CN111525124B - Preparation method of lithium ion battery negative electrode material - Google Patents

Preparation method of lithium ion battery negative electrode material Download PDF

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CN111525124B
CN111525124B CN202010270344.XA CN202010270344A CN111525124B CN 111525124 B CN111525124 B CN 111525124B CN 202010270344 A CN202010270344 A CN 202010270344A CN 111525124 B CN111525124 B CN 111525124B
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zif
salt
cobalt
lithium ion
ion battery
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CN111525124A (en
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韩俊女
赵英杰
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Yunnan Zhongsheng New Material Co.,Ltd.
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Jingmen Noviying New Material Technology 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
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/52—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron
    • H01M4/523—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides of nickel, cobalt or iron for non-aqueous cells
    • 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
    • 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
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • 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 discloses a preparation method of a high-power lithium ion battery cathode material, which comprises the following steps: firstly, preparing Zn/Co-ZIF; then mixing a ferrous salt solution, a cobalt salt solution and a nickel salt solution with a Zn/Co-ZIF solution in a protective gas, adding a 2-methylimidazole solution, uniformly stirring, standing, filtering, washing and drying to obtain Zn/Co-ZIF @ Fe/Co/Ni-ZIF with a core-shell structure; and finally, sequentially calcining Zn/Co-ZIF @ Fe/Co/Ni-ZIF in protective gas and in air to obtain the high-power lithium ion battery cathode material. According to the invention, Zn/Co-ZIF @ Fe/Co/Ni-ZIF with a core-shell structure is used as a precursor to carry out two-step calcination in protective gas and air, so that the high-power lithium battery negative electrode material is obtained, the preparation process is simple, the conditions are mild, and the method is suitable for industrial production.

Description

Preparation method of lithium ion battery negative electrode material
Technical Field
The invention belongs to the technical field of lithium battery cathode materials, and particularly relates to a preparation method of a lithium ion battery cathode material.
Background
With the development and progress of modern science and technology and the use requirements of people on portable electronic devices, the power supply of the portable electronic devices is developed towards the trends of high efficiency, small size, light weight, thin shape and flexible diversification. Among them, lithium batteries have been widely paid attention to due to their advantages of high voltage, high capacity, low consumption, no memory effect, no pollution, small volume, small internal resistance, less self-discharge, and many cycle times.
The negative electrode material is one of key materials determining the performance of the lithium battery, but the existing graphite negative electrode material has a slow lithium ion deintercalation rate due to the limitation of the regular interlayer spacing (d = 0.34) of graphite, thereby influencing the exertion of power performance. Meanwhile, because the theoretical capacity (372 mAh/g) of graphite is low, the proportion of graphite must be reduced and the content of a conductive agent must be increased when a high-power lithium ion battery is manufactured, so that the energy density of the battery is low.
The metal oxide is a potential cathode material and has the advantages of high specific capacity, good power performance and the like. The metal-organic framework material becomes a good precursor for preparing the metal oxide cathode material due to the advantages of high porosity, low density, large specific surface area, regular pore channels, adjustable pore diameter, diversified topological structure, tailorability and the like.
In order to further improve the power performance of the negative electrode material, researchers also coat inorganic substances on the surface of the negative electrode material by adopting a sol-gel method or a solid-phase coating method, but the existing coating method is complicated in operation and process, and a compact coating layer is difficult to form, so that the power performance of the negative electrode material cannot meet the requirement.
Disclosure of Invention
In view of the above, the invention provides a preparation method of a lithium ion battery anode material, which is to prepare Zn/Co-ZIF @ Fe/Co/Ni-ZIF with a core-shell structure, and to perform two-step calcination in protective gas and air by using the Zn/Co-ZIF @ Fe/Co/Ni-ZIF as a precursor, so as to obtain a core-shell structure composite metal oxide anode material with a hollow structure, a rich pore structure and uniformly distributed nano metal oxide particles.
The invention adopts the technical scheme that the preparation method of the lithium ion battery cathode material comprises the following steps:
s1, preparing a zinc/cobalt bimetallic zeolite imidazolate framework material Zn/Co-ZIF;
wherein the mass ratio of Co to Zn is (0.1-1) to 1;
s2, respectively and uniformly dispersing ferrous salt, cobalt salt, nickel salt, 2-methylimidazole and Zn/Co-ZIF prepared by the S1 in a first organic solvent in a protective gas atmosphere to obtain corresponding organic solutions;
s3, mixing the ferrous salt organic solution, the cobalt salt organic solution and the nickel salt organic solution with the Zn/Co-ZIF organic solution in a protective gas atmosphere, adding the 2-methylimidazole organic solution, uniformly stirring, standing, performing suction filtration, washing and drying to obtain Zn/Co-ZIF @ Fe/Co/Ni-ZIF with a core-shell structure;
wherein in the process of mixing the organic solution of ferrous salt, the organic solution of cobalt salt and the organic solution of nickel salt with the organic solution of Zn/Co-ZIF, the mass ratio of the ferrous salt, the cobalt salt and the nickel salt is (1-2) to (2) (1-3);
s4, calcining the Zn/Co-ZIF @ Fe/Co/Ni-ZIF obtained in the step S3 in a protective gas atmosphere at 800-1000 ℃, preserving heat for 1-3 hours, and cooling to obtain an intermediate product;
and S5, calcining the intermediate product obtained in the step S4 in the air atmosphere at the temperature of 300-600 ℃, preserving heat for 1-3 hours, and cooling to obtain a calcined product, namely the lithium ion battery cathode material.
