CN109037552B - Preparation method of diaphragm material for sodium-sulfur battery - Google Patents

Preparation method of diaphragm material for sodium-sulfur battery Download PDF

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CN109037552B
CN109037552B CN201810889058.4A CN201810889058A CN109037552B CN 109037552 B CN109037552 B CN 109037552B CN 201810889058 A CN201810889058 A CN 201810889058A CN 109037552 B CN109037552 B CN 109037552B
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polypyrrole
porous polypyrrole
porous
zinc oxide
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CN109037552A (en
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张永光
杨爽
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Synergy Innovation Institute Of Gdut Heyuan
Hebei University of Technology
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Synergy Innovation Institute Of Gdut Heyuan
Hebei University of Technology
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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
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/403—Manufacturing processes of separators, membranes or diaphragms
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/411—Organic material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/431—Inorganic material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/446—Composite material consisting of a mixture of organic and inorganic materials
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/463—Separators, membranes or diaphragms characterised by their shape
    • 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
    • Y02E60/10—Energy storage using batteries

Abstract

The invention relates to a preparation method of a diaphragm material for a sodium-sulfur battery. According to the method, the three-dimensional ordered porous polypyrrole is prepared, the porous polypyrrole and high-concentration zinc acetate and potassium hydroxide solution are used as raw materials, the porous structure of the obtained material can provide a large specific surface area, nitrogen-containing functional groups on the surface of the polypyrrole and oxygen-containing functional groups of zinc oxide, so that polysulfide can be effectively adsorbed, the shuttle effect is effectively inhibited, and the polypyrrole has high conductivity. The invention can improve the transmission speed of electrons and ions, thereby improving the electrochemical performance and the cycling stability of the lithium-sulfur battery on the whole.

Description

Preparation method of diaphragm material for sodium-sulfur battery
Technical Field
The invention belongs to the technical field of chemical power sources, particularly relates to a nano diaphragm material for a sodium-sulfur battery and a preparation method thereof, and particularly relates to a zinc oxide/porous polypyrrole composite material for the sodium-sulfur battery and a preparation method thereof.
Background
Sodium-sulfur batteries were first invented by Ford corporation of america in 1967. So far 40 years of history. Generally, a battery is composed of a positive electrode, a negative electrode, an electrolyte, a separator, a housing, and the like. The conventional secondary battery such as lead-acid battery, cadmium-nickel battery, etc. is composed of solid electrode and liquid electrolyte, while the sodium-sulfur battery is composed of molten liquid electrode and solid electrolyte, and its working temperature is 300-350 deg.C. The active material of the negative electrode is molten metal sodium, and the active material of the positive electrode is liquid sulfur and sodium polysulfide molten salt. Similar to lithium-sulfur batteries, the theoretical specific capacity of sulfur in sodium-sulfur batteries is 1675mAh g-1. Are currently used in several countries for storing electricity generated by wind power, photovoltaic devices, and conventional power plants.Further, the sodium-sulfur battery is sealed, and thus, does not cause emission pollution when used, and therefore, is considered to be very environmentally friendly, and almost all battery materials can be recycled. In view of these advantages, sodium-sulfur batteries are a valuable research direction in this era when alternative energy sources are sought.
High temperature sodium-sulfur batteries still have many problems to solve. First, the cell must be operated at high temperatures so that the electrode material remains in a molten state; secondly, sodium is very dangerous because it burns or explodes when in contact with water; third, self-discharge. Therefore, for safety and performance considerations, a proper seal is required that can operate at high temperatures and that does not crack. However, since the operating temperature of the high-temperature sodium-sulfur battery is as high as 300 ℃, it is liable to cause risks of explosion, corrosion, etc., and a large amount of energy is consumed to maintain the operating temperature thereof, severely limiting its wide application. Therefore, attempts have been made to study room temperature sodium-sulfur batteries. The room temperature sodium-sulfur battery was first proposed in 2006 by the Hyo-JunAhn project group in korea, and then people began to pay attention and study. However, since metallic sodium is more reactive than lithium, Na-S batteries face more challenges to operating at ambient temperatures than Li-S batteries, particularly in terms of utilization of the sulfur active material and capacity retention during cycling. Similar to the lithium-sulfur battery, when the room temperature sodium-sulfur battery uses liquid electrolyte, polysulfide is easily dissolved in the electrolyte due to the insulation property of sulfur, so that shuttle effect and volume expansion are caused, the utilization rate of sulfur is low, the cycle performance is poor, and the like, so that the electrochemical performance of the sodium-sulfur battery is seriously influenced.
