CN110797518A - Carbon nano tube coated NiCo2S4Load SeS2Positive electrode material of lithium-sulfur battery and preparation method thereof - Google Patents

Carbon nano tube coated NiCo2S4Load SeS2Positive electrode material of lithium-sulfur battery and preparation method thereof Download PDF

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CN110797518A
CN110797518A CN201911031378.7A CN201911031378A CN110797518A CN 110797518 A CN110797518 A CN 110797518A CN 201911031378 A CN201911031378 A CN 201911031378A CN 110797518 A CN110797518 A CN 110797518A
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王燕清
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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    • H01M4/02—Electrodes composed of, or comprising, active material
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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
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/58—Selection of substances as active materials, active masses, active liquids of inorganic compounds other than oxides or hydroxides, e.g. sulfides, selenides, tellurides, halogenides or LiCoFy; of polyanionic structures, e.g. phosphates, silicates or borates
    • H01M4/581—Chalcogenides or intercalation compounds thereof
    • H01M4/5815—Sulfides
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
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    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/028—Positive electrodes
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    • Y02E60/10—Energy storage using batteries

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Abstract

The invention relates to the technical field of lithium-sulfur battery anode materials and discloses a carbon nano tube coated NiCo2S4Load SeS2The positive electrode material of the lithium-sulfur battery and the preparation method thereof comprise the following formula raw materials: hydroxylated carbon nanotube, hollow NiCo2S4Balls, selenium dioxide, sodium sulfide and glacial acetic acid. The carbon nano tube is coated with NiCo2S4Load SeS2Lithium-sulfur battery positive electrode material, preparation method thereof and SeS2Has high conductivity and good electrochemical cycle stability, and is hollow NiCo2S4The sphere has a large specific surface area and a large number of active sites,can well load SeS2Has good adsorption capacity to sulfur lithium compound, promotes the adsorption and catalysis capacity of the anode material to polysulfide, has excellent conductivity, is applied to NiCo2S4Load SeS2A three-dimensional network conductive structure is formed between the two carbon nanotubes, a transmission channel is increased for lithium ions and charges, the transmission and diffusion rates of the ions and the charges are increased, and the polar hydroxyl groups of the carbon nanotubes effectively promote the polar Li2And (4) effective deposition of S.

Description

Carbon nano tube coated NiCo2S4Load SeS2Positive electrode material of lithium-sulfur battery and preparation method thereof
Technical Field
The invention relates to the technical field of lithium-sulfur battery anode materials, in particular to a carbon nano tube coated NiCo2S4Load SeS2A positive electrode material for a lithium-sulfur battery and a method for manufacturing the same.
Background
The lithium-sulfur battery is a kind of lithium battery, it uses sulfide as the battery positive pole, the metal lithium is regarded as the negative pole, the negative pole reaction loses the electron for lithium and turns into the lithium ion during discharging, the positive pole reaction is sulfur and lithium ion and electron reaction produce sulfide, the potential difference of the positive pole and negative pole reaction is the discharge voltage that the lithium-sulfur battery provides, under the effect of external voltage, the positive pole and negative pole reaction of the lithium-sulfur battery go on reversely, namely the charging process, the theoretical specific capacity and battery theoretical specific energy of the lithium-sulfur battery are all higher, and it is smaller to the environmental pollution, it is a kind of lithium battery with very potential.
At present, the anode material of the lithium-sulfur battery mainly comprises a polymer-sulfur composite material, the polymer has good film forming property, the electrode interface constructed by polar functional groups has good thiophilic property, and sulfur particles are easy to coat and fix sulfur on the surface, but the conductivity of the polymer is not high, and the electrochemical performance of the polymer is unstable in the charging and discharging processes of the battery; carbon-sulfur composite material, carbon material is light and good in conductivity, but the capability of physical adsorption of sulfur of porous structure carbon material is limited, and the surface of the carbon material is mostly nonpolar, so that polar Li is inhibited2The effective deposition of S can influence the electronic conductivity of the material when hetero atoms are introduced to increase the polarity of the carbon material interface; the surface of the metal compound is provided with a large number of polar active sites, so that the nano metal compound-sulfur composite material has a good chemical adsorption effect on a sulfur lithium compound, but the chemical adsorption is monomolecular adsorption, so that the adsorption capacity is not high, when the sulfur content in the anode material is high, sulfur ions can diffuse into electrolyte under the action of concentration difference, and the sulfur fixing effect of the anode material is reduced;
disclosure of Invention
Technical problem to be solved
Aiming at the defects of the prior art, the invention provides a carbon nano tube coated NiCo2S4 loaded SeS2 lithium-sulfur battery positive electrode material and a preparation method thereof, solves the problems that the carbon-sulfur composite positive electrode material has limited capability of physically adsorbing sulfur and is easy to inhibit polar Li2The problem of effective deposition of S and the problems of low chemical adsorption capacity and poor sulfur fixation performance of the metal compound-sulfur composite anode material are solved.
