CN120174543A - A sulfonated polyetheretherketone-based diaphragm and its preparation method and application - Google Patents
A sulfonated polyetheretherketone-based diaphragm and its preparation method and application Download PDFInfo
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- D—TEXTILES; PAPER
- D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
- D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
- D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
- D04H1/40—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties
- D04H1/42—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres from fleeces or layers composed of fibres without existing or potential cohesive properties characterised by the use of certain kinds of fibres insofar as this use has no preponderant influence on the consolidation of the fleece
- D04H1/4326—Condensation or reaction polymers
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F1/00—General methods for the manufacture of artificial filaments or the like
- D01F1/02—Addition of substances to the spinning solution or to the melt
- D01F1/10—Other agents for modifying properties
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- D—TEXTILES; PAPER
- D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
- D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
- D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
- D01F6/88—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds
- D01F6/94—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds of other polycondensation products
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- D—TEXTILES; PAPER
- D04—BRAIDING; LACE-MAKING; KNITTING; TRIMMINGS; NON-WOVEN FABRICS
- D04H—MAKING TEXTILE FABRICS, e.g. FROM FIBRES OR FILAMENTARY MATERIAL; FABRICS MADE BY SUCH PROCESSES OR APPARATUS, e.g. FELTS, NON-WOVEN FABRICS; COTTON-WOOL; WADDING ; NON-WOVEN FABRICS FROM STAPLE FIBRES, FILAMENTS OR YARNS, BONDED WITH AT LEAST ONE WEB-LIKE MATERIAL DURING THEIR CONSOLIDATION
- D04H1/00—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres
- D04H1/70—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres
- D04H1/72—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres the fibres being randomly arranged
- D04H1/728—Non-woven fabrics formed wholly or mainly of staple fibres or like relatively short fibres characterised by the method of forming fleeces or layers, e.g. reorientation of fibres the fibres being randomly arranged by electro-spinning
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/02—Details
- H01M8/0202—Collectors; Separators, e.g. bipolar separators; Interconnectors
- H01M8/023—Porous and characterised by the material
- H01M8/0239—Organic resins; Organic polymers
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- 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
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Abstract
本发明提供了一种磺化聚醚醚酮基隔膜及其制备方法和应用，属于液流电池隔膜技术领域。本发明首先对聚醚醚酮进行磺化，得到磺化聚醚醚酮；然后将磺化聚醚醚酮、MXene粉末制成静电纺丝液，对静电纺丝液进行静电纺丝，得到磺化聚醚醚酮基隔膜。本发明以磺化聚醚醚酮和MXene材料为原料通过静电纺丝制备纳米纤维隔膜，一方面MXene和磺化聚醚醚酮之间形成的氢键能够增加纳米纤维隔膜的机械稳定性，另一方面MXene的添加改善了纳米纤维隔膜的吸水率、溶胀度以及孔隙分布，提升了隔膜的实用性能。
The present invention provides a sulfonated polyetheretherketone-based diaphragm and a preparation method and application thereof, belonging to the technical field of liquid flow battery diaphragms. The present invention first sulfonates polyetheretherketone to obtain sulfonated polyetheretherketone; then the sulfonated polyetheretherketone and MXene powder are made into an electrospinning solution, and the electrospinning solution is electrospun to obtain a sulfonated polyetheretherketone-based diaphragm. The present invention uses sulfonated polyetheretherketone and MXene materials as raw materials to prepare a nanofiber diaphragm by electrospinning. On the one hand, the hydrogen bond formed between MXene and sulfonated polyetheretherketone can increase the mechanical stability of the nanofiber diaphragm. On the other hand, the addition of MXene improves the water absorption, swelling degree and pore distribution of the nanofiber diaphragm, thereby improving the practical performance of the diaphragm.
Description
Technical Field
The invention relates to the technical field of flow battery diaphragms, in particular to a sulfonated polyether-ether-ketone-based diaphragm, and a preparation method and application thereof.
Background
The flow battery has the advantages of high safety, long cycle life, recyclable electrolyte, high life cycle cost performance and the like, and is considered as one of the first choice technologies of the large-scale energy storage technology. The iron-chromium flow battery takes iron ions and chromium ions which are rich in raw materials and low in price as active substances, so that the manufacturing cost of the battery can be greatly reduced, and the battery has higher safety. In addition, the iron-chromium flow battery has better environmental adaptability and shows better industrialization and market popularization and application prospects.