Disclosure of Invention
The invention aims to provide a preparation method of a diaphragm material for a sodium-sulfur battery, aiming at the defects in the prior art. According to the invention, porous polypyrrole and high-concentration zinc acetate and potassium hydroxide solution are used as raw materials, the porous structure of the obtained material can provide a large specific surface area, nitrogen-containing functional groups on the surface of the polypyrrole and oxygen-containing functional groups of zinc oxide, so that polysulfide can be effectively adsorbed, the shuttle effect is effectively inhibited, the strong conductivity of the polypyrrole can improve the transmission speed of electrons and ions, and the electrochemical performance and the cycling stability of the lithium-sulfur battery are integrally improved.
The technical scheme of the invention is as follows:
a method of preparing a separator material for a sodium-sulfur battery, the method comprising the steps of:
the method comprises the following steps: preparing monodisperse silicon dioxide microspheres; mixing ethyl orthosilicate and absolute ethyl alcohol to obtain a solution A; mixing ammonia water, absolute ethyl alcohol and deionized water to obtain a solution B; mixing the solution A and the solution B, stirring for 4-12 h, centrifuging, and drying in a vacuum drying oven for 36-48 h; obtaining monodisperse silicon dioxide microspheres;
wherein, in the solution A, the volume ratio is ethyl orthosilicate: anhydrous ethanol ═ 1: 5-15, in the solution B, the volume ratio of ammonia water: anhydrous ethanol: deionized water 1: 1-5: 1-15; volume ratio solution a: solution B ═ 1: 0.5 to 2; the concentration of the ammonia water is 25-28 wt.%;
step two: preparation of a silica template: grinding the monodisperse silicon dioxide microspheres obtained in the previous step, adding the grinded silicon dioxide microspheres into ethanol to prepare 1-10 wt% of suspension, ultrasonically dispersing for 2-24 hours, standing at room temperature, volatilizing, drying, putting into a muffle furnace, and calcining at 500-700 ℃ for 12-18 hours to obtain a silicon dioxide sphere template in order;
step three: preparing three-dimensional ordered porous polypyrrole:
mixing the mixed solution at 0-5 ℃ with the ferric chloride solution at 0-5 ℃, reacting for 8-12 h at 0-5 ℃, then washing the solid with clear water, and soaking in the hydrofluoric acid solution for 7-10 days to obtain porous polypyrrole; the concentration of hydrofluoric acid is 10-60 wt.%;
wherein the mixed solution contains 0.3-0.5 mM sodium acetate and 0.3-0.5 mM pyrrole, and each 10mL of the mixed solution contains 0.3-2 g of silicon dioxide sphere template; the concentration of the ferric chloride solution is 0.3-0.5 mM; volume ratio mixed solution: 2-5: 2-5 of ferric chloride solution;
step four: preparing a zinc oxide/porous polypyrrole composite material:
adding porous polypyrrole into methanol, and performing ultrasonic dispersion for 3-5 hours at 40-55 ℃ to obtain a porous polypyrrole suspension; adding the suspension of the porous polypyrrole material into a methanol solution of zinc acetate, stirring for 20-60 min at 40-55 ℃, then dropwise adding a methanol solution of potassium hydroxide, stirring for 1-1.5 h at 40-55 ℃ after dropwise adding, centrifuging and drying to obtain the zinc oxide/porous polypyrrole composite material;
wherein 2-3 g of porous polypyrrole is added into 100-120 mL of methanol in the porous polypyrrole suspension; adding 2-6 g of zinc acetate into every 150-200 mL of methanol in the methanol solution of the zinc acetate; adding 0.5-2 g of potassium hydroxide into every 100-120 mL of methanol in the methanol solution of potassium hydroxide; volume ratio porous polypyrrole suspension: methanol solution of zinc acetate: the ratio of the methanol solution of potassium hydroxide is 10-12: 15-20: 10-12.
