CN110635122A - Ultrathin folded carbon layer coated ZnS composite interlayer material and preparation method and application thereof - Google Patents
Ultrathin folded carbon layer coated ZnS composite interlayer material and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses an ultrathin folded carbon layer coated zinc sulfide composite interlayer material, a preparation method and application thereof, wherein the material consists of zinc sulfide nano microspheres and a carbon layer coated with zinc sulfide on the surface of the zinc sulfide nano microspheres, the average size of the zinc sulfide nano microspheres is 250nm, the average thickness of the carbon layer is 8nm, and the carbon layer presents a folded appearance similar to a graphene sheet. The preparation method comprises the following steps: preparing zinc sulfide nano microspheres; dispersing zinc sulfide nano microspheres in a mixed solution of water, absolute ethyl alcohol and ammonia water, adding a silicon source, stirring, then adding resorcinol and formaldehyde solution, and stirring the whole mixed solution at a certain temperature for a certain time to obtain a first intermediate product; carbonizing the first intermediate product at a certain temperature for a certain time under the protective atmosphere of a tube furnace to obtain a second intermediate product; and etching the second intermediate product with sodium hydroxide solution at a certain temperature for a certain time to obtain a final product. The zinc sulfide coated by the folded ultrathin carbon layer is used as the interlayer material of the lithium-sulfur battery, so that high cycle stability and high rate performance are realized.
Description
Technical Field
The invention belongs to the technical field of lithium-sulfur battery diaphragm modified sandwich materials, and particularly relates to an ultrathin wrinkled carbon film coated zinc sulfide composite sandwich material, and a preparation method and application thereof.
Background
In recent years, the demand for high energy density, long cycle life portable electronic devices has increased dramatically, and the energy density of conventional lithium ion batteries has faced a limit. Lithium-sulfur batteries are attracting attention as a new generation energy storage system with great development prospects due to the advantages of high energy density (2600Wh/kg), high specific capacity (1673mAh/g), low price, no toxicity and the like. However, lithium sulfur batteries have several disadvantages in practical applications: 1) low conductivity of sulfur and lithium sulfide; 2) bulk changes due to density differences between the sulfur of the cathode material and the lithium sulfide of the final product; 3) the shuttling of lithium polysulfides (shuttle effect) causes a rapid capacity decay.
Most of the existing positive electrode materials start from the structural design of carbon materials or the optimization of the electrical conductivity of polar materials, however, the preparation process of the positive electrode materials is complex and expensive, so that the introduction of an interlayer material between the positive electrode material and a diaphragm to prevent the shuttle effect is a more effective and convenient method. Research shows that the carbon-based interlayer material not only can serve as a macroscopic physical barrier for blocking the shuttling of lithium polysulfide, but also can serve as a second current collector to increase the conductive area of the whole positive electrode material, and the introduction of the polar inorganic substance on the carbon-based material can enhance the adsorption effect of the separator on the lithium polysulfide. Therefore, the method effectively compounds the carbon-based material and the polar substance to construct a 3D conductive network, block shuttle of lithium polysulfide, ensure enough pore size for lithium ion transmission and enhance redox reaction kinetics, and is an effective way for solving shuttle effect of the lithium-sulfur battery and realizing cycle stability and excellent rate performance.
Disclosure of Invention
The invention aims to provide an ultrathin wrinkled carbon layer coated zinc sulfide composite interlayer material and a preparation method thereof.
In order to achieve the above object, the present invention adopts the following technical solutions.
An ultrathin wrinkled carbon layer coated zinc sulfide composite interlayer material is composed of zinc sulfide nano microspheres and a carbon layer coated with zinc sulfide on the surface of the zinc sulfide nano microspheres, the average size of the zinc sulfide nano microspheres is 250nm, the average thickness of the carbon layer coated with zinc sulfide is 8nm, and the carbon layer is in a wrinkled shape similar to a graphene sheet.
The preparation method of the ultrathin wrinkled carbon layer coated zinc sulfide composite interlayer material comprises the following steps:
s1: firstly, uniformly dispersing zinc acetate and thiourea in water, then adding Arabic gum and uniformly stirring to obtain a mixed solution, and carrying out thermal reaction on the mixed solution in a hydrothermal reaction kettle to obtain zinc sulfide nano microspheres;
s2: dispersing the zinc sulfide nano microspheres prepared in the step S1 in a mixed solution of water, absolute ethyl alcohol and ammonia water, adding a certain amount of silicon source, stirring for a certain time, then adding a certain amount of resorcinol and formaldehyde solution, and stirring the whole mixed solution at a certain temperature for a certain time to obtain a first intermediate product;
s3: carbonizing the first intermediate product prepared in the step S2 at a certain temperature for a certain time under the protective atmosphere of a tube furnace to obtain a second intermediate product;
s4: and (3) etching the second intermediate product prepared in the step S3 at a certain temperature by using a sodium hydroxide solution for a certain time to obtain the final product of the ultrathin wrinkled carbon-layer-coated zinc sulfide composite interlayer material.
