CN112164771A - Sulfur/polyaniline nanotube/reduced graphene oxide composite material and preparation method and application thereof - Google Patents

Sulfur/polyaniline nanotube/reduced graphene oxide composite material and preparation method and application thereof Download PDF

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CN112164771A
CN112164771A CN202010862571.1A CN202010862571A CN112164771A CN 112164771 A CN112164771 A CN 112164771A CN 202010862571 A CN202010862571 A CN 202010862571A CN 112164771 A CN112164771 A CN 112164771A
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graphene oxide
sulfur
polyaniline nanotube
composite material
reduced graphene
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王辉
王庆莉
林少雄
许家齐
辛昱
刘盛华
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Hefei Gotion High Tech Power Energy Co Ltd
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Hefei Guoxuan High Tech Power Energy Co Ltd
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    • H—ELECTRICITY
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    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
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    • H01M4/36—Selection of substances as active materials, active masses, active liquids
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    • H—ELECTRICITY
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    • H01M4/02—Electrodes composed of, or comprising, active material
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    • H—ELECTRICITY
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    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
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    • H—ELECTRICITY
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Abstract

The invention discloses a sulfur/polyaniline nanotube/reduced graphene oxide composite material and a preparation method and application thereof. The sulfur/polyaniline nanotube/reduced graphene oxide composite material provided by the invention is used as a lithium-sulfur battery anode material, and can effectively improve the electronic conductivity of a sulfur material, inhibit the shuttle effect of long-chain polysulfide lithium and improve the interface performance of the material, so that the utilization rate and capacity of active substances of the material are improved, and the cycle stability of the material is greatly improved.

Description

Sulfur/polyaniline nanotube/reduced graphene oxide composite material and preparation method and application thereof
Technical Field
The invention relates to the technical field of lithium-sulfur battery materials, in particular to a sulfur/polyaniline nanotube/reduced graphene oxide composite material and a preparation method and application thereof.
Background
With the continuous progress of technology and the rapid development of electronic products, there is an urgent need for a battery system with high energy density and environmental friendliness, and thus lithium-sulfur batteries are gradually coming into the field of researchers. LiCoO as the anode material of traditional lithium ion battery2、LiMn2O4、LiPFeO4Compared with the prior art, the lithium-sulfur battery positive electrode material, namely the sulfur positive electrode, has higher theoretical specific capacity (1675mAh/g) and higher energy density (2600Wh/kg), and is a secondary battery system with the highest energy density except for a lithium-air battery. In addition, the anode raw material has rich sulfur resource, low price and lower battery cost, hardly generates pollution in the charging process and is environment-friendly, so that the anode raw material is widely concerned and researched.
However, compared with the conventional lithium ion battery cathode material, the lithium-sulfur battery has a lower discharge voltage platform, and has two discharge platforms, wherein the first discharge platform is 2.2-2.3V and mainly has S with an annular structure8Conversion of molecules to long-chain Sn 2-(n is more than or equal to 3 and less than or equal to 8) and lithium ions are combined to form long-chain polysulfide lithium; the second discharge platform is mainly between 2.1V and 2.2V and mainly comprises long-chain Sn 2-(n is 3. ltoreq. n.ltoreq.8) S converted into short chainn 2-(n is more than or equal to 1 and less than or equal to 2), and the platform is a main discharge platform. The long-chain polysulfide lithium generated in the charging and discharging process can be dissolved in the electrolyte to cause the loss of active substances, and the active substances are transferred to the lithium cathode for multiple times to react with the lithium cathode to cause the shuttle effect, so that the capacity is reduced, the capacity of the lithium-sulfur battery is rapidly attenuated, and the cycle life is shorter. In addition, the conductivity of elemental sulfur at room temperature is only 5X 10-30S/cm, poor electrochemical activity and low battery capacity.
Disclosure of Invention
Based on the technical problems in the background art, the invention provides a sulfur/polyaniline nanotube/reduced graphene oxide composite material and a preparation method and application thereof.
