KR101754788B1 - CATHODE COMPOSITE MATERIAL FOR All SOLID LITHIUM SECONDARY BATTERY AND METHOD FOR PREPARING THE SAME - Google Patents

Abstract

The present invention relates to a cathode composite material in which cathode active material particles, solid electrolyte particles, and conductive material particles are uniformly compounded and granules are formed. The positive electrode composite material of the present invention can improve the ionic conductivity and the electron conductivity by combining the positive electrode active material, the solid electrolyte and the conductive material and improve the resistance due to ineffective contact in the bulk in the whole solid lithium secondary battery and the resistance at the electrode interface Can be reduced. In addition, the method for producing the positive electrode composite material of the present invention can be easily mass-produced by using the spray drying method, and can uniformly make the positive electrode active material, the solid electrolyte, and the conductive material that make efficient contact in the bulk of the all solid lithium secondary battery electrode It is possible to manufacture a composite granule. Further, by applying a positive electrode composite material in which a positive electrode active material, a solid electrolyte, and a conductive material are combined, it is possible to improve the energy efficiency by manufacturing the all-solid lithium secondary battery.

Description

Technical Field [0001] The present invention relates to a positive electrode composite material for a solid lithium secondary battery, and a method for manufacturing the same. BACKGROUND ART < RTI ID = 0.0 >

More particularly, the present invention relates to a positive electrode composite material in which a positive electrode active material, a solid electrolyte and a conductive material are combined, a method for manufacturing the same, and a positive electrode for a full solid lithium secondary battery using the same And a pre-solid lithium secondary battery.

2. Description of the Related Art With the rapid development of the electronics, communication, and computer industries, the demand for lithium secondary batteries has been increasing as a power source for driving these portable electronic communication devices as camcorders, mobile phones, notebook PCs, and the like have been remarkably developed. In particular, research and development are being actively carried out in Japan, Europe, and the United States, as well as domestic applications for applications such as electric vehicles, uninterruptible power supplies, power tools and satellites as eco-friendly power sources. Furthermore, recent commercialization of lithium secondary batteries has led to a problem of increasing the capacity and safety of lithium secondary batteries.

Lithium cobalt oxide (LiCoO ₂ ) has been mainly used as a cathode material of a lithium secondary battery. Currently, lithium nickel oxide (Li (Ni-Co-Al) O ₂ ) (Li (Ni-Co-Mn) O ₂ ) are also used. In addition, spinel type lithium manganese oxide (LiMn ₂ O ₄ ) of low cost and high stability and olivine type lithium iron phosphate compound (LiFePO ₄ ) are also attracting attention.

However, lithium secondary batteries using lithium cobalt oxide, lithium nickel oxide, lithium composite metal oxide or the like are excellent in basic battery characteristics, but safety, particularly, thermal stability, overcharging characteristics and the like are not sufficient. In order to solve this problem, various safety mechanisms such as a shut-down function of a separator, an additive for an electrolyte, a safety circuit such as a protection circuit and a PTC have been introduced. However, It was designed under circumstances. As a result, when the filling property of the anode material is increased in order to satisfy the demand for higher capacity, the operation of various safety mechanisms tends to be insufficient and the safety is lowered.

In this way, various battery solutions are being developed to innovate the anxiety about safety, limit of increase of energy density, and high cost burden which are pointed out as limitations of lithium secondary battery in the current market. All solid lithium secondary batteries Next-generation sodium-based batteries suitable for storing large amounts of energy, and magnesium batteries utilizing abundant magnesium resources are currently attracting attention as representative next-generation batteries.

In the case of all solid lithium secondary batteries, solid electrolytes are used instead of liquid electrolytes used in conventional lithium ion batteries, which is the most important advantage in ensuring perfect safety. The solid electrolyte is a key material for overcoming limitations of use of existing liquid electrolyte due to high capacity and high voltage of lithium ion battery electrode and assuring the safety of high performance lithium ion battery.