Preferably, the ratio of the sum of the amounts of the substances of the ferrous salt, the cobalt salt and the nickel salt to the amount of the substance of the 2-methylimidazole in S3 is (1-4): 16.
specifically, in the mixing process of the organic solution of ferrous salt, the organic solution of cobalt salt, the organic solution of nickel salt, the organic solution of Zn/Co-ZIF and the organic solution of 2-methylimidazole, the ratio of the sum of the amounts of the substances of the ferrous salt, the cobalt salt and the nickel salt to the amount of the substance of 2-methylimidazole is (1-4): 16 mixing, namely the ratio of the sum of the amount of the substances of the ferrous salt, the cobalt salt and the nickel salt to the amount of the substances of the 2-methylimidazole in the mixed solution is (1-4): 16;
preferably, the mass ratio of the sum of the ferrous salt, the cobalt salt and the nickel salt in the S3 to the Zn/Co-ZIF is (1-4): 2.
specifically, in the process of mixing the ferrous salt organic solution, the cobalt salt organic solution, the nickel salt organic solution and the Zn/Co-ZIF organic solution, the mass ratio of the sum of the masses of the ferrous salt, the cobalt salt and the nickel salt to the Zn/Co-ZIF is (1-4): 2, mixing, namely mixing the mass sum of the ferrous salt, the cobalt salt and the nickel salt in the mixed solution and the mass ratio of the Zn/Co-ZIF to the mixed solution is (1-4): 2;
preferably, the mass concentration of the ferric salt organic solution in S3 is 0.005-0.05 mol/L, the mass concentration of the cobalt salt organic solution is 0.01-0.05 mol/L, the mass concentration of the nickel salt organic solution is 0.01-0.075 mol/L, the mass concentration of the 2-methylimidazole organic solution is 0.1-2.8 mol/L, and the mass concentration of the Zn/Co-ZIF organic solution is 1-8 g/L.
Preferably, in the Zn/Co-ZIF @ Fe/Co/Ni-ZIF obtained by S3, the grain diameter of the Zn/Co-ZIF is 0.1-2 μm, and the thickness of the Fe/Co/Ni-ZIF is 0.1-0.5 μm.
Preferably, the protective gas in S4 is at least one of nitrogen and argon; and the temperature rise rate of the calcination process in the S4 and the S5 is 2-4 ℃/min.
Preferably, the preparation process of Zn/Co-ZIF in S1 is as follows:
respectively dissolving zinc salt, cobalt salt and 2-methylimidazole in a second organic solvent to obtain corresponding organic solutions, uniformly mixing the three solutions, standing to obtain a blue cloudy liquid, and performing suction filtration and drying to obtain blue powder, namely Zn/Co-ZIF.
Preferably, the ratio of the sum of the amounts of the zinc salt and the cobalt salt to the amount of the 2-methylimidazole is (1 to 4): 16.
preferably, in S1 and S2, the ferrous salt is ferrous sulfate or ferrous chloride, the cobalt salt is cobalt nitrate or cobalt chloride, the nickel salt is nickel chloride, and the zinc salt is zinc nitrate or zinc chloride.
Preferably, in S1 and S2, the first organic solvent and the second organic solvent are both at least one of methanol, ethanol, or N, N-dimethylformamide, the shielding gas is at least one of nitrogen and argon, and the drying temperature is 60 to 100 ℃.
The invention has the beneficial effects that: preparing a binary metal framework material Zn/Co-ZIF, and mixing and reacting the binary metal framework material Zn/Co-ZIF with a ferrous salt solution, a cobalt salt solution, a nickel salt solution and a 2-methylimidazole solution to obtain a Zn/Co-ZIF @ Fe/Co/Ni-ZIF core-shell structure taking binary Zn/Co-ZIF as an inner core and ternary Fe/Co/Ni-ZIF as an outer shell; then, Zn/Co-ZIF @ Fe/Co/Ni-ZIF is used as a precursor, and two-step calcination in protective gas and air is carried out to prepare the core-shell structure composite metal oxide anode material which simultaneously has a hollow structure, a rich pore structure and uniform distribution of nano metal oxide particles;
the preparation method disclosed by the invention is simple in process and mild in condition, the ZIF precursor can be prepared only through mixing reaction at room temperature, and the metal oxide support cathode material can be prepared through two-step calcination;
in addition, the internal pore structure can be effectively regulated and controlled by regulating the proportion of the core metal; the size of the inner core is effectively regulated and controlled by adjusting the ratio of metal to imidazole; and the coating thickness of the shell is adjusted by changing the feeding quality, so that the cathode materials with different power performance performances are prepared.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is further described in detail with reference to the following embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.