(II) technical scheme
In order to achieve the purpose, the invention provides the following technical scheme: carbon nano tube coated NiCo2S4Load(s)SeS2The positive electrode material of the lithium-sulfur battery and the preparation method thereof comprise the following formula raw materials in parts by weight: 16-36 parts of hydroxylated carbon nanotube and 15-20 parts of hollow NiCo2S4The preparation method comprises the following steps of ball, 7-8 parts of selenium dioxide, 14-20 parts of sodium sulfide and 28-36 parts of glacial acetic acid: cobalt nitrate, nickel chloride, glycerol, distilled water, thioacetamide and absolute ethyl alcohol.
Preferably, the content of active hydroxyl in the hydroxylated carbon nanotube is more than or equal to 5 percent, the specification is 10-30um in length and 2-8nm in diameter.
Preferably, said hollow NiCo2S4The preparation of the ball comprises the following steps:
(1) adding a proper amount of distilled water into a reaction bottle, adding cobalt nitrate and nickel chloride, stirring at a constant speed until the cobalt nitrate and the nickel chloride are dissolved, sequentially adding absolute ethyl alcohol and glycerol, wherein the volume ratio of the distilled water to the absolute ethyl alcohol to the glycerol is 1:3-5:2-3, transferring the solution into a hydrothermal automatic reaction kettle, heating to 190-, after the reaction is finished, cooling the materials to room temperature, filtering to remove absolute ethyl alcohol to obtain a solid product, washing with absolute ethyl alcohol, heating in an oven to 50-60 ℃, and fully drying to obtain the hollow NiCo2S4A ball.
Preferably, the molar ratio of the nickel chloride to the cobalt nitrate is 1: 2.2-2.5.
Preferably, the mass ratio of the Ni-Co-glycerol precursor to the thioacetamide is 1: 18-25.
Preferably, the carbon nanotube is coated with NiCo2S4Load SeS2The preparation method of the lithium-sulfur battery positive electrode material comprises the following steps:
(1) in-situ method for preparing hollow NiCo2S4Ball negativeCarrier SeS2: adding a proper amount of distilled water and 15-20 parts of hollow NiCo into a reaction bottle2S4Adding 7-8 parts of selenium dioxide, 14-20 parts of sodium sulfide and 28-36 parts of glacial acetic acid into the balls in sequence, stirring until the solids are dissolved, transferring the solution into a hydrothermal synthesis automatic reaction kettle, heating the temperature of the reaction kettle to 80-90 ℃, stirring at a constant speed for reaction for 4-8 hours, cooling the materials to room temperature after the reaction is finished, placing the materials into a high-speed centrifuge for centrifugal separation, removing the upper layer solution to obtain a solid mixture, washing the solid mixture with distilled water, placing the solid mixture into an oven for full drying, and preparing the hollow NiCo2S4Ball load SeS2。
(2) The hollow NiCo obtained above is added2S4Ball load SeS2Adding into a planetary ball mill, adding appropriate amount of anhydrous ethanol, ball milling at revolution rate of 50-80rpm and rotation rate of 580-620rpm until the materials all pass through 1340 mesh sieve, placing the materials passing through the sieve and the anhydrous ethanol into a reaction bottle, adding 16-36 parts of hydroxylated carbon nanotube, placing the reaction bottle into an ultrasonic treatment instrument, heating to 50-60 deg.C, ultrasonic frequency of 22-28KHz, ultrasonic dispersing for 2-5h, centrifuging the materials by a high-speed centrifuge, removing the upper ethanol solution, placing the solidified compound in an oven, heating to 60-80 deg.C, and drying to obtain carbon nanotube-coated NiCo2S4Load SeS2A positive electrode material for a lithium-sulfur battery.
(III) advantageous technical effects
Compared with the prior art, the invention has the following beneficial technical effects:
the carbon nano tube is coated with NiCo2S4Load SeS2Lithium-sulfur battery positive electrode material and preparation method thereof, NiCo prepared by hydrothermal synthesis in-situ method2S4Load SeS2SeS as a main component of the positive electrode material2Has higher conductivity and good electrochemical cycle stability, and the hollow NiCo2S4The ball has large specific surface area and can well load the SeS2And a hollow NiCo2S4The ball has a large number of active sites, and can provide a large number of active sitesPores have good adsorption capacity on the sulfur lithium compound, greatly enhance the sulfur carrying capacity of the anode material and promote the anode material to absorb Li2S2And Li2The adsorption of polysulfide generated by S oxidation enhances the ability of polysulfide to be catalyzed into S simple substance, and effectively improves the energy density and the electric capacity of the lithium-sulfur battery.
The carbon nano tube is coated with NiCo2S4Load SeS2Positive electrode material of lithium-sulfur battery and preparation method thereof, and NiCo coated with hydroxylated carbon nanotube2S4Load SeS2The carbon nanotube has huge specific surface area and complex pore structure, and is reacted with NiCo through the active hydroxyl group2S4Complexing the metal ions in the NiCo2S4Load SeS2Tightly adsorbed in the surface and inner layer of hydroxylated carbon nanotubes and carbon nanotubes with excellent conductivity in NiCo2S4Load SeS2A three-dimensional network conductive structure is formed between the two carbon nanotubes, a transmission channel is improved for lithium ions and charges, the transmission and diffusion rates of the ions and the charges are improved, the conductivity of the anode material is greatly enhanced, and simultaneously, polar hydroxyl groups of the carbon nanotubes promote polar Li2Effective deposition of S, good flexibility and stretchability of carbon nanotube, and SeS-coated2Then, the SeS is middle SeS in the process of charging and discharging the lithium-sulfur battery2The volume expansion provides a buffer structure, and the stability of the matrix of the cathode material is enhanced, so that the rate performance of the cathode material and the electrochemical cycle stability of the lithium-sulfur battery are improved, and the current density is 1.0 A.g through an electrochemical performance test-1When the discharge specific capacity reaches 818.6-821.5 mA.h.g-1When the cycle number of the battery is 500, the rate capacity can still reach 645.2-650.7 mA.h.g-1The capacity retention rate is 78.8-79.3%.