Step five: preparing a modified separator with a zinc oxide/porous polypyrrole coating; placing the prepared zinc oxide/porous polypyrrole composite material, a conductive agent and a binder into a mortar according to the mass ratio of 7-9: 0.5-2.5, grinding and mixing to form slurry, coating the slurry on a polypropylene/polyethylene film in a scraping mode, wherein the coating thickness is 10-20 micrometers, drying at 55-80 ℃ for 10-24 hours, and cutting the polypropylene/polyethylene film into thin sheets by using a cutting machine to obtain the modified diaphragm coated with the zinc oxide/porous polypyrrole.
The above-described method for preparing a modified separator having a zinc oxide/porous polypyrrole coating for a sodium-sulfur battery, wherein the raw materials involved are commercially available, and the equipment and process used are well known to those skilled in the art.
In the invention, in order to solve the problems of the sodium-sulfur battery, porous polypyrrole is prepared by taking silicon dioxide as a template, and a zinc oxide/porous polypyrrole composite material is obtained by further synthesis and is coated on the surface of a polypropylene/polyethylene film to serve as a diaphragm. Firstly, polypyrrole as a conductive polymer can remarkably shorten the transmission path of ions and improve the electrochemical reaction activity of the sodium-sulfur battery; secondly, the porous polypyrrole has a large specific surface area, so that polysulfide generated in the charging and discharging process can be effectively adsorbed, the polysulfide is prevented from being dissolved into electrolyte, and the utilization rate of active substances is improved; and when the zinc oxide is uniformly distributed on the surface of the porous polypyrrole, the oxygen-containing functional group of the zinc oxide has extremely strong adsorption performance, so that the adsorption of polysulfide can be further improved, and the shuttle effect is inhibited. And the porous polypyrrole has light weight and cannot influence the overall density of the sodium-sulfur battery.
Compared with the prior art, the method has the prominent substantive characteristics as follows:
1. the polypyrrole is used as a conductive polymer and has stronger conductive capability, and the active substance sulfur has extremely poor conductivity, so that the polypyrrole is coated on the surface of a common diaphragm to serve as a sodium-sulfur battery diaphragm, so that the conductivity of the active substance can be improved, and the utilization rate of the active substance and the battery capacity can be improved.
2. The porous polypyrrole has a large number of holes, so that the porous polypyrrole has a large specific surface area, and the polypyrrole contains a large number of nitrogen-containing functional groups, which is beneficial to the adsorption capacity of the polypyrrole on polysulfide generated in the charging and discharging processes of a sodium-sulfur battery, and inhibits the polysulfide from being dissolved in electrolyte and generating shuttle effect.
3. The zinc oxide has oxygen-containing functional groups, so that the adsorption effect on polysulfide can be enhanced, the shuttle effect is further inhibited, and the cycle performance of the sodium-sulfur battery is improved.
Compared with the prior art CN 104610569A, the zinc oxide/porous polypyrrole composite material related in the invention has a very large specific surface area due to the porous structure of polypyrrole and the nanometer size of zinc oxide particles, which has a very strong effect on adsorbing polysulfide. Secondly, the polypyrrole surface has rich nitrogen functional groups, and the zinc oxide particles have O2-And the zinc oxide/porous polypyrrole has strong adsorbability, so that the zinc oxide/porous polypyrrole has strong polysulfide adsorbability as a sodium-sulfur battery composite material. And thirdly, the porous polypyrrole is used as a conductive polymer, has excellent conductivity, is beneficial to reducing the internal impedance of the battery, and improves the transmission efficiency of electrons and ions, so that the utilization rate of active substances is improved, and the capacity and the cycling stability of the battery are improved. And the prior artCN 104610569 a has limited ability to adsorb polysulfide by adding sodium ion exchange resin, and requires addition of polyethylene oxide to reduce battery resistance, further reducing the proportion of sodium ion exchange resin adsorbing polysulfide, and further limiting the ability of the separator in CN 104610569 a to adsorb polysulfide in the prior art. Therefore, the electrochemical results obtained in the present invention show excellent cycle performance, with a first discharge capacity of 1400mAh g-1After 100 cycles, the capacity can still reach 930mAh g-1The sodium-sulfur battery with the blank diaphragm which is not coated with the zinc oxide/porous polypyrrole composite material shows extremely poor cycle performance, and the first discharge capacity is 1280mAh g-1After 100 cycles, the attenuation is 170mAh g-1Left and right. While the first discharge capacity in the prior art CN 104610569A is only 700mAh-1About, after 100 cycles, the capacity is only 590mAh-1Left and right.
