CN111293292B - Preparation method of lithium-sulfur battery positive electrode material - Google Patents

Preparation method of lithium-sulfur battery positive electrode material Download PDF

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CN111293292B
CN111293292B CN202010100891.3A CN202010100891A CN111293292B CN 111293292 B CN111293292 B CN 111293292B CN 202010100891 A CN202010100891 A CN 202010100891A CN 111293292 B CN111293292 B CN 111293292B
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silicon dioxide
microspheres
nano tube
carbon nano
carbon nanotube
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CN111293292A (en
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张永光
高万秸
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Zhaoqing South China Normal University Optoelectronics Industry Research Institute
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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
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/15—Nano-sized carbon materials
    • C01B32/158—Carbon nanotubes
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B32/00—Carbon; Compounds thereof
    • C01B32/15—Nano-sized carbon materials
    • C01B32/158—Carbon nanotubes
    • C01B32/16—Preparation
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • 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
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/38—Selection of substances as active materials, active masses, active liquids of elements or alloys
    • 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
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624—Electric conductive fillers
    • H01M4/625—Carbon or graphite
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Abstract

The invention relates to a preparation method of a lithium-sulfur battery anode material, which comprises the steps of preparing silicon dioxide/carbon nanotube microspheres by spray drying, and then preparing porous carbon nanotube microspheres by hydrofluoric acid etching and water vapor etching to be used as the lithium-sulfur battery anode material. The invention further limits the dissolution loss of lithium polysulfide by using the strong adsorption effect of pores. The porous carbon nanotube microsphere positive electrode material is simple in preparation method, large in gap and large in specific surface area, and the porous carbon nanotube forms a conductive network around sulfur, so that the cycling stability and the coulombic efficiency of the battery are obviously improved.