Detailed Description
In order to achieve the purpose, the invention provides the following technical scheme: carbon nano tube coated NiCo2S4Load SeS2The positive electrode material for lithium-sulfur battery comprises the following components in parts by weightThe formula comprises the following raw materials: 16-36 parts of hydroxylated carbon nanotube and 15-20 parts of hollow NiCo2S4The preparation method comprises the following steps of ball, 7-8 parts of selenium dioxide, 14-20 parts of sodium sulfide and 28-36 parts of glacial acetic acid: cobalt nitrate, nickel chloride, glycerol, distilled water, thioacetamide and absolute ethyl alcohol, wherein the content of active hydroxyl in the hydroxylated carbon nano tube is more than or equal to 5 percent, the length is 10-30um, and the diameter is 2-8 nm.
Hollow NiCo2S4The preparation of the ball comprises the following steps:
(1) adding a proper amount of distilled water into a reaction bottle, adding cobalt nitrate and nickel chloride, stirring at a constant speed until the cobalt nitrate and the nickel chloride are dissolved, wherein the molar ratio of the nickel chloride to the cobalt nitrate is 1:2.2-2.5, sequentially adding absolute ethyl alcohol and glycerol, wherein the volume ratio of the distilled water to the absolute ethyl alcohol to the glycerol is 1:3-5:2-3, transferring the solution into a hydrothermal automatic reaction kettle, heating to 190 ℃ to 200 ℃, stirring at a constant speed for reaction for 10-15h, cooling the material to room temperature after the reaction is finished, performing centrifugal separation by a high-speed centrifuge, removing upper-layer liquid to obtain a solid mixture, washing by sequentially using absolute ethyl alcohol to obtain a Ni-Co-glycerol precursor, adding a proper amount of absolute ethyl alcohol into the hydrothermal automatic reaction kettle, sequentially adding a Ni-Co-glycerol precursor and thioacetamide, wherein the mass ratio of the Ni-Co-glycerol precursor to the thioacetamide is 1:18-25, raising the temperature of the reaction kettle to 230 ℃, uniformly stirring and reacting for 15-20h, cooling the materials to room temperature after the reaction is finished, filtering to remove absolute ethyl alcohol to obtain a solid product, washing with absolute ethyl alcohol, heating in a drying oven to 50-60 ℃, and fully drying to obtain the hollow NiCo2S4A ball.
Carbon nanotube coated NiCo2S4Load SeS2The preparation method of the lithium-sulfur battery positive electrode material comprises the following steps:
(1) in-situ method for preparing hollow NiCo2S4Ball load SeS2: adding a proper amount of distilled water and 15-20 parts of hollow NiCo into a reaction bottle2S4Adding 7-8 parts of selenium dioxide, 14-20 parts of sodium sulfide and 28-36 parts of glacial acetic acid into the balls in sequence, stirring until the solids are dissolved, transferring the solution into a hydrothermal synthesis automatic reaction kettle, and raising the temperature of the reaction kettle toStirring at constant speed at 80-90 deg.C for 4-8h, cooling to room temperature after reaction, centrifuging in a high speed centrifuge, removing the upper layer solution to obtain solid mixture, washing with distilled water, and drying in an oven to obtain hollow NiCo2S4Ball load SeS2。
(2) The hollow NiCo obtained above is added2S4Ball load SeS2Adding into a planetary ball mill, adding appropriate amount of anhydrous ethanol, ball milling at revolution rate of 50-80rpm and rotation rate of 580-620rpm until the materials all pass through 1340 mesh sieve, placing the materials passing through the sieve and the anhydrous ethanol into a reaction bottle, adding 16-36 parts of hydroxylated carbon nanotube, placing the reaction bottle into an ultrasonic treatment instrument, heating to 50-60 deg.C, ultrasonic frequency of 22-28KHz, ultrasonic dispersing for 2-5h, centrifuging the materials by a high-speed centrifuge, removing the upper ethanol solution, placing the solidified compound in an oven, heating to 60-80 deg.C, and drying to obtain carbon nanotube-coated NiCo2S4Load SeS2A positive electrode material for a lithium-sulfur battery.
