CN112374539A - Hierarchical porous carbon-coated MoS with shell-core structure2And a method for preparing the same - Google Patents

Hierarchical porous carbon-coated MoS with shell-core structure2And a method for preparing the same Download PDF

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CN112374539A
CN112374539A CN202011267927.3A CN202011267927A CN112374539A CN 112374539 A CN112374539 A CN 112374539A CN 202011267927 A CN202011267927 A CN 202011267927A CN 112374539 A CN112374539 A CN 112374539A
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carrageenan
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冯程程
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Suma Branch Of Anhui Shengyuan Environmental Protection New Material Co Ltd
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Abstract

The invention relates to the technical field of lithium ion batteries, and discloses a hierarchical porous carbon-coated MoS with a shell-core structure2Anode material of, MoS2The nanoflower has an ultra-high specific surface area, is beneficial to exposing more lithium ion intercalation and deintercalation sites, and is coated with carrageenan to form MoS2The nanometer flower is prepared by the following steps of under the action of an initiator,copolymerizing carrageenan and acrylonitrile to obtain polyacrylonitrile grafted carrageenan coated MoS2The nitrogen-doped porous carbon-coated MoS is obtained by pre-oxidizing and carbonizing the nanoflower2The porous structure is rich, the contact area with the electrolyte is increased, the stability and the conductivity of the porous carbon are improved by N doping, and MoS2High dispersion on porous carbon, reduced agglomeration, improved rate capability and theoretical specific capacity, and porous carbon coated MoS2The cycling stability and the electrical conductivity of the cathode material are improved, so that the hierarchical porous carbon of the shell-core structure coats the MoS2The cathode material has excellent conductivity, theoretical specific capacity, cycling stability and rate capability.

Description

Hierarchical porous carbon-coated MoS with shell-core structure2And a negative electrode materialThe preparation method thereof
Technical Field
The invention relates to the technical field of lithium ion batteries, in particular to a hierarchical porous carbon-coated MoS with a shell-core structure2The negative electrode material and a method for producing the same.
Background
The lithium ion battery has the advantages of large energy density, long cycle life and the like, and is widely applied to the fields of mobile phones, electric automobiles and the like, and the negative electrode material of the lithium ion battery is mainly graphite at present, but the theoretical specific capacity of the lithium ion battery is low, so that the pursuit of people for large capacity cannot be met, namely MoS2、SnS2、FeS2The transition metal sulfide is composed of X-M-X type three-molecule layers combined by covalent bonds and is similar to a sandwich-type layered structure, weak van der Waals force and large interlayer spacing exist between the layers, lithium ions are favorably inserted and extracted, and the transition metal sulfide has excellent theoretical specific capacity.
Wherein MoS2The high-performance composite material has excellent theoretical specific capacity and lower cost, has wide application prospect on the lithium ion battery cathode material, but is easy to agglomerate due to weak van der Waals force, has poor conductivity and serious volume effect, can cause structure pulverization, and enables MoS2The cycle stability and rate capability of the negative electrode material are poor, the porous carbon has excellent conductivity, chemical stability, structural stability and higher specific surface area, and the porous carbon is adopted to coat MoS2Can improve MoS2Thereby improving MoS2The cycle stability and the rate capability of the cathode material are improved, and the electrochemical properties of the porous carbon can be further improved by doping elements.
Technical problem to be solved
Aiming at the defects of the prior art, the invention provides a hierarchical porous carbon-coated MoS with a shell-core structure2The cathode material and the preparation method thereof solve the problem of MoS2The conductivity, the cycling stability and the rate capability of the cathode material are poor.