The invention provides a preparation method of a lithium ion battery cathode material, which comprises the following steps:
s1, preparing a zinc/cobalt bimetallic zeolite imidazolate framework material Zn/Co-ZIF;
wherein the mass ratio of Co to Zn is (0.1-1) to 1;
s2, respectively and uniformly dispersing ferrous salt, cobalt salt, nickel salt, 2-methylimidazole and Zn/Co-ZIF prepared by the S1 in a first organic solvent in a protective gas atmosphere to obtain corresponding organic solutions;
s3, mixing the ferrous salt organic solution, the cobalt salt organic solution and the nickel salt organic solution with the Zn/Co-ZIF organic solution in a protective gas atmosphere, adding the 2-methylimidazole organic solution, uniformly stirring, standing, performing suction filtration, washing and drying to obtain Zn/Co-ZIF @ Fe/Co/Ni-ZIF with a core-shell structure;
wherein the mass ratio of the ferrous salt, the cobalt salt and the nickel salt is (1-2) to (2) (1-3);
the complete operation processes of the S2 and the S3 are carried out in a protective atmosphere, and can also be carried out in a glove box;
thus, by taking Zn/Co-ZIF as a core, and through the reaction with ferrous salt, cobalt salt, nickel salt and 2-methylimidazole, coating a layer of Fe/Co/Ni-ZIF shell outside the core to obtain Zn/Co-ZIF @ Fe/Co/Ni-ZIF with a core-shell structure;
s4, calcining the Zn/Co-ZIF @ Fe/Co/Ni-ZIF obtained in the step S3 in a protective gas atmosphere at 800-1000 ℃, preserving heat for 1-3 hours, and cooling to obtain an intermediate product;
and S5, calcining the intermediate product obtained in the step S4 in the air atmosphere at the temperature of 300-600 ℃, preserving heat for 1-3 hours, and cooling to obtain a calcined product, namely the lithium ion battery cathode material. Wherein the mass ratio of the ferrous salt, the cobalt salt and the nickel salt is (1-2) to (2) (1-3);
in this way, the Zn/Co-ZIF @ Fe/Co/Ni-ZIF with the core-shell structure is firstly calcined in a protective gas atmosphere to completely volatilize zinc in the inner core, so that a hollow structure and rich pore spaces are obtained, and meanwhile, the dispersion of nano particles is improved by utilizing the spacing effect among different metal atoms in the hollow structure, so that a metal-carbon compound is obtained; and calcining in the air to obtain the composite metal oxide cathode material with the core-shell structure.
Example 1
The embodiment provides a preparation method of a lithium ion battery cathode material, which comprises the following steps:
s1, preparing a zinc/cobalt bimetallic zeolite imidazolate framework material Zn/Co-ZIF; wherein the mass ratio of Co to Zn is 0.5: 1;
the specific process is as follows:
148.74mg of zinc nitrate is dissolved in methanol to obtain a methanol solution of zinc nitrate with the mass concentration of 0.025mol/L, 32.46mg of cobalt chloride is dissolved in methanol to obtain a methanol solution of cobalt chloride with the mass concentration of 0.025mol/L, 4.8mol of 2-methylimidazole is dissolved in methanol to obtain a methanol solution of 2-methylimidazole with the mass concentration of 1.5mol/L, the three are mixed and stirred uniformly, then the mixture is kept stand for 15 hours to obtain a blue turbid liquid, and the blue liquid is subjected to suction filtration and drying at the temperature of 80 ℃ to obtain blue powder, namely Zn/Co-ZIF;
wherein the ratio of the sum of the amounts of zinc salt and cobalt salt species to the amount of 2-methylimidazole species is 2.5: 16;
s2, dissolving 695mg of ferrous sulfate in methanol to obtain a methanol solution of ferrous sulfate with the mass concentration of 0.025mol/L, dissolving 960.3mg of cobalt nitrate in the methanol to obtain a methanol solution of cobalt nitrate with the mass concentration of 0.03mol/L, dissolving 426.7mg of nickel chloride in the methanol to obtain a methanol solution of nickel chloride with the mass concentration of 0.04mol/L, dissolving 0.045mol of 2-methylimidazole in the methanol to obtain a methanol solution of 2-methylimidazole with the mass concentration of 1.5mol/L, and dissolving 2.082g of Zn/Co-ZIF obtained from S1 in the methanol to obtain a methanol solution of Zn/Co-ZIF with the mass concentration of 4.5g/L in a nitrogen atmosphere;