In a word, the modified diaphragm coated with the zinc oxide/porous polypyrrole, prepared by the invention, has higher conductivity of the polypyrrole, is beneficial to promoting the transmission of electrons and ions, and improves the utilization rate of active substances, and the huge specific surface area provided by the porous structure of the polypyrrole, the nitrogen-containing functional group of the polypyrrole and the adsorption of the oxygen-containing functional group of the zinc oxide jointly adsorb polysulfide generated by reaction, so that the shuttle effect is inhibited, and the capacity, the rate capability and the cycle performance of a sodium-sulfur battery are improved, so that the modified diaphragm has good market prospect.
Drawings
FIG. 1 is an X-ray diffraction pattern of the zinc oxide/porous polypyrrole composite material prepared in example 1.
FIG. 2 is a scanning electron microscope photograph of the zinc oxide/porous polypyrrole composite prepared in example 1.
Fig. 3 is a cycle curve at a current density of 0.1C for the zinc oxide/porous polypyrrole composite prepared in example 1 as a separator material for a sodium-sulfur battery and a blank separator as a separator.
Detailed Description
Example 1
Firstly, preparing monodisperse silicon dioxide microspheres:
ethyl orthosilicate and absolute ethanol solution are mixed according to the ratio of 1: 5 are mixed together. In addition, ammonia, absolute ethanol and deionized water at a concentration of 25 wt.% were mixed in a ratio of 1: 2: 2 are mixed together. The two solutions were mixed as follows 1: mixing the materials together according to the proportion of 0.5, stirring the materials for 4 hours by using a magnetic stirrer, centrifuging the materials, and putting the materials into a vacuum drying oven for drying for 36 hours to obtain the silicon dioxide microspheres with the average diameter of 300 nm.
Step two, preparing a silicon dioxide template:
1000mg of prepared SiO are taken2Grinding the balls into powder, preparing a 5 wt% solution with ethanol, placing the solution in a beaker, and subjecting the beaker to ultrasonic treatment to make SiO2Uniformly dispersing the microspheres in ethanol, standing at room temperature, volatilizing, drying, placing the obtained white precipitate into a magnetic boat, and calcining at 500 deg.C in a muffle furnace for 12 hr to obtain regularly arranged SiO2And (5) template.
Step three, preparing three-dimensional ordered porous polypyrrole:
1000mg of the silica sphere template was weighed into a 200mL beaker, and then 20mL of a solution containing 0.3mM sodium acetate and 0.3mM pyrrole was added thereto, and the mixed solution was placed in a refrigerator and allowed to stand at 5 ℃. Then, a 0.3mM ferric chloride solution was prepared and was also placed in a refrigerator to stand at a temperature of 5 ℃. After standing for 2h, 20mL of ferric chloride solution was weighed and added to the mixed solution of silica, pyrrole and sodium acetate, and the resulting final mixed solution was placed in a refrigerator for reaction at 5 ℃ for 12 h. Finally, washing polypyrrole without the surface appearance of silicon dioxide by using clean water, soaking the polypyrrole in a hydrofluoric acid solution with the concentration of 20 wt.% to etch and dissolve for 10 days, and removing SiO2And (4) template to obtain the porous polypyrrole.
Fourthly, preparing the zinc oxide/porous polypyrrole composite material:
firstly, preparing a porous polypyrrole material suspension, weighing 2g of porous polypyrrole, adding into 100mL of methanol, and putting into an ultrasonic machine for ultrasonic treatment for 3h at 50 ℃ to form the suspension. Then 5.72g of zinc acetate was weighed and added to 150mL of methanol. 1.508g of potassium hydroxide was weighed and added to 100mL of methanol. Stirring the two solutions respectively, wherein the stirring time is 40min, and the stirring temperature is 50 ℃. And finally, adding the porous polypyrrole material suspension into a methanol solution of zinc acetate, and stirring for 60min at the stirring temperature of 50 ℃. Dropwise adding a methanol solution of potassium hydroxide into a mixed methanol solution of zinc acetate and the porous polypyrrole material, stirring for 1.5h after dropwise adding, wherein the stirring temperature is 50 ℃, and centrifuging and drying after the reaction is finished. The zinc oxide content of the obtained zinc oxide/porous polypyrrole composite material is 46.7 percent, but the zinc oxide content of the obtained zinc oxide/porous polypyrrole composite material is below 40 percent in the prior art.
