| KR101062767B1 (en) | Method for manufacturing a membrane for vanadium redox-flow secondary battery and the membrane | |
| Li et al. | Preparation and characterization of composite membranes with ionic liquid polymer-functionalized multiwalled carbon nanotubes for alkaline fuel cells | |
| KR101569719B1 (en) | Crosslinked hydrocarbon polymer electrolyte membranes with diols by radiation and manufacturing method thereof | |
| WO2018214843A1 (en) | Crosslinked porous membrane resulting from hydrolysis of ester group side chain and preparation method therefor | |
| Che et al. | Anion exchange membranes based on long side-chain quaternary ammonium-functionalized poly (arylene piperidinium) s for vanadium redox flow batteries | |
| CN111533938B (en) | Densely sulfonated polyaryletherketone/SiO2Composite proton exchange membrane and preparation method thereof | |
| ul Imaan et al. | In-situ preparation of PSSA functionalized ZWP/sulfonated PVDF composite electrolyte as proton exchange membrane for DMFC applications | |
| KR101646661B1 (en) | Method for Manufacturing Enhanced Ion Exchange Membrane and for Application of the same | |
| CN113437341A (en) | Amphoteric ion conduction membrane for flow battery and preparation method thereof | |
| CN116613362A (en) | Composite amphoteric ion exchange membrane for vanadium battery and preparation method thereof | |
| CN113278151B (en) | Dense alkyl sulfur-containing polyether sulphone polymer with flexible side chain structure and preparation method and application thereof | |
| CN111718505B (en) | Sulfonated polyether-ether-ketone/polyvinylidene fluoride composite ion exchange membrane for all-vanadium redox flow battery and preparation method thereof | |
| KR101750412B1 (en) | Anion conducting body comprising anion conducting block copolymer having polyphenylene-based hydrophilic main chain, preparation method and use thereof | |
| CN110078961B (en) | Polyhydroxy functional polybenzimidazole ion exchange membrane and preparation method thereof | |
| CN110326144B (en) | Polymer electrolyte membrane, method for producing the same, electrochemical cell and flow cell, and composition for polymer electrolyte membrane | |
| CN109103483B (en) | Amphoteric ion membrane for all-vanadium redox flow battery | |
| KR101995039B1 (en) | Brominated polyphenylenesulfide based by polyphenylenesulfide, method for producing the same, brominated and sulfonated polyphenylenesulfide and manufacturing method using the same | |
| CN113912887A (en) | Preparation method of PTFE (polytetrafluoroethylene) hydrophilic porous ion selective membrane composite material | |
| CN112310452A (en) | Phosphotungstic acid doped sulfonated poly (arylene ether nitrile) proton exchange membrane and preparation method thereof | |
| CN111354964A (en) | Amphoteric ion-containing polymer and flow battery electrolyte membrane | |
| CN109411796A (en) | A kind of crosslinking proton exchange membrane and preparation method for vanadium cell |
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 | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |