Method for producing electrode composite powder

Abstract

According to the method of the present disclosure, the mechanical load applied to the device can be suppressed by reducing the adhesion of the kneaded material to the bottom of the kneading container.SOLUTION: The method of the present disclosure for producing an electrode composite powder includes kneading active material particles and a sulfide solid electrolyte to at least partially deform the sulfide solid electrolyte and coat at least a part of the surface of the active material particles with the sulfide solid electrolyte to form an electrode composite powder, wherein the kneading is performed with a frame-type blade in which at least a part on the bottom side of a kneading container is opened.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present disclosure relates to a method for producing an electrode composite powder. [Background technology]

[0002] Sulfide solid electrolytes have both high ionic conductivity and relatively good deformability. Sulfide solid electrolytes are suitable for bulk-type all-solid-state batteries. However, direct contact of the sulfide solid electrolyte with the active material in the electrode can accelerate degradation of the sulfide solid electrolyte. Degradation of the sulfide solid electrolyte can result in, for example, a loss of ionic conductivity.

[0003] To reduce direct contact between the sulfide solid electrolyte and the active material, it has been proposed to form composite particles by coating the active material with an oxide solid electrolyte (e.g., LiNbO3).Furthermore, it has also been proposed to coat the composite particles with the sulfide solid electrolyte to promote interface formation between the composite particles and the sulfide solid electrolyte.

[0004] For example, Patent Document 1 discloses a composite active material characterized by comprising active material particles containing at least one of cobalt, nickel, and manganese and further containing lithium and oxygen, composite particles containing an oxide-based solid electrolyte covering all or part of the surfaces of the active material particles, and a sulfide-based solid electrolyte further covering 76.0% or more of the surfaces of the composite particles. The composite active material described in Patent Document 1 is said to be able to reduce reaction resistance when used in a lithium battery. [Prior art documents] [Patent documents]

[0005] [Patent Document 1] Japanese Patent Application Laid-Open No. 2014-154407 Summary of the Invention [Problem to be solved by the invention]

[0006] When coating active material particles with a sulfide solid electrolyte, a solvent is added and the active material particles and the sulfide solid electrolyte are kneaded to at least partially deform the sulfide solid electrolyte, which then coats the active material particles. When using a commonly used kneading device, the active material particles and the sulfide solid electrolyte may aggregate and adhere to the bottom of the kneading container, which may place an excessive mechanical load on the device.

[0007] Therefore, an object of the present disclosure is to reduce the adhesion of the kneaded material to the bottom of the kneading container, thereby suppressing the mechanical load on the device. [Means for solving the problem]

[0008] The present disclosure achieves the above object by the following means.

[0009] (Aspect 1) kneading active material particles and a sulfide solid electrolyte to at least partially deform the sulfide solid electrolyte and coat at least a portion of the surface of the active material particles with the sulfide solid electrolyte to form an electrode composite powder; The kneading is carried out using a frame-type blade having at least a portion of the bottom side of the kneading container open. Manufacturing method of electrode composite powder. (Aspect 2) The electrode composite powder has a value of 1.30≦D 90 / D 50 And D 95 / D 50 2. The method of embodiment 1, wherein the particle size is ≦1.75. (Aspect 3) Aspect 3. The method according to aspect 1 or 2, wherein the active material particles are pre-coated active material particles, at least a portion of the surface of which is pre-coated with a coating solid electrolyte. (Aspect 4) Aspect 4. The method of aspect 3, wherein the coating solid electrolyte is a fluorine-containing solid electrolyte. (Aspect 5) The solid electrolyte for coating is Li 6-(4-x)b(Ti 1-x Al x ) b The method according to aspect 4, where F6 (0 < x < 1, 0 < b ≤ 1.5). (Aspect 6) A method for manufacturing a battery, including the following steps: Manufacturing an electrode composite powder by the method according to any one of aspects 1 to 5, and Forming an active material layer containing the electrode composite powder. (Aspect 7) An electrode composite powder containing active material particles and a sulfide solid electrolyte, where at least a part of the surface of the active material particles is coated with the sulfide solid electrolyte, and 1.30 ≤ D 90 / D 50 and D 95 / D 50 ≤ 1.75, having a particle size of an electrode composite powder.