A solid-state lithium secondary battery is a cell that applies pressure to ceramic-based solid electrolyte (all-solid-state electrolyte) particles that do not contain any organic solvent. The solid electrolyte is applied to the positive and negative electrodes located on both sides of the electrolyte layer The pore existing in a conventional lithium ion battery electrode has an electrode structure in which an ion conductor solid electrolyte and an electron conductor are uniformly compounded in place of a liquid electrolyte and poses many problems in physical contact with the electrode.

Various methods have been studied to minimize the resistance due to ineffective contact in the electrode bulk and the resistance at the electrode interface. Korean Patent No. 1,456,350 discloses a polyanion structure-containing compound which is formed so as to cover the surface of an oxide positive electrode active material and has a cationic moiety composed of a metal atom to be a conductive ion and a polyanion structure moiety composed of a central atom covalently bonded to a plurality of oxygen atoms And a transition metal reducing layer of 10 nm or less magnetically formed due to the reaction between the transition metal and the polyanion structure-containing compound.

Korean Patent Laid-Open Publication No. 2013-0130862 discloses a positive electrode active material particle for a pre-solid lithium secondary battery comprising a sulfide-based solid electrolyte, wherein the positive electrode active material particle is an aggregate containing two or more particles, And a reaction inhibiting layer for suppressing the reaction is coated on the positive electrode active material.

However, the conventional techniques have not been sufficiently effective in improving the physical contact with the electrode. Therefore, it is an object of the present invention to provide a positive electrode composite material capable of reducing the resistance due to ineffective contact in the bulk and the resistance at the electrode interface in the bulk of a pre-solid lithium secondary battery while improving ionic conductivity and electronic conductivity, It is necessary to develop a manufacturing method which is easy to mass-produce.

SUMMARY OF THE INVENTION The object of the present invention is to solve the above-mentioned problems, and it is an object of the present invention to improve the ionic conductivity and electron conductivity by combining a cathode active material, a solid electrolyte and a conductive material to improve the resistance to ineffective contact in a bulk And a positive electrode composite material capable of reducing the resistance at the electrode interface.

In addition, it is possible to produce granules which are easily mass-produced by the spray drying method and in which a positive electrode active material, a solid electrolyte and a conductive material are uniformly compounded so as to make efficient contact in the bulk of the electrode of the all-solid lithium secondary battery And a method for producing the anode composite material.

Further, the present invention is to improve the energy efficiency by applying a positive electrode composite material composed of a positive electrode active material, a solid electrolyte and a conductive material to a positive electrode and a pre-solid lithium secondary battery including the same.

According to an aspect of the present invention,

There is provided a positive electrode composite material in which positive electrode active material particles, solid electrolyte particles, and conductive material particles are uniformly compounded and granules are formed.

The solid electrolyte particles may include Al-doped lithium lanthanum zirconium oxide (Al-doped LLZO) or non-doped lithium lanthanum zirconium oxide (LLZO).

The LLZO may be represented by the following formula (1).

[Chemical Formula 1]

Li _x La _y Zr _z O ₁₂

Where 6? X? 9, 2? Y? 4, 1? Z?

The Al-doped lithium lanthanum zirconium oxide may be represented by the following formula (2).

(2)

Li _p Al _q La _y Zr _z O ₁₂

Where 5? P <9, 0 <q? 1, 2? Y? 4, 1? Z?

The cathode active material particles may include at least one selected from lithium nickel cobalt manganese oxide (NCM) and LiNi _0.8 Co _0.15 Al _0.05 O ₂ .

The NCM may be represented by the following formula (3).

(3)

LiNi _p Co _q Mn _r O ₂

here 0 <p <0.9, 0 <q <0.5, 0 <r <0.5, p + q + r = 1.

The conductive material particles may include a conductive carbon material.

The conductive material particles may be carbon.

The carbon may be at least one selected from carbon black, graphite, graphene, carbon nanotube (CNT), carbon nanofiber (CNF) and ketjen black.

The granules may have a diameter of 1 to 200 mu m, preferably 10 to 150 mu m.

