KR102241226B1 - Manufacturing method of electrode for lithium secondary battery and lithium secondary battery comprising electrode prepared thereby - Google Patents

Abstract

The present invention relates to a method of manufacturing an electrode for a lithium secondary battery by low-temperature grinding, and to a lithium secondary battery including an electrode manufactured therefrom, by effectively preparing a porous organic electrode active material without heat damage, and mixing it with a carbon conductor and a binder. It provides a method of manufacturing an electrode for a lithium secondary battery.

Description

Manufacturing method of electrode for lithium secondary battery and lithium secondary battery comprising electrode prepared thereby

The present invention relates to a method of manufacturing an electrode for a lithium secondary battery, and more particularly, to a method of manufacturing an electrode for a lithium secondary battery including a porous organic electrode active material and a lithium secondary battery including an electrode manufactured therefrom.

The steadily increasing use of fossil fuels is recognized as a social issue due to the problem of depletion of the energy source and environmental pollution that inevitably occurs in the process of using energy. Accordingly, the demand for a large-capacity energy storage technology that does not cause environmental pollution such as fossil fuels is increasing, and accordingly, the need for an invention for a high-performance secondary battery technology is emerging.

A lithium secondary battery consists of a cathode that participates in a charge and discharge reaction, and a separator wetted with an electrolyte between the anode and both electrodes. In the current secondary battery technology, the anode relies on inorganic materials such as Co, Ni, and Mn, which are mineral resources. In the case of inorganic electrodes, environmental pollutants such as carbon monoxide are generated in the process of processing inorganic active materials. In addition, as the price of the active material increases, the price of the secondary battery increases, and as the charging and discharging reaction of the inorganic material is an exothermic reaction that generates heat, a safety problem such as a battery explosion occurs. In order to solve the problems of such inorganic active materials, there is a need to develop an organic electrode technology having safety, low cost and high performance.

The biggest technical barrier in developing a new battery is the absence of an alternative electrode material having a greater energy density than the existing electrode material.

Meanwhile, a lithium secondary battery includes at least one negative electrode and at least one positive electrode, and has a structure in which a separator impregnated with an electrolyte is disposed between both electrodes. The negative electrode is composed of a lithium metal or lithium alloy sheet selectively supported by a current collector, and the positive electrode contains at least one positive electrode active material capable of reversibly inserting lithium ions, and selectively acts as a binder. It is composed of a current collector containing a polymer and an electron conductive material.

During operation of the cell, lithium ions move from one electrode to another through the electrolyte. During discharge of the battery, a certain amount of lithium reacts with the positive electrode active material from the electrolyte, and a corresponding amount is introduced into the electrolyte from the negative active material, so that the concentration of lithium in the electrolyte is kept constant. The insertion of lithium into the positive electrode is compensated for by supplying electrons from the negative electrode through an external circuit. The opposite occurs during charging.

Various components of the lithium secondary battery are selected so that a battery having high energy density, good cycle stability, and safe operation can be manufactured at low cost. Commercialized technology uses inorganic electrode materials that are mainly based on transition metals such as Co, Mn, Ni or Fe. However, these electrode materials, for example, LiCoO ₂ , LiMnO ₄ , LiFePO _4, etc., have a number of disadvantages such as the risk of battery explosion, high toxicity, difficulty in recycling, high price and/or low specific capacity. Show. In addition, these inorganic substances are generally manufactured from resources of geological origin and consume energy in their manufacture. Considering the expected production capacity of the battery, there is a risk that these inorganic electrode materials will no longer be available in large quantities in the future.

Accordingly, compared to metal oxides based on transition metals, it is easier to secure structural diversity, has high competitiveness in terms of price, and interests in environment-friendly organic material-based electrode materials are increasing.

In this regard, redox organic structures (e.g., nitrogen oxide derivatives, polyaromatic compounds), i.e., one or more reversible oxidation/reduction reactions by exchanging electrons with an electrode and binding with lithium ions at the same time. An organic lithium secondary battery comprising an organic structure capable of performing as a positive electrode active material is advantageous in that it contains chemical elements (especially C, H, N, O, S) that can be further enriched by being potentially derived from renewable resources. Represents.