The separator is an important component of a flow battery, which not only blocks active substances in the electrolyte of the positive electrode and the negative electrode from being mutually connected to avoid self-discharge, but also provides a channel for proton transfer in the electrolyte to balance charges. The ideal flow battery diaphragm has the characteristics of high proton conductivity, high ion selectivity, high electrochemical stability, low cost and the like. However, the current flow battery diaphragm mainly comprises a perfluorosulfonic acid proton exchange membrane represented by Nafion series membranes produced by DuPont company, and the cost is high, so that the large-scale commercialization of the flow battery is limited to a certain extent. To reduce costs, non-perfluorinated proton exchange membranes are becoming a research hotspot. Long et al used crown ether with appropriate cavity size as a cross-linking agent to construct a series of selectively cross-linked sulfonated polyimide membranes with excellent chemical structure and mechanical stability in flow battery cycle.
Polyether-ether-ketone (PEEK) is a commercial high-performance engineering plastic, has the characteristics of good thermal stability, compression resistance, high mechanical strength and the like, and particularly, a polymer main chain of the PEEK has a phenylene oxide structure, so that benzene ring hydrogen has higher electron cloud density, and is favorable for blocking electrolyte, conducting protons and isolating electrons, and has been valued by diaphragm research and development personnel. The Nafion membrane used at present is 100 yuan per milligram, and the PEEK purchased is 300 yuan per kilogram, so the PEEK is selected as the material to prepare the non-perfluorinated proton exchange membrane, and the cost of the membrane can be greatly reduced. Compared with the traditional manufacturing processes such as a solution casting method, a melt stretching method, a chemical vapor deposition method and the like, the nanofiber membrane prepared by the electrostatic spinning method has the advantages of high porosity, large specific surface area, high axial strength and the like, and becomes an emerging battery diaphragm preparation technology. And after dissolving PEEK by using dichloroacetic acid at 180 ℃, coating PEEK spinning solution in a nanofiber shell of spinnable polymer polybutylene succinate by using a coaxial electrostatic spinning process to obtain a nanofiber with a core-shell structure, and removing the shell by low-temperature treatment to obtain the PEEK nanofiber.
However, PEEK has extremely high chemical stability, and is difficult to be dissolved in a general organic solvent at room temperature for electrostatic spinning, so development of PEEK nanofiber membranes faces great difficulty. Sulfonation modification of PEEK by controlling the reaction temperature and time is a major way to improve its room temperature spinnability. Xiong et al prepare ionic liquid filled halloysite nanotube ionic gel, construct halloysite ionic gel/sulfonated polyether ether ketone composite proton exchange membrane by adopting an electrostatic spinning process, and show single cell performance equivalent to that of Nafion212 membrane. At present, the fibrous membrane prepared by taking sulfonated polyether-ether-ketone as a raw material has the problems of high swelling degree and water absorption rate, easiness in damaging the dimensional stability of the membrane, increased ion permeability and reduced battery performance. Therefore, the sulfonated polyether-ether-ketone-based diaphragm and the preparation method thereof are researched, and the sulfonated polyether-ether-ketone-based diaphragm has important significance in the iron-chromium flow battery.
Disclosure of Invention
The invention aims to provide a sulfonated polyether-ether-ketone-based diaphragm, and a preparation method and application thereof, so as to solve the problems of high swelling degree and high water absorption of a fibrous membrane prepared by taking sulfonated polyether-ether-ketone as a raw material in the prior art.
In order to achieve the above object, the present invention provides the following technical solutions:
The invention provides a preparation method of a sulfonated polyether-ether-ketone-based diaphragm, which comprises the following steps:
(1) Sulfonating polyether-ether-ketone to obtain sulfonated polyether-ether-ketone;
(2) Preparing sulfonated polyether-ether-ketone and MXene powder into electrostatic spinning solution, and carrying out electrostatic spinning on the electrostatic spinning solution to obtain the sulfonated polyether-ether-ketone-based diaphragm.
Preferably, the specific step of sulfonation in the step (1) is that the sulfonated polyether-ether-ketone is obtained by mixing polyether-ether-ketone and concentrated sulfuric acid, then carrying out sulfonation reaction, and then cooling, filtering and drying.
