CN108598390B - Preparation method of positive electrode material for lithium-sulfur battery and lithium-sulfur battery - Google Patents

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

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CN108598390B
CN108598390B CN201810272543.7A CN201810272543A CN108598390B CN 108598390 B CN108598390 B CN 108598390B CN 201810272543 A CN201810272543 A CN 201810272543A CN 108598390 B CN108598390 B CN 108598390B
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lithium
sulfur battery
positive electrode
electrode material
carbonizing
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CN108598390A (en
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曹元成
程时杰
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Institute Of New Energy Wuhan Co ltd
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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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B82—NANOTECHNOLOGY
    • B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
    • B82Y40/00—Manufacture or treatment of nanostructures
    • 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
    • H01M4/36—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
    • H01M4/583—Carbonaceous material, e.g. graphite-intercalation compounds or CFx
    • 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
    • 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
    • H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
    • 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 positive electrode material for a lithium-sulfur battery, which comprises the following steps: dissolving cobalt nitrate and 2-methylimidazole in a solvent, standing, and centrifugally drying to obtain ZIF-67; carbonizing ZIF-67 in an inert gas atmosphere, and cooling to room temperature to obtain Co-N-C; and carbonizing the Co-N-C and dicyandiamide in an inert gas atmosphere, and cooling to room temperature to obtain the CNT @ Co-N-C. A lithium-sulfur battery includes a positive electrode material for a lithium-sulfur battery as a positive electrode material of the lithium-sulfur battery. The invention has the beneficial effects that: compared with a single metal organic framework compound-based composite material, the specific surface area and the conductivity are improved, sulfur can be loaded more effectively, the shuttle effect of polysulfide can be inhibited more effectively in the reaction process of the battery, the battery is assembled to be subjected to constant-current discharge test, and the result shows that the electrochemical performance of the composite material with the in-situ grown carbon nano tube is more excellent.