Description

Preparation method of lithium-sulfur battery positive electrode material
Technical Field
The invention relates to a preparation method of a high-specific-capacity lithium-sulfur battery positive electrode material, in particular to a method for preparing a high-specific-capacity lithium-sulfur battery positive electrode material by preparing a porous carbon nanotube microsphere through water vapor etching, and belongs to the field of material chemistry.
Background
With the increasing demand for energy in human society and the increasing exhaustion of natural resources, the demand for new energy is more and more urgent. The research of people on the lithium ion battery which is environment-friendly, long in cycle life, high in specific capacity and stable in structure becomes more and more significant. The theoretical specific capacity of elemental sulfur can also reach 1680mAh/g, and the theoretical specific capacity of the lithium-sulfur battery formed by the elemental sulfur and lithium can reach 2600 Wh/kg. The lithium sulfur battery has wide application prospect in the aspects of reducing the use of fossil fuel and reducing greenhouse effect. Meanwhile, because of rich sulfur content and low price, the lithium-sulfur battery is expected to become a candidate for a next-generation high-energy-density battery system, but the lithium-sulfur battery still keeps performing hard to put into practical application. Due to poor stability of sulfur, generation of polysulfide during discharge and its dissolution in electrolyte lead to a large loss of active material and a sharp drop in electrode capacity. Polysulfides can also deposit and accumulate on the surface of the positive and negative electrodes, damaging the electrode structure and, in severe cases, causing cell failure. In addition, lithium metal as a negative electrode generates dendrite, dead lithium, and electrode powder, resulting in poor cycle performance of a battery, safety problems, and the like, and thus lithium sulfur batteries have not been commercialized.
Research shows that in the lithium-sulfur battery, the shuttle effect of the intermediate product lithium polysulfide permeating the electrolyte to diffuse to the negative electrode is the fundamental reason of poor stability of the lithium-sulfur battery, and in order to solve the problem, the sulfur and the porous carbon nanotube microspheres are considered to be compounded, and the nanopores have strong adsorption effect, so that the capacity retention rate of the battery can be improved by injecting elemental sulfur into the porous carbon nanotube microspheres, and the performance of the lithium-sulfur battery is improved.
Disclosure of Invention
The invention aims to provide a preparation method of a lithium-sulfur battery cathode material so as to break through the limitation of the technical defects. The technical scheme adopted by the invention for solving the technical problem is as follows:
a preparation method of a lithium-sulfur battery positive electrode material specifically comprises the following steps:
(1) preparing the silicon dioxide/carbon nano tube microspheres:
diluting the carbon nano tube dispersion liquid with the mass fraction of 10% to 0.5mg/ml by using deionized water, and performing ultrasonic dispersion to obtain a carbon nano tube dilution liquid; weighing silicon dioxide, and then ultrasonically dispersing the silicon dioxide by using deionized water to obtain silicon dioxide dispersion liquid, wherein the concentration of the silicon dioxide dispersion liquid is 100 mg/ml; and pouring the silicon dioxide dispersion liquid into the carbon nano tube diluent, stirring the mixed liquid, and then carrying out spray drying on the mixed liquid to obtain the silicon dioxide/carbon nano tube microspheres.
Further, the mass ratio of the carbon nanotubes to the silicon dioxide in the mixed solution in the step (1) is 1: 3 to 7.
Further, the spray drying temperature in the step (1) is 200 ℃, and the feeding rate is 2 ml/min. (2) Etching the silicon dioxide/carbon nano tube microspheres by hydrofluoric acid:
and (2) calcining the silicon dioxide/carbon nano tube microspheres prepared in the step (1) at a high temperature, and then cooling to room temperature. And then, etching the sintered silicon dioxide/carbon nano tube microspheres by using 10% hydrofluoric acid, periodically replacing the hydrofluoric acid every day, etching for three to four days, and etching away the silicon dioxide to obtain the carbon nano tube microspheres.
Further, the temperature rise rate of the high-temperature calcination in the step (2) is 5 ℃/min, the calcination temperature is 800 ℃, and the heat preservation time is 2 h.
(3) Water vapor etching of carbon nanotube microspheres:
and (3) carrying out water vapor etching on the carbon nanotube microspheres prepared in the step (2) to obtain the porous carbon nanotube microspheres.
Further, the temperature of the steam etching in the step (2) is 500 ℃, and the time is 5 min.
The invention has the following beneficial effects:
the porous carbon nanotube microspheres are used as active substance carriers, sulfur can be compounded with the porous carbon nanotube microspheres to be limited in the nanometer pore channels of the porous material, and the dissolution loss of lithium polysulfide is further limited by the strong adsorption effect of pores, so that the performance of the lithium-sulfur battery is improved. Meanwhile, the preparation method of the porous carbon nanotube microsphere positive electrode material is simple, and the material is large in gap, large in specific surface area and good in conductivity.
The porous carbon nanotube microsphere material prepared by the invention introduces the carbon nanotube to enhance the conductivity of the electrode material aiming at the defect of insufficient conductivity when the porous material is used as the anode material, and simultaneously, the porous carbon nanotube and sulfur are compounded to prepare the carbon-sulfur composite material due to the special structure of the carbon nanotube, the porous carbon nanotube forms a conductive network around the sulfur, the adsorption effect of the richer pore structure on lithium polysulfide is enhanced, and the cycle stability and the coulombic efficiency of the battery are also obviously improved.
Drawings
The invention is further illustrated with reference to the following figures and examples:
FIG. 1 is an electron microscope image of the hydrofluoric acid etched silica/carbon nanotube microsphere prepared in example 1.
Detailed Description
Example 1:
(1) preparing the silicon dioxide/carbon nano tube microspheres:
2g of carbon nanotube dispersion liquid with the mass fraction of 10% is taken and then diluted to 0.5mg/ml by 400ml of deionized water, so as to obtain the carbon nanotube diluent. 1g of silica was taken, and then diluted with 10ml of deionized water to 100mg/ml, to obtain a silica dispersion. And respectively and continuously performing ultrasonic dispersion on the carbon nano tube diluent and the silicon dioxide dispersion liquid, pouring the silicon dioxide dispersion liquid into the carbon nano tube diluent, stirring the mixed liquid, and then spraying and drying the mixed liquid at 200 ℃ at a feeding rate of 2ml/min to obtain the silicon dioxide/carbon nano tube microspheres.
(2) Etching the silicon dioxide/carbon nano tube microspheres by hydrofluoric acid:
and (2) heating the silicon dioxide/carbon nano tube microspheres prepared in the step (1) at the speed of 10 ℃/min to 800 ℃, preserving the heat for 2h, and then cooling to room temperature. And then, etching the silicon dioxide/carbon nano tube microspheres by adopting 10% hydrofluoric acid, periodically replacing the hydrofluoric acid every day, etching for three days, and etching away the silicon dioxide to obtain the carbon nano tube microspheres.
(3) Water vapor etching of carbon nanotube microspheres:
and (3) carrying out water vapor etching on the carbon nanotube microspheres etched by the hydrofluoric acid in the step (2) at the temperature of 500 ℃ for 5min to obtain the porous carbon nanotube microspheres.
Example 2:
(1) preparing the silicon dioxide/carbon nano tube microspheres:
2g of carbon nanotube dispersion liquid with the mass fraction of 10% is taken and then diluted to 0.5mg/ml by 400ml of deionized water, so as to obtain the carbon nanotube diluent. 0.6g of silica was taken, and then diluted with 6ml of deionized water to 100mg/ml, to obtain a silica dispersion. And (3) continuously performing ultrasonic dispersion on the carbon nano tube diluent and the silicon dioxide dispersion liquid, pouring the silicon dioxide dispersion liquid into the carbon nano tube diluent, and stirring the mixed liquid. And then spraying the mixed solution at 200 ℃ and carrying out spray drying under the condition that the feeding rate is 3ml/min to obtain the silicon dioxide/carbon nano tube microspheres.
(2) Etching the silicon dioxide/carbon nano tube microspheres by hydrofluoric acid:
and (2) heating the silicon dioxide/carbon nano tube microspheres prepared in the step (1) at the speed of 10 ℃/min to 800 ℃, preserving the heat for 2h, and then cooling to room temperature. And then, etching the sintered silicon dioxide/carbon nano tube microspheres by using 10% hydrofluoric acid, periodically replacing the hydrofluoric acid every day, etching for four days, and etching away the silicon dioxide to obtain the carbon nano tube microspheres.
(3) Water vapor etching of carbon nanotube microspheres:
and (3) carrying out water vapor etching on the carbon nano tube microspheres prepared in the step (2) at the temperature of 800 ℃ for 20 min. Obtaining the porous carbon nanotube microspheres.
Example 3:
(1) preparing the silicon dioxide/carbon nano tube microspheres:
2g of carbon nano tube dispersion liquid with the mass fraction of 10 percent is taken and then diluted to 0.5mg/ml by 400ml of deionized water, thus obtaining the carbon nano tube diluent. 1.4g of silica was taken and then diluted to 100mg/ml with 14ml of deionized water to obtain a silica dispersion. And (3) continuously performing ultrasonic dispersion on the carbon nano tube diluent and the silicon dioxide dispersion liquid, pouring the silicon dioxide dispersion liquid into the carbon nano tube diluent, and stirring the mixed liquid. And then spraying the mixed solution at 200 ℃, carrying out spray drying under the condition that the feeding rate is 3ml, and collecting to obtain the silicon dioxide/carbon nano tube microspheres.
(2) Etching the silicon dioxide/carbon nano tube microspheres by hydrofluoric acid:
and (2) heating the silicon dioxide/carbon nano tube microspheres prepared in the step (1) at the speed of 10 ℃/min to 800 ℃, preserving the heat for 2 hours, and then cooling to room temperature. And then, etching the sintered silicon dioxide/carbon nano tube microspheres by using 10% hydrofluoric acid, periodically replacing the hydrofluoric acid every day, etching for four days, and etching away the silicon dioxide to obtain the carbon nano tube microspheres.
(3) Water vapor etching of carbon nanotube microspheres:
and (3) carrying out water vapor etching on the carbon nanotube microspheres prepared in the step (2) at the temperature of 800 ℃ for 20min to obtain the porous carbon nanotube microspheres.

