PREPARATION METHOD FOR NANOSIZED LITHIUM COBALT OXIDE CATHODE MATERIAL AND APPLICATION THEREOF

Abstract

The invention belongs to the technical field of lithium ion battery cathode materials, and discloses a preparation method and application of nanosized lithium cobalt oxide cathode materials, comprising the following steps: mixing the carbonate solution with a dispersant, adding a cobalt salt solution to react, then aging, filtering, drying the filter residue to obtain a nano-CoCO.sub.3 powder, and then calcinating it to obtain a Co.sub.3O.sub.4 precursor; mixing the Co.sub.3O.sub.4 precursor with a lithium salt, and then sintering, cooling, pulverizing and sieving to obtain the nanosized lithium cobalt oxide cathode material. The main advantages of the present invention are that the nano-CoCO.sub.3 synthesis process is simple and easy to control, the process is short, no special temperature control is required, the pH value and other conditions are not required to be precisely controlled during the reaction process, and it is suitable for large-scale industrial production.

Claims

1. A preparation method for a nanosized lithium cobalt oxide cathode material, consisting of the following steps: (1) mixing a carbonate solution with a dispersant, adding a cobalt salt solution to perform a reaction, then aging, filtering to obtain a filter residue, drying the filter residue to obtain a nano-CoCO.sub.3 powder, and then calcinating the nano-CoCO.sub.3 powder to obtain a Co.sub.3O.sub.4 precursor; (2) mixing the Co.sub.3O.sub.4 precursor with a lithium salt, and subjecting a resulting mixture to calcinating, cooling, pulverizing and sieving to obtain the nanosized lithium cobalt oxide cathode material; wherein a total molar amount of Co.sup.2+ in the cobalt salt solution is no more than ⅕ of a total molar amount of carbonate in the carbonate solution; in step (1), the dispersant is one or more selected from the group consisting of methanol, ethanol, ethylene glycol, propanol and glycerol; in step (2), the calcinating is carried out at a temperature of 900-1200° C. for 6-18 h.

2. The preparation method according to claim 1, wherein in step (1), the cobalt salt solution is prepared by dissolving a cobalt salt in water, and the cobalt salt is one or more selected from the group consisting of cobalt sulfate, cobalt nitrate and cobalt chloride; a concentration of the cobalt salt solution is 0.1-2.0 mol/L.

3. The preparation method according to claim 1, wherein in step (1), the carbonate solution is prepared by dissolving a carbonate salt in water, and the carbonate salt is one or more selected from the group consisting of sodium carbonate, sodium bicarbonate, ammonium carbonate, ammonium bicarbonate, potassium carbonate and potassium bicarbonate; a concentration of the carbonate solution is 1.0-2.0 mol/L.

4. The preparation method according to claim 1, wherein in step (1), the total molar amount of Co.sup.2+ in the cobalt salt solution is no more than 1/10 of the total molar amount of carbonate in the carbonate solution.

5. The preparation method according to claim 1, wherein in step (1), the reaction is carried out at a temperature of 0-70° C.

6. The preparation method according to claim 1, wherein in step (1), the calcinating is carried out at a temperature of 300-800° C.

7. The preparation method according to claim 1, wherein in step (2), the lithium salt is one or more selected from the group consisting of lithium carbonate, lithium nitrate, lithium sulfate and lithium oxalate.

8. Use of the preparation method according to claim 1 in the preparation of a lithium ion battery.

9. Use of the preparation method according to claim 2 in the preparation of a lithium ion battery.

10. Use of the preparation method according to claim 3 in the preparation of a lithium ion battery.

11. Use of the preparation method according to claim 4 in the preparation of a lithium ion battery.

12. Use of the preparation method according to claim 5 in the preparation of a lithium ion battery.

13. Use of the preparation method according to claim 6 in the preparation of a lithium ion battery.

14. Use of the preparation method according to claim 7 in the preparation of a lithium ion battery.

Description

BRIEF DESCRIPTION OF DRAWINGS

[0025] The present invention will be further described below in conjunction with the accompanying drawings and examples, wherein:

[0026] FIG. 1 is an SEM image of the nano-CoCO.sub.3 powder in Example 1 of the present invention;

[0027] FIG. 2 is an SEM image of the nano-Co.sub.3O.sub.4 precursor in Example 1 of the present invention;

[0028] FIG. 3 is an SEM image of the nanosized lithium cobalt oxide cathode material in Example 1 of the present invention;

[0029] FIG. 4 is an SEM image of the cobalt carbonate powder in Comparative Example 1 of the present invention;

[0030] FIG. 5 is an SEM image of lithium cobalt oxide in Comparative Example 1 of the present invention.

