CN115911340A - Sulfur-carrying layered poplar charcoal/polyaniline composite positive electrode material and preparation method and application thereof - Google Patents
Sulfur-carrying layered poplar charcoal/polyaniline composite positive electrode material and preparation method and application thereof Download PDFInfo
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- 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
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Abstract
The invention discloses a sulfur-carrying layered poplar charcoal/polyaniline composite material for a lithium-sulfur battery anode and a preparation method thereof, belonging to the field of lithium-sulfur batteries. Catalyzing poplar fiber to carbonize through p-toluenesulfonic acid to obtain a three-dimensional sulfur-carrying layered poplar carbon material with oxygen-containing functional groups on the surface; polyaniline is generated on the surface of the sulfur-carrying layered poplar wood charcoal through in-situ polymerization; by sublimation and deposition of sulfur simple substances, sulfur is distributed on the surface of the three-dimensional porous carbon under the action of surface oxygen functional groups. The obtained sulfur-carrying layered poplar charcoal/polyaniline composite material is used as the positive electrode of the lithium-sulfur batteryThe material has simple preparation process and high specific capacity (about 830.96 mAhg) ‑1 ) And better cycle stability.
Description
Technical Field
The invention belongs to the technical field of biomass charcoal material preparation, relates to a biomass layered carbon anode material and a preparation method thereof, and particularly relates to a sulfur-carrying layered poplar charcoal/polyaniline composite material for a lithium-sulfur battery anode and a preparation method thereof.
Background
The sulfur is found to be rich in nature, the sulfur used as the lithium battery anode material has the advantages of environmental protection, low price and the like, and the lithium-sulfur battery has excellent theoretical specific capacity (1675 mAhg) -1 ) Energy density (2600 Whkg) -1 ) And the like. This makes lithium sulfur batteries a growing research hotspot for a new generation of clean energy storage devices with high energy density. However, volume expansion during cycling of lithium sulfur cells (-80%), polysulfide dissolution, and soluble polysulfide shuttling effect have hindered the commercial application of Li-S cells.
The conventional positive electrode material of the common lithium-sulfur battery comprises porous carbon, carbon nanotubes, carbon fibers or graphene and the like, and the application of the reagent of the double-electrode layer material is limited due to low energy density and single electricity storage mechanism. Therefore, how to prepare a composite electrode material with synergistic effect by using the electric double layer capacitor and the pseudocapacitor material to improve the overall electrochemical performance of the battery is a technical problem to be solved urgently at present.
Disclosure of Invention
The invention aims to solve the problems in the prior art and provides a nitrogen-containing conjugated microporous polymer/carbon composite positive electrode material for a lithium-sulfur battery and a preparation method thereof. The method is simple and easy to implement, is suitable for application, and is a novel method for directly synthesizing the sulfur-carrying layered poplar charcoal/polyaniline composite material by a one-step method under mild conditions; the prepared positive electrode material has good conductivity and strong bonding energy with polysulfide, and can improve the cycle stability of the battery.
Compared with carbon and metal and its oxidation coating technology, polyaniline, which is a typical conductive polymer, has the advantages of easy low cost, easy synthesis and high electrochemical activity, and is often used as a pseudocapacitance material. Research shows that besides the pi conjugated structure, the nitrogen-containing functional group in the main chain of the conductive polymer can be used as an active site or a reactive group for limiting polysulfide shuttle. Therefore, polyaniline is adopted to carry out surface modification on sulfur-carrying layered poplar charcoal, and the polyaniline not only can be used as a sulfur elemental electron conductivity enhancer, but also can inhibit polysulfide shuttling phenomenon.
According to the invention, sulfur-carrying layered poplar charcoal is combined with polyaniline to construct a multilayer conductive network structure, and sulfur simple substance and polysulfide are coated, so that the electron transmission rate can be enhanced, the shuttle effect of polysulfide can be inhibited, the polysulfide can be limited in the anode, the conversion of polysulfide is accelerated, and the battery performance is improved.