Advantages of the Invention

[0010] According to the method of the present disclosure, by reducing the adhesion of the kneaded material to the bottom of the kneading container, the mechanical load on the device can be suppressed.

Brief Description of the Drawings

[0011] [Figure 1] Figure 1 is a diagram showing the values of the average power consumption and the maximum power consumption of the device in the examples.

Modes for Carrying Out the Invention

[0012] ≪Method for Manufacturing Electrode Composite Powder≫ The method of the present disclosure for manufacturing an electrode composite powder is kneading active material particles and a sulfide solid electrolyte to at least partially deform the sulfide solid electrolyte and coat at least a part of the surface of the active material particles with the sulfide solid electrolyte to form an electrode composite powder, where the kneading is performed with a frame-shaped blade having at least a part of the bottom side of the kneading container open.

[0013] According to the method of the present disclosure for producing an electrode composite powder, adhesion of the kneaded material to the bottom of the kneading vessel can be reduced, thereby suppressing the mechanical load on the apparatus.

[0014] In a conventional manufacturing method, a sulfide solid electrolyte and active material particles are kneaded using a frame blade, which applies stress to the sulfide solid electrolyte and deforms at least a portion of the sulfide solid electrolyte, thereby coating the sulfide solid electrolyte on the active material particles.

[0015] However, the present inventors have found that due to the characteristics of the sulfide solid electrolyte, which deforms under stress, the kneaded material tends to aggregate and adhere to the bottom of the container. Therefore, when the sulfide solid electrolyte and active material particles are kneaded between the frame blade and the bottom of the kneading container, the kneaded material may adhere to the bottom of the container.

[0016] In contrast, according to the present disclosure, at least a portion of the frame blade on the container bottom side is open, which prevents the sulfide solid electrolyte and active material particles from being kneaded between the frame blade and the container bottom. This prevents aggregation of the sulfide solid electrolyte and active material particles, adhesion of the kneaded mixture to the container bottom, and excessive mechanical load on the kneading device due to this, while quickly deforming the sulfide solid electrolyte and coating the surfaces of the active material particles with the sulfide solid electrolyte.

[0017] Hereinafter, embodiments of the present disclosure will be described in detail. Note that the present disclosure is not limited to the following embodiments, and various modifications can be made within the scope of the gist of the present disclosure.

[0018] The disclosed method for producing an electrode composite powder includes kneading active material particles and a sulfide solid electrolyte to at least partially deform the sulfide solid electrolyte and to coat at least a portion of the surfaces of the active material particles with the sulfide solid electrolyte to form an electrode composite powder.

[0019] By applying stress to the sulfide solid electrolyte, the particles of the sulfide solid electrolyte can be deformed, thereby coating the active material particles with the sulfide solid electrolyte.

[0020] In the method of the present disclosure, the kneading speed may be 10 rpm or more, 20 rpm or more, or 30 rpm or more, and may be 110 rpm or less, 100 rpm or less, or 90 rpm or less.

[0021] In the method of the present disclosure, the kneading time can be selected arbitrarily within a range that allows the sulfide solid electrolyte and the active material particles to be sufficiently kneaded.

[0022] In the method of the present disclosure, the kneading can be carried out in a low dew point environment, for example, an environment in which the dew point temperature is 0°C or lower, -30°C or lower, -50°C or lower, or -70°C or lower.

[0023] In the method of the present disclosure, kneading can be performed using a planetary mixer or the like as a kneading device.

[0024] (frame-type blade) In the disclosed method for producing an electrode composite powder, kneading is performed using a frame-type blade that is open at least partially on the bottom side of the kneading vessel.

[0025] The frame blade is a kneading blade with an open center in the kneading section. In the method of the present disclosure, at least a portion of the frame blade on the bottom side of the kneading vessel is open. In the method of the present disclosure, 30% or more, 40% or more, or 50% or more of the entire frame blade on the bottom side of the kneading vessel may be open, or 95% or less, 85% or less, or 75% or less of the entire frame blade on the bottom side of the kneading vessel may be open.

[0026] <Each configuration> Each component used in the method of the present disclosure will be described below.

[0027] (electrode composite powder) In the present disclosure, the electrode composite powder contains active material particles and a sulfide solid electrolyte.