(II) technical scheme
To achieve the above object, the present invention provides the following techniquesThe technical scheme is as follows: hierarchical porous carbon-coated MoS with shell-core structure2The shell-core structure of the hierarchical porous carbon-coated MoS2The preparation method of the anode material comprises the following steps:
(1) adding deionized water, thioacetamide, silicotungstic acid and sodium molybdate into a reaction bottle, wherein the mass ratio of the deionized water to the thioacetamide to the silicotungstic acid to the sodium molybdate is 100-;
(2) adding a sodium hydroxide solution and carrageenan into a reaction bottle, uniformly dispersing at 80-110 ℃, adding molybdenum disulfide nanoflowers, uniformly dispersing to obtain a mixed solution, adding chloroform, span 80 and cyclohexane in a volume ratio of 20-35:2-5:100 into another reaction bottle, uniformly dispersing, pouring the mixed solution into the other reaction bottle, emulsifying for 10-25min by using an emulsifying machine, adding epoxy chloropropane, reacting for 3-5h at 30-50 ℃, evaporating the solvent to dryness, washing with absolute ethyl alcohol, and drying to obtain carrageenan-coated molybdenum disulfide nanoflowers;
(3) adding deionized water, carrageenan-coated molybdenum disulfide nanoflowers, emulsifier sodium dodecyl sulfate and buffer ammonium bicarbonate into a reaction bottle, uniformly dispersing in a nitrogen atmosphere, heating to 70-80 ℃, adding acrylonitrile, uniformly dispersing, adding initiator ammonium persulfate, stirring for reaction for 30-90min, adding methanol, standing for precipitation for 3-5h, filtering, soaking in methanol for purification, and drying to obtain polyacrylonitrile-grafted carrageenan-coated molybdenum disulfide nanoflowers;
(4) adding deionized water, zinc chloride and polyacrylonitrile grafted carrageenan to coat the molybdenum disulfide nanoflowers, stirring for 18-36h, drying, placing in a tubular furnace, pre-oxidizing for 1.5-3h at 300 ℃ under 260 ℃ and carbonizing for 2-3h at 800 ℃ under nitrogen atmosphere, centrifuging, washing with an alcohol-water solution of dilute hydrochloric acid to remove zinc chloride, and drying to obtain the shell-core structured hierarchical porous carbon-coated MoS2The negative electrode material of (1).
Preferably, the hydrothermal device in the step (1) comprises a main body, a first partition plate is movably connected in the middle of the main body, a second partition plate is movably connected in the middle of the main body, a motor is movably connected to the bottom of the main body, a first gear is movably connected to the top of the motor, a second gear is movably connected to the left of the first gear, a third gear is movably connected to the right of the second gear, a fourth gear is movably connected to the left of the third gear, an objective table is movably connected to the top of the fourth gear, and a reaction kettle is movably connected to the top of the objective.
Preferably, the mass ratio of the carrageenan, the molybdenum disulfide nanoflower and the epichlorohydrin in the step (2) is 100:180-300: 700-1000.
Preferably, in the step (3), the carrageenan is coated with the molybdenum disulfide nanoflower, the sodium dodecyl sulfate, the ammonium bicarbonate, the acrylonitrile and the ammonium persulfate in a mass ratio of 120-180:0.1-0.4:0.5-1.1:100: 0.4-1.
Preferably, the mass ratio of the zinc chloride to the polyacrylonitrile grafted carrageenan to coat the molybdenum disulfide nanoflower in the step (4) is 45-75: 100.
(III) advantageous technical effects
Compared with the prior art, the invention has the following beneficial technical effects:
the hierarchical porous carbon-coated MoS with shell-core structure2The sodium molybdate reacts with silicotungstic acid to generate dodecamolybdosilicic acid, thioacetamide reacts with water to generate hydrogen sulfide, and the dodecamolybdosilicic acid further reacts with the hydrogen sulfide to generate MoS2Nanosheets, MoS2The nano-sheets are subjected to surface-edge combination and self-assembly to form MoS2Nanoflower, MoS2Unique nano flower-like morphology, super-high specific surface area and contribution to exposing more lithium ion intercalation and deintercalation sites, hydroxyl on the carrageenan and epichlorohydrin are subjected to crosslinking reaction, and then the carrageenan is taken as a shell layer to MoS2Coating the nanoflower to form the carrageenan-coated MoS with a shell-core structure2Nanometer flower, under the action of initiator ammonium persulfate, hydroxyl on shell layer carrageenan removes H atom, generates active free radical and acrylonitrile monomer copolymerization, makes carrageenan and polyacrylonitrile covalently graft, obtains polyacrylonitrile graft carrageenan coating MoS2The nanoflower adopts carrageenan as a carbon source and polyacrylonitrile as a carbon source and a nitrogen sourceZinc chloride is used as a pore-forming agent, and nitrogen-doped hierarchical porous carbon coated MoS with a shell-core structure is obtained through preoxidation and carbonization2Wherein MoS2The nanometer flower is used as a core, the carrageenan carbonized porous carbon is used as an inner shell, and the polyacrylonitrile carbonized porous carbon is used as an outer shell, so that MoS2The nanoflowers are highly dispersed in the hierarchical porous carbon, so that MoS is reduced2The agglomeration phenomenon of the nanoflower is beneficial to exposing more electrochemical active sites.