In addition, their electrochemical properties (ionic and electron conduction properties, oxidation potential, specific capacity) can be adjusted through appropriate functionalization (eg, introduction of electron withdrawing groups close to the redox center). In addition, since the redox organic structure generally ^{has a relative density of about 1 g/cm 3} , they are lighter than inorganic electrode materials, and thus a lithium battery having a reduced weight can be provided.

Π-conjugated conductivity such as, for example, polypyrrole, polythiophene, polyaniline, polyacetylene or polyacryloxy (TEMPO) (TEMPO: 2,2,6,6-tetramethylpiperidine-1-N-oxyl) Polymers (π-conjugated conducting polymers) have been used as positive electrode active materials in lithium secondary batteries.

On the other hand, when using an organic material as an electrode active material, it is necessary to prepare a porous powder in order to have excellent electrode activity, but there is a risk of changing the physical properties of the organic compound with a general grinding method, and it is difficult to obtain a desired degree of porosity. There is.

Korean Patent Publication No. 10-2015-0039977

Green Chem., 2017, 19, 2980

The problem to be solved by the present invention is to provide a method of manufacturing an electrode for a lithium secondary battery by manufacturing a porous organic electrode active material having high electrode activity without denaturation of an organic compound, and a lithium secondary battery including an electrode manufactured therefrom.

According to an aspect of the present invention, the step of preparing a porous organic electrode active material by pulverizing an organic electrode active material base material at a low temperature; And

There is provided a method of manufacturing an electrode for a lithium secondary battery comprising; mixing the porous organic electrode active material with a carbon conductor and a binder.

According to another aspect of the present invention, a lithium secondary battery including an electrode manufactured by the above method is provided.

According to one embodiment of the present invention, a porous organic electrode active material can be easily manufactured without chemical modification from an organic electrode active material base material through an inexpensive process.

According to one embodiment of the present invention, it is possible to provide a lithium secondary battery having excellent electrode activity without using a current collector.

1 is a schematic diagram of a low-temperature grinding device used in a method of manufacturing an electrode for a lithium secondary battery according to an embodiment of the present invention.
2 is an electron microscope photograph of a porous organic electrode active material and an organic electrode active material base material of Preparation Examples 1 to 4 of the present invention.
3 is an electron microscope photograph of a porous electrode active material and an organic electrode active material base material of Preparation Example 5 of the present invention.
4 is a photograph of a porous organic electrode active material and an organic electrode active material base material (PTCDA) of Preparation Examples 1 to 5 of the present invention.
5 is an FT-IR spectrum of a porous organic electrode active material and an organic electrode active material base material DMPZ according to Preparation Examples 1 to 4;
6 is a graph showing the charging and discharging efficiency of the lithium secondary battery coin cells prepared in Examples 1 to 4 and Reference Example 1 of the present invention.
7 is a graph showing the change in Coulomb efficiency according to the number of cycles of the lithium secondary battery coin cells prepared in Examples 1 to 4 and Reference Example 1 of the present invention.
8 is a graph showing the charging and discharging efficiency of the lithium secondary battery coin cells prepared in Example 5 and Reference Example 2 of the present invention.
9 is a graph showing changes in Coulomb efficiency according to the number of cycles of the lithium secondary battery coin cells prepared in Example 5 and Reference Example 2 of the present invention.

Hereinafter, the present invention will be described in detail with reference to the drawings.

A method of manufacturing an electrode for a lithium secondary battery according to an aspect of the present invention comprises: preparing a porous organic electrode active material by pulverizing an organic electrode active material base material at a low temperature; And mixing the porous organic electrode active material with a carbon conductor and a binder.

According to an aspect of the present invention, the preparing of the porous organic electrode active material includes: preparing a vial including an organic electrode active material base material and an impactor; Placing the vial into a chamber of a cryogenic grinding device; Immersing the chamber in a liquefied gas bath to cool the organic electrode active material base material to a temperature below a freezing point; And pulverizing the organic electrode active material base material by applying a magnetic field to the chamber to reciprocate the impactor in the longitudinal direction of the vial.