Wherein the weight ratio of the positive electrode composite material is 20 to 90 parts by weight of the positive electrode active material particles; 10 to 80 parts by weight of the solid electrolyte particles; And 5 to 30 parts by weight of the conductive material particles, preferably 100 parts by weight of the cathode active material particles; 20 to 60 parts by weight of the solid electrolyte particles; And 2 to 6 parts by weight of the conductive material particles.

According to another aspect of the present invention,

A positive electrode comprising the positive electrode composite material is provided.

According to another aspect of the present invention,

There is provided a pre-solid lithium secondary battery including the anode.

According to another aspect of the present invention,

(a) a solid electrolyte; Cathode active material; At least one of a conductive material and a surfactant; And a solvent; (b) stirring the mixed solution to prepare a slurry; And (c) spray drying the slurry to produce a positive electrode composite material.

Wherein the mixed solution of step (a) comprises 20 to 90 parts by weight of the cathode active material; 10 to 80 parts by weight of the solid electrolyte; And 5 to 30 parts by weight of at least one selected from the group consisting of the conductive material and the surfactant.

Wherein the solvent is selected from the group consisting of water, methanol, ethanol, butanol, pentanol, hexanol, trialkylbenzene, p-xylene, hexadecane, butyl acetate, octane, And may include at least one member selected from the group consisting of lauridone, 1,4-dioxane, N, N-dimethylacetamide, triethylphosphate, dimethylsulfoxide and tetrahydrofuran.

The stirring and pulverizing step (b) may be carried out simultaneously or sequentially.

The milling process may be performed by ball milling.

The surfactant can generate carbon by heat treatment.

According to another aspect of the present invention,

There is provided a method of manufacturing a positive electrode comprising a method for producing the positive electrode composite material.

According to another aspect of the present invention,

There is provided a process for producing a pre-solid lithium secondary battery comprising the above-mentioned method for producing an anode.

The positive electrode composite material of the present invention can improve the ionic conductivity and the electron conductivity by combining the positive electrode active material, the solid electrolyte and the conductive material and improve the resistance due to ineffective contact in the bulk in the whole solid lithium secondary battery and the resistance at the electrode interface Can be reduced.

In addition, the method for producing the positive electrode composite material of the present invention can be easily mass-produced by using the spray drying method, and can uniformly make the positive electrode active material, the solid electrolyte, and the conductive material that make efficient contact in the bulk of the all solid lithium secondary battery electrode It is possible to manufacture a composite granule.

Further, by applying a positive electrode composite material in which a positive electrode active material, a solid electrolyte, and a conductive material are combined, it is possible to improve the energy efficiency by manufacturing the all-solid lithium secondary battery.

FIG. 1 is a flowchart sequentially showing a method for producing a positive electrode composite material of the present invention.
2 is an SEM image of a positive electrode composite material produced according to Example 1. Fig.
Fig. 3 shows the results of XRD measurement of the positive electrode composite material produced according to Example 1. Fig.
4 shows the results of measurement of the electrochemical characteristics of all solid lithium secondary batteries manufactured according to the device example 1 and the device comparative example 1. Fig.

Hereinafter, embodiments of the present invention will be described in detail with reference to the accompanying drawings so that those skilled in the art can easily carry out the present invention.

However, the following description does not limit the present invention to specific embodiments. In the following description of the present invention, detailed description of related arts will be omitted if it is determined that the gist of the present invention may be blurred .

The terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. The singular expressions include plural expressions unless the context clearly dictates otherwise. In the present application, the terms "comprises ", or" having ", and the like, specify that the presence of stated features, integers, steps, operations, elements, or combinations thereof, But do not preclude the presence or addition of one or more other features, integers, steps, operations, elements, or combinations thereof.

Hereinafter, the positive electrode composite material of the present invention will be described in detail. However, it should be understood that the present invention is not limited thereto, and the present invention is only defined by the scope of the following claims.