The hierarchical porous carbon-coated MoS with shell-core structure2The anode material, carrageenan and polyacrylonitrile carbonization form nitrogen-doped hierarchical porous carbon with double shells, the pore structure is rich, the specific surface area is ultrahigh, the contact area with electrolyte is increased, the exchange and transfer of lithium ions are accelerated, the stacking of the layered structure of the porous carbon is inhibited by N atom doping, the conversion of amorphous carbon to graphitized carbon is promoted, the stability of the porous carbon is improved, meanwhile, the interaction of lone pair electrons of the N atom and a graphite pi system is promoted, the Fermi level is promoted to be improved to a conduction band, so that the conductivity of the hierarchical porous carbon is improved, and MoS2The nanometer flowers are highly dispersed on the hierarchical porous carbon, so that MoS is reduced2The nanoflower is agglomerated, the specific surface area is increased, the contact with the electrolyte is more sufficient, the transmission of lithium ions is accelerated, the rate capability and the theoretical specific capacity of the cathode material are improved, and meanwhile, the hierarchical porous carbon is MoS2Provides a certain space and inhibits MoS2The volume effect generated in the process of the insertion and the extraction of the lithium ions improves the cycling stability of the cathode material, and the nitrogen-doped hierarchical porous carbon-coated MoS2The nanometer flower reduces the charge transfer resistance of the cathode material, improves the conductivity, and leads the hierarchical porous carbon with the shell-core structure to coat the MoS2The cathode material has excellent conductivity, theoretical specific capacity, cycling stability and rate capability.
Drawings
FIG. 1 is a schematic diagram of a hydrothermal apparatus;
FIG. 2 is a first schematic view of a gear structure;
fig. 3 is a schematic view of a gear structure two.
1. A main body; 2. a first clapboard; 3. a second clapboard; 4. a motor; 5. a first gear; 6. a second gear; 7. a third gear; 8. a fourth gear; 9. an object stage; 10. and (5) a reaction kettle.
Detailed Description
To achieve the above object, the present invention provides the following embodiments and examples: hierarchical porous carbon-coated MoS with shell-core structure2The shell-core structure of the hierarchical porous carbon-coated MoS2The preparation method of the anode material comprises the following steps:
(1) adding deionized water, thioacetamide, silicotungstic acid and sodium molybdate into a reaction bottle, wherein the mass ratio of the deionized water to the thioacetamide to the silicotungstic acid to the sodium molybdate is 100-130:100, the deionized water, the thioacetamide, the silicotungstic acid and the sodium molybdate are uniformly dispersed, the thioacetamide, the silicotungstic acid and the sodium molybdate are moved into a reaction kettle and are arranged in a hydrothermal device, the hydrothermal device comprises a main body, the middle of the main body is movably connected with a first partition plate, the middle of the main body is movably connected with a second partition plate, the bottom of the main body is movably connected with a motor, the top of the motor is movably connected with a first gear, the left side of the first gear is movably connected with a second gear, the right side of the second gear is movably connected with a third gear, the left side of the third gear is movably connected with a fourth gear, the top, obtaining molybdenum disulfide nanoflower;
(2) adding a sodium hydroxide solution and carrageenan into a reaction bottle, uniformly dispersing at 80-110 ℃, adding molybdenum disulfide nanoflowers, uniformly dispersing to obtain a mixed solution, adding trichloromethane, span 80 and cyclohexane in a volume ratio of 20-35:2-5:100 into the other reaction bottle, uniformly dispersing, pouring the mixture into the mixed solution, emulsifying for 10-25min by using an emulsifying machine, adding epoxy chloropropane, wherein the mass ratio of the carrageenan, the molybdenum disulfide nanoflowers to the epoxy chloropropane is 100: 180-;
(3) adding deionized water, carrageenan-coated molybdenum disulfide nanoflowers, emulsifier sodium dodecyl sulfate and buffer ammonium bicarbonate into a reaction bottle, uniformly dispersing in a nitrogen atmosphere, heating to 70-80 ℃, adding acrylonitrile, uniformly dispersing, adding initiator ammonium persulfate, wherein the mass ratio of the carrageenan-coated molybdenum disulfide nanoflowers, the sodium dodecyl sulfate, the ammonium bicarbonate, the acrylonitrile and the ammonium persulfate is 120 plus materials 180:0.1-0.4:0.5-1.1:100:0.4-1, stirring for reaction for 30-90min, adding methanol, standing for precipitation for 3-5h, filtering, soaking and purifying in the methanol, and drying to obtain polyacrylonitrile-grafted carrageenan-coated molybdenum disulfide nanoflowers;
(4) adding deionized water, zinc chloride and polyacrylonitrile grafted carrageenan to coat the molybdenum disulfide nanoflower with the mass ratio of 45-75:100 into a reaction bottle, stirring for 18-36h, drying, placing in a tube furnace, pre-oxidizing for 1.5-3h at the temperature of 260-300 ℃, carbonizing for 2-3h at the temperature of 800 ℃ in the nitrogen atmosphere, centrifuging, washing with an alcohol-water solution of diluted hydrochloric acid to remove zinc chloride, and drying to obtain the shell-core structured hierarchical porous carbon coated MoS2The negative electrode material of (1).