Preferably, the mass volume ratio of the polyether-ether-ketone to the concentrated sulfuric acid is 2-8 g/80-120 mL.
Preferably, the temperature of the sulfonation reaction is 50-70 ℃, and the time of the sulfonation reaction is 6-10 hours.
Preferably, the electrostatic spinning solution in the step (2) is prepared by dispersing MXene powder and sulfonated polyether ether ketone in an organic solvent, wherein the organic solvent comprises one or more of N, N-dimethylformamide, N-dimethylacetamide, dimethyl sulfoxide, tetrahydrofuran and N-methylpyrrolidone.
Preferably, the mass of the MXene powder accounts for 10-20% of the mass of the sulfonated polyether-ether-ketone.
Preferably, the mass of the sulfonated polyether-ether-ketone accounts for 10-25% of the total mass of the sulfonated polyether-ether-ketone and the organic solvent.
Preferably, the electrostatic spinning in the step (2) has the technological parameters of 16-24 kV of spinning voltage, 0.5-4.0 mL/h of propelling speed, 10-15 cm of collecting distance and 1-3 h of spinning time.
The invention also provides the sulfonated polyether-ether-ketone-based diaphragm prepared by the preparation method of the sulfonated polyether-ether-ketone-based diaphragm.
The invention also provides application of the sulfonated polyether-ether-ketone-based diaphragm in an iron-chromium flow battery.
The invention has the beneficial effects that:
(1) According to the invention, the nanofiber membrane is prepared from the sulfonated polyether-ether-ketone and the MXene material by electrostatic spinning, so that on one hand, the mechanical stability of the nanofiber membrane can be increased by a hydrogen bond formed between the MXene and the sulfonated polyether-ether-ketone, and on the other hand, the water absorption, the swelling degree and the pore distribution of the nanofiber membrane are improved by adding the MXene, and the practical performance of the membrane is improved.
(2) The invention obviously reduces the pore space of the nanofiber membrane by introducing MXene, ensures the rapid transmission of ions in the processes of electrolyte permeation and charge and discharge, and further improves the reaction reversibility and electrochemical performance of the battery.
Drawings
FIG. 1 is a graph showing the water absorption, swelling degree, tensile properties and water contact angle of the sulfonated polyether-ether-ketone-based diaphragms prepared in examples 1 to 3 and comparative example 1, wherein a is a graph showing the water absorption and swelling degree, b is a graph showing the tensile properties, and c is a graph showing the water contact angle;
FIG. 2 is a graph of N 2 isothermal adsorption of sulfonated polyether ether ketone based membranes prepared in example 2 and comparative example 1;
FIG. 3 is a graph showing pore size distribution of sulfonated polyether ether ketone based separators prepared in example 2 and comparative example 1;
FIG. 4 is a graph of coulombic efficiency of the sulfonated polyether ether ketone based separator made in example 2;
FIG. 5 is a graph of voltage efficiency of the sulfonated polyether ether ketone based separator made in example 2;
FIG. 6 is an energy efficiency plot of the sulfonated polyether ether ketone based membrane produced in example 2;
FIG. 7 is a process flow diagram of the present invention for preparing a sulfonated polyether ether ketone based membrane.
Detailed Description
The invention provides a preparation method of a sulfonated polyether-ether-ketone-based diaphragm, which comprises the following steps:
(1) Sulfonating polyether-ether-ketone to obtain sulfonated polyether-ether-ketone;
(2) Preparing sulfonated polyether-ether-ketone and MXene powder into electrostatic spinning solution, and carrying out electrostatic spinning on the electrostatic spinning solution to obtain the sulfonated polyether-ether-ketone-based diaphragm.
In the invention, the specific step of sulfonation in the step (1) is that the sulfonated polyether-ether-ketone is obtained by mixing polyether-ether-ketone and concentrated sulfuric acid, then carrying out sulfonation reaction, cooling, filtering and drying.
In the present invention, it is preferable to dry the polyetheretherketone and then mix it with concentrated sulfuric acid at 120℃for 5 hours.
In the invention, the mass volume ratio of the polyether-ether-ketone to the concentrated sulfuric acid is 2-8 g/80-120 mL, preferably 4-6 g/90-110 mL, and more preferably 5 g/100 mL.