The positive electrode composite material of the present invention can uniformly composite positive electrode active material particles, solid electrolyte particles, and conductive material particles and form a granule.

The solid electrolyte particles may include Al-doped lithium lanthanum zirconium oxide (Al-doped LLZO) or non-doped lithium lanthanum zirconium oxide (LLZO).

The LLZO may be represented by the following general formula (1), preferably Li ₇ La ₃ Zr ₂ O ₁₂ .

[Chemical Formula 1]

Li _x La _y Zr _z O ₁₂

Where 6? X? 9, 2? Y? 4, 1? Z?

The Al-doped lithium lanthanum zirconium oxide may be represented by the following general formula (2), preferably Li _{6 . 75} Al _{0 . 25} La ₃ Zr ₂ O ₁₂ .

(2)

Li _p Al _q La _y Zr _z O ₁₂

Where 5? P <9, 0 <q? 1, 2? Y? 4, 1? Z?

The cathode active material particles may include at least one selected from lithium nickel cobalt manganese oxide (NCM) and LiNi _0.8 Co _0.15 Al _0.05 O ₂ .

The NCM may be represented by the following formula (3), preferably LiNi _0.7 Co _0.15 Mn _0.15 O ₂ .

(3)

LiNi _p Co _q Mn _r O ₂

here 0 <p <0.9, 0 <q <0.5, 0 <r <0.5, p + q + r = 1.

The conductive material particles may include a conductive carbon material, and preferably carbon.

The carbon may be carbon black, graphite, graphene, carbon nanotube (CNT), carbon nanofiber (CNF), ketjen black or the like, preferably carbon black.

The diameter of the granules may be from 1 to 200 mu m, preferably from 50 to 150 mu m, more preferably from 70 to 130 mu m.

Wherein the weight ratio of the positive electrode composite material is 20 to 90 parts by weight of the positive electrode active material particles; 10 to 80 parts by weight of the solid electrolyte particles; And 5 to 30 parts by weight of the conductive material particles, preferably 100 parts by weight of the cathode active material particles; 20 to 60 parts by weight of the solid electrolyte particles; And 2 to 6 parts by weight of the conductive material particles.

The present invention also provides a positive electrode comprising the above-described positive electrode composite material.

The present invention also provides a pre-solid lithium secondary battery comprising the above-described anode.

FIG. 1 is a flowchart sequentially showing a method for producing a positive electrode composite material of the present invention.

Hereinafter, a method of manufacturing the positive electrode composite material of the present invention will be described in detail with reference to FIG.

First, a solid electrolyte; Cathode active material; At least one selected from the group consisting of the conductive material particles and the surfactant; And a solvent (step a).

Wherein the mixed solution comprises 20 to 90 parts by weight of the cathode active material; 10 to 80 parts by weight of the solid electrolyte; And 5 to 30 parts by weight of at least one selected from the group consisting of the conductive material and the surfactant.

The solvent may be selected from the group consisting of water, methanol, ethanol, butanol, pentanol, hexanol, trialkylbenzene, p-xylene, hexadecane, butyl acetate, octane, N, N, N-dimethylacetamide, triethylphosphate, dimethylsulfoxide, tetrahydrofuran, and the like, preferably methanol.

The surfactant may be a polymer which forms carbon after heat treatment. Preferably, the surfactant is selected from the group consisting of diethylene glycol (DEG), triethylene glycol (TEG), tetraethylene glycol (TTEG), propylene glycol (PG), butylene glycol BG) may be possible.

When the surfactant forms carbon after the heat treatment, a separate conductive material may not be included in the mixed solution.

Next, the mixed solution is stirred to prepare a slurry (step b).

The stirring and grinding steps may be performed simultaneously or sequentially, and the grinding step may be performed by ball milling.

If performed by ball milling, it is possible to add a process of separating the slurry and the ball used for ball milling after manufacturing the slurry.

Finally, the slurry is spray dried to produce a positive electrode composite (step c).

The positive electrode composite material may have a diameter of 1 to 200 mu m, preferably 50 to 150 mu m, more preferably 70 to 130 mu m.