DETAILED DESCRIPTION OF THE ILLUSTRATED EXAMPLES

[0031] Hereinafter, the concept of the present invention and the technical effects produced by it will be described clearly and completely in conjunction with the examples, so as to fully understand the purpose, features and effects of the present invention. Obviously, the described examples are only a part of the examples of the present invention, rather than all of them. Based on the examples of the present invention, other examples obtained by those skilled in the art without creative work belong to the scope of protection of the present invention.

Example 1

[0032] In this example, a nanosized lithium cobalt oxide cathode material was prepared, and the specific process was as follows:

[0033] (1) Dissolving cobalt sulfate in water to prepare a cobalt salt solution with a concentration of 0.75 mol/L, and dissolving ammonium bicarbonate in water to prepare a carbonate solution with a concentration of 1.65 mol/L;

[0034] (2) Injecting 400 L of carbonate solution into a 600 L volume reactor, adding 50 L of ethanol as a dispersant, starting the reactor , stirring the carbonate solution and the dispersant thoroughly, and keeping the temperature of the reactor at room temperature of 25° C. Injecting the cobalt salt solution into the reactor at a flow rate of 20 L/h until a total of 80 L of cobalt salt solution is injected in 4 hours. Keeping stirring, driving the materials into a centrifuge for dehydration and washing after they are aged in the reactor for 2 hours, then drying them to obtain a nano-CoCO.sub.3 powder, and calcining the nano-CoCO.sub.3 powder at 400° C. for 4 hours to obtain a nano-Co.sub.3O.sub.4 precursor;

[0035] (3) Weighing 1685 g of lithium carbonate and 3500 g of nano-Co.sub.3O.sub.4 precursor according to the cobalt-lithium molar ratio of 1:1.05, mixing the weighed lithium carbonate and nano-Co.sub.3O.sub.4 precursor evenly in the mixer, calcining the mixed materials in an air atmosphere at 1020° C. for 9 hours in a furnace, cooling naturally, pulverizing the product by airflow and sieving to obtain a nanosized lithium cobalt oxide cathode material.

Example 2

[0036] In this example, a nanosized lithium cobalt oxide cathode material was prepared, and the specific process was as follows:

[0037] (1) Dissolving cobalt dichloride in water to prepare a cobalt salt solution with a concentration of 0.8 mol/L, and dissolving sodium bicarbonate in water to prepare a carbonate solution with a concentration of 1.65 mol/L;

[0038] (2) Injecting 400L of carbonate solution into a 600 L reactor, adding 60 L of ethylene glycol as a dispersant, starting the reactor , stirring the carbonate solution and the dispersant thoroughly, and keeping the temperature of the reactor at room temperature of 20° C. Injecting the cobalt salt solution into the reactor at a flow rate of 30 L/h until a total of 75 L of cobalt salt solution is injected in 2.5 hours. Keeping stirring, driving the materials into a centrifuge for dehydration and washing after they are aged in the reactor for 2 hours, then drying them to obtain a nano-CoCO.sub.3 powder, and calcining the nano-CoCO.sub.3 powder at 450° C. for 4 hours to obtain a nano-Co.sub.3O.sub.4 precursor;

[0039] (3) Weighing 1660 g of lithium hydroxide and 3000 g of nano-Co.sub.3O.sub.4 precursor according to the cobalt-lithium molar ratio of 1:1.06, mixing the weighed lithium carbonate and nano-Co.sub.3O.sub.4 precursor evenly in the mixer, calcining the mixed materials in an air atmosphere at 1010° C. for 10 hours in a furnace, cooling naturally, pulverizing the product by airflow and sieving to obtain a nanosized lithium cobalt oxide cathode material.