In order to achieve the purpose, the invention adopts the following technical scheme:
a preparation method of a sulfur-carrying layered poplar charcoal/polyaniline composite positive electrode material specifically comprises the following steps:
(1) Immersing poplar chips in a p-toluenesulfonic acid solution, heating in a water bath, then washing with water and performing ultrasonic treatment to obtain poplar fibers for later use;
(2) Adding p-toluenesulfonic acid and deionized water into the poplar fiber treated in the step (1), carbonizing in a reaction kettle, and dialyzing, ultrasonically treating and freeze-drying with deionized water to obtain sulfur-carrying layered poplar charcoal for later use;
(3) Ultrasonically dispersing the sulfur-carrying layered poplar charcoal treated in the step (2) in hydrochloric acid, respectively dropwise adding aniline and adding ammonium persulfate, carrying out in-situ polymerization on the surface of the sulfur-carrying layered poplar charcoal to form polyaniline, then washing with deionized water and ethanol, and freeze-drying to obtain a sulfur-carrying layered poplar charcoal/polyaniline composite material for later use;
(4) And (3) removing moisture from the elemental sulfur and the sulfur-carrying layered poplar charcoal/polyaniline composite material prepared in the step (3), reacting in a reaction kettle in a nitrogen atmosphere, and heating to obtain the sulfur-carrying layered poplar charcoal/polyaniline composite positive electrode material.
Optionally, the step (3) can be replaced by:
and (3) mixing and grinding the sulfur-loaded layered poplar charcoal treated in the step (2) with polyaniline to obtain the sulfur-loaded layered poplar charcoal/polyaniline composite material.
Optionally, the water bath heating temperature in the step (1) is 70-90 ℃, and the water bath heating time is 5-7 h.
Optionally, in the step (2), adding p-toluenesulfonic acid and deionized water in a volume ratio of 1.
Optionally, in the step (3), the sulfur-carrying layered poplar charcoal/polyaniline is specifically prepared as follows:
preparing 1mol/L hydrochloric acid, dispersing 100-500 mg of sulfur-carrying layered poplar charcoal in 100-500 mL of hydrochloric acid by ultrasound for 5-15 min, dropwise adding 50-500 μ L of aniline into the solution in an ice-water bath, stirring for 20-40 min for uniform dispersion, dissolving 1-3 g of ammonium persulfate in 10-100 mL of hydrochloric acid, slowly dropwise adding 2-20 mL of dissolved ammonium persulfate solution into the aniline/sulfur-carrying layered poplar charcoal hydrochloric acid solution, reacting for 1-3 h in the ice-water bath, after the reaction is finished, washing with deionized water and ethanol, and freeze-drying to obtain the sulfur-carrying layered poplar charcoal/polyaniline composite material.
Optionally, in the step (4), the mass ratio of the sulfur simple substance to the sulfur-carrying layered poplar charcoal/polyaniline composite material is 5:5-7:3, and the moisture is removed at 50-80 ℃.
Optionally, in the step (4), the reaction and heating operation steps in the reaction kettle are as follows: reacting for 10-12 h at 150-160 ℃ in a reaction kettle, and then heating for 30min at 200-220 ℃.
Preferably, the preparation method of the sulfur-carrying layered poplar charcoal/polyaniline composite positive electrode material comprises the following steps:
taking 18g of p-toluenesulfonic acid and 2mL of ionized water, putting into the inner liner of a reaction kettle, adding 1g of treated poplar fiber, tightly sealing the reaction kettle, and carrying out hydrothermal carbonization for 10 hours in an oven at 220 ℃; dialyzing with deionized water, ultrasonic treating, and lyophilizing to obtain sulfur-carrying layered poplar charcoal.
Preparing 1mol/L hydrochloric acid, dispersing 100mg of sulfur-carrying layered poplar wood charcoal in 100mL of hydrochloric acid by ultrasound for 10min, dropwise adding 92 mu L of aniline into the solution in an ice-water bath, stirring for 30min for uniform dispersion, simultaneously dissolving 2.28g of ammonium persulfate in 10mL of hydrochloric acid, slowly dropwise adding 2mL of dissolved ammonium persulfate solution into aniline and sulfur-carrying layered poplar wood charcoal hydrochloric acid solution, reacting for 2h under the condition of the ice-water bath, after the reaction is finished, washing with deionized water and ethanol, and freeze-drying to obtain the sulfur-carrying layered poplar wood charcoal/polyaniline composite material.