s3, mixing the ferrous sulfate methanol solution, the cobalt nitrate methanol solution and the nickel chloride methanol solution with the Zn/Co-ZIF methanol solution in a nitrogen atmosphere, adding the 2-methylimidazole methanol solution, stirring uniformly, standing, performing suction filtration, washing and drying to obtain the core-shell Zn/Co-ZIF @ Fe/Co/Ni-ZIF;
wherein the mass ratio of the ferrous salt to the cobalt salt to the nickel salt is 1.5:2: 2; the mass ratio of the sum of the ferrous salt, the cobalt salt and the nickel salt to the Zn/Co-ZIF is 2: 2; the ratio of the sum of the amounts of the ferrous, cobalt and nickel salts to the amount of the 2-methylimidazole is 2.5: 16;
wherein the grain diameter of Zn/Co-ZIF is 1.1 μm, and the thickness of Fe/Co/Ni-ZIF is 0.25 μm;
s4, calcining the Zn/Co-ZIF @ Fe/Co/Ni-ZIF obtained in the step S3 in nitrogen at 900 ℃ according to the heating rate of 3 ℃/min, preserving heat for 2 hours, and cooling to obtain an intermediate product;
and S5, calcining the intermediate product obtained in the step S4 at 500 ℃ in the air atmosphere according to the heating rate of 3 ℃/min, preserving the heat for 2h, and cooling to obtain a calcined product, namely the lithium ion battery cathode material.
Example 2
The embodiment provides a preparation method of a lithium ion battery cathode material, which comprises the following steps:
s1, preparing a zinc/cobalt bimetallic zeolite imidazolate framework material Zn/Co-ZIF; wherein the mass ratio of Co to Zn is 0.1: 1;
the specific process is as follows:
340.75mg of zinc chloride is dissolved in ethanol to obtain an ethanol solution of zinc chloride with the mass concentration of 0.5mol/L, 72.75mg of cobalt nitrate is dissolved in ethanol to obtain an ethanol solution of cobalt nitrate with the mass concentration of 0.05mol/L, 44mol of 2-methylimidazole is dissolved in ethanol to obtain an ethanol solution of 2-methylimidazole with the mass concentration of 2.8mol/L, the three are mixed, stirred uniformly and then kept stand for 20 hours to obtain a blue turbid liquid, and the blue turbid liquid is subjected to suction filtration and drying at 60 ℃ to obtain blue powder, namely Zn/Co-ZIF;
wherein the ratio of the sum of the amounts of zinc salt and cobalt salt to the amount of 2-methylimidazole is 1: 16;
s2, dissolving 695mg of ferrous chloride in ethanol to obtain an ethanol solution of the ferrous chloride with the mass concentration of 0.005mol/L, dissolving 1.49g of cobalt chloride in ethanol to obtain an ethanol solution of the cobalt chloride with the mass concentration of 0.01mol/L, dissolving 972mg of nickel chloride in ethanol to obtain an ethanol solution of the nickel chloride with the mass concentration of 0.01mol/L, dissolving 0.09mol of 2-methylimidazole in ethanol to obtain an ethanol solution of the 2-methylimidazole with the mass concentration of 0.1mol/L, and dissolving 5.56g of Zn/Co-ZIF obtained from S1 in ethanol to obtain an ethanol solution of the Zn/Co-ZIF with the mass concentration of 1g/L in an argon atmosphere;
s3, mixing the ferrous chloride ethanol solution, the cobalt chloride ethanol solution and the nickel chloride ethanol solution with the Zn/Co-ZIF ethanol solution according to a certain proportion in an argon atmosphere, adding the 2-methylimidazole ethanol solution, stirring uniformly, standing, filtering, washing and drying to obtain Zn/Co-ZIF @ Fe/Co/Ni-ZIF with a core-shell structure;
wherein the mass ratio of the ferrous salt to the cobalt salt to the nickel salt is 1:2: 3; the mass ratio of the sum of the ferrous salt, the cobalt salt and the nickel salt to the Zn/Co-ZIF is 1: 2; the ratio of the sum of the amounts of the ferrous salt, cobalt salt and nickel salt to the amount of the 2-methylimidazole is 1: 16;
wherein the grain diameter of Zn/Co-ZIF is 0.13 μm, and the thickness of Fe/Co/Ni-ZIF is 0.1 μm;
s4, calcining the Zn/Co-ZIF @ Fe/Co/Ni-ZIF obtained in the step S3 at 800 ℃ at a heating rate of 2 ℃/min in nitrogen, preserving heat for 3 hours, and cooling to obtain an intermediate product;
and S5, calcining the intermediate product obtained in the step S4 at 300 ℃ in the air atmosphere according to the heating rate of 2 ℃/min, preserving heat for 3h, and cooling to obtain a calcined product, namely the lithium ion battery cathode material.