In the invention, the mixing mode is room temperature oscillation, the oscillation time is 5-15 min, preferably 8-12 min, and more preferably 10min.
In the invention, the temperature of the sulfonation reaction is 50-70 ℃, preferably 55-65 ℃, more preferably 60 ℃, and the time of the sulfonation reaction is 6-10 hours, preferably 8-10 hours, more preferably 10 hours.
In the invention, the preparation method of the MXene powder preferably comprises the steps of mixing hydrochloric acid solution, lithium fluoride and Ti 3AlC2, then carrying out reaction, washing with dilute hydrochloric acid, centrifuging, washing with deionized water after the reaction is finished, and freeze-drying the obtained precipitate to obtain the MXene powder.
According to the invention, the mass volume ratio of the lithium fluoride to the hydrochloric acid solution is 1-5 g/40 mL, the mass volume ratio of the Ti 3AlC2 to the hydrochloric acid solution is 1-3 g/40 mL, the reaction temperature is 30-50 ℃, the reaction time is 68-74 h, and the concentration of the hydrochloric acid solution is 8-10 mol/L.
In the invention, the MXene layer spacing is larger, the surface is electronegative, and the laminated structure effectively avoids the formation of macropores. In addition, by MXene blending electrospinning, hydrogen bonding between MXene and SPEEK is formed thereby increasing the mechanical stability of the nanofiber membrane. As the amount of MXene doped increases, the water absorption gradually decreases, while the swelling degree decreases and then slightly increases.
In the invention, the preparation step of the electrostatic spinning solution in the step (2) comprises the step of dispersing MXene powder and sulfonated polyether ether ketone in an organic solvent to prepare the electrostatic spinning solution, wherein the organic solvent comprises one or more of N, N-dimethylformamide, N-dimethylacetamide, dimethyl sulfoxide, tetrahydrofuran and N-methylpyrrolidone.
In the invention, the mass of the MXene powder accounts for 10-20%, preferably 15% of the mass of the sulfonated polyether-ether-ketone.
In the invention, the mass of the sulfonated polyether-ether-ketone accounts for 10-25% of the total mass of the sulfonated polyether-ether-ketone and the organic solvent, and is preferably 15-20%.
In the invention, the process parameters of the electrostatic spinning in the step (2) are that the spinning voltage is 16-24 kV, preferably 18-22 kV, more preferably 20kV, the advancing speed is 0.5-4.0 mL/h, preferably 1-3 mL/h, more preferably 2mL/h, the collecting distance is 10-15 cm, preferably 11-14 cm, more preferably 12-13 cm, and the spinning time is 1-3 h, preferably 2h.
The invention also provides the sulfonated polyether-ether-ketone-based diaphragm prepared by the preparation method of the sulfonated polyether-ether-ketone-based diaphragm.
The invention also provides application of the sulfonated polyether-ether-ketone-based diaphragm in an iron-chromium flow battery.
The technical solutions provided by the present invention are described in detail below with reference to examples, but they should not be construed as limiting the scope of the present invention.
Example 1
Drying polyether-ether-ketone (PEEK) particles in vacuum for 5 hours at the temperature of 120 ℃, weighing 5g of dried PEEK particles, placing the PEEK particles in a flask, adding 100mL of concentrated sulfuric acid, vibrating for 10 minutes at room temperature to uniformly mix the PEEK particles with the concentrated sulfuric acid, placing the flask in an oil bath at 60 ℃ for carrying out magnetic stirring for 10 hours to carry out sulfonation reaction, slowly adding reaction liquid into a large amount of ice water after the reaction is finished, repeatedly washing white precipitate with deionized water until the solution is nearly neutral, finally drying the precipitate at the temperature of 60 ℃ for 48 hours to obtain sulfonated polyether-ether-ketone, marking the sulfonated polyether-ether-ketone as SPEEK, and placing the sulfonated polyether-ether-ketone in a dryer for standby.
Adding 40mL of hydrochloric acid solution (with the concentration of 9 mol/L) and 4g of LiF into a polytetrafluoroethylene container, stirring at room temperature for 30min, adding 2g of Ti 3AlC2 into the container, stirring at 400rpm, reacting at 40 ℃ for 72h, washing with dilute hydrochloric acid for 3 times after the reaction is finished, centrifuging at 3500rpm for 5min, washing with deionized water for 5 times, and freeze-drying the collected lower precipitate for 48h to obtain MXene powder.