The sulfur simple substance and the sulfur-carrying layered poplar charcoal/polyaniline are mixed according to the mass ratio of 7:3, grinding, and placing the mixture into an oven at 60 ℃ to remove water. And then placing the mixed powder into the inner liner of a reaction kettle, placing the reaction kettle into a glove box to fill argon, heating the reaction kettle at 155 ℃ for reaction for 12 hours, and then heating the reaction kettle at 200 ℃ for 30 minutes to prepare the sulfur-carrying layered poplar charcoal/polyaniline composite positive electrode material.
The invention also claims a sulfur-carrying layered poplar charcoal/polyaniline composite cathode material prepared by the method, the surface of the sulfur-carrying layered poplar charcoal/polyaniline composite material is covered with a polyaniline particle deposition film, the surface is rough and has no obvious pores, the interior of the composite material is of a layered structure, as shown in figures 5 and 6, the sulfur element distribution of the sulfur-carrying layered poplar charcoal is shown in figure 7, and the sulfur content of the sulfur-carrying layered poplar charcoal is 3%.
Specifically, firstly, catalyzing poplar fiber to carbonize through p-toluenesulfonic acid to obtain a three-dimensional sulfur-carrying layered carbon material with an oxygen-containing functional group on the surface; then polyaniline is polymerized on the surface and the interlayer of the sulfur-carrying layered poplar wood charcoal in an in-situ polymerization mode; finally, by sublimation and deposition of elemental sulfur, under the action of a surface nitrogen-containing functional group, sulfur is distributed on the surface of the three-dimensional layered carbon, so that the sulfur-loaded layered poplar charcoal/polyaniline composite positive electrode material is finally prepared.
The invention also discloses application of the sulfur-carrying layered poplar charcoal/polyaniline composite positive electrode material prepared by the method in a lithium-sulfur battery.
Specifically, the sulfur-carrying layered poplar charcoal/polyaniline composite positive electrode material can be used as a positive electrode material of a lithium-sulfur battery, and the method for preparing the battery by using the sulfur-carrying layered poplar charcoal/polyaniline composite positive electrode material comprises the following steps:
carrying out a sulfur-carrying layered poplar charcoal/polyaniline composite positive electrode material, super-P and polyvinylidene fluoride (PVDF) according to a mass ratio of 8:1:1, mixing and grinding to obtain anode slurry; pouring the slurry on the surface of an aluminum foil which is wiped cleanly, scraping a film by using a scraper with the height of 10 mu m, then processing for 10 hours at 50 ℃ under the vacuum condition, and cutting into small round pieces with the diameter of 14 mu m to obtain the sulfur-carrying layered poplar charcoal/polyaniline positive plate.
And then assembling the battery according to the order of 2032 positive electrode shell, positive electrode plate, 90mL electrolyte, celgard2400 diaphragm, 90mL electrolyte, lithium plate, gasket, spring plate and 2032 negative electrode shell, and packaging to obtain the sulfur-carrying layered poplar charcoal/polyaniline lithium sulfur battery.
Optionally, the electrolyte formula required for preparing the battery is as follows:
1.0M lithium bis (trifluoromethanesulfonyl) imide (LiTFSI), solvent 1:1 of Dioxolane (DOL) and ethylene glycol dimethyl ether (DME), and 1.0 mass percent of lithium nitrate (LiNO) 3 )。
In addition, the preparation reaction device of the sulfur-carrying poplar wood charcoal is a microwave muffle furnace, a high-pressure reaction kettle or a tubular resistance furnace; the lining of the reaction kettle for preparing the sulfur-carrying poplar charcoal is made of polytetrafluoroethylene, stainless steel or titanium alloy; the inert gas required by the preparation of the sulfur-carrying poplar charcoal is nitrogen or argon.