Example 1
(1) Adding deionized water, thioacetamide, silicotungstic acid and sodium molybdate into a reaction bottle, wherein the mass ratio of the deionized water, the thioacetamide, the silicotungstic acid and the sodium molybdate is 100:100:100, uniformly dispersing, transferring the reaction bottle into a reaction kettle, and placing the reaction bottle into a hydrothermal device, wherein the hydrothermal device comprises a main body, the middle of the main body is movably connected with a first partition plate, the middle of the main body is movably connected with a second partition plate, the bottom of the main body is movably connected with a motor, the top of the motor is movably connected with a first gear, the left side of the first gear is movably connected with a second gear, the right side of the second gear is movably connected with a third gear, the left side of the third gear is movably connected with a fourth gear, the top of the fourth gear is movably connected with a stage, the top of the stage is movably connected with the reaction;
(2) adding a sodium hydroxide solution and carrageenan into a reaction bottle, uniformly dispersing at 80 ℃, adding molybdenum disulfide nanoflowers, uniformly dispersing to obtain a mixed solution, adding trichloromethane, span 80 and cyclohexane in a volume ratio of 20:2:100 into another reaction bottle, uniformly dispersing, pouring the mixture into the mixed solution, emulsifying for 10min by using an emulsifying machine, adding epoxy chloropropane, reacting for 3h at 30 ℃, evaporating the solvent, washing with absolute ethyl alcohol, and drying to obtain carrageenan-coated molybdenum disulfide nanoflowers, wherein the mass ratio of the carrageenan, the molybdenum disulfide nanoflowers to the epoxy chloropropane is 100:180: 700;
(3) adding deionized water, carrageenan-coated molybdenum disulfide nanoflowers, emulsifier sodium dodecyl sulfate and buffer ammonium bicarbonate into a reaction bottle, uniformly dispersing in a nitrogen atmosphere, heating to 70 ℃, adding acrylonitrile, uniformly dispersing, and adding initiator ammonium persulfate, wherein the mass ratio of the carrageenan-coated molybdenum disulfide nanoflowers to the sodium dodecyl sulfate to the ammonium bicarbonate to the acrylonitrile to the ammonium persulfate is 120:0.1:0.5:100:0.4, stirring for reaction for 30min, adding methanol, standing for precipitation for 3h, filtering, soaking in the methanol for purification, and drying to obtain polyacrylonitrile-grafted carrageenan-coated molybdenum disulfide nanoflowers;
(4) adding deionized water, zinc chloride and polyacrylonitrile grafted carrageenan to coat molybdenum disulfide nanoflowers in a mass ratio of 45:100 into a reaction bottle, stirring for 18h, drying, placing in a tubular furnace, pre-oxidizing for 1.5h at 260 ℃, carbonizing for 2h at 700 ℃ in a nitrogen atmosphere, centrifuging, washing with an alcohol-water solution of dilute hydrochloric acid to remove zinc chloride, and drying to obtain the shell-core structured hierarchical porous carbon-coated MoS2The negative electrode material of (1).