The sulfur/polyaniline nanotube/reduced graphene oxide composite material provided by the invention is composed of elemental sulfur, a polyaniline nanotube and a reduced graphene oxide nanosheet, wherein the elemental sulfur is loaded in the polyaniline nanotube, and the reduced graphene oxide nanosheet is coated on the outer surface of the polyaniline nanotube.
Preferably, the mass of the elemental sulfur accounts for 60-80% of the total mass of the sulfur/polyaniline nanotube/reduced graphene oxide composite material, and the mass of the reduced graphene oxide nanosheet accounts for 2-8% of the total mass of the sulfur/polyaniline nanotube/reduced graphene oxide composite material.
Preferably, the reduced graphene oxide nanosheets are bonded with the polyaniline nanotubes through amide bonds and coated on the outer surfaces of the polyaniline nanotubes.
A preparation method of the sulfur/polyaniline nanotube/reduced graphene oxide composite material comprises the following steps:
s1, uniformly dispersing the polyaniline nanotube and the graphene oxide nanosheet with the surface containing carboxyl in a solvent, and carrying out acylation reaction under the action of a catalyst to bond the graphene oxide nanosheet on the outer surface of the polyaniline nanotube through an amido bond to obtain the polyaniline nanotube/graphene oxide composite material; in the step S1, performing acylation reaction between amino groups on the surface of the polyaniline nanotube and carboxyl groups on the surface of the graphene oxide nanosheet, and coating the graphene oxide on the surface of the polyaniline in an anchor manner;
s2, uniformly dispersing the polyaniline nanotube/graphene oxide composite material prepared in the step S1 in water, and adding hydrazine hydrate for reduction reaction to obtain the polyaniline nanotube/reduced graphene oxide composite material; in the step S2, reducing oxygen-containing functional groups on the surface of the graphene through hydrazine hydrate, and preventing the material from consuming irreversible lithium ions in the charging and discharging process, so that the first coulombic efficiency is reduced;
s3, uniformly mixing the polyaniline nanotube/reduced graphene oxide composite material prepared in the step S2 with hydrochloric acid and a sodium thiosulfate solution, carrying out a disproportionation reaction, and generating elemental sulfur in the polyaniline nanotube to obtain a sulfur/polyaniline nanotube/reduced graphene oxide composite material; in step S3, elemental sulfur is uniformly deposited inside the polyaniline nanotube by in-situ deposition.
Preferably, the mass ratio of the polyaniline nanotube to the graphene oxide nanosheet with the carboxyl group on the surface is (60-95): (5-40), wherein the mass ratio of the catalyst to the graphene oxide nanosheets with carboxyl groups on the surfaces is (5-10): (95-90); the mass ratio of the hydrazine hydrate to the graphene oxide nanosheet with the carboxyl group on the surface is (1-3) to 1; the mass ratio of the sodium thiosulfate to the polyaniline nanotube/reduced graphene oxide composite material is (7-20): 1; the molar ratio of the hydrochloric acid to the sodium thiosulfate is (2-3): 1.
preferably, in the step S1, the temperature of the acylation reaction is 20 to 60 ℃, the time is 6 to 24 hours, the catalyst is concentrated sulfuric acid, and the solvent is tetrahydrofuran; in the step S2, the time of the reduction reaction is 0.5-4 h;
preferably, the preparation method of the polyaniline nanotube comprises the following steps: uniformly dispersing an aniline monomer in water, adding an acrylic acid monomer, uniformly stirring, then adding isopropanol and ammonium persulfate in an inert atmosphere for polymerization reaction, centrifuging, washing the obtained product with hot water until the pH value is neutral, and drying to obtain a polyaniline nanotube; the molar ratio of the acrylic acid monomer to the aniline monomer is (1-4) to 1; the mass ratio of the isopropanol to the acrylic monomer is (5-15): (85-95); the mass ratio of the ammonium persulfate to the acrylic monomer is (5-15): (85-95); the polymerization reaction is carried out at the temperature of 60-100 ℃ for 2-6 h, and the inert atmosphere is one or more of nitrogen, argon, helium, neon and krypton. The method comprises the steps of polymerizing an acrylic monomer to form high-molecular-weight polyacrylic acid, forming polyaniline from an aniline monomer, coating the surface of the high-molecular-weight polyacrylic acid through electrostatic action to form a nanotube with a relatively large aperture and a relatively long length, and washing with hot water to remove a polyacrylic acid template to obtain the polyaniline nanotube.