Compared with the prior art, the sulfur-carrying layered poplar charcoal/polyaniline composite positive electrode material and the preparation method and application thereof have the following excellent effects:
1. the sulfur-carrying layered poplar charcoal/polyaniline composite positive electrode material manufactured by the invention is a carbon material which has simple production process and low price and can be used for the positive electrode of a lithium-sulfur battery.
2. The sulfur-carrying layered poplar charcoal/polyaniline composite positive electrode material prepared by the method has higher specific capacity, and the surface of the composite material is covered with a polyaniline particle deposition film, so that the material has rough surface and no obvious pores, but the poplar charcoal layer structure in the material is obvious.
3. The sulfur-carrying layered poplar charcoal/polyaniline composite positive electrode material provided by the invention is used as a positive electrode material of a lithium sulfur battery, has rich N-containing and O-containing functional groups, can better limit and inhibit a polysulfide shuttling effect, and the prepared lithium sulfur battery has excellent impedance performance.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to the provided drawings without creative efforts.
Fig. 1 is a cyclic voltammetry curve of a lithium-sulfur battery of a sulfur-carrying layered poplar charcoal/polyaniline composite positive electrode material under different scanning rates.
Fig. 2 is the rate performance of a lithium-sulfur battery with a sulfur-carrying layered poplar charcoal/polyaniline composite positive electrode material.
Fig. 3 is a cycle life curve of a lithium-sulfur battery with a sulfur-carrying layered poplar charcoal/polyaniline composite positive electrode material.
Fig. 4 is an EIS impedance spectrum of a lithium sulfur battery with a sulfur-loaded layered poplar charcoal/polyaniline composite positive electrode material.
FIG. 5 is the scanning electron micrograph of the sulfur-carrying layered poplar charcoal/polyaniline composite positive electrode material.
FIG. 6 is a transmission electron micrograph of the sulfur-carrying layered poplar charcoal/polyaniline composite positive electrode material.
FIG. 7 is a schematic diagram of sulfur distribution of sulfur-loaded layered poplar charcoal; wherein, (a) is a scanning electron microscope photo, and (b) is a sulfur element distribution photo.
Detailed Description
The technical solutions disclosed in the present invention will be described clearly and completely with reference to the accompanying drawings, and obviously, the described embodiments are only a part of the embodiments of the present invention, not all of the embodiments. All other embodiments, which can be obtained by a person skilled in the art without making any creative effort based on the embodiments in the present invention, belong to the protection scope of the present invention.
The present invention will be further specifically illustrated by the following examples for better understanding, but the present invention is not to be construed as being limited thereto, and certain insubstantial modifications and adaptations of the invention by those skilled in the art based on the foregoing disclosure are intended to be included within the scope of the invention.
Example 1:
taking 18g of p-toluenesulfonic acid and 2mL of ionized water, putting the p-toluenesulfonic acid and the ionized water into the inner liner of a reaction kettle, adding 1g of treated p-toluenesulfonic acid treated poplar fiber, tightly sealing the reaction kettle, and carrying out hydrothermal carbonization for 10 hours in an oven at 220 ℃; dialyzing with deionized water, ultrasonic treating, and lyophilizing to obtain sulfur-carrying layered poplar charcoal.
Preparing 1mol/L hydrochloric acid, dispersing 100mg of sulfur-carrying layered poplar wood charcoal in 100mL of hydrochloric acid by ultrasonic waves for 10min, dropwise adding 92 mu L of aniline into the solution in an ice-water bath, stirring for 30min for uniform dispersion, simultaneously dissolving 2.28g of ammonium persulfate in 10mL of hydrochloric acid, slowly dropwise adding 2mL of dissolved ammonium persulfate solution into aniline and sulfur-carrying layered poplar wood charcoal hydrochloric acid solution, reacting for 2h under the condition of the ice-water bath, washing with deionized water and ethanol after the reaction is finished, and freeze-drying to obtain the sulfur-carrying layered poplar wood charcoal/polyaniline composite cathode material.
Carrying out mixing on sulfur-carrying layered poplar charcoal/polyaniline and a sulfur simple substance according to a mass ratio of 3:7, and mixing and grinding the mixture according to the proportion to obtain the sulfur-carrying layered poplar charcoal/polyaniline sulfur-mixed material.