Furthermore, the mass ratio of the zinc acetate to the thiourea in S1 is 1: 1-1: 2, the molar concentration of zinc ions in the mixed solution is 0.1-0.2 mol/L, and the mass concentration of the Arabic gum in the mixed solution is 10-20 g/L.
Further, the thermal reaction in S1 is carried out at 100-200 ℃ for 10-30 h.
Further, the volume ratio of the absolute ethyl alcohol to the water in the step S2 is 5: 1-10: 1, the volume percentage concentration of ammonia water is 2-5%, the mass concentration of zinc sulfide is 0.1-10 g/L, the volume percentage concentration of a silicon source is 1-5%, the mass concentration of resorcinol is 0.1-5 g/L, and the volume percentage concentration of a formaldehyde solution is 0.01-0.1%, wherein the volume percentage concentration is that the volume of the component accounts for the volume of a mixed solution of water, absolute ethyl alcohol and ammonia water in S2, the mass concentration is the mass of the component in a unit volume of the mixed solution, and the mixed solution is the mixed solution of water, absolute ethyl alcohol and ammonia water in S2.
Further, adding a silicon source in the step S2, and stirring for 5-50 minutes at room temperature; and stirring the whole mixed solution in the S2 at room temperature for 12-48 h.
Further, in S2, the silicon source is methyl orthosilicate, ethyl orthosilicate, or propyl orthosilicate.
Further, the protective atmosphere in S3 is argon or nitrogen; the temperature in S3 is 700-900 ℃, and the time is 2-8 h.
Further, the concentration of the sodium hydroxide solution in S4 is 0.5-5 mol/L, the etching temperature is 40-80 ℃, and the etching time is 10-30 hours.
The ultrathin wrinkled carbon layer coated zinc sulfide composite interlayer material is used as an interlayer material of a lithium-sulfur battery.
The invention has the beneficial effects that: the preparation method and the process are simple and safe, the equipment requirement is not high, the cost is low, the phase of the prepared product is analyzed and displayed by X-ray diffraction (XRD) spectrum diffraction peak, the diffraction peak is from the characteristic peak of pure zinc sulfide and carbon layer diffraction, and is displayed by Transmission Electron Microscope (TEM) and Scanning Electron Microscope (SEM) photos, the average size of the zinc sulfide microsphere is 250nm, the average thickness of the carbon layer coating the zinc sulfide is only 8nm, and the ultrathin carbon layer presents the wrinkle appearance similar to a graphene sheet after being etched. The ultrathin folded carbon layer coated zinc sulfide composite material enables an interlayer to have the effects of conductivity and macroscopic physical barrier, and can also have the effect of adsorbing lithium polysulfide, meanwhile, the redox kinetics is enhanced, the initial discharge capacity under 0.2C current reaches 1370.3mAh/g, the discharge capacity and the cycle stability of the zinc sulfide coated by the folded carbon layer at the first circle are better than those of a pure carbon layer and zinc sulfide under 0.5C current, the discharge capacity of 685mHh/g and the coulombic efficiency of 96.15% can be still maintained after 600 circles of 1C cycle, and the fact that the folded ultrathin coated zinc sulfide coated by the folded carbon layer as the interlayer material of the lithium sulfur battery is favorable for achieving high cycle stability and high rate performance is strongly proved.
Drawings
FIG. 1 is a schematic diagram of a method for preparing an ultra-thin wrinkled carbon-coated zinc sulfide composite interlayer material according to an embodiment of the present invention;
FIG. 2 is an X-ray diffraction (XRD) pattern of the pleated ultra-thin carbon layer coated zinc sulfide interlayer material prepared in example 2 according to an embodiment of the present invention;
FIG. 3 is a Scanning Electron Microscope (SEM) image of the wrinkled ultrathin carbon layer coated zinc sulfide interlayer material prepared in example 2 according to the embodiment of the invention;
FIG. 4 is a Transmission Electron Microscope (TEM) image of the wrinkled ultrathin carbon-coated zinc sulfide interlayer material prepared in example 2 according to the embodiment of the invention;
fig. 5 shows the cycle performance of the wrinkled ultra-thin carbon layer coated zinc sulfide interlayer material and the interlayer material made of pure carbon layer and pure zinc sulfide under 0.5C discharge, prepared in example 2 according to the embodiment of the present invention;
fig. 6 shows the cycle performance of the wrinkled ultra-thin carbon layer coated zinc sulfide interlayer material prepared in example 2 under 1C discharge in the embodiment of the present invention.