Example 1:
(1) preparation of hollow NiCo2S4A ball step: adding a proper amount of distilled water into a reaction bottle, adding cobalt nitrate and nickel chloride, stirring at a constant speed until the cobalt nitrate and the nickel chloride are dissolved, wherein the molar ratio of the nickel chloride to the cobalt nitrate is 1:2.2, sequentially adding absolute ethyl alcohol and glycerol, wherein the volume ratio of the distilled water to the absolute ethyl alcohol to the glycerol is 1:3:2, transferring the solution into a hydrothermal automatic reaction kettle, heating to 190 ℃, stirring at a constant speed for 10 hours, cooling the material to room temperature after the reaction is finished, performing centrifugal separation by a high-speed centrifuge, removing the upper-layer liquid to obtain a solid mixture, sequentially washing by using the absolute ethyl alcohol to obtain a Ni-Co-glycerol precursor, adding a proper amount of absolute ethyl alcohol into the hydrothermal automatic reaction kettle, sequentially adding a Ni-Co-glycerol precursor and thioacetamide, wherein the mass ratio of the Ni-Co-glycerol precursor to the thioacetamide is 1:18, heating the reaction kettle to 220 deg.C, stirring at constant speed for reaction for 15h, cooling the materials to room temperature after the reaction is finished, filtering to remove anhydrous ethanol to obtain solid product, and usingWashing with absolute ethyl alcohol, heating in a drying oven to 50 deg.C, and drying to obtain hollow NiCo2S4Ball component 1.
(2) In-situ method for preparing hollow NiCo2S4Ball load SeS2: a reaction flask was charged with appropriate amounts of distilled water and 15 parts of hollow NiCo2S4Adding 7 parts of selenium dioxide, 14 parts of sodium sulfide and 28 parts of glacial acetic acid into a ball component 1 in sequence, stirring until the solids are dissolved, transferring the solution into a hydrothermal synthesis automatic reaction kettle, heating the temperature of the reaction kettle to 80 ℃, stirring at a constant speed for reaction for 4 hours, cooling the materials to room temperature after the reaction is finished, placing the materials in a high-speed centrifuge for centrifugal separation, removing the upper layer solution to obtain a solid mixture, washing the solid mixture with distilled water, fully drying the solid mixture in an oven, and preparing the hollow NiCo2S4Ball load SeS2And (3) component 1.
(3) Preparation of carbon nanotube-coated NiCo2S4Load SeS2Lithium-sulfur battery positive electrode material: the hollow NiCo obtained above is added2S4Ball load SeS2Adding the component 1 into a planetary ball mill, adding a proper amount of absolute ethyl alcohol, carrying out ball milling at a revolution speed of 50rpm and a rotation speed of 580rpm until the materials completely pass through a 1340-mesh screen, putting the materials passing through the screen and the absolute ethyl alcohol into a reaction bottle, adding 36 parts of hydroxylated carbon nano tubes, putting the reaction bottle into an ultrasonic treatment instrument, heating to 50 ℃, carrying out ultrasonic frequency of 22KHz, carrying out ultrasonic dispersion for 2 hours, then carrying out centrifugal treatment on the materials through a high-speed centrifuge, removing an upper layer of ethanol solution, putting a solidified compound into an oven, heating to 60 ℃, and fully drying to obtain the carbon nano tube coated NiCo2S4Load SeS2The positive electrode material of the lithium-sulfur battery comprises a component 1.
Example 2:
(1) preparation of hollow NiCo2S4A ball step: adding a proper amount of distilled water into a reaction bottle, adding cobalt nitrate and nickel chloride, stirring at a constant speed until the cobalt nitrate and the nickel chloride are dissolved, wherein the molar ratio of the nickel chloride to the cobalt nitrate is 1:2.2, sequentially adding absolute ethyl alcohol and glycerol, and the volume ratio of the distilled water to the absolute ethyl alcohol to the glycerol is 1:3.5:2, and transferring the solution into the reaction bottleHeating to 195 ℃ in a hydrothermal automatic reaction kettle, stirring at a constant speed for reaction for 10 hours, cooling the materials to room temperature after the reaction is finished, performing centrifugal separation by a high-speed centrifuge, removing upper-layer liquid to obtain a solid mixture, washing with absolute ethyl alcohol in sequence to obtain a Ni-Co-glycerol precursor, adding a proper amount of absolute ethyl alcohol into the hydrothermal automatic reaction kettle, then adding the Ni-Co-glycerol precursor and thioacetamide in sequence, wherein the mass ratio of the Ni-Co-glycerol precursor to the thioacetamide is 1:20, heating the temperature of the reaction kettle to 220 ℃, stirring at a constant speed for reaction for 17 hours, cooling the materials to room temperature after the reaction is finished, filtering to remove the absolute ethyl alcohol to obtain a solid product, washing with the absolute ethyl alcohol, heating in an oven to 55 ℃, and fully drying to obtain the hollow NiCo2S4Ball component 2.
(2) In-situ method for preparing hollow NiCo2S4Ball load SeS2: a reaction flask was charged with appropriate amounts of distilled water and 16 parts of hollow NiCo2S4Adding 7 parts of selenium dioxide, 15 parts of sodium sulfide and 30 parts of glacial acetic acid into the spherical component 2 in sequence, stirring until the solids are dissolved, transferring the solution into a hydrothermal synthesis automatic reaction kettle, heating the temperature of the reaction kettle to 85 ℃, stirring at a constant speed for reaction for 6 hours, cooling the materials to room temperature after the reaction is finished, placing the materials into a high-speed centrifuge for centrifugal separation, removing the upper layer solution to obtain a solid mixture, washing the solid mixture by using distilled water, placing the solid mixture into an oven for full drying, and preparing the hollow NiCo2S4Ball load SeS2And (3) component 2.