Mixing a sulfur-carrying layered poplar charcoal/polyaniline mixed sulfur material, super-P and polyvinylidene fluoride (PVDF) according to a mass ratio of 8:1:1 to obtain the anode slurry. Pouring the slurry on the surface of an aluminum foil cleaned by wiping, scraping the film by using a scraper with the height of 10 mu m, then treating for 12h at 50 ℃ under the vacuum condition to obtain the sulfur-carrying poplar charcoal/polyaniline lithium sulfur battery positive electrode material, and cutting into electrodes with the diameter of 14 mu m.
Through testing, the initial specific capacity of the prepared sulfur-carrying poplar charcoal/polyaniline lithium sulfur battery is 600.52mAh/g. Under the same condition, the initial specific capacity of the prepared sulfur-carrying poplar charcoal lithium sulfur battery is 551.45mAh/g.
Example 2:
the method for preparing the positive electrode slurry in example 1 was adopted, but the dosage of the aniline dropwise added into the solution was 184 μ L, and the initial specific capacity of the prepared sulfur-loaded layered poplar charcoal/polyaniline lithium sulfur battery was 402.99mAh/g, in reference to the button cell preparation method in example 1. Under the same condition, the initial specific capacity of the prepared sulfur-carrying poplar charcoal lithium sulfur battery is 383.95mAh/g.
Example 3:
referring to example 1, sulfur-carrying layered poplar charcoal/polyaniline and elemental sulfur were mixed at a mass ratio of 3:7, and placing the mixture into an oven at 60 ℃ to remove water. And then, putting the mixed powder into a reaction kettle, filling argon, heating at 155 ℃ for 12h, and heating at 200 ℃ for 30min to obtain the sulfur-carrying layered poplar charcoal/polyaniline composite cathode material. The initial specific capacity of the prepared sulfur-carrying layered poplar charcoal/polyaniline lithium sulfur battery is 633.46mAh/g. Under the same condition, the initial specific capacity of the prepared sulfur-carrying poplar charcoal lithium sulfur battery is 603.18mAh/g.
Example 4:
referring to example 3, the prepared sulfur-carrying layered poplar charcoal/polyaniline lithium sulfur battery positive electrode has an initial specific capacity of 454mAh/g. Under the same condition, the initial specific capacity of the prepared sulfur-carrying poplar charcoal lithium sulfur battery is 402.74mAh/g.
Example 5:
preparing 1mol/L hydrochloric acid, dropwise adding 92 mu L aniline into 100mL hydrochloric acid solution in an ice-water bath, stirring for 30min for uniform dispersion, simultaneously dissolving 2.28g ammonium persulfate into 10mL hydrochloric acid, slowly dropwise adding 2mL dissolved ammonium persulfate solution into the aniline solution, reacting for 2h in the ice-water bath, after the reaction is finished, washing with deionized water and ethanol, and freeze-drying to obtain the polyaniline.
The sulfur-loaded layered poplar charcoal/polyaniline lithium sulfur battery prepared in reference example 1, which was obtained by mixing and grinding sulfur-loaded layered poplar charcoal and polyaniline in an amount of 10% by mass thereof, had an initial specific capacity of 608.21mAh/g. Under the same condition, the initial specific capacity of the prepared sulfur-carrying poplar charcoal lithium sulfur battery is 556.91mAh/g.
Example 6:
the polyaniline prepared in reference example 5 was mixed and ground with sulfur-loaded layered poplar charcoal and polyaniline in an amount of 25% by mass thereof to obtain sulfur-loaded layered poplar charcoal/polyaniline, and the initial specific capacity of the sulfur-loaded layered poplar charcoal/polyaniline lithium sulfur battery prepared in reference example 1 was 830.96mAh/g. Under the same condition, the initial specific capacity of the prepared sulfur-carrying poplar charcoal lithium sulfur battery is 742.31mAh/g.