The present invention also provides a method for producing a positive electrode comprising the above-described method for producing a positive electrode composite material.

The present invention also provides a process for producing a pre-solid lithium secondary battery comprising the above-described process for producing the anode.

[Example]

Hereinafter, preferred embodiments of the present invention will be described. However, this is for illustrative purposes only, and thus the scope of the present invention is not limited thereto.

Production Example 1: Preparation of solid electrolyte (LLZO)

A starting material aqueous solution was prepared in which lanthanum nitrate (La (NO ₃ ) ₃ .6H ₂ O) and zirconium nitrate (ZrO (NO ₃ ) ₂ .6H ₂ O) were mixed in a molar ratio of 3: 2. The starting aqueous solution, the complexing agent (NH ₄ OH) and the pH adjusting solution (NaOH) of the reactor were charged into a coprecipitation reactor and co-precipitated to prepare a precipitate. The precipitate was washed, dried and pulverized to form a precursor powder. Lithium powder (LiOH.H ₂ O) was mixed with the precursor powder and ball milled to prepare lithium secondary precursor powder by dissolving lithium. The second precursor powder was heat-treated at 900 ° C to prepare a solid electrolyte powder, LLZO.

Preparation Example 2: Preparation of solid electrolyte (Al doped LLZO)

(La (NO ₃ ) ₃ .6H ₂ O), zirconium nitrate (ZrO (NO ₃ ) ₂ .2H ₂ O) so that the molar ratio of La: Zr: Al in distilled water is 3: And aluminum nitrate (Al (NO ₃ ) ₃ .9H ₂ O) were dissolved to prepare a starting material aqueous solution having a starting molar concentration of 1 mol. The starting aqueous solution, the complexing agent (NH ₄ OH) and the pH adjusting solution (NaOH) of the reactor were charged into a coprecipitation reactor and co-precipitated to prepare a precipitate. The precipitate was washed, dried and pulverized to form a precursor powder. Lithium powder (LiOH.H ₂ O) was mixed with the precursor powder and ball milled to prepare lithium secondary precursor powder by dissolving lithium. The second precursor powder was heat-treated at 900 ° C to prepare solid-electrolyte powdered Al-doped LLZO.

Example  1: Manufacture of anode composite material

30 g of LLZO prepared in Preparation Example 1, 70 g of NCM of 70% Ni, 3 g of Super P as a conductive material and 10 wt% of PEG as a binder were dissolved in 700 mL of methanol to prepare a mixed solution. The mixed solution was ball-milled for 16 hours and filtered to separate the slurry and the ball. The slurry was sprayed for 2 hours at an inlet temperature of 140 to 150 ° C and an outlet temperature of 70 to 80 ° C by using a disk type spray dryer and dried at room temperature for about one hour A positive electrode composite material was prepared.

Example  2: Manufacture of anode composite material

A positive electrode composite material was prepared in the same manner as in Example 1, except that Al-doped LLZO prepared in Production Example 2 was used in place of LLZO prepared in Production Example 1. [

Example  3: Preparation of positive electrode

The slurry was prepared by mixing the positive electrode composite material prepared in Example 1 and polyethylene oxide (PEO) as a binder in a weight ratio of 80:20. The slurry was coated on an aluminum substrate, dried, and pressed to prepare a positive electrode.

Example 4: Preparation of positive electrode

A positive electrode was prepared in the same manner as in Example 3, except that Al-doped LLZO prepared according to Production Example 2 was used instead of LLZO prepared according to Production Example 1. [

Device Example 1: Preparation of a pre-solid lithium secondary battery

The slurry was prepared in a mass ratio of 90:10 by using the solid electrolyte prepared in Preparation Example 1 and PEO, and then coated on the anode prepared in Example 3 to prepare an electrode. In the dry room, the electrode was punched to a size of 14, and lithium metal was placed on the electrode to prepare a pre-solid lithium secondary battery with a 2032 coin half cell.