1 is a schematic diagram of a low-temperature grinding device used in a method of manufacturing an electrode for a lithium secondary battery according to an embodiment of the present invention.

The low-temperature grinding device is not particularly limited, and a low-temperature quenching means such as a chamber containing liquid nitrogen is provided, and can be used as long as it can control the grinding time and conditions, and commercially available ones can be purchased and used. .

First, a vial 4 including an organic electrode active material base material 3 and an impactor 2 is prepared.

As the organic electrode active material base material 3, any material that can be used as a positive electrode active material in an organic lithium secondary battery may be used without limitation.

For example, an organic free radical or a non-conjugated polymer having redox activity, an organic sulfur compound, and a carbonyl group-containing compound may be mentioned. Specifically, DMPZ (dimethylphenazine), PTCDA (perylenetetracarboxylic anhydride), tetraethyl thiuram disulfide, 2,2,6,6-tetramethyl piperidine-1-oxyl ( 2,2,6,6-tetramethyl piperidine-1-oxyl (TEMPO)), DD-TCNQ (7,7,8,8-tetracyanoquinodimethane), and PEDOT (poly(3,4-ethylenedioxythiophene)).

As the impactor 2, a bar type may be used, and a stainless steel material may be used as the material, but the material is not particularly limited.

The impactor may have a length of 1/3 to 1/2 of the vial length, and one having a diameter of 1/2 or more of the vial may be used. When the length and diameter fall within the above range, the pulverization process can be effectively performed. For example, when the vial has a diameter of 2 cm and a length of 10 cm, an impactor having a diameter of 1 cm and a length of 5 cm may be used.

The material of the vial 4 can be used without limitation as long as it is not denatured with respect to the organic electrode active material and has resistance to impact by an impactor. For example, stainless steel or polycarbonate material may be used.

Next, the vial 4 including the organic electrode active material base material 3 and the impactor 2 is placed in the chamber 5 of the low-temperature grinding device 10.

Then, by immersing the chamber 5 in a liquefied gas bath (not shown), the electrode active material base material is brought to a temperature below the freezing point. To cool. The liquefied gas is, for example, liquid nitrogen or liquid helium.

That is, the chamber is immersed in a liquefied gas bath, for example, a liquid nitrogen bath, and then closed for a certain period of time, for example, 20 to 30 minutes. During the above time When cooled, the base material of the organic electrode active material is rapidly cooled and becomes brittle so that it is easily broken by an external impact, for example, an impact from an impactor.

When the organic electrode active material base material is sufficiently cooled, a magnetic field is applied to the chamber 5 to reciprocate the impactor 2 in the longitudinal direction of the vial 4 to pulverize the electrode active material base material 3.

A method of applying a magnetic field to the chamber is not particularly limited, but may be performed in a magnetic field induction coil method by flowing a current through a coil wound around the outer wall of the chamber. That is, when a current flows through the coil, an induced magnetic field is generated, and the magnetic poles of the magnetic bodies 1 at both ends of the vial are repeatedly changed, so that the impactor inside the vial reciprocates in the longitudinal direction of the vial.

According to an aspect of the present invention, the impactor ^{is reciprocated with an acceleration of 10 m/s 2} to 30 m/s ² and an impact pressure of 4 kPa to 12 kPa.

For example, a reciprocating motion is performed with an acceleration of ^{30 m/s 2 and an impact pressure of 12 kPa.}

By reciprocating the impactor with the acceleration and impact pressure within the above range to apply an impact to the organic electrode active material base material, a porous organic electrode active material suitable for use as an electrode active material can be obtained.

Specifically, if the acceleration of the reciprocating motion of the impactor ^{is less than 10 m/s 2} and the impact pressure is less than 4 kPa, the organic electrode active material base material may not be sufficiently crushed, and the acceleration is ^{greater than 30 m/s 2} and the impact pressure is less than 12 kPa. If it is large, the base material of the organic electrode active material is well pulverized, but when pulverized for 3 minutes or more at the impact pressure, pores formed in the pulverized powder may rather disappear due to excessive milling.