Claims (5)

1. A preparation method of a lithium-sulfur battery positive electrode material is characterized by comprising the following specific steps:
(1) preparing the silicon dioxide/carbon nano tube microspheres:
diluting the carbon nano tube dispersion liquid with the mass fraction of 10% to 0.5mg/mL by using deionized water, and performing ultrasonic dispersion to obtain a carbon nano tube dilution liquid; weighing silicon dioxide, and then ultrasonically dispersing the silicon dioxide by using deionized water to obtain silicon dioxide dispersion liquid, wherein the concentration of the silicon dioxide dispersion liquid is 100 mg/mL; pouring the silicon dioxide dispersion liquid into the carbon nano tube diluent, stirring the mixed liquid, and then carrying out spray drying on the mixed liquid to obtain silicon dioxide/carbon nano tube microspheres;
(2) etching the silicon dioxide/carbon nano tube microspheres by hydrofluoric acid:
calcining the silicon dioxide/carbon nano tube microspheres prepared in the step (1) at high temperature, then cooling to room temperature, then adopting 10% hydrofluoric acid to etch the silicon dioxide/carbon nano tube microspheres after being calcined, periodically replacing the hydrofluoric acid every day, etching for three to four days, and etching away the silicon dioxide to obtain the carbon nano tube microspheres;
(3) water vapor etching of the carbon nanotube microspheres:
carrying out water vapor etching on the carbon nanotube microspheres prepared in the step (2) to obtain porous carbon nanotube microspheres;
(4) and (4) taking the porous carbon nanotube microspheres obtained in the step (3) as active substance carriers, compounding sulfur and the porous carbon nanotube microspheres, and limiting the sulfur in the nanopores of the porous carbon nanotube microspheres.
2. The production method according to claim 1, wherein the mass ratio of the carbon nanotubes to the silica in the mixed solution in the step (1) is 1: 3 to 7.
3. The process according to claim 1, wherein the spray-drying temperature in the step (1) is 200 ℃ and the feed rate is 2 mL/min.
4. The preparation method according to claim 1, wherein the temperature rise rate of the high-temperature calcination in the step (2) is 5 ℃/min, the calcination temperature is 800 ℃, and the holding time is 2 hours.
5. The method according to claim 1, wherein the water vapor etching temperature in the step (2) is 500 ℃ and the time is 5 min.
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