Example 3
The embodiment provides a preparation method of a lithium ion battery cathode material, which comprises the following steps:
s1, preparing a zinc/cobalt bimetallic zeolite imidazolate framework material Zn/Co-ZIF; wherein the mass ratio of Co to Zn is 0.8: 1;
the specific process is as follows:
170.38mg of zinc chloride is dissolved in methanol to obtain a methanol solution of zinc chloride with the mass concentration of 0.02mol/L, 129.84mg of cobalt chloride is dissolved in methanol to obtain a methanol solution of cobalt chloride with the mass concentration of 0.02mol/L, 18mol of 2-methylimidazole is dissolved in methanol to obtain a methanol solution of 2-methylimidazole with the mass concentration of 2mol/L, then the three are mixed, stirred uniformly and then kept stand for 15h to obtain a blue cloudy liquid, the blue cloudy liquid is filtered and dried at 100 ℃ to obtain blue powder, namely Zn/Co-ZIF;
wherein the ratio of the sum of the amounts of zinc salt and cobalt salt to the amount of 2-methylimidazole is 2: 16;
s2, dissolving 556mg of ferrous sulfate in ethanol to obtain an ethanol solution of the ferrous sulfate with the mass concentration of 0.02mol/L, dissolving 1.19g of cobalt chloride in the ethanol to obtain an ethanol solution of the cobalt chloride with the mass concentration of 0.02mol/L, dissolving 259.2mg of nickel chloride in the ethanol to obtain an ethanol solution of the nickel chloride with the mass concentration of 0.03mol/L, dissolving 0.064mol of 2-methylimidazole in the ethanol to obtain an ethanol solution of the 2-methylimidazole with the mass concentration of 1mol/L, and dissolving 1.34g of Zn/Co-ZIF obtained from S1 in the ethanol to obtain an ethanol solution of the Zn/Co-ZIF with the mass concentration of Zn/Co-ZIF;
s3, mixing the ferrous sulfate ethanol solution, the cobalt chloride ethanol solution and the nickel chloride ethanol solution with the Zn/Co-ZIF ethanol solution according to a certain proportion in a nitrogen atmosphere, adding the 2-methylimidazole ethanol solution, stirring uniformly, standing, filtering, washing and drying to obtain the Zn/Co-ZIF @ Fe/Co/Ni-ZIF with the core-shell structure;
wherein the mass ratio of the ferrous salt to the cobalt salt to the nickel salt is 1:2: 1; the mass ratio of the sum of the ferrous salt, the cobalt salt and the nickel salt to the Zn/Co-ZIF is 3: 2; the ratio of the sum of the amounts of the ferrous, cobalt and nickel salts to the amount of the 2-methylimidazole is 2: 16;
wherein the grain diameter of Zn/Co-ZIF is 0.9 μm, and the thickness of Fe/Co/Ni-ZIF is 0.5 μm;
s4, calcining the Zn/Co-ZIF @ Fe/Co/Ni-ZIF obtained in the step S3 in nitrogen at 1000 ℃ according to the heating rate of 4 ℃/min, preserving heat for 1h, and cooling to obtain an intermediate product;
and S5, calcining the intermediate product obtained in the step S4 at 400 ℃ in an air atmosphere according to the heating rate of 2 ℃/min, preserving heat for 3h, and cooling to obtain a calcined product, namely the lithium ion battery cathode material.