Example 7:
the polyaniline was prepared according to reference example 5, and sulfur-loaded layered poplar charcoal/polyaniline was obtained by mixing and grinding sulfur-loaded layered poplar charcoal with polyaniline accounting for 40% of the mass thereof, and the initial specific capacity of the sulfur-loaded layered poplar charcoal/polyaniline lithium sulfur battery prepared according to reference example 1 was 730mAh/g. Under the same condition, the initial specific capacity of the prepared sulfur-carrying poplar charcoal lithium sulfur battery is 690.26mAh/g.
Example 8:
the polyaniline prepared in reference example 5 was mixed and ground with sulfur-loaded layered poplar charcoal, which was 55% of the mass of the polyaniline, to obtain sulfur-loaded layered poplar charcoal/polyaniline, and the initial specific capacity of the sulfur-loaded layered poplar charcoal/polyaniline lithium sulfur battery prepared in reference example 1 was 444.86mAh/g. Under the same condition, the initial specific capacity of the prepared sulfur-carrying layered poplar charcoal lithium sulfur battery is 403.33mAh/g.
In addition, in order to further verify the superiority of the technology of the present invention, the inventors performed performance tests on lithium-sulfur batteries prepared by using sulfur-loaded layered poplar charcoal/polyaniline materials, specifically as follows:
the cyclic voltammogram of the sulfur-loaded layered poplar charcoal/polyaniline lithium sulfur cell prepared in example 6 showed the characteristic redox characteristics of the Li-S cell, and two distinct cathode peaks appeared at about 1.96V and 2.24V (see fig. 1), which is attributable to the fact that the lithium sulfur cell was obtained from S 8 The molecules are converted to high-order LiPs and further reduced to Li 2 S 2 And Li 2 S。
At 0.1C, the initial discharge specific capacity of the battery is 830.96mAh/g, and reaches 49.6% of the theoretical specific capacity (1675 mAh/g, see figure 2).
At a current density of 50mAcm -2 When the battery is charged and discharged for 40 times with constant current, the specific capacity is 402.73mAh/g (see attached figure 3), which shows that the battery is charged with large currentIn the discharge process, the material can still be charged and discharged for many times.
The impedance performance of the cell is as follows: the solution resistance Rs was 3.68 Ω, the charge transfer resistance Rct was 87.9 Ω, and Li + Diffusion coefficient of 1.63X 10 -5 cm 2 s -1 Its Warburg impedance is 0.003344 Ω (see FIG. 4). Rct and Rs are much larger than Warburg impedance, indicating that the electrode reactions of the cell are controlled by the charge transfer process.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (9)
1. The preparation method of the sulfur-carrying layered poplar charcoal/polyaniline composite positive electrode material is characterized by comprising the following steps of:
(1) Immersing poplar chips in a p-toluenesulfonic acid solution, heating in a water bath, and then washing with water and ultrasonically cleaning for later use;
(2) Adding p-toluenesulfonic acid and deionized water into the poplar fiber treated in the step (1), carbonizing in a reaction kettle, and dialyzing, ultrasonically treating and freeze-drying to obtain sulfur-carrying layered poplar charcoal for later use;
(3) Ultrasonically dispersing the sulfur-carrying layered poplar charcoal treated in the step (2) in hydrochloric acid, respectively dropwise adding aniline and ammonium persulfate solution, carrying out in-situ polymerization on the surface of the sulfur-carrying layered poplar charcoal to form polyaniline, then washing with deionized water and ethanol, and freeze-drying to obtain a sulfur-carrying layered poplar charcoal/polyaniline composite material for later use;
(4) And (3) removing moisture from the elemental sulfur and the sulfur-carrying layered poplar charcoal/polyaniline composite material prepared in the step (3), reacting in a reaction kettle in a nitrogen atmosphere, and heating to obtain the sulfur-carrying layered poplar charcoal/polyaniline composite positive electrode material.
2. The preparation method of the sulfur-carrying layered poplar charcoal/polyaniline composite cathode material as claimed in claim 1, wherein the step (3) can be replaced by:
and (3) mixing and grinding the sulfur-loaded layered poplar charcoal treated in the step (2) with polyaniline to obtain the sulfur-loaded layered poplar charcoal/polyaniline composite material.
3. The preparation method of the sulfur-carrying layered poplar charcoal/polyaniline composite cathode material as claimed in claim 1, wherein the water bath heating temperature in the step (1) is 70-90 ℃ and the water bath heating time is 5-7 h.