Detailed Description
The present invention will be described in further detail with reference to the following detailed description and accompanying drawings. It should be emphasized that the following description is merely exemplary in nature and is not intended to limit the scope of the invention or its application.
It should be noted that, in all the following examples: analytical reagents were used except as indicated.
XRD measurement of the sample was carried out with a Bruke D8 advanced X-ray diffractometer at a scanning speed of 10 DEG min-1。
SEM measurement of sample Using ZEISS
55 scanning electron microscope.
TEM measurements of the samples were performed using a TEOL-201 transmission electron microscope.
The cycle performance of the sample under discharge was tested using a CT2001A blue cell tester.
As used herein, room temperature means 20 to 35 ℃ and preferably 23 to 30 ℃.
As shown in fig. 1, the invention provides a preparation method of an ultrathin wrinkled carbon layer coated zinc sulfide composite interlayer material, which comprises the following steps:
s1: firstly, uniformly dispersing zinc acetate and thiourea in water, then adding Arabic gum and uniformly stirring to obtain a mixed solution, carrying out thermal reaction on the mixed solution in a hydrothermal reaction kettle, and carrying out suction filtration and washing to obtain a zinc sulfide nano microsphere filter cake;
s2: dispersing the zinc sulfide nano microspheres prepared in the step S1 in a mixed solution of water, absolute ethyl alcohol and ammonia water, adding a certain amount of silicon source, stirring for a certain time, then adding a certain amount of resorcinol and formaldehyde solution, stirring the whole mixed solution at a certain temperature for a certain time to obtain orange precipitate, centrifuging, collecting and drying to obtain a first intermediate product;
s3: carbonizing the first intermediate product prepared in the step S2 at a certain temperature for a certain time under the protective atmosphere of a tube furnace to obtain a second intermediate product;
s4: and (3) etching the second intermediate product prepared in the step S3 at a certain temperature by using a sodium hydroxide solution for a certain time to obtain the final product of the ultrathin wrinkled carbon-layer-coated zinc sulfide composite interlayer material.
Wherein, in some embodiments, the mass ratio of the zinc acetate to the thiourea in S1 is 1: 1-1: 2, the molar concentration of zinc ions in the mixed solution is 0.1-0.2 mol/L, the mass concentration of the gum arabic in the mixed solution is 10-20 g/L, and the thermal reaction in S1 is at 100-200 ℃ for 10-30 h. For example, step S1 may preferably include the steps of:
s11: under the stirring state, sequentially adding zinc acetate and thiourea into a reaction bottle, and then adding Arabic gum;
s12: and (4) pouring the solution prepared in the step (S11) into a tetrafluoroethylene tank, placing the tetrafluoroethylene tank into a hydrothermal reaction kettle, reacting for 10-30 h at 100-200 ℃, and naturally cooling the hydrothermal reaction kettle to room temperature after the reaction is finished to obtain the reaction product zinc sulfide nano microspheres.
In some embodiments, in S2, the volume ratio of absolute ethanol to water is 5: 1-10: 1, the volume percentage concentration of ammonia water is 2-5%, the mass concentration of zinc sulfide is 0.1-10 g/L, the volume percentage concentration of a silicon source is 1-5%, the mass concentration of resorcinol is 0.1-5 g/L, and the volume percentage concentration of a formaldehyde solution is 0.01-0.1%, wherein the volume percentage concentration is that the volume of the component accounts for the volume of a mixed solution of water, absolute ethyl alcohol and ammonia water in S2, the mass concentration is the mass of the component in a unit volume of the mixed solution, and the mixed solution is the mixed solution of water, absolute ethyl alcohol and ammonia water in S2. For example, step S2 may preferably include the steps of:
s21: adding the mixture into a stirring state, wherein the volume ratio is 5: 1-10: 1, a water-alcohol mixed solution and an ammonia water solution with the volume percentage concentration of 2-5 percent;
s22: adding the zinc sulfide microspheres prepared in the step S1 and a silicon source with the volume percentage concentration of 1% -5% into the solution in sequence, and stirring for 5-50 minutes at room temperature; the silicon source can be methyl orthosilicate, ethyl orthosilicate or propyl orthosilicate;
s23: adding resorcinol with the mass concentration of 0.1-5 g/L and formaldehyde solution with the volume percentage concentration of 0.01-0.1% into the solution prepared in the S22;
s24: and (3) reacting the solution prepared in the step S23 at room temperature for 12-48 h, centrifuging, and drying at 80 ℃ to obtain a first intermediate product.