Description

Preparation method of positive electrode material for lithium-sulfur battery and lithium-sulfur battery
Technical Field
The invention relates to the technical field of energy storage, in particular to a preparation method of a positive electrode material for a lithium-sulfur battery and the lithium-sulfur battery.
Background
With the successful commercial application of graphite cathodes, lithium ion batteries have been widely used in portable electronic devices such as smart phones and notebook computers. After more than 20 years of development, the existing lithium ion battery based on the lithium intercalation compound anode is close to the theoretical capacity, but still cannot meet the requirements of industries such as the electronic industry with high-speed development and emerging electric automobiles, and the like, and the search for a battery system with higher energy density is urgent. For example, lithium sulfur batteries are a new generation of lithium ion secondary batteries using metallic lithium as the negative electrode and elemental sulfur as the positive electrode active material, wherein the metallic lithium has the lowest density (0.53 g/cm) in nature3) Metallic elements with the lowest standard potential (-3.04Vvs. SHE), the lowest electrochemical equivalent (0.26g/Ah) and the highest theoretical specific capacity (3861mAh/g), so that the metallic lithium has very high contentThe energy density is higher, and the metal lithium battery assembled by the lithium ion battery serving as a negative electrode material has higher energy density and working voltage. The elemental sulfur is widely distributed in nature and Li is utilized2The reversible transformation between S and S has a theoretical specific capacity of 1672mAh/g, and the theoretical energy density is 2600Wh/kg according to the average voltage of 2.1V. The lithium-sulfur combination is the highest energy density solid-state electrode combination of all known chemically reversible systems.
Although the lithium-sulfur battery has the above-mentioned obvious advantages compared with the conventional lithium ion battery, the problems of low utilization rate of active materials, poor cycle performance, low coulombic efficiency, high self-discharge rate and the like still exist, and the practical application of the lithium-sulfur battery is delayed. Li dissolved in organic electrolyte2Sn(4. ltoreq. n.ltoreq.8) in the presence of a concentration gradient, the electrolyte is electrochemically oxidized into long-chain lithium polysulfide Li with relatively long chain length in the vicinity of the positive electrode2Sn(n is more than or equal to 6 and less than or equal to 8) is diffused to the lithium cathode through the diaphragm and directly reacts with the metal lithium to generate short-chain polysulfide lithium Li with relatively short chain length2Sn(4≤n≤6)、Li2S2And Li2S, ultimately leading to a decrease in lithium sulfur cell coulombic efficiency.
Disclosure of Invention
The invention aims to provide a preparation method of a positive electrode material for a lithium-sulfur battery and the lithium-sulfur battery, so as to overcome the defects in the prior art.
The technical scheme for solving the technical problems is as follows: a preparation method of a positive electrode material for a lithium-sulfur battery comprises the following steps:
s100, dissolving cobalt nitrate and 2-methylimidazole in a solvent, and obtaining ZIF-67 after the reaction is finished;
s200, carbonizing ZIF-67 in an inert gas atmosphere to obtain Co-N-C;
s300, carbonizing the Co-N-C and dicyandiamide in an inert gas atmosphere to obtain the CNT @ Co-N-C.
The invention has the beneficial effects that: compared with a single metal organic framework compound-based composite material, the composite material has the advantages of improving the specific surface area and the conductivity, being capable of loading sulfur more effectively and inhibiting the shuttle effect of polysulfide more effectively in the battery reaction process.
On the basis of the technical scheme, the invention can be further improved as follows.
Further, the specific steps for preparing ZIF-67 in S100 are as follows:
dissolving cobalt nitrate and 2-methylimidazole in methanol, standing for 6-12 h, then centrifugally drying at the drying temperature of 60-80 ℃ for 12h to obtain ZIF-67.
Further, the specific steps for preparing Co-N-C in S200 are as follows:
and carbonizing the ZIF-67 in an argon atmosphere at 700-900 ℃ to obtain Co-N-C.
Further, the specific preparation steps of the Co-N-C are as follows:
and carbonizing the ZIF-67 at 700-900 ℃ at a heating rate of 5 ℃/min in an argon atmosphere for 2h, and cooling to room temperature to obtain Co-N-C.
Adopt above-mentioned further beneficial effect to do: can effectively ensure that the reaction is carried out quickly and fully.
Further, the specific steps for preparing CNT @ Co-N-C in S300 are as follows:
and carbonizing the Co-N-C and dicyandiamide at the carbonization temperature of 700-900 ℃ in an argon atmosphere to obtain the CNT @ Co-N-C.
Further, the specific preparation steps of the CNT @ Co-N-C are as follows:
and carbonizing the Co-N-C and dicyandiamide at 700-900 ℃ at the heating rate of 5 ℃/min in the argon atmosphere for 2h, and cooling to room temperature to obtain the CNT @ Co-N-C.
Adopt above-mentioned further beneficial effect to do: can effectively ensure that the reaction is carried out quickly and fully.
Further, the mass fraction of dicyandiamide is 1% -50%.
A lithium-sulfur battery includes a positive electrode material for a lithium-sulfur battery as a positive electrode material of the lithium-sulfur battery.
Adopt above-mentioned further beneficial effect to do: the battery capacity is improved: the specific capacity of 670mAh/g of the battery is still maintained under the condition of 5C high rate at normal temperature; the battery has long cycle life: the capacity retention rate of 79.8 percent is still maintained after 500 cycles of charge and discharge under the multiplying power of 0.2C.
Further, according to the active substance: acetylene black: PVDF 7: 2: 1, preparing a positive plate, wherein the active substance is prepared by mixing and grinding sulfur and a positive material for a lithium-sulfur battery and then heating the mixture for 6 to 10 hours at the temperature of between 155 and 158 ℃ in a reaction kettle; a lithium sheet is taken as a cathode, the lithium-sulfur battery is assembled in a glove box filled with argon, the electrolyte is 1mol/L of LITFSI and the mass fraction is 1 percent of LiNO3The mixed solution of (1).
Drawings
FIG. 1 is a schematic diagram illustrating the synthesis of a positive electrode material for a lithium sulfur battery according to the present invention;
FIG. 2 is an SEM image of a cathode material for a lithium-sulfur battery according to the present invention at 500 nm;
FIG. 3 is an SEM image of a cathode material for a lithium-sulfur battery according to the present invention at 500 nm;
FIG. 4 shows characteristic peaks of crystal structures of different materials measured by X-ray diffraction;
FIG. 5 is a graph of charge and discharge performance of an electrode material under different magnification conditions;
FIG. 6 is a graph of the long-cycle charge and discharge performance of the CNT @ Co-N-C/S electrode material under a rate condition of 0.2C.
Detailed Description
The principles and features of this invention are described below in conjunction with examples which are set forth to illustrate, but are not to be construed to limit the scope of the invention.
A preparation method of a positive electrode material for a lithium-sulfur battery is shown in figure 1, and mainly relates to 4 key steps of organic framework molecule construction, metal complexation, element doping, nanotube growth and the like.
The specific details are as follows:
s100, mixing cobalt nitrate and 2-methylimidazole according to the weight ratio of 1: 4, dissolving in methanol, standing for 6-12 h, centrifuging, and drying in a vacuum drying oven at 60-80 ℃ for 12h, wherein the drying standard is to remove methanol and trace water to obtain ZIF-67; the scanning electron microscope results are shown in FIG. 2, in which the crystal structure is tetragonal.
S200, carbonizing ZIF-67 at 700-900 ℃ at a heating rate of 5 ℃/min in an inert gas atmosphere composed of argon for 2h, and cooling to room temperature to obtain Co-N-C;
s300, placing Co-N-C and dicyandiamide with the mass fraction of 1% -50% in a tube furnace, carbonizing at 700 ℃ -900 ℃ at the heating rate of 5 ℃/min in the inert gas atmosphere for 2h, and cooling to room temperature to obtain CNT @ Co-N-C.
As a result, as shown in FIG. 3, the cubic surface was covered with carbon nanotubes, and the uniformity was good. The X-ray diffraction results are shown in fig. 4, and the prepared product is well matched with the standard pattern.
In the preparation method, the adding sequence and the adding time of the cobalt nitrate, the 2-methylimidazole and the dicyandiamide are strictly limited, the dicyandiamide cannot be added before the first carbonization, because the cobalt nitrate can generate simple substance cobalt during the carbonization, the simple substance cobalt is used as a catalyst to react with the subsequently added dicyandiamide to generate the carbon nano tube (the dicyandiamide is decomposed and reacts to generate the carbon nano tube by using a chemical catalysis method), and finally the carbon nano tube is ensured to grow on the Co-N-C material and is integrated, which has great significance for an electrode material. A lithium sulfur battery comprising, in terms of active material: acetylene black: PVDF (polyvinylidene fluoride) ═ 7: 2: 1, wherein the active substance is prepared by mixing sulfur and a positive electrode material for a lithium-sulfur battery according to a ratio of 4: 1, mixing and grinding the mixture according to the proportion, and heating the mixture in a reaction kettle at the temperature of between 155 and 158 ℃ for 6 to 10 hours to obtain the product; a lithium sheet is taken as a cathode, the lithium-sulfur battery is assembled in a glove box filled with argon, and the electrolyte adopts 1mol/L of LITFSI and 1% of LiNO by mass3And dimethoxymethane and dioxolane, dimethoxymethane: the volume fraction percentage of dioxolane is 1: 1 in a liquid mixture.
The assembled battery is placed on a blue battery test system, the multiplying power performance test result is shown in fig. 5, and the result shows that the active substance can perform charge-discharge circulation under different multiplying powers, and the capacity retention rate is good. Further, constant current charge and discharge tests are performed at a rate of 0.2C to obtain the electrochemical performance of the battery material, and the results shown in fig. 6 indicate that the capacity retention rate of the prepared product is optimal when the battery material is cycled for 500 times.
Although embodiments of the present invention have been shown and described above, it is understood that the above embodiments are exemplary and should not be construed as limiting the present invention, and that variations, modifications, substitutions and alterations can be made to the above embodiments by those of ordinary skill in the art within the scope of the present invention.