Example 3

[0040] In this example, a nanosized lithium cobalt oxide cathode material was prepared, and the specific process was as follows:

[0041] (1) Dissolving cobalt nitrate in water to prepare a cobalt salt solution with a concentration of 0.7 mol/L, and dissolving sodium carbonate in water to prepare a carbonate solution with a concentration of 1.5 mol/L;

[0042] (2) Injecting 350 L of carbonate solution into a 600 L reactor, adding 50 L of propyl alcohol as a dispersant, starting the reactor , stirring the carbonate solution and the dispersant thoroughly, and keeping the temperature of the reactor at room temperature of 20° C. Injecting the cobalt salt solution into the reactor at a flow rate of 20 L/h until a total of 60 L of cobalt salt solution is injected in 3 hours. Keeping stirring, driving the materials into a centrifuge for dehydration and washing after they are aged in the reactor for 2 hours, then drying them to obtain a nano-CoCO.sub.3 powder, and calcining the nano-CoCO.sub.3 powder at 430° C. for 5 hours to obtain a nano-Co.sub.3O.sub.4 precursor;

[0043] (3) Weighing 1912 g of lithium carbonate and 4000 g of nano-Co.sub.3O.sub.4 precursor according to the cobalt-lithium molar ratio of 1:1.04, mixing the weighed lithium carbonate and nano-Co.sub.3O.sub.4 precursor evenly in the mixer, calcining the mixed materials in an air atmosphere at 1050° C. for 8 hours in a furnace, cooling naturally, pulverizing the product by airflow and sieving to obtain a nanosized lithium cobalt oxide cathode material.

Comparative Example 1

[0044] In this comparative example, a lithium cobalt oxide cathode material was prepared, and the specific process was as follows:

[0045] (1) Dissolving cobalt sulfate in water to prepare a cobalt salt solution with a concentration of 1.5 mol/L, and dissolving sodium bicarbonate in water to prepare a carbonate solution with a concentration of 2 mol/L

[0046] (2) Adding 400 L of water into a 600 L batch reactor, stirring and heating, keeping the temperature of the reactor at 50° C., and injecting the cobalt salt solution and carbonate solution at the same time. The materials in the reactor are drained of the clear liquid through the thickener. Cobalt carbonate particles continue to grow in the reactor. When the particle size reaches D50=6.0 um, the feeding liquid is stopped. Driving the materials in the reactor into a centrifuge for dehydration and washing, drying the CoCO.sub.3 powder, and calcining it at 400° C. for 6 hours to obtain a Co.sub.3O.sub.4 precursor;

[0047] (3) Weighing 1930 g of lithium carbonate and 4000 g of nano-Co.sub.3O.sub.4 precursor according to the cobalt-lithium molar ratio of 1:1.05, mixing the weighed lithium carbonate and nano-Co.sub.3O.sub.4 precursor evenly in the mixer, calcining the mixed materials in an air atmosphere at 1070° C. for 10 hours in a furnace, cooling naturally, pulverizing the product by airflow to obtain a lithium cobalt oxide cathode material.

[0048] The main difference between Comparative Example 1 and the example is that the preparation process of the CoCO.sub.3 powder in step (2) is different, and the particle size of the obtained particles is of a micron scale.

Comparative Example 2

[0049] In this comparative example, a lithium cobalt oxide cathode material was prepared, and the specific process was as follows:

[0050] (1) Dissolving cobalt chloride in water to prepare a cobalt salt solution with a concentration of 1.5 mol/L, and dissolving ammonium bicarbonate in water to prepare a carbonate solution with a concentration of 2 mol/L

[0051] (2) Adding 400 L of water into a 600 L batch reactor, stirring and heating, keeping the temperature of the reactor at 45° C., and injecting the cobalt salt solution and carbonate solution at the same time. The materials in the reactor are drained of the clear liquid through the thickener. Cobalt carbonate particles continue to grow in the reactor. When the particle size reaches D50=6.0 um, the feeding liquid is stopped. Driving the materials in the reactor into a centrifuge for dehydration and washing, drying the CoCO.sub.3 powder, and calcining it at 450° C. for 4.5 hours to obtain a Co.sub.3O.sub.4 precursor;

[0052] (3) Weighing 1936 g of lithium carbonate and 4000 g of nano-Co.sub.3O.sub.4 precursor according to the cobalt-lithium molar ratio of 1:1.05, mixing the weighed lithium carbonate and nano-Co.sub.3O.sub.4 precursor evenly in the mixer, calcining the mixed materials in an air atmosphere at 1080° C. for 9 hours in a furnace, cooling naturally, pulverizing the product by airflow to obtain a lithium cobalt oxide cathode material.

[0053] The main difference between Comparative Example 2 and the example is that the preparation process of the CoCO.sub.3 powder in step (2) is different, and the particle size of the obtained particles is of a micron scale.