Example 2
(1) Adding deionized water, thioacetamide, silicotungstic acid and sodium molybdate into a reaction bottle, wherein the mass ratio of the deionized water, the thioacetamide, the silicotungstic acid and the sodium molybdate is 110:110:100, uniformly dispersing, transferring the reaction bottle into a reaction kettle, and placing the reaction bottle into a hydrothermal device, wherein the hydrothermal device comprises a main body, the middle of the main body is movably connected with a first partition plate, the middle of the main body is movably connected with a second partition plate, the bottom of the main body is movably connected with a motor, the top of the motor is movably connected with a first gear, the left side of the first gear is movably connected with a second gear, the right side of the second gear is movably connected with a third gear, the left side of the third gear is movably connected with a fourth gear, the top of the fourth gear is movably connected with a stage, the top of the stage is movably connected with the reaction;
(2) adding a sodium hydroxide solution and carrageenan into a reaction bottle, uniformly dispersing at 90 ℃, adding molybdenum disulfide nanoflowers, uniformly dispersing to obtain a mixed solution, adding trichloromethane, span 80 and cyclohexane in a volume ratio of 25:3:100 into another reaction bottle, uniformly dispersing, pouring the mixture into the mixed solution, emulsifying for 15min by using an emulsifying machine, adding epoxy chloropropane, reacting for 3.5h at 35 ℃, evaporating the solvent, washing with absolute ethyl alcohol, and drying to obtain carrageenan-coated molybdenum disulfide nanoflowers, wherein the mass ratio of the carrageenan, the molybdenum disulfide nanoflowers to the epoxy chloropropane is 100:220: 800;
(3) adding deionized water, carrageenan-coated molybdenum disulfide nanoflowers, emulsifier sodium dodecyl sulfate and buffer ammonium bicarbonate into a reaction bottle, uniformly dispersing in a nitrogen atmosphere, heating to 75 ℃, adding acrylonitrile, uniformly dispersing, and adding initiator ammonium persulfate, wherein the mass ratio of the carrageenan-coated molybdenum disulfide nanoflowers to be 140:0.2:0.7:100:0.6, stirring and reacting for 50min, adding methanol, standing and precipitating for 3.5;
(4) adding deionized water, zinc chloride and polyacrylonitrile grafted carrageenan to coat molybdenum disulfide nanoflowers in a mass ratio of 55:100 into a reaction bottle, stirring for 24h, drying, placing in a tubular furnace, pre-oxidizing for 2h at 270 ℃, carbonizing for 2.5h at 730 ℃ in a nitrogen atmosphere, centrifuging, washing with an alcohol-water solution of dilute hydrochloric acid to remove zinc chloride, and drying to obtain the shell-core structured hierarchical porous carbon-coated MoS2The negative electrode material of (1).
Example 3
(1) Adding deionized water, thioacetamide, silicotungstic acid and sodium molybdate into a reaction bottle, wherein the mass ratio of the deionized water, the thioacetamide, the silicotungstic acid and the sodium molybdate is 120:120:100, uniformly dispersing, transferring the reaction bottle into a reaction kettle, and placing the reaction bottle into a hydrothermal device, wherein the hydrothermal device comprises a main body, the middle of the main body is movably connected with a first partition plate, the middle of the main body is movably connected with a second partition plate, the bottom of the main body is movably connected with a motor, the top of the motor is movably connected with a first gear, the left side of the first gear is movably connected with a second gear, the right side of the second gear is movably connected with a third gear, the left side of the third gear is movably connected with a fourth gear, the top of the fourth gear is movably connected with a stage, the top of the stage is movably connected with the reaction;
(2) adding a sodium hydroxide solution and carrageenan into a reaction bottle, uniformly dispersing at 100 ℃, adding molybdenum disulfide nanoflowers, uniformly dispersing to obtain a mixed solution, adding trichloromethane, span 80 and cyclohexane in a volume ratio of 30:4:100 into another reaction bottle, uniformly dispersing, pouring the mixture into the mixed solution, emulsifying for 20min by using an emulsifying machine, adding epoxy chloropropane, reacting for 4h at 40 ℃, evaporating the solvent, washing with absolute ethyl alcohol, and drying to obtain carrageenan-coated molybdenum disulfide nanoflowers, wherein the mass ratio of the carrageenan, the molybdenum disulfide nanoflowers to the epoxy chloropropane is 100:260: 900;