According to an aspect of the present invention, the pulverizing step may be performed for 1 minute to 10 minutes, for example 3 minutes to 5 minutes. When the pulverization is performed during the above range, a porous organic electrode active material having a size and porosity suitable for an electrode for a lithium secondary battery may be obtained.

In addition, while performing the crushing step, the reciprocating motion of the impactor may proceed in a repeating cycle of crushing/resting, for example, it may proceed with a repeating cycle of 1 minute crushing/1 minute resting. By having a pause time in the middle of the reciprocating motion, the temperature can be kept at a cryogenic temperature and chemical damage to the organic electrode active material due to heat generated during pulverization can be prevented.

According to an exemplary embodiment of the present invention, the porous organic electrode active material may have a BET specific surface area value of 0.48m ² /g to 0.58m ² /g. When an electrode for a lithium secondary battery is manufactured using an electrode active material having a BET specific surface area of the above range, and a lithium secondary battery is manufactured using the electrode active material, a lithium secondary battery having excellent performance can be provided.

According to an aspect of the present invention, the porous organic electrode active material may have an average pore size of 6.9 nm to 9.4 nm, and an average pore volume of 0.0039 cm ³ /g to 0.0051 cm ³ /g. When an electrode for a lithium secondary battery is manufactured using a porous organic electrode active material having a pore size and a pore volume in the above range, and a lithium secondary battery is manufactured using the same, a lithium secondary battery having an improved current density can be provided.

According to an embodiment of the present invention, a method of manufacturing an electrode for a lithium secondary battery includes: after preparing a porous organic electrode active material, the porous organic electrode active material; Carbon conductor; And a step of mixing a binder; Specifically, a porous organic electrode active material, a carbon conductor; And obtaining an electrode paste by mixing a binder with a solvent, applying the electrode paste to at least one support, and drying the electrode paste to obtain an electrode in the form of a supported film. .

According to an aspect of the present invention, the carbon conductor may be included in an amount of about 10 to 80% by weight and about 30 to 50% by weight of the lithium secondary battery electrode.

The carbon conductor may be at least one selected from carbon black, Super P carbon, acetylene black, carbon fibers and nanofibers, carbon nanotubes, graphene, and graphite.

Preferably, it may be at least one selected ^{from Ketjenblack 600JD ®} , Ketjenblack 700JD ^® and Timcal Ensaco 350G ^®.

The lithium secondary battery electrode may include a binder of about 2 to 30% by weight, preferably about 5 to 30% by weight, more preferably 10 to 20% by weight based on the total weight of the lithium secondary battery electrode. .

Ethylene as the binder; Propylene; Ethylene oxide, methylene oxide, propylene oxide, epichlorohydrin, allyl glycidyl ether, vinyl chloride, vinylidene fluoride (PVDF), vinylidene chloride, tetrafluoroethylene, chlorotrifluoroethylene, vinylidene fluoride , And (co)polymer of at least one monomer selected from hexafluoropropylene; Acrylates such as polymethyl methacrylate; Polyalcohols such as polyvinyl alcohol (PVA); Polyaniline, polypyrrole, polyfluorene, polystyrene, polyazulene, polycarbazole, polyindole, polyazepine, polythiophene, poly(p-phenylene-vinylene), polycarbazole, polyindole, polyazepine, polythione Ion conductive polymers such as opene, poly(p-phenylene sulfide) or mixtures thereof; Polyethyleneimine (PEI), polyaniline, polyaniline in the form of emeraldine (ES) salt, poly(quaternary N-vinylimidazole), poly(acrylamide-co-diallyldimethylammonium chloride) (AMAC) or mixtures thereof Cationic type polymers, such as; Poly(styrenesulfonate), gelatin or pectin; And mixtures thereof. Also, PTFE is preferred.

A lithium secondary battery according to another aspect of the present invention includes an electrode manufactured by the above method. In this case, the electrode for the lithium secondary battery may be a positive electrode.