Claims (9)

1. A preparation method of a positive electrode material for a lithium-sulfur battery is characterized by comprising the following steps:
s100, dissolving cobalt nitrate and 2-methylimidazole in a solvent, and obtaining ZIF-67 after the reaction is finished;
s200, carbonizing ZIF-67 in an inert gas atmosphere to obtain Co-N-C;
s300, carbonizing the Co-N-C and dicyandiamide in an inert gas atmosphere to obtain the CNT @ Co-N-C.
2. The method for preparing the positive electrode material for the lithium-sulfur battery according to claim 1, wherein the specific steps for preparing ZIF-67 in S100 are as follows:
dissolving cobalt nitrate and 2-methylimidazole in methanol, standing for 6-12 h, then centrifugally drying at the drying temperature of 60-80 ℃ for 12h to obtain ZIF-67.
3. The method of claim 2, wherein the step of preparing Co-N-C in S200 is as follows:
and carbonizing the ZIF-67 in an argon atmosphere at 700-900 ℃ to obtain Co-N-C.
4. The method for preparing the positive electrode material for the lithium-sulfur battery according to claim 3, wherein the specific preparation steps of Co-N-C are as follows:
and carbonizing the ZIF-67 at 700-900 ℃ at a heating rate of 5 ℃/min in an argon atmosphere for 2h, and cooling to room temperature to obtain Co-N-C.
5. The method of claim 1, wherein the step of preparing CNT @ Co-N-C in S300 is as follows:
and carbonizing the Co-N-C and dicyandiamide at the carbonization temperature of 700-900 ℃ in an argon atmosphere to obtain the CNT @ Co-N-C.
6. The method of claim 5, wherein the CNT @ Co-N-C is prepared by the following steps:
and carbonizing the Co-N-C and dicyandiamide at 700-900 ℃ at the heating rate of 5 ℃/min in the argon atmosphere for 2h, and cooling to room temperature to obtain the CNT @ Co-N-C.
7. The method for preparing a positive electrode material for a lithium-sulfur battery according to claim 1, 5 or 6, wherein the mass fraction of dicyandiamide in S300 is 1% -50%.
8. A lithium-sulfur battery, characterized by comprising, as a positive electrode material for the lithium-sulfur battery, a positive electrode material for a lithium-sulfur battery produced by the production method according to any one of claims 1 to 7.
9. The lithium sulfur battery of claim 8, wherein the ratio of active material: acetylene black: PVDF 7: 2: 1, preparing a positive plate, wherein the active substance is prepared by mixing and grinding sulfur and a positive material for a lithium-sulfur battery and then heating the mixture for 6 to 10 hours at the temperature of between 155 and 158 ℃ in a reaction kettle; lithium sheet is taken as a negative electrode, a lithium-sulfur battery is assembled in a glove box filled with argon, and the electrolyte is LITFSI with 1mol/LAnd LiNO with a mass fraction of 1%3The mixed solution of (1).
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