(3) adding deionized water, carrageenan-coated molybdenum disulfide nanoflowers, emulsifier sodium dodecyl sulfate and buffer ammonium bicarbonate into a reaction bottle, uniformly dispersing in a nitrogen atmosphere, heating to 75 ℃, adding acrylonitrile, uniformly dispersing, and adding initiator ammonium persulfate, wherein the mass ratio of the carrageenan-coated molybdenum disulfide nanoflowers, the sodium dodecyl sulfate, the ammonium bicarbonate, the acrylonitrile and the ammonium persulfate is 160:0.3:0.9:100:0.8, stirring and reacting for 70min, adding methanol, standing and precipitating for 4h, filtering, soaking and purifying in the methanol, and drying to obtain polyacrylonitrile-grafted carrageenan-coated molybdenum disulfide nanoflowers;
(4) adding deionized water, zinc chloride and polyacrylonitrile grafted carrageenan to coat molybdenum disulfide nanoflowers in a mass ratio of 65:100 into a reaction bottle, stirring for 30h, drying, placing in a tube furnace, pre-oxidizing for 2.5h at 280 ℃, carbonizing for 2.5h at 760 ℃ in nitrogen atmosphere, centrifuging, washing with an alcohol-water solution of dilute hydrochloric acid to remove zinc chloride, and drying to obtain the shell-core structured hierarchical porous carbon-coated MoS2The negative electrode material of (1).
Example 4
(1) Adding deionized water, thioacetamide, silicotungstic acid and sodium molybdate into a reaction bottle, wherein the mass ratio of the deionized water, the thioacetamide, the silicotungstic acid and the sodium molybdate is 130:130:100, uniformly dispersing, transferring the reaction bottle into a reaction kettle, and placing the reaction bottle into a hydrothermal device, wherein the hydrothermal device comprises a main body, the middle of the main body is movably connected with a first partition plate, the middle of the main body is movably connected with a second partition plate, the bottom of the main body is movably connected with a motor, the top of the motor is movably connected with a first gear, the left side of the first gear is movably connected with a second gear, the right side of the second gear is movably connected with a third gear, the left side of the third gear is movably connected with a fourth gear, the top of the fourth gear is movably connected with a carrying platform, the top of the carrying platform is movably connected with;
(2) adding a sodium hydroxide solution and carrageenan into a reaction bottle, uniformly dispersing at 110 ℃, adding molybdenum disulfide nanoflowers, uniformly dispersing to obtain a mixed solution, adding trichloromethane, span 80 and cyclohexane in a volume ratio of 35:5:100 into another reaction bottle, uniformly dispersing, pouring the mixture into the mixed solution, emulsifying for 25min by using an emulsifying machine, adding epoxy chloropropane, reacting for 5h at 50 ℃, evaporating the solvent, washing with absolute ethyl alcohol, and drying to obtain carrageenan-coated molybdenum disulfide nanoflowers, wherein the mass ratio of the carrageenan, the molybdenum disulfide nanoflowers to the epoxy chloropropane is 100:300:1000, and the reaction is carried out for 5h at 50 ℃;
(3) adding deionized water, carrageenan-coated molybdenum disulfide nanoflowers, emulsifier sodium dodecyl sulfate and buffer ammonium bicarbonate into a reaction bottle, uniformly dispersing in a nitrogen atmosphere, heating to 80 ℃, adding acrylonitrile, uniformly dispersing, and adding initiator ammonium persulfate, wherein the mass ratio of the carrageenan-coated molybdenum disulfide nanoflowers to the sodium dodecyl sulfate to the ammonium bicarbonate to the acrylonitrile to the ammonium persulfate is 180:0.4:1.1:100:1, stirring and reacting for 90min, adding methanol, standing and precipitating for 5h, filtering, soaking and purifying in the methanol, and drying to obtain polyacrylonitrile-grafted carrageenan-coated molybdenum disulfide nanoflowers;
(4) adding deionized water, zinc chloride and polyacrylonitrile grafted carrageenan into a reaction bottleCoating molybdenum disulfide nanoflowers with the mass ratio of 75:100, stirring for 36h, drying, placing in a tubular furnace, pre-oxidizing for 3h at 300 ℃, carbonizing for 3h at 800 ℃ in nitrogen atmosphere, centrifuging, washing with an alcohol-water solution of dilute hydrochloric acid to remove zinc chloride, and drying to obtain the shell-core structured hierarchical porous carbon-coated MoS2The negative electrode material of (1).