According to an embodiment of the present invention, the lithium secondary battery includes the step of assembling the positive electrode, the negative electrode, and the porous separator for the lithium secondary battery, and impregnating the obtained assembly into a liquid electrolyte, or before the assembling step, the porous separator. It can be prepared by a method comprising the step of impregnating the electrolyte.

By using the electrode for a lithium secondary battery according to an embodiment of the present invention, it is possible to manufacture a lithium secondary battery having excellent performance without a current collector.

The present invention will be described in more detail through the following examples, and the present invention is not limited to the following examples.

Preparation of porous organic electrode active material

Manufacturing Example 1

In a vial made of polycarbonate material having a diameter of 2 cm and a length of 10 cm, 1 g of dimethylphenazine (DMPZ) and a stainless steel rod corresponding to the size of the vial as an impactor (diameter 1 cm, length 5 cm) were placed.

The vial was placed in a chamber in a liquid nitrogen bath of a low-temperature grinding device (6775 Freezer-mill equipment), and the device was operated to rapidly cool down to a temperature below the freezing point of dimethylphenazine inside the vial for 20 minutes.

Then, an electric field is applied to the chamber to generate a magnetic field with a magnetic field induction coil surrounding the chamber, and the impactor in the vial ^{reciprocates with an acceleration of 30 m/sec 2} and an impact pressure of 12 kPa for about 1 minute. The organic electrode active material base material was pulverized. Thereafter, the power of the low-temperature grinding device was turned off, and the vial was taken out to obtain a porous organic electrode active material.

Manufacturing Example 2

A porous organic electrode active material was obtained in the same manner as in Preparation Example 1, except that the impactor was reciprocated to rest for a total of 3 minutes and rest for a total of 3 minutes with a repeat cycle of 1 minute pulverization/1 minute rest.

Manufacturing Example 3

A porous organic electrode active material was obtained in the same manner as in Preparation Example 1, except that the impactor was subjected to a reciprocating motion so as to rest for a total of 5 minutes and to rest for a total of 5 minutes in a repeat cycle of 1 minute pulverization/1 minute pause.

Manufacturing Example 4

A porous organic electrode active material was obtained in the same manner as in Preparation Example 1, except that the impactor was reciprocated so as to rest for a total of 10 minutes/9 minutes in a repeat cycle of 1 minute pulverization/1 minute pause.

Manufacturing Example 5

The same as in Preparation Example 1, except that perylenetetracarboxylic anhydride (PTCDA) was used instead of DMPZ, and the impactor was reciprocated for a total of 30 minutes pulverization/29 minutes rest with a repeat cycle of 1 minute pulverization/1 minute rest. A porous organic electrode active material was obtained by the method.

The organic electrode active material base material, crushing acceleration, crushing impact pressure, and crushing time used in Preparation Example are summarized in Table 1 below.

Organic electrode active material base material Crushing acceleration
(m/sec ² ) Crushing impact pressure
(kPa) Crushing time
(minute) Manufacturing Example 1 DMPZ 30 12 One Manufacturing Example 2 DMPZ 30 12 3 Manufacturing Example 3 DMPZ 30 12 5 Manufacturing Example 4 DMPZ 30 12 10 Manufacturing Example 5 PTCDA 30 12 30

2A to 2D are electron micrographs of the porous organic electrode active materials of Preparation Examples 1 to 4 of the present invention, respectively, and FIG. 2E is an electron micrograph of the organic electrode active material base material DMPZ (manufacturer name: Hitachi, model name: S- 4800, magnification: 2000 and 30000 times). In addition, Figures 3a (3500 magnification) and Figure 3b (100,000 magnification) are electron micrographs of the organic electrode active material base material PTCDA, and Figures 3c (3500 magnification) and 3d (100,000 magnification) are according to Preparation Example 5 of the present invention. This is an electron micrograph of a porous organic electrode active material.