Device Example 2: Preparation of a pre-solid lithium secondary battery

The slurry was prepared in a mass ratio of 90:10 by using the solid electrolyte prepared in Preparation Example 2 and PEO in an amount of 90:10, and then coated on the anode prepared in Example 4 to prepare an electrode. In the dry room, the electrode was punched to a size of 14, and lithium metal was placed on the electrode to prepare a pre-solid lithium secondary battery with a 2032 coin half cell.

COMPARATIVE EXAMPLE 1 Preparation of a Whole Solid Lithium Secondary Battery

30 parts by weight of LLZO, 70 parts by weight of NCM having a composition of 70% Ni, and 5 parts by weight of Super P, which is a conductive material, and PEO as a binder were mixed at a weight ratio of 80:20. The slurry was coated on an aluminum substrate, dried, and pressed to prepare a positive electrode. In the dry room, the electrode was punched to a size of 14, and lithium metal was placed on the electrode to prepare a pre-solid lithium secondary battery with a 2032 coin half cell.

[Test Example]

Test Example 1: SEM measurement

An SEM image of the positive electrode composite material prepared according to Example 1 is shown in FIG.

Referring to FIG. 2, it was confirmed that the LLZO particles, the NCM particles, and the conductive material particles were uniformly mixed to produce a positive electrode composite material in the form of granules.

Test Example 2: XRD measurement

FIG. 3 shows the XRD measurement results of the positive electrode composite material prepared according to Example 1. FIG.

Referring to FIG. 3, it can be seen that the composition ratio of NCM and LLZO of the anode composite material is substantially similar to the weight ratio (70:30) of the mixed solution before spray drying.

Therefore, it is possible to design a uniformly composite anode composite by the spray drying method using the spray drying equipment. It can be optimized by adjusting the ratio of the cathode active material / solid electrolyte / conductive material to the granule ) Can be produced.

Test Example 3: Evaluation of electrochemical characteristics

4 shows the results of measurement of the electrochemical characteristics of all solid lithium secondary batteries manufactured according to the device example 1 and the device comparative example 1. Fig. The measurement conditions were a voltage range of 3.0 to 4.3 V, a current condition of 0.0001 C, and a temperature of 70 캜 in CC-CV mode.

Referring to FIG. 4, in the case of the all-solid lithium secondary battery manufactured according to Comparative Example 1, the resistance at the bulk or the interface was too high, so that an overvoltage was applied as soon as the current was applied to exceed the voltage safety standard. On the other hand, in the case of the all-solid-state lithium secondary battery manufactured according to the Embodiment 1, the overvoltage was slightly applied in the early stage and the charging was started at 4V or more, but charging and discharging proceeded for a predetermined time in the set voltage range.

Therefore, the entire solid lithium secondary battery using the positive electrode composite material of the present invention in which the granules are formed by uniformly compounding the entire solid lithium secondary battery using the cathode active material / solid electrolyte / And the electrochemical characteristics were better.

Test Example 4: Evaluation of Capacity and Cycle Characteristics

Capacity and cycle characteristics of the all-solid lithium secondary battery produced according to the device example 1, the device example 2, and the device comparative example 1 were evaluated and shown in Table 1 below. The measurement conditions were a voltage range of 3.0 to 4.3 V, a current condition of 0.0001 C, and a capacity recovery rate after 20 cycles of 70 ° C. in the CC-CV mode.

Initial discharge capacity (mAh / g) Capacity recovery rate after 20 cycles (%) Device Embodiment 1 40 25 Device Example 2 50 30 Device Comparative Example 1 -
(Safe mode due to overvoltage) -

Referring to Table 1, the initial discharge capacities of the all-solid lithium secondary batteries produced according to the Device Example 1 and the Device Example 2 were 40 mAh / g and 50 mAh / g, respectively, and the capacity recovery rates after 20 cycles were 25% and 30% respectively. On the contrary, all the solid lithium lithium batteries manufactured according to the comparative example 1 exceeded the voltage safety standard because of the overvoltage as soon as the electric current was applied.