[0028] The amount of the sulfide solid electrolyte to be blended may be, for example, 0.1 to 20 parts by mass, or 0.5 to 15 parts by mass, per 100 parts by mass of the active material.

[0029] The sulfide solid electrolyte is preferably coated on the surfaces of the active material particles with a uniform thickness, but may have a non-uniform thickness as long as it does not impair the effects of the manufacturing method of the present disclosure. The thickness of the sulfide solid electrolyte may be, for example, 0.1 nm or more, 0.5 nm or more, or 1 nm or more, or 100 nm or less, 80 nm or less, 60 nm or less, or 40 nm or less.

[0030] In the present disclosure, the average particle diameter D of the electrode composite powder 90 / D 50 may be 1.20 or more, 1.30 or more, or 1.40 or more, and may be 1.80 or less, 1.70 or less, or 1.60 or less. 95 / D 50 may be 1.20 or more, 1.30 or more, or 1.40 or more, and may be 1.80 or less, 1.70 or less, or 1.60 or less. In the present disclosure, the average particle diameter of the electrode composite powder is 1.30≦D 90 / D 50 And D 95 / D 50 It may be ≦1.75.

[0031] The average particle diameter of the particles in the present disclosure is calculated by the following procedure. Examples of the method for calculating the average particle diameter of the particles are as follows. As the particle diameter measurement device, a particle diameter analyzer XPT-C (manufactured by Sanyo Trading Co., Ltd.) for a dispersion liquid or the like can be used. By feeding the sample dispersion liquid to the measurement device, taking an image of the sample dispersion liquid during feeding, and detecting the particles by subjecting the image to binarization processing, the particle diameter can be measured. In each measurement, a plurality of images, for example, 1000 images, can be taken, and / or the measurement can be performed a plurality of times, for example, 3 times, and the average value of all the measurement results can be taken as the average particle diameter.

[0032] (Active material particles) In the present disclosure, the active material particles are contained in the electrode composite powder and are coated with a sulfide solid electrolyte by the method of the present disclosure.

[0033] Regarding the present disclosure, the "active material particles" may be either "positive electrode active material" or "negative electrode active material".

[0034] The active material particles are not particularly limited, but may be preliminarily coated active material particles having a coating layer made of a solid electrolyte for coating. The coating layer contains a substance having lithium ion conduction performance, low reactivity with the active material particles and the solid electrolyte, and capable of maintaining the form of the coating layer that does not flow even when in contact with the active material particles and the solid electrolyte. Specific examples of the solid electrolyte for coating include, in addition to LiNbO3, Li4Ti5O 12 , Li3PO4, etc., but are not limited thereto. In particular, when the solid electrolyte for coating is a fluorine-containing solid electrolyte, for example, Li 2.7 Ti 0.3 Al 0.7 F6 such as an LTAF electrolyte (Li 6-(4-x)b (Ti 1-x Al x ) b F6 (0 < x < 1, 0 < b ≤ 1.5)), the solvent and the preliminarily coated active material particles are less compatible, whereby the solvent is locally distributed and an excessive mechanical load is likely to be applied to the kneading device, so the method of the present disclosure can be effectively used.

[0035] When the active material particles are pre-coated active material particles having a coating layer made of a coating solid electrolyte, the sulfide solid electrolyte can coat the surfaces of such pre-coated active material particles.

[0036] (Cathode active material) The material of the positive electrode active material is not particularly limited. Examples of the positive electrode active material include lithium cobalt oxide (LiCoO), lithium nickel oxide (LiNiO), lithium manganese oxide (LiMnO), and nickel-cobalt-manganese lithium oxide (NCM:LiCO 1 / 3 Ni 1 / 3 Mn 1 / 3 O2), lithium nickel-cobalt-aluminate (LiNi 0.8 (CoAl) 0.2 O2), Li 1+x Mn 2-x-y M y The material may be, but is not limited to, a different element-substituted Li-Mn spinel having a composition represented by O4 (M is one or more metal elements selected from Al, Mg, Co, Fe, Ni, and Zn).

[0037] (active material) The active material is the core of the pre-coated active material particle. The active material is in a particulate form. The active material may be, for example, a secondary particle. The secondary particle is an aggregate of primary particles. The D of the secondary particle 50 The average particle diameter D may be, for example, 1 to 30 μm, 3 to 20 μm, or 5 to 15 μm. The average Feret diameter of the primary particles may be, for example, 0.01 to 3 μm. 50 is the particle size (median size) at 50% cumulative value in the volume-based particle size distribution determined by laser diffraction / scattering method.