In some embodiments, the protective atmosphere in S3 may be one of argon or nitrogen. The certain temperature is 700-900 ℃ and the certain time is 2-8 h.
In some embodiments, the concentration of the sodium hydroxide solution in step S4 is 0.5-5 mol/L, the etching temperature is 40-80 ℃, and the etching time is 10-30 hours.
The invention is further illustrated by the following specific examples.
Example 1
S1: under the stirring state, 0.015mol of zinc acetate and 0.03mol of thiourea are sequentially added into 100ml of water solution, and then 2g of Arabic gum is added to obtain a mixed solution; pouring the mixed solution into a tetrafluoroethylene tank, placing the tetrafluoroethylene tank into a hydrothermal reaction kettle, reacting for 30 hours at 200 ℃, and naturally cooling the hydrothermal reaction kettle to room temperature after the reaction is finished to obtain a reaction product, namely the zinc sulfide nano microspheres;
s2: dispersing the prepared zinc sulfide nano-microspheres of 0.2g in a mixed solution of 10ml of water, 100ml of alcohol and 5ml of ammonia water, adding 5ml of methyl orthosilicate, and stirring at room temperature for 50 min; adding 100mg of resorcinol and 100 mu L of formaldehyde solution into the solution, stirring the whole mixed solution at room temperature for 24 hours to obtain orange precipitate, centrifuging, collecting, and drying at 80 ℃ to obtain a first intermediate product;
s3: carbonizing the collected first intermediate product at 700 ℃ for 2 hours in a nitrogen protective atmosphere of a tube furnace to obtain a second intermediate product;
s4: and etching the second intermediate product by using 100ml of 1.8mol/L sodium hydroxide solution at 80 ℃ for 24 hours to obtain the final product, namely the wrinkled ultrathin carbon layer coated zinc sulfide.
Example 2
S1: under the stirring state, 0.015mol of zinc acetate and 0.028mol of thiourea are sequentially added into 100ml of aqueous solution, and then 1.8g of Arabic gum is added to obtain mixed solution; pouring the mixed solution into a tetrafluoroethylene tank, placing the tetrafluoroethylene tank into a hydrothermal reaction kettle, reacting for 24 hours at 180 ℃, and naturally cooling the hydrothermal reaction kettle to room temperature after the reaction is finished to obtain a reaction product, namely the zinc sulfide nano microspheres;
s2: dispersing the prepared 0.18g of zinc sulfide nano microspheres in a mixed solution of 10ml of water, 90ml of alcohol and 4ml of ammonia water, adding 4ml of methyl orthosilicate, and stirring at room temperature for 30 min; adding 80mg of resorcinol and 80 mu L of formaldehyde solution into the solution, stirring the whole mixed solution at room temperature for 20 hours to obtain orange precipitate, centrifuging, collecting, and drying at 80 ℃ to obtain a first intermediate product;
s3: carbonizing the collected first intermediate product at 750 ℃ for 2 hours in a nitrogen protective atmosphere of a tubular furnace to obtain a second intermediate product;
s4: and etching the second intermediate product by using 100ml of 2mol/L sodium hydroxide solution at 75 ℃ for 22 hours to obtain the final product, namely the wrinkled ultrathin carbon layer coated zinc sulfide.
The prepared product is shown in figure 2, the diffraction peak analysis of the phase by an X-ray diffraction (XRD) spectrum shows that the diffraction peak is from pure zinc sulfide and the characteristic peak of the carbon layer caused by diffraction, as shown in figures 3 and 4, the Transmission Electron Microscope (TEM) and Scanning Electron Microscope (SEM) pictures show that the average size of the zinc sulfide microspheres is 250nm, the average thickness of the carbon layer coated with zinc sulfide is only 8nm, and the ultrathin carbon layer shows the wrinkle appearance similar to a graphene sheet after being etched. The initial discharge capacity of the zinc sulfide coated by the wrinkled carbon under the current of 0.2C reaches 1370.3mAh/g, as shown in fig. 5 and fig. 6, the discharge capacity and the cycle stability of the zinc sulfide coated by the wrinkled carbon at the first cycle are better than those of a pure carbon layer and zinc sulfide under the current of 0.5C, the discharge capacity of 685mHh/g and the coulombic efficiency of 96.15% can be still maintained after 600 cycles of 1C, and the fact that the zinc sulfide coated by the wrinkled ultrathin carbon layer is adopted as the lithium-sulfur battery interlayer material is strongly proved to be beneficial to achieving high cycle stability and high rate performance.