Preferably, the preparation method of the graphene oxide nanosheet with the carboxyl group on the surface comprises the following steps: adding the crystalline flake graphite into a nitric acid solution, carrying out heating reflux reaction, then carrying out ultrasonic dispersion and centrifugation, and heating the obtained supernatant for a certain time to obtain a graphene oxide nanosheet with a carboxyl group on the surface; the concentration of the nitric acid solution is 4-10 mol/L; the heating reflux reaction is carried out at the temperature of 60-120 ℃ for 12-24 h; the heating temperature of the supernatant is 150-250 ℃, and the heating time is 6-24 h. Carrying out concentrated nitric acid oxidation on flake graphite, stripping, heating, refluxing, carrying out ultrasonic dispersion and centrifuging to obtain graphene oxide, and heating supernatant to make the surface of the graphene oxide carboxylated as much as possible to obtain the graphene oxide nanosheet with carboxyl on the surface.
The application of the sulfur/polyaniline nanotube/reduced graphene oxide composite material as a positive active material of a lithium-sulfur battery.
The invention has the following beneficial effects:
according to the invention, the reduced graphene oxide nanosheet is coated on the surface of the polyaniline nanotube and serves as a carbon skeleton, so that sulfur is deposited in situ in the polyaniline nanotube, and the prepared sulfur/polyaniline nanotube/reduced graphene oxide composite material has a multi-layer tubular core-shell structure similar to a sandwich structure, wherein the sulfur is uniformly deposited in situ in the polyaniline nanotube, and the reduced graphene oxide nanosheet is bonded on the surface of polyaniline through acylation reaction. On one hand, the polyaniline nanotube and the reduced graphene oxide can improve the electronic conductivity of sulfur and the reaction product lithium sulfide, thereby reducing polarization; on the other hand, the polyaniline nanotube has larger specific surface area and stronger adsorption effect, and can adsorb long-chain polysulfide lithium as a reaction intermediate product into the nanotube, even if part of the polyaniline nanotube is dissolved out, the reduced graphene oxide coating layer on the outer surface of the polyaniline nanotube has larger specific surface area, the long-chain polysulfide lithium can be fixed on the surface of the polyaniline nanotube through secondary adsorption, and the shuttle effect is further inhibited through the synergistic effect of the polyaniline nanotube and the reduced graphene oxide; in addition, the polyaniline nanotube can also improve the interface performance of the material. Therefore, the sulfur/polyaniline nanotube/reduced graphene oxide composite material provided by the invention can be used as a lithium-sulfur battery positive electrode material, can effectively improve the electronic conductivity of a sulfur material, inhibit the shuttle effect of long-chain polysulfide lithium, and improve the material interface performance, so that the utilization rate and capacity of active substances of the material are improved, and the cycle stability of the material is greatly improved.
Drawings
Fig. 1 is a schematic diagram of a sulfur/polyaniline nanotube/reduced graphene oxide composite material prepared by the present invention, wherein 1 represents elemental sulfur, 2 represents a polyaniline nanotube, and 3 represents a reduced graphene oxide nanosheet.
Fig. 2 is an SEM image of the sulfur/polyaniline nanotube/reduced graphene oxide composite material prepared in example 1 of the present invention.
Fig. 3 is a first charge and discharge curve of the batteries assembled in example 1 of the present invention and comparative example 1.
Fig. 4 is a graph of the cycle performance at a current density of 0.1C for the cells assembled in example 1 of the present invention and comparative example 1.
Fig. 5 is a graph of the ac impedance of the first cycle of the assembled cells of example 1 of the present invention and comparative example 1.