As can be seen in FIGS. 2 and 3, the organic electrode active material prepared according to Preparation Examples 1 to 5 of the present invention has a homogeneous particle size of several μm at several hundreds nm as low-temperature pulverization is performed on particles having a size of several tens of micrometers. And at the same time, pores are formed inside the particles. It can be inferred that the surface area of the porous organic electrode active material increases due to the pores in the formed particles.

4A is a photograph of a porous organic electrode active material according to Preparation Examples 1 to 4 of the present invention from the left, and FIG. 4B is a photograph of the organic electrode active material base material PTCDA (left) and a porous organic electrode active material according to Preparation Example 5 (right). It's a picture.

As shown in FIG. 4, it can be seen that the obtained porous organic electrode active material has pores formed inside the particles, so that the diffuse reflection of light intensifies, and the color of the existing particles is darker than before the low-temperature grinding.

5 is an FT-IR spectrum (manufacturer name of the device used: Jasco, model name: FT-IR 4100) of a porous organic electrode active material and an organic electrode active material base material DMPZ according to Preparation Examples 1 to 4 of the present invention. 5A is an FT-IR spectrum in a section of 400 to 3500cm ^-1 , and FIG. 5B is an FT-IR spectrum in a section ^{of 700 to 1500cm -1.}

As can be seen from FIG. 5, it can be seen that the chemical bonds of the base material of the organic electrode active material were not destroyed or deformed by the low-temperature grinding.

Example 1

The porous organic electrode active material prepared in Preparation Example 1 was used in a weight ratio of 4:4:2 with a carbon conductor (Ketjen Black, purchase: Mitsibish chemical, brand name: Ketjen black EC 600JD) and a binder (PTFE, purchase: Sigma-Aldrich). The mixture was mixed using a mortar and then pressed to obtain an electrode material for a lithium secondary battery. At this time, a roll press was used so that the bonding density of the electrode was 1 to 1.1 g/cm ³ . The obtained electrode was cut into a positive electrode having a desired size, and a coin cell for performance evaluation was manufactured using a 2032 coin cell. Specifically, the gasket was placed on the coin cell case, and the prepared electrode material was placed in the center of the bottom of the coin cell case. Then, the GF/F (Glass Microfiber Filter) separator was raised, and 85 μL of the electrolyte was dropped onto the separator. Then, the spacer and the Li metal were brought into close contact with each other. A spring and a cap were put on it in order, and the coin cell was compressed with a presser to produce a cell, and then left for 30 minutes to allow the electrolyte to sufficiently permeate the electrode and the separator to prepare a lithium secondary battery coin cell.

Examples 2 to 5

In Examples 2 to 5, a lithium secondary battery coin cell was always manufactured in the same manner as in Example 1 except for using the porous organic electrode active material prepared in Preparation Examples 2 to 5, respectively.

Reference Example 1

A lithium secondary battery coin cell was manufactured in the same manner as in Example 1, except that the organic electrode active material base material DMPZ was used instead of the porous organic electrode active material.

Reference Example 2

A lithium secondary battery coin cell was manufactured in the same manner as in Example 1, except that the organic electrode active material base material PTCDA was used instead of the porous organic electrode active material.

Property evaluation

The charging/discharging efficiency of the lithium secondary battery coin cells prepared in Examples 1 to 4 and Reference Example 1 and Coulomb efficiency according to the number of cycles were measured, respectively, and are shown in FIGS. 6 and 7, respectively. In addition, the charge/discharge efficiency of the lithium secondary batteries prepared in Example 5 and Reference Example 2 and the coulomb efficiency according to the number of cycles were measured, respectively, and are shown in FIGS. 8 and 9, respectively.

As can be seen in FIGS. 6 and 7, although there is a change in Coulomb efficiency of less than 5% due to the particle size and porosity of the organic electrode active material, it can be seen that a synergistic effect of about 20% or more of the initial discharge capacity is exhibited. This can be considered because the entire area of the organic electrode active material can be utilized for energy storage by reducing the particle size and porosity of the porous organic electrode active material prepared by the manufacturing method of the present invention.

