A kind of lithium battery cathode material precursor with mesoscopic structure and preparation method thereof

Abstract

The invention discloses a lithium battery cathode material precursor with a mesoscopic structure and a preparation method thereof. The method comprises the following steps: (1) one-step co-synthesis: mixing the lithium salt solution and the nickel-cobalt-manganese mixed solution, adjusting the pH value to 5.5-7.5 through a carbon dioxide-lithium hydroxide buffer system, and stirring for 2-5 hours; (2 ) Two-step co-synthesis: Concentrate the product obtained in step (1) until the volume is reduced by 1 / 2 to 2 / 3, pass through protective gas to maintain the pressure at 1.01 to 10.0 MPa, and then perform solid-liquid separation after aging for 5 to 24 hours , to collect the solid phase product; (3) pyrolyze the solid phase product in a vacuum, and then dry it at 90-130°C. The reaction process of the present invention does not require an external complexing agent, and a nano-scale, independent lithium-nickel-cobalt-manganese quaternary precursor spherical particle with a mesoscopic structure can be prepared, which simplifies reaction control and reduces production costs.

Description

technical field

[0001] The invention belongs to the technical field of lithium batteries, and in particular relates to a lithium battery cathode material precursor with a mesoscopic structure and a preparation method thereof. Background technique

[0002] Benefiting from the promotion of the new energy vehicle industry policy, China is already the world's largest electric vehicle market. The automotive lithium-ion power battery market is coming out of the introduction period and entering a period of rapid growth. In the next few years, the largest driving force for the growth of the lithium-ion battery market will undoubtedly come from the electric vehicle market. The global production of lithium-ion power batteries and their materials is mainly concentrated in China, Japan and South Korea. The main cathode materials include modified lithium manganate, nickel-cobalt lithium manganate or nickel-cobalt lithium aluminate. The demand for high-energy-density lithium-ion power b...

Examples

Embodiment 1

[0039] A preparation method of a lithium battery cathode material precursor with a mesoscopic structure, comprising the following steps:

[0040] (1) Solution deployment: the lithium sulfate solid soluble in water and deionized water are made into the lithium salt solution that concentration is 5mol / L; Lithium hydroxide solid and deionized water are made into the hydroxide that concentration is 5mol / L Lithium solution; water-soluble nickel sulfate, cobalt sulfate, manganese sulfate solid according to Ni 2+ :Mn 2+ :Co 2+ The molar ratio was 5:2:3, and then the mixture was dissolved in deionized water to form a mixed solution of manganese, cobalt and nickel salts with a concentration of 4 mol / L.

[0041] (2) One-time co-synthesis reaction: Add the mixed solution of nickel-cobalt-manganese salt and lithium salt solution obtained in step (1) into the synthesis reaction device with stirring and heating, and add the solution to the solution according to the 2m 3 The flow rate of / h...

Embodiment 2

[0048] A preparation method of a lithium battery cathode material precursor with a mesoscopic structure, comprising the following steps:

[0049] (1) Solution preparation: water-soluble lithium chloride solid and deionized water are made into lithium salt solution with a concentration of 9mol / L; lithium hydroxide solid and deionized water are made into hydrogen with a concentration of 6mol / L Lithium oxide solution; water-soluble nickel chloride, cobalt chloride, manganese chloride solid according to Ni 2+ :Mn 2+ :Co 2+ The molar ratio was 6:2:2, and then the mixture was dissolved with deionized water to form a mixed solution of manganese, cobalt and nickel salts with a concentration of 5 mol / L.

[0050] (2) One-time co-synthesis reaction: add the mixed solution of nickel-cobalt-manganese salt and lithium salt solution obtained in step (1) into the synthesis reaction device with stirring and heating, 3 The flow rate of / h is fed into carbon dioxide gas, and the pH automatic ...

experiment example

[0059] The precursors prepared in Example 1, Example 2 and Comparative Example were respectively used as raw materials to prepare lithium battery positive electrodes, and then according to the non-ferrous metal industry standard of the People's Republic of China (YST 798-2012), it was tested for charge and discharge performance. The results are shown in Table 1.