[0038] The active material may have any shape, such as a sphere, an ellipsoid, a flake, a fiber, etc. The active material may be a solid particle or a hollow particle.

[0039] (Negative electrode active material) The material of the negative electrode active material is not particularly limited, and may be metallic lithium or a material capable of absorbing and releasing metal ions such as lithium ions. Examples of materials capable of absorbing and releasing metal ions such as lithium ions include alloy-based negative electrode active materials, carbon materials, and lithium titanate (Li4Ti5O 12 ) and the like can be mentioned, but are not limited to these.

[0040] The alloy-based negative electrode active material is not particularly limited, and examples thereof include Si alloy-based negative electrode active materials and Sn alloy-based negative electrode active materials. Si alloy-based negative electrode active materials include silicon, silicon oxide, silicon carbide, silicon nitride, etc., or solid solutions thereof. Si alloy-based negative electrode active materials can also include metal elements other than silicon, such as Fe, Co, Sb, Bi, Pb, Ni, Cu, Zn, Ge, In, Sn, Ti, etc. Sn alloy-based negative electrode active materials can also include tin, tin oxide, tin nitride, etc., or solid solutions thereof. Sn alloy-based negative electrode active materials can also include metal elements other than tin, such as Fe, Co, Sb, Bi, Pb, Ni, Cu, Zn, Ge, In, Ti, Si, etc.

[0041] The carbon material is not particularly limited, and examples thereof include hard carbon, soft carbon, graphite, and the like.

[0042] The negative electrode active material is in the form of particles. The negative electrode active material may be in the form of primary particles or secondary particles formed by agglomeration of a plurality of primary particles. The average particle diameter D of the negative electrode active material 50 The average particle diameter D may be, for example, 1 nm or more, 5 nm or more, or 10 nm or more, and may be 500 μm or less, 100 μm or less, 50 μm or less, or 30 μm or less. 50 is the particle size (median size) at 50% cumulative value in the volume-based particle size distribution determined by laser diffraction / scattering method.

[0043] (Sulfide solid electrolyte) In the present disclosure, the sulfide solid electrolyte is contained in the electrode composite powder and coats the active material particles.

[0044] Examples of sulfide solid electrolytes include, but are not limited to, sulfide-based amorphous solid electrolytes, sulfide-based crystalline solid electrolytes, and argyrodite-type solid electrolytes. Examples of sulfide solid electrolytes include Li2S-P2S5-based (Li7P3S 11 , Li3PS4, Li8P2S9, etc.), Li2S-SiS2, LiI-Li2S-SiS2, LiI-Li2S-P2S5, LiI-LiBr-Li2S-P2S5, Li2S-P2S5-GeS2(Li 13 GeP3S 16 , Li 10 GeP2S 12 ), LiI-Li2S-P2O5, LiI-Li3PO4-P2S5, Li 7-x PS 6-x Cl x These may include, but are not limited to, the following:

[0045] The sulfide solid electrolyte may be glass or crystallized glass (glass ceramics).

[0046] In the method for producing an electrode composite powder, the sulfide solid electrolyte used as a raw material may be in the form of particles. 50 The thickness may be, for example, 0.01 to 1 μm, or 0.1 to 0.9 μm.

[0047] (solvent) In the present disclosure, the solvent may be added when the active material particles and the sulfide solid electrolyte are kneaded together.

[0048] The solvent is a liquid. The solvent can promote adhesion between the active material particles and the sulfide solid electrolyte during kneading. The solvent can function as a dispersion medium in the slurry. The solvent can contain any component. For example, the solvent may contain at least one selected from the group consisting of aromatic hydrocarbons, esters, alcohols, ketones, and lactams. For example, the solvent may contain at least one selected from the group consisting of tetralin (1,2,3,4-tetrahydronaphthalene, THN), butyl butyrate, heptane, and N-methyl-2-pyrrolidone (NMP).

