CN109326780B - Preparation method of tungsten disulfide negative electrode material coated sulfur composite material - Google Patents

Preparation method of tungsten disulfide negative electrode material coated sulfur composite material Download PDF

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CN109326780B
CN109326780B CN201811085617.2A CN201811085617A CN109326780B CN 109326780 B CN109326780 B CN 109326780B CN 201811085617 A CN201811085617 A CN 201811085617A CN 109326780 B CN109326780 B CN 109326780B
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negative electrode
tungsten disulfide
composite material
electrode material
sulfur composite
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CN109326780A (en
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张正富
范苏晓
徐嘉辉
任艳昆
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Kunming University of Science and Technology
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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
    • H01M4/366—Composites as layered products
    • 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
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • 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
    • H01M4/36—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
    • 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
    • H01M2004/021—Physical characteristics, e.g. porosity, surface area
    • 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
    • H01M2004/027—Negative electrodes
    • 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 tungsten disulfide negative electrode material coated sulfur composite material, and belongs to the technical field of lithium ion batteries. Adding sulfur powder and ammonium tetrathiotungstate into deionized water according to the mass ratio of 1: 1.5-1: 4, ultrasonically stirring until the sulfur powder is uniformly dispersed in the solution, then adding a hydrochloric acid solution to adjust the pH value to 1-3, reacting for 4-6 h to generate a precipitate, and filtering, washing and drying to obtain the precipitate; and (3) preserving the obtained precipitate for 1-4 h at the temperature of 200-300 ℃ in a protective atmosphere, and naturally cooling to obtain the tungsten disulfide negative electrode material coated sulfur composite material. The method has simple process and little environmental pollution, and the obtained product has uniform granularity and excellent electrochemical performance and can reach the standard required by the current market.