Detailed Description
The technical solution of the present invention will be described in detail below with reference to specific examples.
Example 1
A sulfur/polyaniline nanotube/reduced graphene oxide composite material is composed of elemental sulfur, a polyaniline nanotube and a reduced graphene oxide nanosheet, wherein the elemental sulfur is loaded in the polyaniline nanotube, and the reduced graphene oxide nanosheet is bonded with the polyaniline nanotube through an amido bond and is coated on the outer surface of the polyaniline nanotube; the mass of the elemental sulfur accounts for 80% of the total mass of the sulfur/polyaniline nanotube/reduced graphene oxide composite material, and the mass of the reduced graphene oxide nanosheet accounts for 8% of the total mass of the sulfur/polyaniline nanotube/reduced graphene oxide composite material.
The preparation method of the sulfur/polyaniline nanotube/reduced graphene oxide composite material comprises the following steps:
s1, uniformly dispersing 0.83g of polyaniline nanotube and 0.5g of graphene oxide nanosheet with carboxyl on the surface in tetrahydrofuran, adding 0.05g of concentrated sulfuric acid, and performing acylation reaction at 60 ℃ for 6 hours to obtain a polyaniline nanotube/graphene oxide composite material;
s2, uniformly dispersing the polyaniline nanotube/graphene oxide composite material prepared in the step S1 in water, and adding 0.5g of hydrazine hydrate for reduction reaction for 4 hours to obtain 1.2g of the polyaniline nanotube/reduced graphene oxide composite material;
s3, uniformly mixing the polyaniline nanotube/reduced graphene oxide composite material prepared in the step S2 with hydrochloric acid and sodium thiosulfate solution, carrying out disproportionation reaction, and generating elemental sulfur in the polyaniline nanotube to obtain the sulfur/polyaniline nanotube/reduced graphene oxide composite material, wherein the hydrochloric acid is 0.3mol, and the sodium thiosulfate is 0.15mol (23.7 g).
The preparation method of the polyaniline nanotube comprises the following steps: uniformly dispersing 46.5g (0.5mol) of aniline monomer in 100mL of water, adding 36g (0.5mol) of acrylic acid monomer, uniformly stirring, then adding 1.9g of isopropanol and 1.9g of ammonium persulfate in a high-purity nitrogen atmosphere, carrying out polymerization reaction for 6h at the temperature of 60 ℃, centrifuging, washing the obtained product with hot water until the pH value is neutral, and drying to obtain the aniline monomer.
The preparation method of the graphene oxide nanosheet with the carboxyl group on the surface comprises the following steps: adding 1g of crystalline flake graphite into a nitric acid solution with the concentration of 10mol/L, heating and refluxing for reaction for 12h at the temperature of 120 ℃, then ultrasonically dispersing and centrifuging, and heating the obtained supernatant for 6h at the temperature of 250 ℃ in an oil bath to obtain the graphite.
Fig. 2 is an SEM image of the sulfur/polyaniline nanotube/reduced graphene oxide composite material prepared as described above, and it can be found that the composite material exists mainly in a nanotube tubular form, and sulfur is uniformly distributed in the inner wall of the tube.
The prepared sulfur/polyaniline nanotube/reduced graphene oxide composite material is used as a positive electrode active substanceAnd dispersing the carbon black, the conductive agent Keqin carbon black and a binder polyvinylidene fluoride (PVDF) in N-methyl pyrrolidone (NMP) according to the mass ratio of 6:3:1 of the positive active substance, the conductive agent and the binder, and coating and drying the aluminum foil to prepare the sulfur composite material electrode. And (3) taking the prepared sulfur composite material electrode as a positive electrode and a metal lithium sheet as a negative electrode, and dropwise adding a proper amount of electrolyte to assemble the battery. Lithium salt in the electrolyte is bis (trifluoromethane sulfonyl) imide Lithium (LITFSI), the concentration of the lithium salt is 1mol/L, the solvent is Dimethoxyethane (DME) and 1, 3-Dioxolane (DOL) (volume ratio is 1:1), and LiNO is added3As the film forming additive, the mass of the film forming additive accounts for 1 percent of the total mass of the electrolyte. The first charge-discharge curve of the battery at 0.1C multiplying power is tested.