Dispersing 0.3g of MXene powder in N, N-Dimethylformamide (DMF), carrying out ultrasonic treatment in an ultrasonic breaker for 30min, stirring for 1h by using a magnetic stirrer, adding 3g of SPEEK, and continuing stirring until a uniform electrostatic spinning solution is obtained, wherein the mass of the SPEEK in the electrostatic spinning solution accounts for 20% of the total mass of the DMF and the SPEEK, and the mass of the MXene powder accounts for 10% of the mass of the SPEEK.
And (3) taking release paper as a substrate, and carrying out electrostatic spinning on the electrostatic spinning solution, wherein the technological parameters are that the spinning voltage is set to be 20kV, the advancing speed of the spinning solution is 2mL/h, the collecting distance is 12cm, and the spinning time is 2h, so that the sulfonated polyether-ether-ketone-based diaphragm is prepared and is recorded as MXene/SPEEK-10%.
Example 2
The difference from example 1 was that the amount of MXene powder added was 0.45g, the mass of MXene powder was 15% of the mass of SPEEK, and the same conditions were the same, to prepare a sulfonated polyether ether ketone based separator, designated as MXene/SPEEK-15%.
Example 3
The difference from example 1 is that the amount of MXene powder added was 0.6g, the mass of MXene powder was 20% of the mass of SPEEK, and the other conditions were the same, to prepare a sulfonated polyether ether ketone based separator, designated as MXene/SPEEK-20%.
Comparative example 1
Drying polyether-ether-ketone (PEEK) particles in vacuum for 5 hours at the temperature of 120 ℃, weighing 5g of dried PEEK particles, placing the PEEK particles in a flask, adding 100mL of concentrated sulfuric acid, vibrating the PEEK particles at room temperature for 10 minutes to uniformly mix the PEEK particles with the concentrated sulfuric acid, placing the flask in an oil bath at 60 ℃ for carrying out magnetic stirring for 10 hours to carry out sulfonation reaction, slowly adding reaction liquid into a large amount of ice water after the reaction is finished, repeatedly washing white precipitate with deionized water until the solution is nearly neutral, finally drying the precipitate at the temperature of 60 ℃ for 48 hours, and placing the precipitate in a dryer for standby to obtain the sulfonated polyether-ether-ketone, which is marked as SPEEK.
3G of SPEEK is dispersed in N, N-Dimethylformamide (DMF), and stirred until the SPEEK is completely dissolved to obtain a uniform electrostatic spinning solution, wherein the mass of the SPEEK in the electrostatic spinning solution accounts for 20% of the total mass of the DMF and the SPEEK.
And (3) taking release paper as a substrate, and carrying out electrostatic spinning on the electrostatic spinning solution, wherein the technological parameters are that the spinning voltage is set to be 20kV, the advancing speed of the spinning solution is 2mL/h, the collecting distance is 12cm, and the spinning time is 2h, so that the sulfonated polyether-ether-ketone-based diaphragm is obtained and is marked as SPEEK.
Performance test:
(1) The swelling degree and water absorption rate of the sulfonated polyether ether ketone-based diaphragms prepared in examples 1-3 and comparative example 1 are tested, and the water absorption rate of the diaphragms can be measured according to the ASTMD570 standard, specifically, the method comprises the steps of cutting a diaphragm to be measured into small diaphragms with the size of 5cm multiplied by 5cm, putting the diaphragms into a DZF-6050 type vacuum oven (Beijing Liu Xi technology Co., ltd.) at the temperature of 80 ℃ for drying to constant weight, weighing the dry film, recording the weight as W dry, putting the dry film into a beaker, adding deionized water into the beaker for complete immersion, and balancing the water absorption of the diaphragm under the condition of room temperature. The film was taken out, the moisture on the surface of the film was rapidly sucked with filter paper and then the mass thereof was precisely weighed and recorded as W wet, and the area S wet of the wet film was recorded, and the water absorption of the separator was calculated from formula (1-1). The wet film was then dried to constant weight in a vacuum oven at 80 ℃, the measurement was taken out and the area of the dry film was recorded S dry, and the swelling degree of the separator was calculated according to formula (1-2).