And a fifth step of preparing a modified separator coated with zinc oxide/porous polypyrrole:
and (2) putting the prepared zinc oxide/porous polypyrrole composite material, a conductive agent and a binder into a mortar according to the mass ratio of 8: 1, grinding and mixing to obtain slurry, uniformly scraping and coating the slurry on a polyethylene film, drying at 60 ℃ for 12 hours to obtain a thin sheet, and cutting the thin sheet into sheets by using a cutting machine to obtain the modified diaphragm coated with the zinc oxide/porous polypyrrole.
Sixthly, preparing a battery positive plate and assembling a battery:
mixing sulfur and graphene according to the weight ratio of 2:1 is put into a mortar for grinding for 1 hour, then put into a reaction kettle and put into a furnace for heating for 12 hours at 155 ℃. And then placing the obtained sulfur/graphene composite material, a conductive agent and a binder in a mortar according to the mass ratio of 8: 1, grinding and mixing to obtain slurry, uniformly scraping and coating the slurry on a carbon-containing aluminum foil, drying at 60 ℃ for 24 hours, and pressing into a sheet by using a tablet press under the pressure of 5MPa to obtain the positive plate. And (3) taking the obtained sulfur/graphene as a positive electrode, a metal Li sheet as a negative electrode, a zinc oxide/porous polypyrrole coated modified diaphragm as a diaphragm, adding electrolyte, and assembling the battery in a glove box to obtain the button type CR2025 half-battery with the modified diaphragm. And adding electrolyte into the battery by taking the obtained sulfur/graphene as a positive electrode, a metal Li sheet as a negative electrode and a blank diaphragm as a diaphragm, and assembling the battery in a glove box to obtain the button type CR2025 half-battery with the blank diaphragm.
The prepared samples were subjected to electrochemical performance analysis (BTS-5V5mA, Newway).
FIG. 1 is an X-ray diffraction pattern of the zinc oxide/porous polypyrrole composite material prepared in example 1. As can be seen, there is a relatively broad peak at 26, which is the peak of polypyrrole. And the other peaks correspond to the peaks of the zinc oxide, thereby proving the successful synthesis of the zinc oxide/porous polypyrrole composite material.
FIG. 2 is a scanning electron microscope image of the zinc oxide/porous polypyrrole composite prepared in example 1. It can be seen that the obtained polypyrrole has uniformly and orderly distributed round holes with the average diameter of 300nm on the surface, and the zinc oxide cannot be observed due to the small size.
Fig. 3 is a cycle curve at a current density of 0.1C for the zinc oxide/porous polypyrrole modified separator prepared in example 1 as a separator for a sodium-sulfur battery. The first discharge capacity of the sodium-sulfur battery taking the zinc oxide/porous polypyrrole modified diaphragm as the diaphragm is 1400mAh g-1After 100 cycles, the capacity can still reach 930mAh g-1And excellent cycle stability is exhibited. The battery assembled by the blank diaphragm does not have a zinc oxide/porous polypyrrole interlayer, and the electrochemical performance shows that the first discharge specific capacity of the battery is only 1280mAh g-1Due to the serious shuttle effect and poor conductivity, the capacity of the battery rapidly decays, and the capacity decays to 215mAh g after only 4 times of circulation-1。
Example 2
The procedure is as in example 1 except that the first step of the reaction is carried out in a 1: 10 are mixed together. In addition, concentrated ammonia, absolute ethyl alcohol and deionized water were mixed in a ratio of 1: 3: 3 are mixed together. The two solutions were mixed together, stirred with a magnetic stirrer for 4h, centrifuged and placed in a vacuum oven to dry for 36 h. The obtained porous polypyrrole has pore diameter distribution of about 330nm, reduced specific surface area, reduced adsorption capacity, reduced zinc oxide content of 43.1%, and first discharge capacity of 1360mAh g of electrochemical data obtained by coating the porous polypyrrole on a diaphragm and assembling a battery-1Cycle ofThe specific discharge capacity obtained after the ring is cycled for 100 times is 881mAh g-1。
Example 3
The procedure is as in example 1 except that the first step of the reaction is carried out in a 1: 15 are mixed together. In addition, concentrated ammonia, absolute ethyl alcohol and deionized water were mixed in a ratio of 1: 5: 5 are mixed together. The two solutions were mixed together, stirred with a magnetic stirrer for 4h, centrifuged and placed in a vacuum oven to dry for 36 h. The obtained porous polypyrrole has pore diameter distribution of about 380nm, reduced specific surface area, reduced adsorption capacity, reduced zinc oxide content of 39.8%, and first discharge capacity of 1390mAh g of electrochemical data obtained by coating the porous polypyrrole on a diaphragm and assembling a battery-1And the specific discharge capacity obtained after 100 times of circulation is 850mAh g-1。
The invention is not the best known technology.