Description

Preparation method of tungsten disulfide negative electrode material coated sulfur composite material
Technical Field
The invention relates to a preparation method of a tungsten disulfide negative electrode material coated sulfur composite material, and belongs to the technical field of lithium ion batteries.
Background
The tungsten disulfide is used as a material with a larger prospect, has a wide application field, can be used in aerospace, automobiles, carbon anti-friction materials and the like, and can also replace graphite to be used as a lithium ion battery cathode material. Although tungsten disulfide has a graphite-like lamellar structure, there are still many problems to be solved in order to completely replace graphite as a negative electrode of a lithium battery. On the one hand, the production of tungsten disulfide is mainly prepared by a vapor deposition method at present, the yield is low, and the highly toxic gas hydrogen sulfide pollutes the air. On the other hand, the actual specific capacity of the tungsten disulfide is influenced by a plurality of factors and can not meet the quality requirement of industrial production.
The invention adopts a precipitation method to prepare the tungsten disulfide negative electrode material coated sulfur composite material, not only solves the problem of environmental pollution, but also improves the actual specific capacity of the material by compounding with sulfur, so that the actual specific capacity of the material completely reaches the standard required by the current market.
Disclosure of Invention
Aiming at the problems and the defects in the prior art, the invention provides a preparation method of a tungsten disulfide negative electrode material coated sulfur composite material. The method has simple process and little environmental pollution, and the obtained product has uniform granularity and excellent electrochemical performance and can reach the standard required by the current market. The invention is realized by the following technical scheme.
A preparation method of a sulfur composite material coated by a tungsten disulfide negative electrode material comprises the following specific steps:
step 1, adding sulfur powder and ammonium tetrathiotungstate into deionized water according to the mass ratio of 1: 1.5-1: 4, ultrasonically stirring until the sulfur powder is uniformly dispersed in the solution, then adding a hydrochloric acid solution to adjust the pH value to 1-3, reacting for 4-6 h to generate a precipitate, and filtering, washing and drying to obtain the precipitate;
and 2, preserving the heat of the precipitate obtained in the step 1 at the temperature of 200-300 ℃ for 1-4 h in a protective atmosphere, and naturally cooling to obtain the tungsten disulfide negative electrode material coated sulfur composite material.
In the step 1, the particle size of the sulfur powder is 2-5 mu m.
The concentration of the ammonium tetrathiotungstate in the solution obtained in the step 1 is 0.2-0.6 mol/L.
The concentration of the hydrochloric acid solution in the step 1 is 4-8 mol/L.
The invention has the beneficial effects that:
(1) the tungsten disulfide negative electrode material coated sulfur composite material prepared by the invention has higher specific capacity, and can provide a reliable negative electrode material for the production of large-capacity lithium ion batteries.
(2) The preparation process is easy to control, the granularity of the material in the reaction process can be controlled by controlling the pH value and the annealing heat preservation time, the requirements of various products are met, and the pollution in the whole production process is small.
Drawings
FIG. 1 is an XRD pattern of a tungsten disulfide negative electrode material coated sulfur composite obtained in example 1 of the present invention;
FIG. 2 is a charge/discharge curve diagram of a lithium ion battery prepared from a sulfur composite coated with a tungsten disulfide negative electrode material obtained in example 1 of the present invention at a current density of 100 mA/g;
fig. 3 is a cycle curve diagram of a lithium ion battery prepared by coating a sulfur composite material with a tungsten disulfide negative electrode material obtained in example 1 of the present invention at different rates.
Detailed Description
The invention is further described with reference to the following drawings and detailed description.
Example 1
The preparation method of the tungsten disulfide negative electrode material coated sulfur composite material comprises the following specific steps:
step 1, adding 1g of sulfur powder and 1.5g of ammonium tetrathiotungstate into deionized water according to the mass ratio of 1:1.5, ultrasonically stirring until the sulfur powder is uniformly dispersed in the solution, then adding a hydrochloric acid solution (the concentration of the hydrochloric acid solution is 4mol/L) to adjust the pH value to 1.5, reacting for 5 hours to generate a precipitate, and filtering, washing and drying to obtain the precipitate; wherein the particle size of the sulfur powder is 2-5 mu m, and the concentration of the ammonium tetrathiotungstate is 0.2 mol/L;
and 2, keeping the precipitate obtained in the step 1 at the temperature of 280 ℃ for 2h under a protective atmosphere (nitrogen, the flow is 2L/min), naturally cooling to obtain the tungsten disulfide negative electrode material coated sulfur composite material, wherein the XRD (X-ray diffraction) diagram of the obtained tungsten disulfide negative electrode material coated sulfur composite material is shown in figure 1, and the main crystal phase of the outer layer coating material can be seen as tungsten disulfide in figure 1.
The tungsten disulfide negative electrode material prepared in this example was coated with a sulfur composite material to perform electrochemical performance testing: mixing and grinding the composite material powder, acetylene black and polyvinylidene fluoride (PVDF) according to the mass ratio of 8:1:1 to assemble the CR2025 button cell; and (3) testing the charge and discharge performance after standing for 24 hours, wherein the specific process is as follows:
weighing the obtained tungsten disulfide negative electrode material coated sulfur composite material powder, acetylene black and polyvinylidene fluoride (PVDF) according to the mass ratio of 8:1:1, placing the materials in an agate mortar, and dropwise adding a proper amount of N-methyl-2-pyrrolidone (NMP) for uniform grinding; coating the copper foil on a Cu foil with the thickness of 0.15mm, drying the copper foil in a vacuum drying oven at 90 ℃ for 24h, and taking out the pole piece to serve as a negative electrode.
② metal lithium sheets are used as negative electrode and reference electrode, polypropylene microporous membrane is used as diaphragm, 1mol/L LiPF6The + EC/DMC/EMC is electrolyte, and is assembled into a CR2025 stainless steel button cell in a glove box filled with argon and with the moisture content lower than 2 ppm; and testing the charge and discharge performance after standing for 24 hours.
The charge-discharge curve of the lithium ion battery prepared by the tungsten disulfide negative electrode material coated sulfur composite material prepared in the embodiment under the current density of 100mA/g is shown in fig. 2, and it can be seen from fig. 2 that the first specific discharge capacity is 1078.5mA hg-1The capacity can still be 996.4mA hg after 50 cycles-1The capacity retention rate reaches 92.4%. The cycle curve of the lithium ion battery prepared by the tungsten disulfide negative electrode material coated sulfur composite material obtained in the embodiment under different multiplying factors is shown in fig. 3, and it can be seen from fig. 3 that the multiplying factor performance of the material is excellent, and the cycle is still stable when the multiplying factor is increased.
Example 2
The preparation method of the tungsten disulfide negative electrode material coated sulfur composite material comprises the following specific steps:
step 1, adding 1g of sulfur powder and 4g of ammonium tetrathiotungstate into deionized water according to the mass ratio of 1:4, ultrasonically stirring until the sulfur powder is uniformly dispersed in the solution, then adding a hydrochloric acid solution (the concentration of the hydrochloric acid solution is 8mol/L) to adjust the pH value to 1, reacting for 4 hours to generate a precipitate, and filtering, washing and drying to obtain the precipitate; wherein the particle size of the sulfur powder is 2-5 mu m, and the concentration of the ammonium tetrathiotungstate is 0.6 mol/L;
and 2, keeping the precipitate obtained in the step 1 at the temperature of 200 ℃ for 4h under a protective atmosphere (nitrogen, with the flow rate of 2L/min), and naturally cooling to obtain the tungsten disulfide negative electrode material coated sulfur composite material.
Example 3
The preparation method of the tungsten disulfide negative electrode material coated sulfur composite material comprises the following specific steps:
step 1, adding 1g of sulfur powder and 2.5g of ammonium tetrathiotungstate into deionized water according to the mass ratio of 1:2.5, ultrasonically stirring until the sulfur powder is uniformly dispersed in the solution, then adding a hydrochloric acid solution (the concentration of the hydrochloric acid solution is 6mol/L) to adjust the pH value to 3, reacting for 6 hours to generate a precipitate, and filtering, washing and drying to obtain the precipitate; wherein the particle size of the sulfur powder is 2-5 mu m, and the concentration of the ammonium tetrathiotungstate is 0.4 mol/L;
and 2, keeping the precipitate obtained in the step 1 at the temperature of 300 ℃ for 1h under a protective atmosphere (nitrogen, with the flow rate of 2L/min), and naturally cooling to obtain the tungsten disulfide negative electrode material coated sulfur composite material.
While the present invention has been described in detail with reference to the embodiments shown in the drawings, the present invention is not limited to the embodiments, and various changes can be made without departing from the spirit and scope of the present invention.