Example 3
S1: under the stirring state, 0.015mol of zinc acetate and 0.024mol of thiourea are sequentially added into 100ml of water solution, and then 1.6g of Arabic gum is added to obtain mixed solution; pouring the mixed solution into a tetrafluoroethylene tank, placing the tetrafluoroethylene tank into a hydrothermal reaction kettle, reacting for 12 hours at 140 ℃, and naturally cooling the hydrothermal reaction kettle to room temperature after the reaction is finished to obtain a reaction product, namely the zinc sulfide nano microspheres;
s2: dispersing the prepared 0.16g of zinc sulfide nano microspheres in a mixed solution of 10ml of water, 80ml of alcohol and 3ml of ammonia water, adding 3ml of ethyl orthosilicate, and stirring at room temperature for 20 min; adding 70mg of resorcinol and 70 mu L of formaldehyde solution into the solution, stirring the whole mixed solution at room temperature for 18 hours to obtain orange precipitate, centrifugally collecting, and drying at 80 ℃ to obtain a first intermediate product;
s3: carbonizing the collected first intermediate product at 750 ℃ for 4 hours in a nitrogen protective atmosphere of a tubular furnace to obtain a second intermediate product;
s4: and etching the second intermediate product by using 100ml of 2mol/L sodium hydroxide solution at 70 ℃ for 20 hours to obtain the final product, namely the wrinkled ultrathin carbon layer coated zinc sulfide.
Example 4
S1: under the stirring state, 0.015mol of zinc acetate and 0.020mol of thiourea are sequentially added into 100ml of water solution, and then 1.5g of Arabic gum is added to obtain a mixed solution; pouring the mixed solution into a tetrafluoroethylene tank, placing the tetrafluoroethylene tank into a hydrothermal reaction kettle, reacting for 12 hours at 120 ℃, and naturally cooling the hydrothermal reaction kettle to room temperature after the reaction is finished to obtain a reaction product, namely the zinc sulfide nano microspheres;
s2: dispersing the prepared 0.14g of zinc sulfide nano microspheres in a mixed solution of 10ml of water, 60ml of absolute ethyl alcohol and 3ml of ammonia water, adding 3ml of ethyl orthosilicate, and stirring at room temperature for 20 min; adding 60mg of resorcinol and 60 mu L of formaldehyde solution into the solution, stirring the whole mixed solution at room temperature for 16 hours to obtain orange precipitate, centrifugally collecting, and drying at 80 ℃ to obtain a first intermediate product;
s3: carbonizing the collected first intermediate product at 800 ℃ for 2 hours in a tube furnace argon protective atmosphere to obtain a second intermediate product;
s4: and etching the second intermediate product by using 100ml of 3mol/L sodium hydroxide solution at 65 ℃ for 16 hours to obtain the final product, namely the wrinkled ultrathin carbon layer coated zinc sulfide.
Example 5
S1: under the stirring state, 0.015mol of zinc acetate and 0.015mol of thiourea are sequentially added into 100ml of water solution, and then 1.4g of Arabic gum is added to obtain a mixed solution; pouring the mixed solution into a tetrafluoroethylene tank, placing the tetrafluoroethylene tank into a hydrothermal reaction kettle, reacting for 10 hours at 100 ℃, naturally cooling the hydrothermal reaction kettle to room temperature after the reaction is finished to obtain a reaction product zinc sulfide nano microsphere, and performing suction filtration and washing to obtain a zinc sulfide nano microsphere filter cake;
s2: dispersing 0.12g of the prepared zinc sulfide nano microspheres in a mixed solution of 10ml of water, 50ml of absolute ethyl alcohol and 3ml of ammonia water, adding 2ml of propyl orthosilicate, and stirring at room temperature for 20 min; adding 50mg of resorcinol and 50 mu L of formaldehyde solution into the solution, stirring the whole mixed solution at room temperature for 12 hours to obtain orange precipitate, centrifugally collecting, and drying at 80 ℃ to obtain a first intermediate product;
s3: carbonizing the collected first intermediate product at 900 ℃ for 4 hours in the protective atmosphere of argon in a tube furnace to obtain a second intermediate product;
s4: and etching the second intermediate product by using 100ml of 4mol/L sodium hydroxide solution at 60 ℃ for 12 hours to obtain the final product, namely the wrinkled ultrathin carbon layer coated zinc sulfide.