(3) Preparation of carbon nanotube-coated NiCo2S4Load SeS2Lithium-sulfur battery positive electrode material: the hollow NiCo obtained above is added2S4Ball load SeS2Adding the component 2 into a planetary ball mill, adding a proper amount of absolute ethyl alcohol, carrying out ball milling at a revolution speed of 60rpm and a rotation speed of 600rpm until the materials completely pass through a 1340-mesh sieve, putting the materials passing through the sieve and the absolute ethyl alcohol into a reaction bottle, adding 32 parts of hydroxylated carbon nano tubes, putting the reaction bottle into an ultrasonic treatment instrument, heating to 50 ℃, carrying out ultrasonic dispersion for 2 hours at an ultrasonic frequency of 22KHz, then carrying out centrifugal treatment on the materials by a high-speed centrifuge, and removing the upper layer of the second layerThe solidified compound is placed in an oven to be heated to 60 ℃ and fully dried by the alcoholic solution to obtain the carbon nano tube coated NiCo2S4Load SeS2And (3) a positive electrode material component 2 of the lithium-sulfur battery.
Example 3:
(1) preparation of hollow NiCo2S4A ball step: adding a proper amount of distilled water into a reaction bottle, adding cobalt nitrate and nickel chloride, stirring at a constant speed until the cobalt nitrate and the nickel chloride are dissolved, wherein the molar ratio of the nickel chloride to the cobalt nitrate is 1:2.3, sequentially adding absolute ethyl alcohol and glycerol, wherein the volume ratio of the distilled water to the absolute ethyl alcohol to the glycerol is 1:4:2.5, transferring the solution into a hydrothermal automatic reaction kettle, heating to 195 ℃, stirring at a constant speed for 12 hours, cooling the material to room temperature after the reaction is finished, performing centrifugal separation by a high-speed centrifuge, removing the upper-layer liquid to obtain a solid mixture, sequentially washing by using the absolute ethyl alcohol to obtain a Ni-Co-glycerol precursor, adding a proper amount of absolute ethyl alcohol into the hydrothermal automatic reaction kettle, sequentially adding a Ni-Co-glycerol precursor and thioacetamide, wherein the mass ratio of the Ni-Co-glycerol precursor to the thioacetamide is 1:22, heating the temperature of the reaction kettle to 225 ℃, stirring at a constant speed for reaction for 17 hours, cooling the materials to room temperature after the reaction is finished, filtering to remove absolute ethyl alcohol to obtain a solid product, washing with absolute ethyl alcohol, heating in an oven to 55 ℃, and fully drying to obtain hollow NiCo2S4Ball component 3.
(2) In-situ method for preparing hollow NiCo2S4Ball load SeS2: a reaction flask was charged with appropriate amounts of distilled water and 17 parts of hollow NiCo2S4Adding 7.5 parts of selenium dioxide, 16.5 parts of sodium sulfide and 32 parts of glacial acetic acid into the component 3 in sequence, stirring until the solids are dissolved, transferring the solution into a hydrothermal synthesis automatic reaction kettle, heating the temperature of the reaction kettle to 85 ℃, stirring at a constant speed for reaction for 6 hours, cooling the materials to room temperature after the reaction is finished, placing the materials in a high-speed centrifuge for centrifugal separation, removing the upper layer solution to obtain a solid mixture, washing the solid mixture with distilled water, fully drying the solid mixture in an oven, and preparing the hollow NiCo2S4Ball load SeS2And (3) component.
(3) Preparation of carbon nanotube-coated NiCo2S4Load SeS2Lithium-sulfur battery positive electrode material: the hollow NiCo obtained above is added2S4Ball load SeS2Adding the component 3 into a planetary ball mill, adding a proper amount of absolute ethyl alcohol, carrying out ball milling at a revolution speed of 60rpm and a rotation speed of 600rpm until the materials completely pass through a 1340-mesh screen, putting the materials passing through the screen and the absolute ethyl alcohol into a reaction bottle, adding 27 parts of hydroxylated carbon nano tubes, putting the reaction bottle into an ultrasonic treatment instrument, heating to 55 ℃, carrying out ultrasonic frequency of 25KHz, carrying out ultrasonic dispersion for 3 hours, then carrying out centrifugal treatment on the materials through a high-speed centrifuge, removing an upper layer of ethanol solution, putting a solidified compound into an oven, heating to 70 ℃, and fully drying to obtain the carbon nano tube coated NiCo2S4Load SeS2And 3, a positive electrode material of the lithium-sulfur battery.