As can be seen in FIGS. 8 and 9, there is no change in the charge/discharge capacity of the coin cell using the material as a positive electrode before and after low-temperature grinding, but the coulomb efficiency increases according to the number of cycles and the shuttle effect in which the charging capacity behaves abnormally decreases. have. Through this, the porous organic electrode active material manufactured by the manufacturing method of the present invention reduces the diffusion distance of lithium ions by reducing the particle size and porosity, and the entire area of the organic electrode active material can be utilized for energy storage. It can be seen that it can be manufactured.

As described above, it can be seen that by using the electrode manufactured by the manufacturing method according to the exemplary embodiment of the present invention, a lithium secondary battery having excellent performance can be manufactured without a current collector.

So far, the present invention has been looked at around its preferred embodiments. Those of ordinary skill in the art to which the present invention pertains will be able to understand that the present invention may be implemented in a modified form without departing from the essential characteristics of the present invention. Therefore, the disclosed embodiments should be considered from an illustrative point of view rather than a limiting point of view. The scope of the present invention is shown in the claims rather than the foregoing description, and all differences within the scope equivalent thereto should be construed as being included in the present invention.

1: magnetic body
2: impactor
3: Organic electrode active material base material
4: vials
5: chamber
10: low temperature grinding device

Claims (15)

Pulverizing the organic electrode active material base material at a low temperature to prepare a porous organic electrode active material; And
Including; mixing the porous organic electrode active material with a carbon conductor and a binder,
The preparing of the porous organic electrode active material may include preparing a vial including the organic electrode active material base material and an impactor;
Placing the vial into a chamber of a cryogenic grinding device;
Immersing the chamber in a liquefied gas bath to cool the organic electrode active material base material to a temperature below a freezing point; And
Comprising: applying a magnetic field to the chamber to reciprocate the impactor in the longitudinal direction of the vial to pulverize the organic electrode active material base material; Including,
The grinding step is performed for 1 to 5 minutes,
Applying a magnetic field to the chamber is performed by a magnetic field induction coil method,
Magnetic bodies are disposed at both ends of the vial,
When a magnetic field is applied to the chamber, an induced magnetic field is generated so that the magnetic pole of the magnetic body is repeatedly changed, so that the impactor inside the vial makes a reciprocating motion in the longitudinal direction of the vial,
Method of manufacturing an electrode for a lithium secondary battery.
delete The method of claim 1,
The porous organic electrode active material has a BET specific surface area value of 0.48m ² /g to 0.58m ² /g.
The method of claim 1,
The porous organic electrode active material has an average pore size of 6.9 nm to 9.4 nm, and an average pore volume of 0.0039 cm ³ /g to 0.0051 cm ³ /g.
The method of claim 1,
The organic electrode active material base material is a method of manufacturing an electrode for a lithium secondary battery comprising at least one selected from a non-conjugated polymer having an organic free radical or redox active, an organic sulfur compound, and a carbonyl group-containing compound .
The method of claim 1,
The impactor is a method of manufacturing an electrode for a lithium secondary battery made of stainless steel.
The method of claim 1,
The impactor is a method of manufacturing an electrode for a lithium secondary battery having a length of 1/3 to 1/2 of the vial length.
The method of claim 1,
The vial is a method of manufacturing an electrode for a lithium secondary battery made of stainless steel or polycarbonate .
The method of claim 1,
The liquefied gas is liquid nitrogen or liquid helium, a method of manufacturing an electrode for a lithium secondary battery.
The method of claim 1,
The cooling is a method of manufacturing an electrode for a lithium secondary battery performed for 20 to 30 minutes.
delete The method of claim 1,
The reciprocating motion is performed with an acceleration of 10 m/s ² to 30 m/s ² and an impact pressure of 4 kPa to 12 kPa.
delete The method of claim 1,
The pulverizing step is a method of manufacturing an electrode for a lithium secondary battery that proceeds in a repeating cycle of 1 minute pulverization/1 minute pause.
A lithium secondary battery comprising an electrode manufactured by the method according to any one of claims 1, 3 to 10, 12, and 14.

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