4. The preparation method of the sulfur-carrying layered poplar charcoal/polyaniline composite cathode material as claimed in claim 1, wherein in the step (2), p-toluenesulfonic acid and deionized water in a volume ratio of 1 to 1.
5. The preparation method of the sulfur-carrying layered poplar charcoal/polyaniline composite cathode material as claimed in claim 1, wherein the specific preparation operation of the sulfur-carrying layered poplar charcoal/polyaniline in the step (3) is as follows:
preparing 1mol/L hydrochloric acid, dispersing 100-500 mg of sulfur-carrying layered poplar charcoal in 100-500 mL of hydrochloric acid by ultrasound for 5-15 min, dropwise adding 50-500 μ L of aniline into the solution in an ice-water bath, stirring for 20-40 min for uniform dispersion, dissolving 1-3 g of ammonium persulfate in 10-100 mL of hydrochloric acid, slowly dropwise adding 2-20 mL of dissolved ammonium persulfate solution into the aniline/sulfur-carrying layered poplar charcoal hydrochloric acid solution, reacting for 1-3 h in the ice-water bath, after the reaction is finished, washing with deionized water and ethanol, and freeze-drying to obtain the sulfur-carrying layered poplar charcoal/polyaniline composite material.
6. The preparation method of the sulfur-carrying layered poplar charcoal/polyaniline composite cathode material as claimed in claim 1, wherein in the step (4), the mass ratio of the sulfur simple substance to the sulfur-carrying layered poplar charcoal/polyaniline composite material is 5:5-7:3, and the moisture is removed at 50-80 ℃.
7. The preparation method of the sulfur-carrying layered poplar charcoal/polyaniline composite cathode material as claimed in claim 1, wherein in the step (4), the reaction and heating operation steps in the reaction kettle are as follows: reacting for 10-12 h at 150-160 ℃ in a reaction kettle, and then heating for 30min at 200-220 ℃.
8. The sulfur-loaded layered poplar charcoal/polyaniline composite positive electrode material prepared by the method according to any one of claims 1 to 7, wherein the surface of the sulfur-loaded layered poplar charcoal/polyaniline composite material is covered with a polyaniline particle deposition film, the surface is rough and has no obvious pores, and the sulfur-loaded layered poplar charcoal is arranged inside the composite positive electrode material.
9. The application of the sulfur-carrying layered poplar charcoal/polyaniline composite positive electrode material prepared by the method according to any one of claims 1 to 7 or the sulfur-carrying layered poplar charcoal/polyaniline composite positive electrode material according to claim 8 in a lithium-sulfur battery.
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| CN110336036A (en) * | 2019-07-17 | 2019-10-15 | 安徽师范大学 | Semi-spherical hollow shape titanium dioxide/carbon particle/Polyaniline-Supported sulphur composite material and preparation method, lithium-sulphur cell positive electrode and battery |
| CN111844307A (en) * | 2020-06-11 | 2020-10-30 | 东北林业大学 | Carbonized wood, preparation method thereof and solar steam generation device |
| CN114477125A (en) * | 2020-10-26 | 2022-05-13 | 东北林业大学 | Sulfur-carrying poplar charcoal electrode material and preparation method and application thereof |
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| CN104362316A (en) * | 2014-10-28 | 2015-02-18 | 华南师范大学 | Lithium-sulfur battery composite cathode material, and preparation method and application thereof |
| KR20190044313A (en) * | 2017-10-20 | 2019-04-30 | 광주과학기술원 | Selenium-sulfur compound electrode material coated with polyaniline for lithium-sulfur battery and lithium-sulfur battery using the same |
| CN110336036A (en) * | 2019-07-17 | 2019-10-15 | 安徽师范大学 | Semi-spherical hollow shape titanium dioxide/carbon particle/Polyaniline-Supported sulphur composite material and preparation method, lithium-sulphur cell positive electrode and battery |
| CN111844307A (en) * | 2020-06-11 | 2020-10-30 | 东北林业大学 | Carbonized wood, preparation method thereof and solar steam generation device |
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