Comparative Example 3

[0054] In this comparative example, a kind of nano-Co.sub.3O.sub.4 was prepared by hydrothermal method, and the specific process was as follows:

[0055] Dissolving a certain amount of cobalt acetate in diethylene glycol (DEG), adding a certain amount of PVP surfactant, then adding a certain amount of urea, stirring to form a uniform solution, subjecting it to reacting in a sealed hydrothermal kettle under a high temperature and high pressure to obtain CoCO.sub.3 nanoparticles with regular morphology. The Co.sub.3O.sub.4 nanoparticles with regular morphology were prepared by calcining the CoCO.sub.3 particles at high temperature. Nano particles with different morphologies in peanut shape, capsule shape and square shape were obtained by controlling the amount of urea.

[0056] The main difference between Comparative Example 3 and the example lies in the preparation process of CoCO.sub.3 nanoparticles. Even though nanoparticles can be obtained in the end, the operation process of this comparative example is delicate and complicated, and the control of reaction conditions is difficult, and it is difficult to scale up and apply in actual production.

Performance Testing

[0057] The following physical and chemical index tests were performed on the above Examples 1-3 and Comparative Examples 1-2:

[0058] The particle size was measured in accordance with the national standard GB/T 19077 “Laser Diffraction Method for Particle Size Analysis”, using the Malvern 3000 laser particle size analyzer. The electric performance was tested as follows: the lithium cobalt oxide materials prepared in the examples and comparative examples were used as active materials, acetylene black was used as a conductive agent, PVDF was used as a binder. Weighing the active material, conductive agent and binder in a ratio of 92:4:4, adding a certain amount of organic solvent NMP, stirring and coating the mixture on aluminum foil to make a positive electrode sheet; adopting lithium metal sheet as negative electrode, and making CR2430 button battery in a glove box filled with argon. The electric performance was tested on a CT2001A LAND battery test system. Test conditions: 3.0-4.48V, current density 1C=180 mAh/g, test temperature: 25±1° C. .

[0059] The test results are shown in Table 1:

TABLE-US-00001 0.1 C/ 4.48 V 1 C/4.48 V 2 C/4.4 V 5 C/4.48 V sample D10 (μm) D50 (μm) D90 (μm) (mAh (mAh/g) (mAh/g) (mAh/g) Example 1 0.21 0.45 0.86 210.2 202.5 188.7 161.5 Example 2 0.18 0.56 0.92 210.1 201.4 188.4 162.2 Example 3 0.32 0.60 0.95 210.5 201.9 189.0 162.7 Comparative 3.43 5.82 8.76 209.0 197.2 176.4 136.2 Example1 Comparative 4.02 6.21 8.93 208.9 197.0 176.2 138.5 Example 2

[0060] It can be seen from Table 1 that the median particle size of the materials of Comparative Example 1-2 is about 6 μm, and the particle sizes of the materials of Examples 1-3 are all below 1 um, reaching the nanometer level, which is much smaller than that of the Comparative Example. The first discharge specific capacity of the example is not much different from the comparison under the low rate (0.1C), but is significantly higher than the comparison under the high rate (2C, 5C).

[0061] FIG. 1 is an SEM picture of the nano-CoCO.sub.3 powder of Example 1. It can be seen from the figure that the particles have a uniform short rod-like morphology, and the particle size is below 1 μm. FIG. 2 is an SEM picture of the nano-Co.sub.3O.sub.4 precursor in Example 1. It can be seen from the figure that the morphology of the precursor basically inherits the morphology of the CoCO.sub.3 powder and still maintains the nano-short rod shape. FIG. 3 is an SEM picture of the nanosized lithium cobalt oxide of Example 1. It can be seen from the figure that the particles are in the form of dispersed particles, and the particle size is all less than 1 μm. FIG. 4 is a SEM picture of the cobalt carbonate powder in Comparative Example 1. It can be seen from the figure that the prepared cobalt carbonate particles are spherical with a particle size of about 6 μm. FIG. 5 is an SEM picture of lithium cobalt oxide in Comparative Example 1. It can be seen from the figure that the lithium cobalt oxide particles prepared in Comparative Example 1 have a granular morphology with a smooth surface and a particle size of about 4-8 μm. It can be seen that nanosized lithium cobalt oxide particles with uniform particle size, good dispersibility, and no agglomeration can be obtained by means of the preparation method of the present invention.

[0062] The examples of the present invention are described in detail above with reference to the accompanying drawings. However, the present invention is not limited to the above-mentioned examples. Within the scope of knowledge possessed by those of ordinary skill in the art, various modifications can be made without departing from the purpose of the present invention. In addition, in the case of no conflict, the examples of the present invention and the features in the examples can be combined with each other.