Claims (4)

1. A preparation method of a sulfur composite material coated by a tungsten disulfide negative electrode material is characterized by comprising the following specific steps:
step 1, adding sulfur powder and ammonium tetrathiotungstate into deionized water according to the mass ratio of 1: 1.5-1: 4, ultrasonically stirring until the sulfur powder is uniformly dispersed in the solution, then adding a hydrochloric acid solution to adjust the pH value to 1-3, reacting for 4-6 h to generate a precipitate, and filtering, washing and drying to obtain the precipitate;
and 2, preserving the heat of the precipitate obtained in the step 1 at the temperature of 200-300 ℃ for 1-4 h in a protective atmosphere, and naturally cooling to obtain the tungsten disulfide negative electrode material coated sulfur composite material.
2. The preparation method of the tungsten disulfide negative electrode material coated sulfur composite material according to claim 1, characterized in that: in the step 1, the particle size of the sulfur powder is 2-5 mu m.
3. The preparation method of the tungsten disulfide negative electrode material coated sulfur composite material according to claim 1, characterized in that: the concentration of the ammonium tetrathiotungstate in the solution obtained in the step 1 is 0.2-0.6 mol/L.
4. The preparation method of the tungsten disulfide negative electrode material coated sulfur composite material according to claim 1, characterized in that: the concentration of the hydrochloric acid solution in the step 1 is 4-8 mol/L.
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CN114628673A (en) * 2020-12-11 2022-06-14 中国科学院大连化学物理研究所 Three-dimensional macroporous tungsten disulfide/carbon composite material and preparation method and application thereof

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