The foregoing is a more detailed description of the invention in connection with specific/preferred embodiments and is not intended to limit the practice of the invention to those descriptions. It will be apparent to those skilled in the art that various substitutions and modifications can be made to the described embodiments without departing from the spirit of the invention, and such substitutions and modifications are to be considered as within the scope of the invention.
Claims (10)
1. The ultrathin wrinkled carbon layer coated zinc sulfide composite interlayer material is characterized by consisting of zinc sulfide nano microspheres and a carbon layer coated with zinc sulfide on the surface of the zinc sulfide nano microspheres, wherein the average size of the zinc sulfide nano microspheres is 250nm, the average thickness of the carbon layer coated with zinc sulfide is 8nm, and the carbon layer is in a wrinkled shape similar to a graphene sheet.
2. The method of preparing an ultra-thin pleated carbon layer coated zinc sulfide composite sandwich material as claimed in claim 1, comprising the steps of:
s1: firstly, uniformly dispersing zinc acetate and thiourea in water, then adding Arabic gum and uniformly stirring to obtain a mixed solution, and carrying out thermal reaction on the mixed solution in a hydrothermal reaction kettle to obtain zinc sulfide nano microspheres;
s2: dispersing the zinc sulfide nano microspheres prepared in the step S1 in a mixed solution of water, absolute ethyl alcohol and ammonia water, adding a certain amount of silicon source, stirring for a certain time, then adding a certain amount of resorcinol and formaldehyde solution, and stirring the whole mixed solution at a certain temperature for a certain time to obtain a first intermediate product;
s3: carbonizing the first intermediate product prepared in the step S2 at a certain temperature for a certain time under the protective atmosphere of a tube furnace to obtain a second intermediate product;
s4: and (3) etching the second intermediate product prepared in the step S3 at a certain temperature by using a sodium hydroxide solution for a certain time to obtain the final product of the ultrathin wrinkled carbon-layer-coated zinc sulfide composite interlayer material.
3. The method according to claim 2, wherein the mass ratio of the zinc acetate to the thiourea in S1 is 1:1 to 1:2, the molar concentration of zinc ions in the mixed solution is 0.1 to 0.2mol/L, and the mass concentration of the gum arabic in the mixed solution is 10 to 20 g/L.
4. The method according to claim 2, wherein the thermal reaction in S1 is carried out at 100-200 ℃ for 10-30 h.
5. The method according to claim 2, wherein the volume ratio of the absolute ethanol to the water in S2 is 5: 1-10: 1, the volume percentage concentration of ammonia water is 2-5%, the mass concentration of zinc sulfide is 0.1-10 g/L, the volume percentage concentration of a silicon source is 1-5%, the mass concentration of resorcinol is 0.1-5 g/L, and the volume percentage concentration of a formaldehyde solution is 0.01-0.1%, wherein the volume percentage concentration is that the volume of the component accounts for the volume of a mixed solution of water, absolute ethyl alcohol and ammonia water in S2, the mass concentration is the mass of the component in a unit volume of the mixed solution, and the mixed solution is the mixed solution of water, absolute ethyl alcohol and ammonia water in S2.
6. The method according to claim 2, wherein the silicon source is added in S2 and stirred at room temperature for 5-50 minutes; and stirring the whole mixed solution in the S2 at room temperature for 12-48 h.
7. The method according to claim 2, wherein the protective atmosphere in S3 is argon or nitrogen; the temperature in S3 is 700-900 ℃, and the time is 2-8 h.
8. The preparation method according to claim 2, wherein the concentration of the sodium hydroxide solution in S4 is 0.5-5 mol/L, the etching temperature is 40-80 ℃, and the etching time is 10-30 hours.
9. The method according to any one of claims 2 to 8, wherein the silicon source in S2 is methyl orthosilicate, ethyl orthosilicate, or propyl orthosilicate.
10. Use of the ultra-thin pleated carbon layer coated zinc sulfide composite interlayer material of claim 1 as an interlayer material for a lithium sulfur battery.
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