The test results are shown in fig. 1a, and it can be seen from the graph that the swelling degree and the water absorption rate of SPEEK of comparative example 1 are 26.2% and 36.6%, respectively, because the membrane prepared from sulfonated polyether ether ketone as a raw material contains a sulfonic group, the hydrophilicity of the membrane is good, but excessive water molecules cause the water channel to become large, the swelling degree and the water absorption rate of the membrane are improved, proper water absorption rate can provide a guarantee for efficient ion conduction, and the membrane is transported through a carrying mechanism and a jump mechanism, but the dimensional stability of the membrane is damaged due to the increase of the swelling degree after excessive water absorption, which leads to the increase of ion permeability and the decrease of battery performance. Examples 1-3 reduce the swelling degree and water absorption of sulfonated polyether ether ketone based membranes by adding a certain amount of MXene powder because the MXene material has a larger interlayer spacing and the surface is electronegative, and adding MXene powder effectively avoids the formation of macropores in the membrane, and in addition, through electrostatic spinning after blending of MXene powder and SPEEK, hydrogen bonds formed between MXene and SPEEK further increase the mechanical stability of the nanofiber membrane. With the increase of the doping amount of the MXene powder, the water absorption and the swelling degree gradually decrease, and when the doping amount of the MXene is 15%, the water absorption and the swelling degree of the MXene/SPEEK-15% are respectively 12.7% and 14.3%.
(2) The sulfonated polyether-ether-ketone-based membrane prepared in examples 1-3 was tested for tensile properties by using a XLW-B type electronic tensile tester (Jinan Sei electronic technology Co., ltd.) and the thickness of the nanofiber membrane was tested by using a CHY-CB film thickness tester (Jinan Guangdong, china), the width of the nanofiber membrane sample was cut to 2cm, the length was 10cm, and the sample strip was placed on the electronic tensile tester, and the tensile speed was adjusted to 25mm/min, and the sample strip was stretched until it was broken. As shown in the test result in the graph (b) of FIG. 1, as the MXene and SPEEK blended yarn is used for preparing the fiber diaphragm, part of MXene is directly exposed on the surface of the fiber, the aggregation phenomenon is easier to occur, the contact area between the fibers is reduced, the nanofiber diaphragm is easy to slip in the stretching process, and the fracture strain of the nanofiber diaphragm is reduced. But the MXene doping amount is increased, the fracture stress is gradually increased, and the mechanical property of the nanofiber membrane is enhanced to a certain extent.
(3) The water contact angles of the sulfonated polyether ether ketone based diaphragms prepared in examples 1-3 and comparative example 1 are tested, and the result is shown in figure 1c, wherein the water contact angle of the MXene/SPEEK-20% diaphragm in example 3 is 4.7 degrees, and the hydrophilic performance of the MXene doped SPEEK nanofiber diaphragm is further improved due to the fact that the MXene has certain hydrophilicity.
(4) The adsorption performance of the sulfonated polyether ether ketone based membranes prepared in example 2 and comparative example 1 was tested, and specific surface area and porosity analysis (BET) were tested by taking 0.1g of sample for isothermal N 2 adsorption and desorption, and by performing calculation analysis by means of relative pressure and adsorption amount, specific surface area and pore distribution of the sample were determined. As shown in the test results of figures 2-3, the nitrogen adsorption amount curve shows an obvious IV-type curve, which shows that the nitrogen adsorption amount curve has a micropore (1.8 nm) and a mesoporous structure (about 6 nm), the specific surface area (8.2722 m 2/g) of the MXene/SPEEK-15% nanofiber membrane of the embodiment 2 is higher than that of the SPEEK nanofiber membrane (5.9941 m 2/g), and the pore volume (0.014198 cm 3/g) is higher than that of the SPEEK nanofiber membrane (0.010606 cm 3/g), because the pores of the nanofiber membrane are obviously reduced due to the introduction of the MXene, the reaction reversibility and electrochemical performance of the battery are further improved while the rapid transmission of ions in the electrolyte permeation and charge-discharge processes are ensured. FIG. 3 shows that the MXene/SPEEK-15% nanofiber membrane is mainly mesoporous, has a pore diameter of 6-10nm, optimizes an ion transmission channel, and improves diffusion dynamics.