Example 4
The embodiment provides a preparation method of a lithium ion battery cathode material, which comprises the following steps:
s1, preparing a zinc/cobalt bimetallic zeolite imidazolate framework material Zn/Co-ZIF; wherein the mass ratio of Co to Zn is 0.3: 1;
the specific process is as follows:
dissolving 91.32mg of zinc chloride in methanol to obtain a methanol solution of zinc chloride with the mass concentration of 0.02mol/L, dissolving 25.97mg of cobalt chloride in methanol to obtain a methanol solution of cobalt chloride with the mass concentration of 0.02mol/L, dissolving 4.64mol of 2-methylimidazole in methanol to obtain a methanol solution of 2-methylimidazole with the mass concentration of 2mol/L, mixing the three solutions, uniformly stirring, standing for 15h to obtain a blue turbid liquid, performing suction filtration, and drying at 100 ℃ to obtain blue powder, namely Zn/Co-ZIF;
wherein the ratio of the sum of the amounts of zinc salt and cobalt salt to the amount of 2-methylimidazole is 3: 16;
s2, dissolving 1.112g of ferrous sulfate in ethanol in a nitrogen atmosphere to obtain an ethanol solution of ferrous sulfate with the mass concentration of 0.04mol/L, dissolving 1.19g of cobalt chloride in ethanol to obtain an ethanol solution of cobalt chloride with the mass concentration of 0.04mol/L, dissolving 259.2mg of nickel chloride in ethanol to obtain an ethanol solution of nickel chloride with the mass concentration of 0.05mol/L, dissolving 0.053mol of 2-methylimidazole in ethanol to obtain an ethanol solution of 2-methylimidazole with the mass concentration of 2mol/L, and dissolving 1.28g of Zn/Co-ZIF obtained from S1 in ethanol to obtain an ethanol solution of Zn/Co-ZIF with the mass concentration of 6 g/L;
s3, mixing the ferrous sulfate ethanol solution, the cobalt chloride ethanol solution and the nickel chloride ethanol solution with the Zn/Co-ZIF ethanol solution according to a certain proportion in a nitrogen atmosphere, adding the 2-methylimidazole ethanol solution, stirring uniformly, standing, filtering, washing and drying to obtain the Zn/Co-ZIF @ Fe/Co/Ni-ZIF with the core-shell structure;
wherein the mass ratio of the ferrous salt to the cobalt salt to the nickel salt is 2:2: 1; the mass ratio of the sum of the ferrous salt, the cobalt salt and the nickel salt to the Zn/Co-ZIF is 4: 2; the ratio of the sum of the amounts of the ferrous salt, cobalt salt and nickel salt to the amount of the 2-methylimidazole is 3: 16;
wherein the grain diameter of Zn/Co-ZIF is 1.5 μm, and the thickness of Fe/Co/Ni-ZIF is 0.4 μm;
s4, calcining the Zn/Co-ZIF @ Fe/Co/Ni-ZIF obtained in the step S3 at 800 ℃ at a heating rate of 2 ℃/min in nitrogen, preserving heat for 3 hours, and cooling to obtain an intermediate product;
and S5, calcining the intermediate product obtained in the step S4 at 450 ℃ in the air atmosphere according to the heating rate of 2 ℃/min, preserving heat for 3h, and cooling to obtain a calcined product, namely the lithium ion battery cathode material.
Example 5
The embodiment provides a preparation method of a lithium ion battery cathode material, which comprises the following steps:
s1, preparing a zinc/cobalt bimetallic zeolite imidazolate framework material Zn/Co-ZIF; wherein the mass ratio of Co to Zn is 1: 1;
the specific process is as follows:
148.75mg of zinc nitrate is dissolved in N, N-Dimethylformamide (DMF) to obtain a DMF solution of zinc nitrate with the mass concentration of 0.01mol/L, 145.5mg of cobalt nitrate is dissolved in N, N-dimethylformamide to obtain a DMF solution of cobalt nitrate with the mass concentration of 0.01mol/L, 4mol of 2-methylimidazole is dissolved in N, N-dimethylformamide to obtain a DMF solution of 2-methylimidazole with the mass concentration of 0.1mol/L, the three solutions are mixed, stirred uniformly and then kept stand for 25h to obtain a blue turbid liquid, and the blue turbid liquid is filtered and dried at 90 ℃ to obtain blue powder, namely Zn/Co-ZIF;
wherein the ratio of the sum of the amounts of zinc salt and cobalt salt to the amount of 2-methylimidazole is 4: 16;
s2, dissolving 1.39g of ferrous sulfate in ethanol in a nitrogen atmosphere to obtain an ethanol solution of ferrous sulfate with the mass concentration of 0.05mol/L, dissolving 1.49g of cobalt chloride in ethanol to obtain an ethanol solution of cobalt chloride with the mass concentration of 0.05mol/L, dissolving 972mg of nickel chloride in ethanol to obtain an ethanol solution of nickel chloride with the mass concentration of 0.075mol/L, dissolving 0.07mol of 2-methylimidazole in ethanol to obtain an ethanol solution of 2-methylimidazole with the mass concentration of 2.8mol/L, and dissolving 3.08g of Zn/Co-ZIF obtained from S1 in ethanol to obtain an ethanol solution of Zn/Co-ZIF with the mass concentration of 8 g/L;
s3, mixing the ferrous sulfate ethanol solution, the cobalt chloride ethanol solution and the nickel chloride ethanol solution with the Zn/Co-ZIF ethanol solution according to a certain proportion in a nitrogen atmosphere, adding the 2-methylimidazole ethanol solution, stirring uniformly, standing, filtering, washing and drying to obtain the Zn/Co-ZIF @ Fe/Co/Ni-ZIF with the core-shell structure;
wherein the mass ratio of the ferrous salt to the cobalt salt to the nickel salt is 2:2: 3; the mass ratio of the sum of the ferrous salt, the cobalt salt and the nickel salt to the Zn/Co-ZIF is 2.5: 2; the ratio of the sum of the amounts of the ferrous, cobalt and nickel salts to the amount of the 2-methylimidazole is 4: 16; the grain diameter of Zn/Co-ZIF is 1.8 mu m, and the thickness of Fe/Co/Ni-ZIF is 0.2 mu m;
s4, calcining the Zn/Co-ZIF @ Fe/Co/Ni-ZIF obtained in the step S3 in nitrogen at 1000 ℃ according to the heating rate of 4 ℃/min, preserving heat for 1h, and cooling to obtain an intermediate product;
and S5, calcining the intermediate product obtained in the step S4 at 600 ℃ in the air atmosphere according to the heating rate of 4 ℃/min, preserving the heat for 1h, and cooling to obtain a calcined product, namely the lithium ion battery cathode material.
