Method for preparing anode active material, anode active material, and anode material

Abstract

The present invention relates to a method for preparing an anode active material, an anode active material, and an anode material, and carbonizes a metal-organic framework and uses same as a raw material. Specifically, the method for preparing an anode active material (100) comprises: (S100) a carbonization step of carbonizing a material formed from a metal-organic framework powder (110); (S200) a separation step of corroding metal substances in the carbonized material and removing same after the carbonization step; (S300) a washing step of washing the carbonized powder after the separation step; and (S400) a drying step of drying the carbonized powder after the washing step.

Description

Method for manufacturing negative electrode active material, negative electrode active material, negative electrode material

[0001] The present invention relates to a method for manufacturing a negative electrode active material, a negative electrode active material, and a negative electrode material, and aims to use a metal organic framework by carbonizing it as a raw material.

[0002]

[0003] Patent inventions 001 to 003 have technical relevance to the present invention,

[0004] Patent invention 001 is a negative electrode active material for a secondary battery and a method for manufacturing the same.

[0005] Patent invention 002 is a negative electrode active material composite and a method for manufacturing the same.

[0006] Patent invention 003 is a negative electrode active material for a secondary battery and a method for manufacturing the same.

[0007] The present invention and patented inventions 001 to 003 have similarities in the manufacture of negative electrode active materials for secondary batteries.

[0008] However, patent inventions 001 to 003 do not describe or contain the carbonized MOF of the present invention in an identical or similar manner.

[0009] (Patent Document 001) KR 10-2539805 B1 (Registration Date: May 31, 2023)

[0010] (Patent Document 002) KR 10-2540348 B1 (Registration Date: May 31, 2023)

[0011] (Patent Document 003) KR 10-1820577 B1 (Registration Date: January 15, 2018)

[0012]

[0013] The present invention relates to a method for manufacturing a negative electrode active material, a negative electrode active material, and a negative electrode material, and is characterized by using a metal organic framework carbonized and used as a raw material.

[0014] The present invention relates to a method for manufacturing a negative electrode active material, a negative electrode active material, and a negative electrode material, and is characterized by using a metal organic framework carbonized and used as a raw material.

[0015]

[0016] The present invention relates to a method for manufacturing a negative electrode active material (100), and specifically, it is composed of sequential steps including a carbonization step (S100) of carbonizing a material composed of a metal organic framework powder (110); a separation step (S200) of removing a metal component in the carbide by corrosion after the carbonization step; a washing step (S300) of washing the carbonized powder after the separation step; and a drying step (S400) of drying the carbonized powder after the washing step.

[0017] The present invention relates to a method for manufacturing a negative electrode active material (100), and in the invention presented above, the carbonization step comprises steps including a supply step (S120) of supplying the powder to a heating furnace; a gas injection step (S130) of injecting nitrogen gas (120) into the heating furnace after the supply step; a heating step (S140) of heating the heating furnace to a set temperature after the gas injection step; and a maintenance step (S150) of maintaining the set time during the heating step.

[0018] The present invention relates to a method for manufacturing a negative electrode active material (100), and in the invention presented above, the separation step is comprised of a step including a corrosion step (S210) of immersing carbonized powder in salt water (130) to corrode a metal component.

[0019] The present invention relates to a method for manufacturing a negative electrode active material (100), and in the invention presented above, the washing step comprises steps including, after the separation step, a filtering step (S310) for separating corroded iron (140) from carbonized powder; and, after the filtering step, a washing step (S320) for washing the carbonized powder with distilled water (150).

[0020] The present invention relates to a method for manufacturing a negative electrode active material (100), and in the invention presented above, the drying step comprises steps including a drying receiving step (S410) of receiving carbonized powder in a drying furnace; a vacuum maintenance step (S420) of maintaining the drying furnace in a vacuum in real time after the drying receiving step; and a temperature maintenance step (S430) of maintaining the temperature of the drying furnace at a set temperature after the vacuum maintenance step.

[0021] The present invention relates to a method for manufacturing a negative electrode active material (100), and comprises a step including a material preparation step (S110) of preparing a metal organic framework in powder form before the carbonization step in the invention presented above.

[0022] The present invention relates to a negative electrode active material (100), and includes a negative electrode active material produced by the invention presented above.