Comparative example 1
Sublimed sulfur is used as a positive electrode active substance, and is dispersed in N-methyl pyrrolidone (NMP) together with conductive agent Keqin carbon black and binder polyvinylidene fluoride (PVDF) according to the mass ratio of the positive electrode active substance, the conductive agent and the binder being 6:3:1, and a sulfur electrode is prepared by coating and drying aluminum foil. And (3) taking the prepared sulfur electrode as a positive electrode and a metal lithium sheet as a negative electrode, and dropwise adding a proper amount of electrolyte to assemble the battery. Lithium salt in the electrolyte is bis (trifluoromethane sulfonyl) imide Lithium (LITFSI), the concentration of the lithium salt is 1mol/L, the solvent is Dimethoxyethane (DME) and 1, 3-Dioxolane (DOL) (volume ratio is 1:1), and LiNO is added3As the film forming additive, the mass of the film forming additive accounts for 1 percent of the total mass of the electrolyte. The first charge-discharge curve of the battery at 0.1C multiplying power is tested.
Fig. 3 is a first charge and discharge curve of the batteries assembled in example 1 and comparative example 1. As shown in fig. 3, the first discharge capacity of the battery assembled in example 1 exceeded 1249.5mAh/g, the first coulombic efficiency was 95.5%, and the first discharge capacity of the battery assembled in comparative example 1 exceeded 861mAh/g, and it can be seen that the utilization rate of the positive electrode active material of example 1 was improved as compared to comparative example 1.
Fig. 4 is a cycle test curve of the assembled batteries in example 1 and comparative example 1. As shown in fig. 4, when a cycle test was performed at a current density of 0.1C, the battery was cycled 50 times, the specific discharge capacity of the battery assembled in example 1 was maintained at 1024.1mAh/g, the capacity retention rate was 81.97%, the specific discharge capacity of the battery assembled in comparative example 1 was maintained at 502mAh/g, and the capacity retention rate of the battery was 58.3%. It can be seen that the shuttle effect of the assembled cell of example 1 is significantly reduced compared to comparative example 1.
Fig. 5 is an ac impedance curve of the assembled cells of example 1 and comparative example 1. It was found that the positive electrode active material of example 1 had a lower charge transfer resistance and a higher electron conductivity than those of comparative example 1.
Example 2
A sulfur/polyaniline nanotube/reduced graphene oxide composite material is composed of elemental sulfur, a polyaniline nanotube and a reduced graphene oxide nanosheet, wherein the elemental sulfur is loaded in the polyaniline nanotube, and the reduced graphene oxide nanosheet is bonded with the polyaniline nanotube through an amido bond and is coated on the outer surface of the polyaniline nanotube; the mass of the elemental sulfur accounts for 60% of the total mass of the sulfur/polyaniline nanotube/reduced graphene oxide composite material, and the mass of the reduced graphene oxide nanosheet accounts for 2% of the total mass of the sulfur/polyaniline nanotube/reduced graphene oxide composite material.
The preparation method of the sulfur/polyaniline nanotube/reduced graphene oxide composite material comprises the following steps:
s1, uniformly dispersing 9.5g of polyaniline nanotubes and 0.5g of graphene oxide nanosheets with carboxyl groups on the surfaces in tetrahydrofuran, adding 0.05g of concentrated sulfuric acid, and performing acylation reaction at 20 ℃ for 24 hours to obtain a polyaniline nanotube/graphene oxide composite material;
s2, uniformly dispersing the polyaniline nanotube/graphene oxide composite material prepared in the step S1 in water, and adding 1.5g of hydrazine hydrate for carrying out reduction reaction for 0.5h to obtain 9g of the polyaniline nanotube/reduced graphene oxide composite material;
s3, uniformly mixing the polyaniline nanotube/reduced graphene oxide composite material prepared in the step S2 with hydrochloric acid and a sodium thiosulfate solution, and carrying out a disproportionation reaction to generate elemental sulfur in the polyaniline nanotube, wherein the hydrochloric acid is 0.844mol, and the sodium thiosulfate is 66.66g (0.422 mol).