Comparative example 1
The same preparation method as that of example 1, except that in the zinc/cobalt bimetallic zeolite imidazolate framework material Zn/Co-ZIF prepared in S1, the mass ratio of Co to Zn is 10: 1.
Comparative example 2
The same preparation method as that of example 1 was repeated, except that the zeolitic imidazolate framework material prepared in S1 was Zn-ZIF, i.e., ZIF-8.
Comparative example 3
The preparation method is the same as that of the embodiment 1, except that no ferrous salt is added in S2, namely the Zn/Co-ZIF @ Co/Ni-ZIF material is prepared by S2, and then the material is used as a precursor to carry out the calcination process of S3.
Comparative example 4
The preparation method is the same as that of the example 1, except that no cobalt salt is added in S2, namely the Zn/Co-ZIF @ Fe/Ni-ZIF material is prepared by S2, and then the material is used as a precursor to carry out the calcination process of S3.
Comparative example 5
The preparation method is the same as that of the example 1, except that no nickel salt is added in S2, namely the Zn/Co-ZIF @ Fe/Co-ZIF material is prepared by S2, and then the material is used as a precursor to carry out the calcination process of S3.
Comparative example 6
The same preparation method as in example 1 was followed, except that the calcination step in the air atmosphere was not performed in S3, that is, Zn/Co-ZIF @ Fe/Co/Ni-ZIF of the core-shell structure obtained in S2 was calcined only in the nitrogen atmosphere.
Comparative example 7
The same preparation method as that of example 1, except that the step of calcining in a protective gas atmosphere was not performed in S3, that is, Zn/Co-ZIF @ Fe/Co/Ni-ZIF of the core-shell structure obtained in S2 was directly calcined in an air atmosphere.
The lithium ion battery negative electrode materials in the embodiments 1 to 5 of the invention all have good electrochemical properties, the negative electrode materials in the embodiments 1 to 5 are subjected to a BET specific surface area test, and a transmission electron microscope test is performed to obtain the core particle size and the shell thickness, and the table 1 is a structural data table of the negative electrode materials in the embodiments 1 to 5.
Table 1 table of structural data of negative electrode materials of examples 1 to 5
Figure DEST_PATH_IMAGE001
As can be seen from table 1: the samples in the embodiments 1 to 5 are all core-shell structures, and when the core Zn/Co-ZIF is prepared, the particle size of the Zn/Co-ZIF is increased along with the increase of the addition ratio of 2-methylimidazole; meanwhile, in the coating process, the thickness of the shell is related to the particle size of the inner core and the addition amount of the 2-methylimidazole in the coating process of the shell.
The lithium ion battery negative electrode materials of the embodiments 1 to 5 have good electrochemical performance, the negative electrode material of the embodiment 1 is taken as an example, and the negative electrode material and the samples of the comparative examples 1 to 9 are jointly subjected to battery performance test, and the test results are shown in table 1:
TABLE 2 TABLE of Battery Performance data for samples of example 1, comparative examples 1 to 9
Figure 614766DEST_PATH_IMAGE002
As can be seen from Table 2, the power performance and cycle of example 1 are both significantly better than those of comparative example 7, which indicates that calcining the precursor with the core-shell structure in a protective gas atmosphere is necessary, because calcining the precursor in the protective gas atmosphere is helpful for improving the dispersion of the nanoparticles and maintaining high porosity; comparing the performance data of example 1 with the performance data of comparative example 6, it can be seen that the precursor with the core-shell structure is calcined only in the protective gas atmosphere, so that the metal oxide with higher capacity cannot be obtained, and the graphitized carbon generated at high temperature only exerts the capacity; compared with the performance data of the embodiment 1 and the comparative examples 3-5, the high content of Co is beneficial to improving the capacity of the material, the content of Fe is beneficial to improving the cycle performance of the material, and the content of Ni is beneficial to improving the rate capability of the material; comparing the performance data of example 1 with that of comparative example 1, it can be seen that when the Zn content is small, the formation of a hollow structure is not facilitated, and meanwhile, the porosity is low and the power performance is poor; comparing example 1 with comparative example 2, it can be seen that in comparative example 2, the metal of the core material is only zinc, that is, the ZIF-8 is used as a precursor, and after two times of calcination, the zinc of the core is completely volatilized, and the core forms a complete hollow structure, which is beneficial to improving the capacity, but the structure is unstable, and finally the cycle retention rate is poor.