[0023] The present invention relates to a negative electrode material, and proposes a negative electrode material manufactured by a manufacturing method comprising: a slurry forming step (S10) of mixing a conductive material (310), a binder (320), and a solvent (330) with the negative electrode active material (100) presented above to produce a slurry-state negative electrode material mixture (410); a forming step (S20) of forming a shape in the form of a sheet or rod after the slurry forming step; a first drying step (S30) of drying after the forming step; a pressing step (S40) of pressing after the drying step; and a second drying step (S50) of drying after the pressing step.

[0024]

[0025] The MOF material of the present invention contains numerous pores on its surface, allowing it to accept or discharge fluids (gases and liquids) as needed. When the carbonized MOF is used as an anode material, it exhibits high charge / discharge efficiency and increases the lithium ion capture capacity. Furthermore, since there is no swelling phenomenon, it is highly safe and can have the effect of extending the battery life.

[0026]

[0027] Figure 1 is a detailed photograph of the MOF material of the present invention before and after carbonization.

[0028] Figure 2 is a flow chart of the steps for manufacturing the negative electrode active material of the present invention.

[0029] Figure 3 is a flow chart of the MOF material preparation steps used in the negative electrode active material of the present invention.

[0030] Figure 4 is a process diagram for manufacturing a cathode material of the present invention.

[0031]

[0032] Hereinafter, the most preferred embodiments of the present invention will be described in detail to enable those skilled in the art to easily practice the present invention. Reference numbers in the examples are not limited to the designated numbers and may be used in any number. The configurations presented in the examples can be expanded to achieve the same purpose and effect. Sub-concepts of the configurations presented in the examples can be considered inherent even if not explicitly described.

[0033]

[0034] [Example 1-1] The present invention relates to a method for manufacturing a negative electrode active material (100), and specifically, it is composed of sequential steps including a carbonization step (S100) of carbonizing a material composed of a metal organic framework powder (110); a separation step (S200) of removing a metal component in the carbide by corrosion after the carbonization step; a washing step (S300) of washing the carbonized powder after the separation step; and a drying step (S400) of drying the carbonized powder after the washing step.

[0035] [Example 1-2] The present invention relates to a method for manufacturing a negative electrode active material, and in Example 1-1, after the carbonization step, includes a cooling step (S500) for cooling the carbonized powder.

[0036] [Example 1-3] The present invention relates to a method for manufacturing a negative electrode active material, and in Example 1-1, after the washing step, includes a filtering step (S600) of filtering carbonized powder.

[0037] The present invention (Examples 1-1 to 1-3) relates to a method for producing an active material used in the production of a negative electrode material. The negative electrode material is used as an electrode incorporated in a secondary battery.

[0038] As a technical feature of the present invention, a metal-organic framework (MOF) carbonized material is used as a raw material. That is, in manufacturing an anode active material, a chronological sequence of carbonization, separation, cleaning, and drying steps is established, and in particular, the carbonization step for securing MOF carbonized material and the separation step for removing metal by corrosion after carbonization of MOF powder are essential steps. In addition, the carbonized MOF is washed to remove foreign substances, and a drying step follows to completely remove detergents, etc.

[0039] The MOF of the present invention is a crystalline material having a skeletal structure in which metal ions and organic molecules are linked, and since the surface of the MOF material includes a large number of pores, it has the effect of receiving or discharging fluids (gases and liquids) as needed. The pores are made to have a size of about 1 to 100 nm. An anode material manufactured from a carbonized MOF has high charge / discharge efficiency and has the effect of increasing the amount of lithium ions captured. In addition, since there is no swelling phenomenon (swelling phenomenon), it is highly safe and can have the effect of extending the life of the battery.

[0040]

[0041] [Example 2-1] The present invention relates to a method for manufacturing a negative electrode active material (100), and in Example 1-1, the carbonization step comprises steps including a supply step (S120) of supplying the powder to a heating furnace; a gas injection step (S130) of injecting nitrogen gas (120) into the heating furnace after the supply step; a heating step (S140) of heating the heating furnace to a set temperature after the gas injection step; and a maintenance step (S150) of maintaining the set time during the heating step.