Example 4:
(1) preparation of hollow NiCo2S4A ball step: adding a proper amount of distilled water into a reaction bottle, adding cobalt nitrate and nickel chloride, stirring at a constant speed until the cobalt nitrate and the nickel chloride are dissolved, wherein the molar ratio of the nickel chloride to the cobalt nitrate is 1:2.5, sequentially adding absolute ethyl alcohol and glycerol, wherein the volume ratio of the distilled water to the absolute ethyl alcohol to the glycerol is 1:4:3, transferring the solution into a hydrothermal automatic reaction kettle, heating to 200 ℃, stirring at a constant speed for 12 hours, cooling the material to room temperature after the reaction is finished, performing centrifugal separation by a high-speed centrifuge, removing the upper-layer liquid to obtain a solid mixture, sequentially washing by using the absolute ethyl alcohol to obtain a Ni-Co-glycerol precursor, adding a proper amount of absolute ethyl alcohol into the hydrothermal automatic reaction kettle, sequentially adding a Ni-Co-glycerol precursor and thioacetamide, wherein the mass ratio of the Ni-Co-glycerol precursor to the thioacetamide is 1:22, heating the temperature of the reaction kettle to 225 ℃, stirring at a constant speed for reaction for 17 hours, cooling the materials to room temperature after the reaction is finished, filtering to remove absolute ethyl alcohol to obtain a solid product, washing with absolute ethyl alcohol, heating in an oven to 60 ℃ and fully drying to obtain hollow NiCo2S4Ball component 4.
(2) In-situ method for preparing hollow NiCo2S4Ball load SeS2: adding appropriate amount of distilled water and 18 into the reaction flaskHollow NiCo2S4Adding 8 parts of selenium dioxide, 18 parts of sodium sulfide and 34 parts of glacial acetic acid into the ball component 4 in sequence, stirring until the solids are dissolved, transferring the solution into a hydrothermal synthesis automatic reaction kettle, heating the temperature of the reaction kettle to 90 ℃, stirring at a constant speed for reaction for 6 hours, cooling the materials to room temperature after the reaction is finished, placing the materials into a high-speed centrifuge for centrifugal separation, removing the upper layer solution to obtain a solid mixture, washing the solid mixture by using distilled water, placing the solid mixture into an oven for full drying, and preparing the hollow NiCo2S4Ball load SeS2And (4) component.
(3) Preparation of carbon nanotube-coated NiCo2S4Load SeS2Lithium-sulfur battery positive electrode material: the hollow NiCo obtained above is added2S4Ball load SeS2Adding the component 1 into a planetary ball mill, adding a proper amount of absolute ethyl alcohol, carrying out ball milling at a revolution speed of 80rpm and a rotation speed of 600rpm until the materials completely pass through a 1340-mesh screen, putting the materials passing through the screen and the absolute ethyl alcohol into a reaction bottle, adding 22 parts of hydroxylated carbon nano tubes, putting the reaction bottle into an ultrasonic treatment instrument, heating to 50 ℃, carrying out ultrasonic frequency of 25KHz, carrying out ultrasonic dispersion for 5 hours, then carrying out centrifugal treatment on the materials through a high-speed centrifuge, removing an upper layer of ethanol solution, putting a solidified compound into an oven, heating to 80 ℃, and fully drying to obtain the carbon nano tube coated NiCo2S4Load SeS2And 4, a positive electrode material component of the lithium-sulfur battery.
Example 5:
(1) preparation of hollow NiCo2S4A ball step: adding a proper amount of distilled water into a reaction bottle, adding cobalt nitrate and nickel chloride, stirring at a constant speed until the cobalt nitrate and the nickel chloride are dissolved, wherein the molar ratio of the nickel chloride to the cobalt nitrate is 1:2.5, sequentially adding absolute ethyl alcohol and glycerol, wherein the volume ratio of the distilled water to the absolute ethyl alcohol to the glycerol is 1:5:3, transferring the solution into a hydrothermal automatic reaction kettle, heating to 200 ℃, stirring at a constant speed for reaction for 15 hours, cooling the material to room temperature after the reaction is finished, performing centrifugal separation by a high-speed centrifuge, removing the upper-layer liquid to obtain a solid mixture, sequentially washing by using the absolute ethyl alcohol to obtain a Ni-Co-glycerol precursor, and performing hydrothermal automatic reaction on the Ni-Co-glycerol precursorAdding a proper amount of absolute ethyl alcohol into a kettle, sequentially adding a Ni-Co-glycerol precursor and thioacetamide in a mass ratio of 1:25, heating the temperature of the reaction kettle to 230 ℃, stirring at a constant speed for reaction for 20 hours, cooling the materials to room temperature after the reaction is finished, filtering to remove the absolute ethyl alcohol to obtain a solid product, washing with the absolute ethyl alcohol, heating in an oven to 60 ℃, and fully drying to obtain the hollow NiCo2S4Ball component 5.
(2) In-situ method for preparing hollow NiCo2S4Ball load SeS2: a reaction flask was charged with appropriate amounts of distilled water and 20 parts of hollow NiCo2S4Adding 8 parts of selenium dioxide, 20 parts of sodium sulfide and 36 parts of glacial acetic acid into the ball component 5 in sequence, stirring until the solids are dissolved, transferring the solution into a hydrothermal synthesis automatic reaction kettle, heating the temperature of the reaction kettle to 90 ℃, stirring at a constant speed for reaction for 8 hours, cooling the materials to room temperature after the reaction is finished, placing the materials into a high-speed centrifuge for centrifugal separation, removing the upper layer solution to obtain a solid mixture, washing the solid mixture by using distilled water, placing the solid mixture into an oven for full drying, and preparing the hollow NiCo2S4Ball load SeS2And (5) component.
