Metal-coated foamy copper-based self-supporting lithium cobalt oxide electrode material and manufacturing method thereof

Abstract

The invention relates to a metal-coated foamy copper-based self-supporting lithium cobalt oxide electrode material and a manufacturing method thereof. The manufacturing method of the lithium cobalt oxide electrode material comprises the following steps of S1, preparing Li@ZIF67; S2, carrying out in-situ deposition of Li@ZIF67 on a metal-coated foamy copper substrate; and S3, manufacturing a metal-coated foamy copper-based self-supporting LiCoO2 material. The metal-coated foamy copper substrate of the invention is an important path for charge transmission and storage and is an excellent substrate for supporting an active material. Based on advantages of the ZIF67 precursor and a three-dimensional substrate structure, a metal-coated foamy copper-based self-supporting LiCoO2 material electrode manufactured by the manufacturing method has a large reversible capacity, a high porosity, an excellent rate capability and remarkable cycling stability. And due to remarkable electrochemical performance, the manufacturing method of the metal-coated foamy copper-based self-supporting LiCoO2 material of a nano polyhedron structure can also provide guidance for manufacturing of a leading-edge high-performance flexible lithium ion battery positive electrode material.

Description

technical field

[0001] The invention relates to the technical field of lithium cobalt oxide cathode materials for lithium ion batteries, in particular to a lithium cobalt oxide composite material with ZIF67 as a template and a preparation method thereof. Background technique

[0002] As people pay more and more attention to the environment and energy, lithium-ion batteries as green energy are more and more popular due to their advantages such as high working voltage, long cycle life, low self-discharge rate, good safety performance, and no memory effect. It is widely used in electronic products such as notebook computers, mobile phones, and digital cameras. At the same time, the application of lithium-ion batteries is rapidly developing in the fields of electric vehicles, aviation and navigation, which puts forward higher requirements for the safety performance, power density, energy density and cycle life of lithium-ion batteries.

[0003] In lithium-ion battery electrode ...

Examples

preparation example Construction

[0060] see figure 1 , in fact, the flow chart of the method for preparing metal-coated foamed copper-based self-supporting lithium cobaltate electrode material of the present invention, the method has the following steps:

[0061] Step S1: Preparation of Li@ZIF67;

[0062] Co(NO 3 ) 2 ·6H 2 O and cetyltrimethylammonium bromide (CTAB) were dissolved in methanol to prepare solution A, and then 2-methylimidazole and Li 2 CO 3 Dissolved in methanol to prepare solution B, then quickly pour solution B into solution A to form mixed solution C, centrifuge the mixed solution C after microwave reaction, wash, and dry to prepare lithium-ion-doped ZIF67 (Li@ ZIF67).

[0063] ZIF series materials are usually synthesized by one-step method, through the reaction of metal salts and organic ligands in a solvent. The commonly used preparation methods also include solvothermal method, liquid phase diffusion method, microwave-assisted method, electrochemical method and mechanochemical synt...

Embodiment 1

[0076] Step S1: Preparation of Li@ZIF67;

[0077] S101: Dissolved, 2.4g of 99% Co(NO 3 ) 2 ·6H 2 O, 0.2g purity is that the CTAB of 99% is dissolved in the 30mL methyl alcohol, stirs and makes it dissolve completely, makes solution A; With 3.3g purity is 99% 2-methylimidazole, 0.4gLi 2 CO 3 Dissolve in 60mL of methanol, stir to dissolve completely, and obtain solution B;

[0078] S102: Microwave reaction, quickly pour solution B into solution A to form a mixed solution, then place the mixed solution in a microwave reactor at a constant temperature of 50°C for 5 minutes, and cool it to room temperature after obtaining a purple solution;

[0079] S103: Centrifuge, centrifuge the purple solution at a speed of 7000r / min for 3 minutes, and collect the solid product;

[0080] S104: washing and drying, using methanol to ultrasonically clean the solid product three times, and vacuum-drying the washed solid product at 60° C. for 24 hours to prepare Li@ZIF67.

[0081] Step S2: in-...