Comparative example 1
(1) Adding deionized water, thioacetamide, silicotungstic acid and sodium molybdate into a reaction bottle, wherein the mass ratio of the deionized water to the thioacetamide to the silicotungstic acid to the sodium molybdate is 80:70:100, dispersing the deionized water, thioacetamide to the silicotungstic acid to the sodium molybdate, transferring the mixture into a reaction kettle, and placing the mixture into a hydrothermal device, wherein the hydrothermal device comprises a main body, the middle of the main body is movably connected with a first partition plate, the middle of the main body is movably connected with a second partition plate, the bottom of the main body is movably connected with a motor, the top of the motor is movably connected with a first gear, the left side of the first gear is movably connected with a second gear, the right side of the second gear is movably connected with a third gear, the left side of the third gear is movably connected with a fourth gear, the top of the fourth;
(2) adding a sodium hydroxide solution and carrageenan into a reaction bottle, uniformly dispersing at 95 ℃, adding molybdenum disulfide nanoflowers, uniformly dispersing to obtain a mixed solution, adding trichloromethane, span 80 and cyclohexane in a volume ratio of 15:1:100 into another reaction bottle, uniformly dispersing, pouring the mixture into the mixed solution, emulsifying for 10min by using an emulsifying machine, adding epoxy chloropropane, reacting for 4h at 40 ℃, evaporating the solvent, washing with absolute ethyl alcohol, and drying to obtain carrageenan-coated molybdenum disulfide nanoflowers, wherein the mass ratio of the carrageenan to the molybdenum disulfide nanoflowers to the epoxy chloropropane is 100:120: 500;
(3) adding deionized water, carrageenan-coated molybdenum disulfide nanoflowers, emulsifier sodium dodecyl sulfate and buffer ammonium bicarbonate into a reaction bottle, uniformly dispersing in a nitrogen atmosphere, heating to 75 ℃, adding acrylonitrile, uniformly dispersing, and adding initiator ammonium persulfate, wherein the mass ratio of the carrageenan-coated molybdenum disulfide nanoflowers to the sodium dodecyl sulfate to the ammonium bicarbonate to the acrylonitrile to the ammonium persulfate is 100:0.05:0.3:100:0.2, stirring and reacting for 60min, adding methanol, standing and precipitating for 4h, filtering, soaking and purifying in the methanol, and drying to obtain polyacrylonitrile-grafted carrageenan-coated molybdenum disulfide nanoflowers;
(4) adding deionized water, zinc chloride and polyacrylonitrile grafted carrageenan to coat molybdenum disulfide nanoflowers in a mass ratio of 40:100 into a reaction bottle, stirring for 24h, drying, placing in a tubular furnace, pre-oxidizing for 2h at 280 ℃, carbonizing for 2.5h at 750 ℃ in a nitrogen atmosphere, centrifuging, washing with an alcohol-water solution of dilute hydrochloric acid to remove zinc chloride, and drying to obtain the shell-core structured hierarchical porous carbon-coated MoS2The negative electrode material of (1).
Conductive acetylene black, a binder polyvinylidene fluoride, and the shell-core structured hierarchical porous carbon-coated MoS obtained in examples and comparative examples were added to an N-methylpyrrolidone solution in a mass ratio of 1:1:82The negative electrode material is uniformly mixed, uniformly coated on a copper foil, dried, and made into an electrode plate serving as a positive electrode, a metal lithium plate serving as a negative electrode, Celgard 2500 serving as a diaphragm and 1mol/L electrolyte of LiPF (lithium ion plasma display panel)6And assembling a button cell in the glove box, and performing constant-current charge and discharge test on the assembled cell on a DBM-Z4815 test system according to the test standard GB/T36276-2018.