(5) Test example 2 cell performance of sulfonated polyether ether ketone based separator the separator was subjected to charge-discharge cycle test using CT-4008-5V6A-DB-F type single cell test system (New energy technology Co., ltd. In Shenzhen city), and the effective size of the membrane was 10cm. Times.10 cm. Constant current charge and discharge cycle test was conducted under the condition of a current density of 140mA/cm 2, and the stability of the membrane was detected. The positive and negative electrode electrolyte consisted of 80mL of 1.2mol/L FeCl 2·4H2O、1.4mol/L CrCl3·3H2 O and 2.5mol/L HCl. And conveying the electrolyte by adopting a peristaltic pump with the flow rate of 20 mL/min. Is circulated at a constant flow rate of 20 mL/min. Constant current charge and discharge cycle test was conducted under the condition of a current density of 140mA/cm 2, and the stability of the membrane was detected. The test results are shown in figures 4-6, wherein MXene/SPEEK-15% has coulomb efficiency up to 96% or more and energy efficiency up to 70% or more. The MXene/SPEEK-15% nanofiber membrane shows excellent coulombic efficiency in the tested membrane, and the membrane has no obvious attenuation on the efficiency after 22 cycles, and the MXene/SPEEK-15% nanofiber membrane basically meets the performance requirements of the iron-chromium flow battery. This is because by means of MXene blending electrostatic spinning, an ion interpenetrating crosslinked network is constructed between MXene and SPEEK, so that swelling is reduced, fiber aperture is reduced, and the synergistic effect of the two results in higher coulomb efficiency of the MXene/SPEEK nanofiber membrane than that of a pure SPEEK nanofiber membrane.
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 sulfonated polyether-ether-ketone-based diaphragm is characterized by comprising the following steps of:
(1) Sulfonating polyether-ether-ketone to obtain sulfonated polyether-ether-ketone;
(2) Preparing sulfonated polyether-ether-ketone and MXene powder into electrostatic spinning solution, and carrying out electrostatic spinning on the electrostatic spinning solution to obtain the sulfonated polyether-ether-ketone-based diaphragm.
2. The preparation method of the sulfonated polyether-ether-ketone-based membrane according to claim 1, wherein the specific step of sulfonation in the step (1) is that the sulfonated polyether-ether-ketone is obtained by mixing polyether-ether-ketone and concentrated sulfuric acid, then performing sulfonation reaction, and then cooling, filtering and drying.
3. The preparation method of the sulfonated polyether-ether-ketone-based membrane according to claim 2, wherein the mass-volume ratio of the polyether-ether-ketone to the concentrated sulfuric acid is 2-8 g/80-120 mL.
4. The method for preparing the sulfonated polyether-ether-ketone-based membrane according to claim 2 or 3, wherein the temperature of the sulfonation reaction is 50-70 ℃, and the time of the sulfonation reaction is 6-10 hours.
5. The preparation method of the sulfonated polyether-ether-ketone-based membrane according to claim 4, wherein the preparation step of the electrostatic spinning solution in the step (2) is to disperse MXene powder and sulfonated polyether-ether-ketone in an organic solvent to prepare the electrostatic spinning solution, wherein the organic solvent comprises one or more of N, N-dimethylformamide, N-dimethylacetamide, dimethyl sulfoxide, tetrahydrofuran and N-methylpyrrolidone.
6. The preparation method of the sulfonated polyether-ether-ketone-based membrane according to claim 1,2 or 5, wherein the mass of the MXene powder accounts for 10-20% of the mass of the sulfonated polyether-ether-ketone.
7. The preparation method of the sulfonated polyether-ether-ketone-based membrane according to claim 5, wherein the mass of the sulfonated polyether-ether-ketone is 10-25% of the total mass of the sulfonated polyether-ether-ketone and the organic solvent.
8. The preparation method of the sulfonated polyether-ether-ketone-based membrane according to claim 3,5 or 7, wherein the electrostatic spinning process parameters in the step (2) are that the spinning voltage is 16-24 kV, the propelling speed is 0.5-4.0 mL/h, the collecting distance is 10-15 cm, and the spinning time is 1-3 h.
9. The sulfonated polyether ether ketone-based membrane prepared by the preparation method of the sulfonated polyether ether ketone-based membrane according to any one of claims 1 to 8.
10. Use of the sulfonated polyether ether ketone based separator of claim 9 in an iron-chromium flow battery.
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