Embodiment 2

[0090] Step S1: Preparation of Li@ZIF67;

[0091] S101: Dissolve, 2.0g of 99% Co(NO 3 ) 2 ·6H 2 O, the CTAB that 0.1g purity is 99% is dissolved in the 30mL methyl alcohol, stirs and makes it dissolve completely, makes solution A; 3.0g purity is 99% 2-methylimidazole, 0.35gLi 2 CO 3 Dissolve in 60mL of methanol, stir to dissolve completely, and obtain solution B;

[0092] S102: Microwave reaction, quickly pour solution B into solution A to form a mixed solution, then place the mixed solution in a microwave reactor at a constant temperature of 50°C for 5 minutes, and cool it to room temperature after obtaining a purple solution;

[0093] S103: Centrifuge, centrifuge the purple solution at a speed of 7000r / min for 3 minutes, and collect the solid product;

[0094] S104: washing and drying, using methanol to ultrasonically clean the solid product three times, and vacuum-drying the washed solid product at 60° C. for 24 hours to prepare Li@ZIF67.

[0095] Step S2: in-situ dep...

technical field

[0001] The invention relates to the technical field of lithium cobalt oxide cathode materials for lithium ion batteries, in particular to a lithium cobalt oxide composite material with ZIF67 as a template and a preparation method thereof. Background technique

[0002] As people pay more and more attention to the environment and energy, lithium-ion batteries as green energy are more and more popular due to their advantages such as high working voltage, long cycle life, low self-discharge rate, good safety performance, and no memory effect. It is widely used in electronic products such as notebook computers, mobile phones, and digital cameras. At the same time, the application of lithium-ion batteries is rapidly developing in the fields of electric vehicles, aviation and navigation, which puts forward higher requirements for the safety performance, power density, energy density and cycle life of lithium-ion batteries.

[0003] In lithium-ion battery electrode ...

Examples

preparation example Construction

[0060] see figure 1 , in fact, the flow chart of the method for preparing metal-coated foamed copper-based self-supporting lithium cobaltate electrode material of the present invention, the method has the following steps:

[0061] Step S1: Preparation of Li@ZIF67;

[0062] Co(NO 3 ) 2 ·6H 2 O and cetyltrimethylammonium bromide (CTAB) were dissolved in methanol to prepare solution A, and then 2-methylimidazole and Li 2 CO 3 Dissolved in methanol to prepare solution B, then quickly pour solution B into solution A to form mixed solution C, centrifuge the mixed solution C after microwave reaction, wash, and dry to prepare lithium-ion-doped ZIF67 (Li@ ZIF67).

[0063] ZIF series materials are usually synthesized by one-step method, through the reaction of metal salts and organic ligands in a solvent. The commonly used preparation methods also include solvothermal method, liquid phase diffusion method, microwave-assisted method, electrochemical method and mechanochemical synt...

Embodiment 1

[0076] Step S1: Preparation of Li@ZIF67;

[0077] S101: Dissolved, 2.4g of 99% Co(NO 3 ) 2 ·6H 2 O, 0.2g purity is that the CTAB of 99% is dissolved in the 30mL methyl alcohol, stirs and makes it dissolve completely, makes solution A; With 3.3g purity is 99% 2-methylimidazole, 0.4gLi 2 CO 3 Dissolve in 60mL of methanol, stir to dissolve completely, and obtain solution B;

[0078] S102: Microwave reaction, quickly pour solution B into solution A to form a mixed solution, then place the mixed solution in a microwave reactor at a constant temperature of 50°C for 5 minutes, and cool it to room temperature after obtaining a purple solution;

[0079] S103: Centrifuge, centrifuge the purple solution at a speed of 7000r / min for 3 minutes, and collect the solid product;

[0080] S104: washing and drying, using methanol to ultrasonically clean the solid product three times, and vacuum-drying the washed solid product at 60° C. for 24 hours to prepare Li@ZIF67.

[0081] Step S2: in-...

Embodiment 2

[0090] Step S1: Preparation of Li@ZIF67;

[0091] S101: Dissolve, 2.0g of 99% Co(NO 3 ) 2 ·6H 2 O, the CTAB that 0.1g purity is 99% is dissolved in the 30mL methyl alcohol, stirs and makes it dissolve completely, makes solution A; 3.0g purity is 99% 2-methylimidazole, 0.35gLi 2 CO 3 Dissolve in 60mL of methanol, stir to dissolve completely, and obtain solution B;

[0092] S102: Microwave reaction, quickly pour solution B into solution A to form a mixed solution, then place the mixed solution in a microwave reactor at a constant temperature of 50°C for 5 minutes, and cool it to room temperature after obtaining a purple solution;

[0093] S103: Centrifuge, centrifuge the purple solution at a speed of 7000r / min for 3 minutes, and collect the solid product;

[0094] S104: washing and drying, using methanol to ultrasonically clean the solid product three times, and vacuum-drying the washed solid product at 60° C. for 24 hours to prepare Li@ZIF67.

[0095] Step S2: in-situ dep...

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