Therefore, all the solid lithium lithium secondary batteries manufactured according to Comparative Example 1 have a relatively large resistance at the bulk or interface, and all solid lithium batteries produced according to the Device Example 1 and the Device Example 2 have resistance at the bulk or interface It is judged that the initial discharge capacity and the capacity recovery rate are excellent.

The scope of the present invention is defined by the appended claims rather than the detailed description and all changes or modifications derived from the meaning and scope of the claims and their equivalents are to be construed as being included within the scope of the present invention do.

Claims (20)

(a) a solid electrolyte; Cathode active material; At least one of a conductive material and a surfactant; And a solvent;
(b) stirring the mixed solution to prepare a slurry; And
(c) spray drying the slurry to produce a positive electrode composite material,
The positive electrode composite material is a positive electrode composite material in which cathode active material particles, solid electrolyte particles, and conductive material particles are uniformly compounded and granules are formed,
Wherein the solid electrolyte particle comprises an Al-doped lithium lanthanum zirconium oxide (Al-doped LLZO) or a non-doped lithium lanthanum zirconium oxide (LLZO). Gt; delete The method according to claim 1,
Wherein the LLZO is represented by the following formula (1).
[Chemical Formula 1]
Li _x La _y Zr _z O ₁₂
Where 6? X? 9, 2? Y? 4, 1? Z? The method according to claim 1,
Wherein the Al-doped lithium lanthanum zirconium oxide is represented by the following formula (2).
(2)
Li _p Al _q La _y Zr _z O ₁₂
Where 5? P <9, 0 <q? 1, 2? Y? 4, 1? Z? The method according to claim 1,
Wherein the positive electrode active material particles comprise at least one selected from lithium nickel cobalt manganese oxide (NCM) and LiNi _0.8 Co _0.15 Al _0.05 O ₂ . 6. The method of claim 5,
Wherein the NCM is represented by the following formula (3).
(3)
LiNi _p Co _q Mn _r O ₂
here 0 <p <0.9, 0 <q <0.5, 0 <r <0.5, p + q + r = 1. The method according to claim 1,
Wherein the conductive material particles comprise a conductive carbon material. 8. The method of claim 7,
Wherein the conductive material particles are carbon. 9. The method of claim 8,
Wherein the carbon is at least one selected from the group consisting of carbon black, graphite, graphene, carbon nanotube (CNT), carbon nanofiber (CNF), and ketjen black. The method according to claim 1,
Wherein the granules have a diameter of 1 to 200 占 퐉. The method according to claim 1,
Wherein the weight ratio of the positive electrode composite material,
20 to 90 parts by weight of the positive electrode active material particles;
10 to 80 parts by weight of the solid electrolyte particles; And
5 to 30 parts by weight of the conductive material particles; Wherein the positive electrode composite material is produced by a method comprising the steps of: delete delete delete The method according to claim 1,
Wherein the mixed solution of step (a)
20 to 90 parts by weight of the cathode active material;
10 to 80 parts by weight of the solid electrolyte; And
5 to 30 parts by weight of at least one selected from the group consisting of the conductive material and the surfactant; Wherein the positive electrode composite material has an average particle diameter of about 5 to 10 nm. The method according to claim 1,
Wherein the solvent is selected from the group consisting of water, methanol, ethanol, butanol, pentanol, hexanol, trialkylbenzene, p-xylene, hexadecane, butyl acetate, octane, Wherein the positive electrode composite material comprises at least one selected from the group consisting of sodium carbonate, sodium carbonate, potassium carbonate, sodium carbonate, potassium carbonate, sodium carbonate, potassium carbonate, The method according to claim 1,
Wherein the stirring and pulverizing step (b) are carried out simultaneously or sequentially. The method according to claim 1,
Wherein the surfactant generates carbon by heat treatment. A method for manufacturing a positive electrode composite material according to claim 1. A method for manufacturing a pre-solid lithium secondary battery comprising the method of manufacturing the anode of claim 19.

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