Claims (1)

1. A method for preparing a separator material for a sodium-sulfur battery, characterized in that the method comprises the steps of:
the method comprises the following steps: preparing monodisperse silicon dioxide microspheres; mixing ethyl orthosilicate and absolute ethyl alcohol to obtain a solution A; mixing ammonia water, absolute ethyl alcohol and deionized water to obtain a solution B; mixing the solution A and the solution B, stirring for 4-12 h, centrifuging, and drying in a vacuum drying oven for 36-48 h; obtaining monodisperse silicon dioxide microspheres;
wherein, in the solution A, the volume ratio of ethyl orthosilicate: anhydrous ethanol ═ 1: 5-15, in the solution B, the volume ratio of ammonia water: anhydrous ethanol: deionized water 1: 1-5: 1-15; volume ratio solution a: solution B ═ 1: 0.5 to 2; the concentration of the ammonia water is 25-28 wt.%;
step two: preparation of a silica template: grinding the monodisperse silicon dioxide microspheres obtained in the previous step, adding the grinded silicon dioxide microspheres into ethanol to prepare 1-10 wt% of suspension, ultrasonically dispersing for 2-24 hours, standing at room temperature, volatilizing, drying, putting into a muffle furnace, and calcining for 12-18 hours at 500-700 ℃ to obtain a silicon dioxide sphere template which is orderly arranged;
step three: preparing three-dimensional ordered porous polypyrrole:
mixing the mixed solution at 0-5 ℃ with the ferric chloride solution at 0-5 ℃, reacting for 8-12 h at 0-5 ℃, then washing the solid with clear water, and soaking in the hydrofluoric acid solution for 7-10 days to obtain porous polypyrrole; the concentration of hydrofluoric acid is 10-60 wt.%;
wherein the mixed solution contains 0.3-0.5 mM sodium acetate and 0.3-0.5 mM pyrrole, and each 10mL of the mixed solution contains 0.3-2 g of silicon dioxide sphere template; the concentration of the ferric chloride solution is 0.3-0.5 mM; volume ratio mixed solution: 2-5: 2-5 of ferric chloride solution;
step four: preparing a zinc oxide/porous polypyrrole composite material:
adding porous polypyrrole into methanol, and performing ultrasonic dispersion for 3-5 hours at 40-55 ℃ to obtain a porous polypyrrole suspension; adding the suspension of the porous polypyrrole material into a methanol solution of zinc acetate, stirring for 20-60 min at 40-55 ℃, then dropwise adding a methanol solution of potassium hydroxide, stirring for 1-1.5 h at 40-55 ℃ after dropwise adding, centrifuging and drying to obtain the zinc oxide/porous polypyrrole composite material;
wherein 2-3 g of porous polypyrrole is added into 100-120 mL of methanol in the porous polypyrrole suspension; adding 2-6 g of zinc acetate into every 150-200 mL of methanol in the methanol solution of the zinc acetate; adding 0.5-2 g of potassium hydroxide into every 100-120 mL of methanol in the methanol solution of potassium hydroxide; volume ratio porous polypyrrole suspension: methanol solution of zinc acetate: a methanol solution of potassium hydroxide is 10-12: 15-20: 10-12;
step five: preparing a modified separator with a zinc oxide/porous polypyrrole coating; placing the prepared zinc oxide/porous polypyrrole composite material, a conductive agent and a binder into a mortar according to the mass ratio of 7-9: 0.5-2.5, grinding and mixing to form slurry, coating the slurry on a polypropylene/polyethylene film in a scraping mode, wherein the coating thickness is 10-20 micrometers, drying at 55-80 ℃ for 10-24 hours, and cutting the polypropylene/polyethylene film into thin sheets by using a cutting machine to obtain the modified diaphragm coated with the zinc oxide/porous polypyrrole.
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