The preparation method of the polyaniline nanotube comprises the following steps: uniformly dispersing 11.625g (0.125mol) of aniline monomer in 100mL of water, adding 36g (0.5mol) of acrylic acid monomer, uniformly stirring, then adding 6.35g of isopropanol and 6.35g of ammonium persulfate in a high-purity argon atmosphere, carrying out polymerization reaction for 2h at 100 ℃, centrifuging, washing the obtained product with hot water until the pH value is neutral, and drying to obtain the aniline monomer.
The preparation method of the graphene oxide nanosheet with the carboxyl group on the surface comprises the following steps: adding 1g of crystalline flake graphite into a nitric acid solution with the concentration of 4mol/L, heating and refluxing for 24 hours at the temperature of 60 ℃, then ultrasonically dispersing and centrifuging, and heating the obtained supernatant in an oil bath for 24 hours at the temperature of 150 ℃ to obtain the graphite.
Example 3
A sulfur/polyaniline nanotube/reduced graphene oxide composite material is composed of elemental sulfur, a polyaniline nanotube and a reduced graphene oxide nanosheet, wherein the elemental sulfur is loaded in the polyaniline nanotube, and the reduced graphene oxide nanosheet is bonded with the polyaniline nanotube through an amido bond and is coated on the outer surface of the polyaniline nanotube; the mass of the elemental sulfur accounts for 70% of the total mass of the sulfur/polyaniline nanotube/reduced graphene oxide composite material, and the mass of the reduced graphene oxide nanosheet accounts for 5% of the total mass of the sulfur/polyaniline nanotube/reduced graphene oxide composite material.
The preparation method of the sulfur/polyaniline nanotube/reduced graphene oxide composite material comprises the following steps:
s1, uniformly dispersing 2g of polyaniline nanotubes and 0.34g of graphene oxide nanosheets with carboxyl groups on the surfaces in tetrahydrofuran, adding 0.034g of concentrated sulfuric acid, and performing acylation reaction at 40 ℃ for 12 hours to obtain a polyaniline nanotube/graphene oxide composite material;
s2, uniformly dispersing the polyaniline nanotube/graphene oxide composite material prepared in the step S1 in water, and adding 1g of hydrazine hydrate for carrying out reduction reaction for 2 hours to obtain 2g of the polyaniline nanotube/reduced graphene oxide composite material;
s3, uniformly mixing the polyaniline nanotube/reduced graphene oxide composite material prepared in the step S2 with hydrochloric acid and a sodium thiosulfate solution, carrying out a disproportionation reaction, and generating elemental sulfur in the polyaniline nanotube to obtain the sulfur/polyaniline nanotube/reduced graphene oxide composite material, wherein the hydrochloric acid is 0.292mol, and the sodium thiosulfate is 23.04g (0.146 mol).
The preparation method of the polyaniline nanotube comprises the following steps: uniformly dispersing 23.25g (0.25mol) of aniline monomer in 100mL of water, adding 36g (0.5mol) of acrylic acid monomer, uniformly stirring, adding 4g of isopropanol and 4g of ammonium persulfate in a high-purity helium atmosphere, carrying out polymerization reaction for 4h at 80 ℃, centrifuging, washing the obtained product with hot water until the pH value is neutral, and drying to obtain the aniline monomer.
The preparation method of the graphene oxide nanosheet with the carboxyl group on the surface comprises the following steps: adding 1g of crystalline flake graphite into a nitric acid solution with the concentration of 8mol/L, heating and refluxing for reaction for 12h at the temperature of 80 ℃, then ultrasonically dispersing and centrifuging, and heating the obtained supernatant for 12h at the temperature of 200 ℃ in an oil bath to obtain the graphite.