[0060] Table 1 Lithium battery cathode charging performance

[0061]

[0062] From the data in Table 1, it can be seen that the performance of the positive electrodes of lithium batteries prepared using the precursors prepared in Example 1 and Example 2 of the present invention as raw materials is almost the same, and both are higher than the industry standard, and are far better than the comparative example, which shows that , only with the cooperation of the method and process conditions of the present invention, can the lithium-nickel-cobalt-manganese quaternary precursor with nanoscale and mesoscopic structure...

technical field

[0001] The invention belongs to the technical field of lithium batteries, and in particular relates to a lithium battery cathode material precursor with a mesoscopic structure and a preparation method thereof. Background technique

[0002] Benefiting from the promotion of the new energy vehicle industry policy, China is already the world's largest electric vehicle market. The automotive lithium-ion power battery market is coming out of the introduction period and entering a period of rapid growth. In the next few years, the largest driving force for the growth of the lithium-ion battery market will undoubtedly come from the electric vehicle market. The global production of lithium-ion power batteries and their materials is mainly concentrated in China, Japan and South Korea. The main cathode materials include modified lithium manganate, nickel-cobalt lithium manganate or nickel-cobalt lithium aluminate. The demand for high-energy-density lithium-ion power b...

Examples

Embodiment 1

[0039] A preparation method of a lithium battery cathode material precursor with a mesoscopic structure, comprising the following steps:

[0040] (1) Solution deployment: the lithium sulfate solid soluble in water and deionized water are made into the lithium salt solution that concentration is 5mol / L; Lithium hydroxide solid and deionized water are made into the hydroxide that concentration is 5mol / L Lithium solution; water-soluble nickel sulfate, cobalt sulfate, manganese sulfate solid according to Ni 2+ :Mn 2+ :Co 2+ The molar ratio was 5:2:3, and then the mixture was dissolved in deionized water to form a mixed solution of manganese, cobalt and nickel salts with a concentration of 4 mol / L.

[0041] (2) One-time co-synthesis reaction: Add the mixed solution of nickel-cobalt-manganese salt and lithium salt solution obtained in step (1) into the synthesis reaction device with stirring and heating, and add the solution to the solution according to the 2m 3 The flow rate of / h...

Embodiment 2

[0048] A preparation method of a lithium battery cathode material precursor with a mesoscopic structure, comprising the following steps:

[0049] (1) Solution preparation: water-soluble lithium chloride solid and deionized water are made into lithium salt solution with a concentration of 9mol / L; lithium hydroxide solid and deionized water are made into hydrogen with a concentration of 6mol / L Lithium oxide solution; water-soluble nickel chloride, cobalt chloride, manganese chloride solid according to Ni 2+ :Mn 2+ :Co 2+ The molar ratio was 6:2:2, and then the mixture was dissolved with deionized water to form a mixed solution of manganese, cobalt and nickel salts with a concentration of 5 mol / L.

[0050] (2) One-time co-synthesis reaction: add the mixed solution of nickel-cobalt-manganese salt and lithium salt solution obtained in step (1) into the synthesis reaction device with stirring and heating, 3 The flow rate of / h is fed into carbon dioxide gas, and the pH automatic ...

experiment example

[0059] The precursors prepared in Example 1, Example 2 and Comparative Example were respectively used as raw materials to prepare lithium battery positive electrodes, and then according to the non-ferrous metal industry standard of the People's Republic of China (YST 798-2012), it was tested for charge and discharge performance. The results are shown in Table 1.

[0060] Table 1 Lithium battery cathode charging performance

[0061]

[0062] From the data in Table 1, it can be seen that the performance of the positive electrodes of lithium batteries prepared using the precursors prepared in Example 1 and Example 2 of the present invention as raw materials is almost the same, and both are higher than the industry standard, and are far better than the comparative example, which shows that , only with the cooperation of the method and process conditions of the present invention, can the lithium-nickel-cobalt-manganese quaternary precursor with nanoscale and mesoscopic structure...

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