[0042] [Example 2-2] The present invention relates to a method for manufacturing a negative electrode active material, and includes, in Example 2-1, a temperature increase rate during the heating step being formed at 5°C / min.

[0043] [Example 2-3] The present invention relates to a method for manufacturing a negative electrode active material, and in Example 2-1, the supply step includes placing the powder in a saga and supplying it to a heating furnace.

[0044] The present invention (Examples 2-1 to 2-3) specifies a carbonization step. The carbonization step is to manufacture an anode active material by carbonizing a powdered MOF. The carbonization step is performed in a time-series manner by a supply step, a gas injection step, a heating step, and a maintenance step. To achieve this, the MOF powder is supplied to a heating furnace, which is filled with nitrogen gas, heated to a set temperature, and maintained at the set temperature for a certain period of time. The heating step is performed by gradually increasing the temperature, increasing the temperature by 4 to 8°C per minute, and preferably by 5°C. After gradually returning to room temperature, the final temperature is increased to about 700 to 900°C. It is preferable to maintain the temperature at about 800°C. The process lasts for 2 to 4 hours from the point of maximum temperature increase. Preferably, 3 hours is appropriate.

[0045] During this process, the metallic substances present in the MOF powder are carbonized. Heating in nitrogen gas is necessary to block the oxygen supply. The powder fed into the furnace is made of ceramic material to maintain safety and prevent breakage, and is housed in a container-shaped chamber.

[0046] As another embodiment, MOF powder is supplied to a rotary kiln, and the MOF powder is transported by the rotation of the rotary kiln. During the transport process, the MOF powder is carbonized and the temperature can be maintained, which can improve productivity through a continuous process.

[0047]

[0048] [Example 3-1] The present invention relates to a method for manufacturing a negative electrode active material (100), and in Example 1-1, the separation step is comprised of a step including a corrosion step (S210) of immersing carbonized powder in salt water (130) to corrode a metal component.

[0049] [Example 3-2] The present invention relates to a method for manufacturing a negative electrode active material, and in Example 3-1, prior to the corrosion step, includes a salt precipitation forming step (S211) of dissolving hydrochloric acid in ultrapure water to form salt precipitation.

[0050] [Example 3-3] The present invention relates to a method for manufacturing a negative electrode active material, and in Example 3-1, it includes a stirring step (S212) of homogeneously stirring salt water and carbonized powder during the corrosion step.

[0051] [Example 3-4] The present invention relates to a method for manufacturing a negative electrode active material, and in Example 3-1, it includes a corrosion maintenance step (S213) of maintaining salt water and carbon powder at a set time and temperature during the corrosion step.

[0052] [Example 3-5] The present invention relates to a method for manufacturing a negative electrode active material, and in Example 3-2, it includes a mixing ratio setting step (S214) for setting a mixing ratio of hydrochloric acid and ultrapure water during the salt precipitation forming step.

[0053] The present invention (Examples 3-1 to 3-5) specifies a corrosion step. The corrosion step of the present invention consists of a salt precipitation formation step, a stirring step, and a corrosion maintenance step. The salt precipitation is formed by mixing a strong acid, hydrochloric acid, and ultrapure water. That is, the salt precipitation formation step requires a step of mixing hydrochloric acid and ultrapure water at a certain ratio. The salt precipitation is contained inside a corrosion vessel, and carbonized powder is introduced. During the introduction process, a stirring step is simultaneously performed by the rotation of blades inside the corrosion vessel. During the corrosion step, the corrosion vessel must maintain a constant temperature. In addition, a temperature maintenance device is built in to block temperature changes, and a stirring maintenance device is required to control the rotation of the stirring motor.

[0054]

[0055] [Example 4-1] The present invention relates to a method for manufacturing a negative electrode active material (100), and in Example 1-1, the washing step comprises steps including, after the separation step, a filtering step (S310) for separating corroded iron (140) from carbonized powder; and, after the filtering step, a washing step (S320) for washing the carbonized powder with distilled water (150).