Example 4
A sulfur/polyaniline nanotube/reduced graphene oxide composite material is composed of elemental sulfur, a polyaniline nanotube and a reduced graphene oxide nanosheet, wherein the elemental sulfur is loaded in the polyaniline nanotube, and the reduced graphene oxide nanosheet is bonded with the polyaniline nanotube through an amido bond and is coated on the outer surface of the polyaniline nanotube; the mass of the elemental sulfur accounts for 75% of the total mass of the sulfur/polyaniline nanotube/reduced graphene oxide composite material, and the mass of the reduced graphene oxide nanosheet accounts for 6% of the total mass of the sulfur/polyaniline nanotube/reduced graphene oxide composite material.
The preparation method of the sulfur/polyaniline nanotube/reduced graphene oxide composite material comprises the following steps:
s1, uniformly dispersing 4g of polyaniline nanotubes and 1g of oxidized graphene nanosheets with carboxyl groups on the surfaces in tetrahydrofuran, adding 0.1g of concentrated sulfuric acid, and performing acylation reaction at 40 ℃ for 12 hours;
s2, uniformly dispersing the polyaniline nanotube/graphene oxide composite material prepared in the step S1 in water, and adding 1g of hydrazine hydrate for carrying out reduction reaction for 2 hours to obtain 4g of the polyaniline nanotube/reduced graphene oxide composite material;
s3, uniformly mixing the polyaniline nanotube/reduced graphene oxide composite material prepared in the step S2 with hydrochloric acid and a sodium thiosulfate solution, carrying out a disproportionation reaction, and generating elemental sulfur in the polyaniline nanotube to obtain the sulfur/polyaniline nanotube/reduced graphene oxide composite material, wherein the hydrochloric acid is 0.75mol, and the sodium thiosulfate is 59.25g (0.375 mol).
The preparation method of the polyaniline nanotube comprises the following steps: uniformly dispersing 15.5g (0.167mol) of aniline monomer in 100mL of water, adding 36g (0.5mol) of acrylic acid monomer, uniformly stirring, then adding 4g of isopropanol and 3g of ammonium persulfate in a high-purity helium atmosphere, carrying out polymerization reaction for 4h at 80 ℃, centrifuging, washing the obtained product with hot water until the pH value is neutral, and drying to obtain the aniline monomer.
The preparation method of the graphene oxide nanosheet with the carboxyl group on the surface comprises the following steps: adding the crystalline flake graphite into a nitric acid solution with the concentration of 6mol/L, heating and refluxing for reaction for 12 hours at the temperature of 100 ℃, then carrying out ultrasonic dispersion and centrifugation, and heating the obtained supernatant for 12 hours at the temperature of 200 ℃ in an oil bath to obtain the graphite.
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art should be considered to be within the technical scope of the present invention, and the technical solutions and the inventive concepts thereof according to the present invention should be equivalent or changed within the scope of the present invention.

Claims (9)

1. The sulfur/polyaniline nanotube/reduced graphene oxide composite material is characterized by comprising elemental sulfur, a polyaniline nanotube and a reduced graphene oxide nanosheet, wherein the elemental sulfur is loaded inside the polyaniline nanotube, and the reduced graphene oxide nanosheet is coated on the outer surface of the polyaniline nanotube.
2. The sulfur/polyaniline nanotube/reduced graphene oxide composite material as claimed in claim 1, wherein the mass of elemental sulfur accounts for 60-80% of the total mass of the sulfur/polyaniline nanotube/reduced graphene oxide composite material, and the mass of reduced graphene oxide nanosheets accounts for 2-8% of the total mass of the sulfur/polyaniline nanotube/reduced graphene oxide composite material.
3. The sulfur/polyaniline nanotube/reduced graphene oxide composite material according to claim 1 or 2, wherein the reduced graphene oxide nanosheets are bonded to the polyaniline nanotubes through amide bonds and coated on the outer surface of the polyaniline nanotubes.