(3) Preparation of carbon nanotube-coated NiCo2S4Load SeS2Lithium-sulfur battery positive electrode material: the hollow NiCo obtained above is added2S4Ball load SeS2Adding the component 5 into a planetary ball mill, adding a proper amount of absolute ethyl alcohol, carrying out ball milling at a revolution speed of 80rpm and a rotation speed of 620rpm until the materials completely pass through a 1340-mesh screen, putting the materials passing through the screen and the absolute ethyl alcohol into a reaction bottle, adding 16 parts of hydroxylated carbon nano tubes, putting the reaction bottle into an ultrasonic treatment instrument, heating to 60 ℃, carrying out ultrasonic frequency of 28KHz, carrying out ultrasonic dispersion for 5 hours, then carrying out centrifugal treatment on the materials through a high-speed centrifuge, removing an upper layer of ethanol solution, putting a solidified compound into an oven, heating to 80 ℃, and fully drying to obtain the carbon nano tube coated NiCo2S4Load SeS2And 5, a positive electrode material component of the lithium-sulfur battery.
The method comprises the steps of respectively adding the examples 1-5 into N-methyl pyrrolidone, respectively adding an appropriate amount of acetylene black as a conductive agent and polyvinylidene fluoride as an adhesive, respectively and uniformly coating the conductive agent and the polyvinylidene fluoride on an aluminum foil, respectively, drying and rolling to prepare electrodes, and testing the discharge specific capacity, the electrical impedance and the rate capacity of the electrodes of the examples 1-5 by a cyclic voltammetry method and a constant current charge-discharge method, wherein the test is shown in the table 1-2.
Table 1 examples 1-5 specific discharge capacity and electrical impedance testing
Figure BDA0002250247740000111
Table 2 examples 1-5 rate capability tests were performed
Item Example 1 Example 2 Example 3 Example 4 Example 5
Current density/A.g-1 1.0 1.0 1.0 1.0 1.0
Number of cycles 500 500 500 500 500
Multiplying power capacity/mA.h.g-1 650.7 645.2 650.2 648.6 649.7
Capacity retention ratio/%) 79.2 78.8 79.3 79.0 79.1
In summary, the carbon nanotube coated NiCo2S4Load SeS2Lithium-sulfur battery positive electrode material and preparation method thereof, NiCo prepared by hydrothermal synthesis in-situ method2S4Load SeS2SeS as a main component of the positive electrode material2Has higher conductivity and good electrochemical cycle stability, and the hollow NiCo2S4The ball has large specific surface area and can well load the SeS2And a hollow NiCo2S4The spheres have a large number of active sites, can provide a large number of pores, have good adsorption capacity on sulfur lithium compounds, greatly enhance the sulfur carrying capacity of the anode material, and promote the anode material to absorb Li2S2And Li2The adsorption of polysulfide generated by S oxidation enhances the ability of polysulfide to be catalyzed into S simple substance, and effectively improves the energy density and the electric capacity of the lithium-sulfur battery.
The carbon nanotube is coatedNiCo2S4Load SeS2Positive electrode material of lithium-sulfur battery and preparation method thereof, and NiCo coated with hydroxylated carbon nanotube2S4Load SeS2The carbon nanotube has huge specific surface area and complex pore structure, and is reacted with NiCo through the active hydroxyl group2S4Complexing the metal ions in the NiCo2S4Load SeS2Tightly adsorbed in the surface and inner layer of hydroxylated carbon nanotubes and carbon nanotubes with excellent conductivity in NiCo2S4Load SeS2A three-dimensional network conductive structure is formed between the two carbon nanotubes, a transmission channel is improved for lithium ions and charges, the transmission and diffusion rates of the ions and the charges are improved, the conductivity of the anode material is greatly enhanced, and simultaneously, polar hydroxyl groups of the carbon nanotubes promote polar Li2Effective deposition of S, good flexibility and stretchability of carbon nanotube, and SeS-coated2Then, the SeS is middle SeS in the process of charging and discharging the lithium-sulfur battery2The volume expansion provides a buffer structure, and the stability of the matrix of the cathode material is enhanced, so that the rate performance of the cathode material and the electrochemical cycle stability of the lithium-sulfur battery are improved, and the current density is 1.0 A.g through an electrochemical performance test-1When the discharge specific capacity reaches 818.6-821.5 mA.h.g-1When the cycle number of the battery is 500, the rate capacity can still reach 645.2-650.7 mA.h.g-1The capacity retention rate is 78.8-79.3%.

Claims (6)

1. Carbon nano tube coated NiCo2S4Load SeS2The positive electrode material of the lithium-sulfur battery and the preparation method thereof comprise the following formula raw materials in parts by weight, and are characterized in that: 16-36 parts of hydroxylated carbon nanotube and 15-20 parts of hollow NiCo2S4The preparation method comprises the following steps of ball, 7-8 parts of selenium dioxide, 14-20 parts of sodium sulfide and 28-36 parts of glacial acetic acid: cobalt nitrate, nickel chloride, glycerol, distilled water, thioacetamide and absolute ethyl alcohol.