[0056]

[0057] [Example 5-1] The present invention relates to a method for manufacturing a negative electrode active material (100), and in Example 1-1, the drying step comprises steps including a drying receiving step (S410) of receiving carbonized powder in a drying furnace; a vacuum maintaining step (S420) of maintaining the drying furnace in a vacuum in real time after the drying receiving step; and a temperature maintaining step (S430) of maintaining the temperature of the drying furnace at a set temperature after the vacuum maintaining step.

[0058] The present invention (Examples 4-1 and 5-1) specifies a cleaning step. The cleaning step of the present invention is performed in the following order: a filtration step and a washing step. The purpose of the filtration step is to separate corroded iron, and the washing step is to wash the carbonized powder from which iron has been removed with distilled water.

[0059] Next, the carbonized powder is placed in a vacuum drying oven, where it is dried by vacuum drying to remove any remaining distilled water. Vacuum drying is used to completely remove any remaining distilled water within the pores formed in the carbonized powder. The drying process is conducted at a constant temperature for a set period of time to minimize changes in the physical properties of the carbonized powder.

[0060]

[0061] [Example 6-1] The present invention relates to a method for manufacturing a negative electrode active material (100), and comprises a step including, in Example 1-1, a material preparation step (S110) of preparing a metal organic framework in powder form before the carbonization step.

[0062] [Example 6-2] The present invention relates to a method for manufacturing a negative electrode active material, and in Example 6-1, the material preparation step includes a mixing step (S111) of mixing a metal source (211), an organic ligand (212), and a solvent (213) to form a mixture (210); after the mixing step, a reaction step (S112) of reacting the mixture at a set time and temperature to form a reactant (220); after the reaction step, an extraction step (S113) of extracting only a solid material from the reactant; after the extraction step, a first washing step (S114) of washing the reactant with ultrapure water (230); and after the first washing step, a second washing step (S115) of washing the reactant with ethanol (240).

[0063] [Example 6-3] The present invention relates to a method for manufacturing a negative electrode active material, and in Example 6-1, after the second washing step, it includes a drying step (S116) of drying the reactant; after the drying step, a crushing step (S118) of crushing the reactant; and after the crushing step, a selection step (S119) of selecting the size of the reactant.

[0064] [Example 6-4] The present invention relates to a method for manufacturing a negative electrode active material, and in Example 6-1, includes a stabilization step (S117) for stabilizing the reactant by maintaining a set time and temperature before the drying step.

[0065] The present invention (Examples 6-1 to 6-4) specifies a material preparation step. The material of the present invention is composed of a metal-organic framework. The metal-organic framework uses an organic ligand, a solvent, and a metal source as source materials. The source materials are combined through a physical and chemical process to form a metal-organic framework. Among the source materials, the organic ligand maintains a mass ratio of 36% with respect to the metal source, and among the source materials, the solvent maintains a mass ratio of 87% with respect to the metal source, and the solvent is formed of ultrapure water. In addition, the metal source is formed of iron nitrate powder. The material preparation step consists of a time-series procedure of a mixing step, a reaction step, an extraction step, a first washing step, a second washing step, a drying step, a pulverizing step, a screening step, and a stabilization step. The mixing step includes a first mixing step of first mixing the metal source and the solvent; a second mixing step of second mixing the organic ligand after the first mixing step; The times of the first mixing step and the second mixing step are configured to be the same or different. The reaction step is composed of a temperature increasing step of increasing the temperature to 120°C; an isothermal maintenance step of maintaining the temperature at 120°C for a predetermined period of time after the temperature increasing step; and a stirring step of stirring the reactants during the isothermal maintenance step. The second washing step is repeated with ethanol. During the second washing step, the ethanol ratio is configured to be the same or different depending on the number of washings. The stabilization step is composed of a slow cooling step of slow cooling at room temperature for 24 hours; and a drying step of drying at a temperature of 80°C for 12 hours after the slow cooling step; and the pulverization step forms the particle size of the reactants into 10 to 20 μm.

[0066]

[0067] [Example 7-1] The present invention relates to a negative electrode active material, and includes a negative electrode active material manufactured by the manufacturing method of Examples 1-1 to 6-1.

[0068] The present invention (Example 7-1) relates to a negative electrode active material. The negative electrode active material of the present invention is a raw material used as a negative electrode material for a secondary battery, and is manufactured using the manufacturing methods of Examples 1-1 to 6-1 of the present invention. This is a product specific to the manufacturing method, and the time-series procedure and numerical range used in the manufacturing method affect the resulting material.