4. A method for preparing a sulfur/polyaniline nanotube/reduced graphene oxide composite material as claimed in any one of claims 1 to 3, comprising the steps of:
s1, uniformly dispersing the polyaniline nanotube and the graphene oxide nanosheet with the surface containing carboxyl in a solvent, and carrying out acylation reaction under the action of a catalyst to bond the graphene oxide nanosheet on the outer surface of the polyaniline nanotube through an amido bond to obtain the polyaniline nanotube/graphene oxide composite material;
s2, uniformly dispersing the polyaniline nanotube/graphene oxide composite material prepared in the step S1 in water, and adding hydrazine hydrate for reduction reaction to obtain the polyaniline nanotube/reduced graphene oxide composite material;
s3, uniformly mixing the polyaniline nanotube/reduced graphene oxide composite material prepared in the step S2 with hydrochloric acid and a sodium thiosulfate solution, carrying out a disproportionation reaction, and generating elemental sulfur in the polyaniline nanotube to obtain the sulfur/polyaniline nanotube/reduced graphene oxide composite material.
5. The preparation method of the sulfur/polyaniline nanotube/reduced graphene oxide composite material as claimed in claim 4, wherein the mass ratio of the polyaniline nanotube to the graphene oxide nanosheet with carboxyl groups on the surface is (60-95): (5-40), wherein the mass ratio of the catalyst to the graphene oxide nanosheets with carboxyl groups on the surfaces is (5-10): (95-90); the mass ratio of the hydrazine hydrate to the graphene oxide nanosheet with the carboxyl group on the surface is (1-3) to 1; the mass ratio of the sodium thiosulfate to the polyaniline nanotube/reduced graphene oxide composite material is (7-20): 1; the molar ratio of the hydrochloric acid to the sodium thiosulfate is (2-3): 1.
6. the method for preparing the sulfur/polyaniline nanotube/reduced graphene oxide composite material as claimed in claim 4 or 5, wherein in the step S1, the temperature of the acylation reaction is 20-60 ℃, the time is 6-24 h, the catalyst is concentrated sulfuric acid, and the solvent is tetrahydrofuran; in the step S2, the time of the reduction reaction is 0.5-4 h.
7. The method for preparing the sulfur/polyaniline nanotube/reduced graphene oxide composite material according to any one of claims 4 to 6, wherein the method for preparing the polyaniline nanotube comprises the following steps: uniformly dispersing an aniline monomer in water, adding an acrylic acid monomer, uniformly stirring, then adding isopropanol and ammonium persulfate in an inert atmosphere for polymerization reaction, centrifuging, washing the obtained product with hot water until the pH value is neutral, and drying to obtain a polyaniline nanotube; the molar ratio of the acrylic acid monomer to the aniline monomer is (1-4) to 1; the mass ratio of the isopropanol to the acrylic monomer is (5-15): (85-95); the mass ratio of the ammonium persulfate to the acrylic monomer is (5-15): (85-95); the polymerization reaction is carried out at the temperature of 60-100 ℃ for 2-6 h, and the inert atmosphere is one or more of nitrogen, argon, helium, neon and krypton.
8. The method for preparing the sulfur/polyaniline nanotube/reduced graphene oxide composite material as claimed in any one of claims 4 to 7, wherein the method for preparing the graphene oxide nanosheets with carboxyl groups on the surface comprises: adding the crystalline flake graphite into a nitric acid solution, carrying out heating reflux reaction, then carrying out ultrasonic dispersion and centrifugation, and heating the obtained supernatant for a certain time to obtain a graphene oxide nanosheet with a carboxyl group on the surface; the concentration of the nitric acid solution is 4-10 mol/L; the heating reflux reaction is carried out at the temperature of 60-120 ℃ for 12-24 h; the heating temperature of the supernatant is 150-250 ℃, and the heating time is 6-24 h.
9. Use of the sulfur/polyaniline nanotube/reduced graphene oxide composite material according to any one of claims 1 to 3 as a positive electrode active material for a lithium-sulfur battery.
CN202010862571.1A 2020-08-25 2020-08-25 Sulfur/polyaniline nanotube/reduced graphene oxide composite material and preparation method and application thereof Pending CN112164771A (en)

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