2. The carbon nanotube package of claim 1Coated with NiCo2S4Load SeS2The positive electrode material of the lithium-sulfur battery and the preparation method thereof are characterized in that: the content of active hydroxyl in the hydroxylated carbon nanotube is more than or equal to 5 percent, the length is 10-30um, and the diameter is 2-8 nm.
3. The carbon nanotube coated NiCo of claim 12S4Load SeS2The positive electrode material of the lithium-sulfur battery and the preparation method thereof are characterized in that: the hollow NiCo2S4The preparation of the ball comprises the following steps:
(1) adding a proper amount of distilled water into a reaction bottle, adding cobalt nitrate and nickel chloride, stirring at a constant speed until the cobalt nitrate and the nickel chloride are dissolved, sequentially adding absolute ethyl alcohol and glycerol, wherein the volume ratio of the distilled water to the absolute ethyl alcohol to the glycerol is 1:3-5:2-3, transferring the solution into a hydrothermal automatic reaction kettle, heating to 190-, after the reaction is finished, cooling the materials to room temperature, filtering to remove absolute ethyl alcohol to obtain a solid product, washing with absolute ethyl alcohol, heating in an oven to 50-60 ℃, and fully drying to obtain the hollow NiCo2S4A ball.
4. The carbon nanotube coated NiCo of claim 32S4Load SeS2The positive electrode material of the lithium-sulfur battery and the preparation method thereof are characterized in that: the mass molar ratio of the nickel chloride to the cobalt nitrate is 1: 2.2-2.5.
5. The carbon nanotube coated NiCo of claim 12S4Load SeS2The positive electrode material of the lithium-sulfur battery and the preparation method thereof are characterized in that: the Ni-Co-glycerol precursor and thioacetamideThe quantity ratio is 1: 18-25.
6. The carbon nanotube coated NiCo of claim 12S4Load SeS2The positive electrode material of the lithium-sulfur battery and the preparation method thereof are characterized in that: the carbon nanotube is coated with NiCo2S4Load SeS2The preparation method of the lithium-sulfur battery positive electrode material comprises the following steps:
(1) in-situ method for preparing hollow NiCo2S4Ball load SeS2: adding a proper amount of distilled water and 15-20 parts of hollow NiCo into a reaction bottle2S4Adding 7-8 parts of selenium dioxide, 14-20 parts of sodium sulfide and 28-36 parts of glacial acetic acid into the balls in sequence, stirring until the solids are dissolved, transferring the solution into a hydrothermal synthesis automatic reaction kettle, heating the temperature of the reaction kettle to 80-90 ℃, stirring at a constant speed for reaction for 4-8 hours, cooling the materials to room temperature after the reaction is finished, placing the materials into a high-speed centrifuge for centrifugal separation, removing the upper layer solution to obtain a solid mixture, washing the solid mixture with distilled water, placing the solid mixture into an oven for full drying, and preparing the hollow NiCo2S4Ball load SeS2。
(2) The hollow NiCo obtained above is added2S4Ball load SeS2Adding into a planetary ball mill, adding appropriate amount of anhydrous ethanol, ball milling at revolution rate of 50-80rpm and rotation rate of 580-620rpm until the materials all pass through 1340 mesh sieve, placing the materials passing through the sieve and the anhydrous ethanol into a reaction bottle, adding 16-36 parts of hydroxylated carbon nanotube, placing the reaction bottle into an ultrasonic treatment instrument, heating to 50-60 deg.C, ultrasonic frequency of 22-28KHz, ultrasonic dispersing for 2-5h, centrifuging the materials by a high-speed centrifuge, removing the upper ethanol solution, placing the solidified compound in an oven, heating to 60-80 deg.C, and drying to obtain carbon nanotube-coated NiCo2S4Load SeS2A positive electrode material for a lithium-sulfur battery.
CN201911031378.7A 2019-10-28 2019-10-28 Carbon nano tube coated NiCo2S4Load SeS2Positive electrode material of lithium-sulfur battery and preparation method thereof Pending CN110797518A (en)

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111463026A (en) * 2020-03-31 2020-07-28 深圳大学 Nickel-cobalt-sulfur/carbon nanotube composite material and preparation method and application thereof
CN111710850A (en) * 2020-07-17 2020-09-25 樊梦林 NiCo with shell-core structure2S4Porous microsphere-graphene negative electrode material and preparation method thereof

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111463026A (en) * 2020-03-31 2020-07-28 深圳大学 Nickel-cobalt-sulfur/carbon nanotube composite material and preparation method and application thereof
CN111463026B (en) * 2020-03-31 2022-05-10 深圳大学 Nickel-cobalt-sulfur/carbon nanotube composite material and preparation method and application thereof
CN111710850A (en) * 2020-07-17 2020-09-25 樊梦林 NiCo with shell-core structure2S4Porous microsphere-graphene negative electrode material and preparation method thereof
CN111710850B (en) * 2020-07-17 2021-06-29 吉林中溢炭素科技有限公司 NiCo with shell-core structure2S4Porous microsphere-graphene negative electrode material and preparation method thereof

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