[0069]

[0070] [Example 8-1] The present invention relates to a negative electrode material, and specifically, includes a negative electrode material manufactured by a manufacturing method including a slurry forming step (S10) of mixing the negative electrode active material (100), conductive material (310), binder (320), and solvent (330) of Example 7-1 to produce a slurry-state negative electrode material mixture (410); a forming step (S20) of forming a shape in the form of a sheet or rod after the slurry forming step; a first drying step (S30) of drying after the forming step; a shaping step (S40) of shaping a size after the drying step; and a second drying step (S50) of drying after the shaping step.

[0071] The present invention (Example 8-1) relates to a negative electrode material. The negative electrode material is a material used as an electrode of a secondary battery, and can be formed into a rod or plate shape as needed. The negative electrode active material presented above is in powder form, which is mixed with a conductive material and a binder to form a slurry. The mixture in slurry form is formed into a rod or sheet shape through extrusion, rolling, and drawing processes. After the forming step, moisture is removed through a drying step, solidification is achieved, and an external shape is formed into a set size through a shaping step. In addition, a complete shape is completed through secondary drying. Primary drying refers to a condition in which the external shape is dried, and secondary drying refers to a condition in which the internal part is also dried.

[0072] 100: Negative active material 110: Metal organic framework powder

[0073] 130: Salt water 140: Iron

[0074] 150: Distilled water

[0075] 210: Mixture 211: Metal Source

[0076] 212: Organic ligand 213: Solvent

[0077] 220: reactant 230: ultrapure water

[0078] 240: Ethanol

[0079] 310: Challenger 320: Binder

[0080] 330: Solvent

[0081] 410: Cathode material mixture

Claims

1. In the method for manufacturing a negative electrode active material (100), A carbonization step (S100) for carbonizing a material composed of metal organic framework powder (110); After the above carbonization step, a separation step (S200) for removing the metal component in the carbide by corrosion; After the above separation step, a cleaning step (S300) for washing the carbonized powder; After the above washing step, a drying step (S400) for drying the carbonized powder; A method for manufacturing a negative electrode active material comprising:

2. In claim 1, The above carbonization step includes a supply step (S120) of supplying the powder to a heating furnace; After the above supply step, a gas injection step (S130) of injecting nitrogen gas (120) into the inside of the heating furnace; After the above gas injection step, a heating step (S140) of heating the heating furnace to a set temperature; During the above heating step, a maintenance step (S150) for maintaining a set time; A method for manufacturing a negative electrode active material comprising:

3. In claim 1, The above separation step is a corrosion step (S210) that corrodes metal components by immersing carbon powder in salt water (130); A method for manufacturing a negative electrode active material comprising:

4. In claim 1, The above cleaning step is a filtration step (S310) for separating corroded iron (140) from the carbon powder after the separation step; After the above filtration step, a washing step (S320) of washing the carbonized powder with distilled water (150); A method for manufacturing a negative electrode active material comprising:

5. In claim 1, The above drying step includes a drying receiving step (S410) for receiving carbonized powder in a drying furnace; After the above drying acceptance step, a vacuum maintenance step (S420) for maintaining the drying furnace in vacuum in real time; After the above vacuum maintenance step, a temperature maintenance step (S430) of maintaining the temperature of the drying oven at a set temperature; A method for manufacturing a negative electrode active material comprising:

6. In claim 1, Before the above carbonization step, a material preparation step (S110) for preparing a metal organic framework in powder form A method for manufacturing a negative electrode active material comprising:

7. In the negative electrode active material, A negative electrode active material manufactured by the manufacturing method of claims 1 to 6.

8. In the cathode material, By mixing the negative active material (100), conductive material (310), binder (320), and solvent (330) of claim 7 A slurry forming step (S10) for producing a slurry-state negative electrode mixture (410); After the above slurry forming step, a forming step (S20) of forming a shape in the form of a sheet or rod; After the above molding step, a first drying step (S30) is performed; After the above drying step, a pressing forming step (S40); After the above-mentioned standardization step, a second drying step (S50) is performed; A cathode material manufactured by the manufacturing method.

Images