Figure BDA0002776684110000111

Claims (5)

1. Hierarchical porous carbon-coated MoS with shell-core structure2The negative electrode material of (2), characterized in that: hierarchical porous carbon-coated MoS of the shell-core structure2The preparation method of the anode material comprises the following steps:
(1) adding thioacetamide, silicotungstic acid and sodium molybdate into deionized water according to the mass ratio of 100-;
(2) adding carrageenan into a sodium hydroxide solution, uniformly dispersing at 80-110 ℃, adding molybdenum disulfide nanoflowers, uniformly dispersing to obtain a mixed solution, adding trichloromethane, span 80 and cyclohexane in a volume ratio of 20-35:2-5:100 into another reaction bottle, uniformly dispersing, pouring the mixture into the mixed solution, emulsifying for 10-25min by using an emulsifying machine, adding epoxy chloropropane, reacting for 3-5h at 30-50 ℃, evaporating the solvent, washing and drying to obtain carrageenan-coated molybdenum disulfide nanoflowers;
(3) adding carrageenan coated molybdenum disulfide nanoflowers, emulsifier sodium dodecyl sulfate and buffer ammonium bicarbonate into deionized water, uniformly dispersing in a nitrogen atmosphere, heating to 70-80 ℃, adding acrylonitrile, uniformly dispersing, adding initiator ammonium persulfate, stirring for reaction for 30-90min, adding methanol, standing for precipitation for 3-5h, filtering, soaking in methanol for purification, and drying to obtain polyacrylonitrile grafted carrageenan coated molybdenum disulfide nanoflowers;
(4) adding zinc chloride and polyacrylonitrile grafted carrageenan to coat the molybdenum disulfide nanoflower into deionized water, stirring for 18-36h, drying, placing in a tube furnace, pre-oxidizing for 1.5-3h at the temperature of 260-plus-one and 300 ℃, carbonizing for 2-3h at the temperature of 700-plus-one and 800 ℃ in a nitrogen atmosphere, centrifuging, washing and drying to obtain the shell-core structured hierarchical porous carbon-coated MoS2The negative electrode material of (1).
2. The shell-core structured hierarchical porous carbon coated MoS of claim 12The negative electrode material of (2), characterized in that: the medium-temperature water heating device in the step (1) comprises a main body, wherein a first partition plate is movably connected to the middle of the main body, a second partition plate is movably connected to the middle of the main body, a motor is movably connected to the bottom of the main body, the top of the motor is movably connected with a first gear, the left side of the first gear is movably connected with a second gear, the right side of the second gear is movably connected with a third gear, the left side of the third gear is movably connected with a fourth gear, the top of the fourth gear is movably connected with an objective table, and the top of.
3. A shell-core structured graded porous carbon pack as claimed in claim 1MoS-coated2The negative electrode material of (2), characterized in that: in the step (2), the mass ratio of the carrageenan, the molybdenum disulfide nanoflower and the epichlorohydrin is 100:180-300: 700-1000.
4. The shell-core structured hierarchical porous carbon coated MoS of claim 12The negative electrode material of (2), characterized in that: in the step (3), the carrageenan is coated with the molybdenum disulfide nanoflower, the sodium dodecyl sulfate, the ammonium bicarbonate, the acrylonitrile and the ammonium persulfate according to the mass ratio of 120-180:0.1-0.4:0.5-1.1:100: 0.4-1.
5. The shell-core structured hierarchical porous carbon coated MoS of claim 12The negative electrode material of (2), characterized in that: in the step (4), the mass ratio of the zinc chloride to the polyacrylonitrile grafted carrageenan to coat the molybdenum disulfide nanoflower is 45-75: 100.
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CN113451054A (en) * 2021-06-28 2021-09-28 鹏盛国能(深圳)新能源集团有限公司 Lithium ion capacitor battery and preparation method thereof
CN115367745A (en) * 2021-05-19 2022-11-22 北京化工大学 Tungsten-containing substance hybrid and nitrogen-doped porous carbon material and preparation method thereof

Cited By (3)

* Cited by examiner, † Cited by third party
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CN115367745A (en) * 2021-05-19 2022-11-22 北京化工大学 Tungsten-containing substance hybrid and nitrogen-doped porous carbon material and preparation method thereof
CN115367745B (en) * 2021-05-19 2023-11-24 北京化工大学 Tungsten-containing substance hybridization and nitrogen-doped porous carbon material and preparation method thereof
CN113451054A (en) * 2021-06-28 2021-09-28 鹏盛国能(深圳)新能源集团有限公司 Lithium ion capacitor battery and preparation method thereof

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