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention are included in the scope of the present invention. Therefore, the protection scope of the present invention shall be subject to the protection scope of the claims.

Claims (10)

1. The preparation method of the lithium ion battery negative electrode material is characterized by comprising the following steps of:
s1, preparing a zinc/cobalt bimetallic zeolite imidazolate framework material Zn/Co-ZIF;
wherein the mass ratio of Co to Zn is (0.1-1) to 1;
s2, respectively and uniformly dispersing ferrous salt, cobalt salt, nickel salt, 2-methylimidazole and Zn/Co-ZIF prepared by the S1 in a first organic solvent in a protective gas atmosphere to obtain corresponding organic solutions;
s3, mixing a ferrous salt organic solution, a cobalt salt organic solution and a nickel salt organic solution with a Zn/Co-ZIF organic solution in a protective gas atmosphere, adding a 2-methylimidazole organic solution, stirring uniformly, standing, filtering, washing and drying to obtain Zn/Co-ZIF @ Fe/Co/Ni-ZIF with a core-shell structure;
wherein the mass ratio of the ferrous salt, the cobalt salt and the nickel salt is (1-2) to (2) (1-3);
s4, calcining the Zn/Co-ZIF @ Fe/Co/Ni-ZIF obtained in the step S3 in a protective gas atmosphere at 800-1000 ℃, preserving heat for 1-3 hours, and cooling to obtain an intermediate product;
and S5, calcining the intermediate product obtained in the step S4 in the air atmosphere at the temperature of 300-600 ℃, preserving heat for 1-3 hours, and cooling to obtain a calcined product, namely the lithium ion battery cathode material.
2. The method for preparing the negative electrode material of the lithium ion battery according to claim 1, wherein the ratio of the sum of the amounts of the ferrous salt, the cobalt salt and the nickel salt to the amount of the 2-methylimidazole in S3 is (1-4): 16.
3. the preparation method of the negative electrode material of the lithium ion battery according to claim 1, wherein the mass ratio of the sum of the masses of the ferrous salt, the cobalt salt and the nickel salt to the Zn/Co-ZIF in S3 is (1-4): 2.
4. the preparation method of the negative electrode material of the lithium ion battery according to any one of claims 1 to 3, wherein the amount concentration of the substance in the ferrous salt organic solution in S3 is 0.005 to 0.05mol/L, the amount concentration of the substance in the cobalt salt organic solution is 0.01 to 0.05mol/L, the amount concentration of the substance in the nickel salt organic solution is 0.01 to 0.075mol/L, the amount concentration of the substance in the 2-methylimidazole organic solution is 0.1 to 2.8mol/L, and the mass concentration of the Zn/Co-ZIF organic solution is 1 to 8 g/L.
5. The preparation method of the lithium ion battery anode material according to claim 4, wherein in the Zn/Co-ZIF @ Fe/Co/Ni-ZIF obtained in S3, the particle size of the Zn/Co-ZIF is 0.1-2 μm, and the thickness of the Fe/Co/Ni-ZIF is 0.1-0.5 μm.
6. The method for preparing the negative electrode material of the lithium ion battery according to claim 1, wherein the shielding gas in the step S4 is at least one of nitrogen and argon; and the temperature rise rate of the calcination process in the S4 and the S5 is 2-4 ℃/min.
7. The preparation method of the anode material of the lithium ion battery according to claim 1, wherein the preparation process of Zn/Co-ZIF in S1 is as follows:
respectively dissolving zinc salt, cobalt salt and 2-methylimidazole in a second organic solvent to obtain corresponding organic solutions, uniformly mixing the three solutions, standing to obtain a blue cloudy liquid, and performing suction filtration and drying to obtain blue powder, namely Zn/Co-ZIF.
8. The method for preparing the negative electrode material of the lithium ion battery according to claim 7, wherein the ratio of the sum of the amounts of the zinc salt and the cobalt salt to the amount of the 2-methylimidazole is (1-4): 16.
9. the method of claim 1 or 7, wherein in S1 and S2, the ferrous salt is ferrous sulfate or ferrous chloride, the cobalt salt is cobalt nitrate or cobalt chloride, the nickel salt is nickel chloride, and the zinc salt is zinc nitrate or zinc chloride.
10. The method for preparing the negative electrode material of the lithium ion battery according to claim 7, wherein in the S1 and the S2, the first organic solvent and the second organic solvent are both at least one of methanol, ethanol or N, N-dimethylformamide, the shielding gas is at least one of nitrogen and argon, and the drying temperature is 60-100 ℃.
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