[0049] Butyl butyrate is expected to be less likely to deteriorate the sulfide solid electrolyte than, for example, NMP, etc. THN is expected to be less likely to deteriorate the sulfide solid electrolyte than, for example, butyl butyrate, NMP, etc. When the solvent contains THN, for example, it is expected that the initial resistance will be reduced.

[0050] <Battery manufacturing method> The method for manufacturing a battery in the present disclosure includes the following steps: Producing an electrode composite powder by the method described herein; and forming an active material layer containing the electrode composite powder;

[0051] The active material layer of the battery produced by the method of the present disclosure may be provided by a composite slurry containing an electrode composite powder and a dispersing medium, and the active material layer may be formed by applying the composite slurry to a substrate and then drying and removing the dispersing medium.

[0052] The present disclosure will be described in more detail with reference to the following examples, but the scope of the present disclosure is not limited to these examples. [Example]

[0053] Hereinafter, an electrode composite powder and a solid state battery were manufactured and examined according to the manufacturing method according to the embodiment.

[0054] (Preparation of Pre-Coated Active Material Particles) Li(NiCoAl)O2 was prepared as the active material. Hereinafter, "Li(NiCoAl)O2" may be abbreviated as "NCA."

[0055] A fluoride solid electrolyte was synthesized as a coating solid electrolyte by mixing LiF, TiF4, and AlF3 in a planetary ball mill. 2.7 Ti 0.3 Al 0.7 F6. This fluoride solid electrolyte may be abbreviated as "LTAF."

[0056] A "Nobilta NOB-MINI (manufactured by Hosokawa Micron Corporation)" was used as an apparatus for pre-coating the active material particles. In this apparatus, 48.7 parts by mass of NCA and 1.3 parts by mass of LTAF were kneaded to form pre-coated active material particles. The operating conditions of the apparatus are as follows:

[0057] Power: 12W per gram of material Rotation speed: 6000 rpm Processing time: 30 minutes

[0058] (Other ingredients) For the examples of this disclosure, the following materials were prepared: Sulfide solid electrolyte: Li2S-P2S5 (glass ceramics) Solvent:THN Hereinafter, "Li2S-P2S5" may be abbreviated as "LPS."

[0059] Example 1 The subsequent operations were carried out in an environment where the dew point temperature was controlled to -70°C or below. An ultrasonic homogenizer was used as the dispersion device. The sulfide solid electrolyte was dispersed in the solvent using the ultrasonic homogenizer to prepare a dispersion liquid.

[0060] A planetary mixer equipped with a frame-type blade with 90% of the bottom side of the container open was prepared as a kneading device. The pre-coated active material particles prepared as described above were supplied to the kneading device, and the dispersion liquid prepared as described above was also supplied to the kneading device.

[0061] An electrode composite powder was produced by performing "kneading" and "adding solvent during kneading" in the following order. In the "adding solvent during kneading" step, the solvent was added with a dropper while kneading the pre-coated active material particles and the sulfide solid electrolyte. An evaluation sample according to Example 1 was then obtained, which was an electrode composite powder in which the pre-coated active material particles were coated with the sulfide solid electrolyte. When Example 1 was performed 10 times, no adhesion of the kneaded material to the bottom of the container occurred during kneading.

[0062] (1) Mixing: Rotation speed = low, time = short (2) Add solvent during kneading: THN, rotation speed = low, time = short (3) Mixing: Rotation speed = medium, time = medium (4) Add solvent during kneading: THN, rotation speed = low, time = short (5) Mixing: Rotation speed = medium, time = medium (6) Kneading: Rotation speed = high, time = long

[0063] Using an ultrasonic homogenizer, the electrode composite powder, ion conductive material (LPS), and electron conductive material (AB+VGCF) were dispersed in a solvent (THN) to prepare a slurry. The slurry was applied to the surface of a substrate and dried to produce a positive electrode. A solid-state battery including the positive electrode was then manufactured. The configuration of the solid-state battery is as follows:

[0064] Exterior: Aluminum laminated film Negative electrode active material: Li4Ti5O 12

[0065] Example 2 Except for replacing the LTAF with LiNbO3, an electrode composite powder, that is, an evaluation sample according to Example 2, was obtained in the same manner as in Example 1. When Example 2 was carried out 10 times, no adhesion of the kneaded material to the bottom of the container occurred during kneading.

[0066] Comparative Example 1 Except for replacing the frame-type blade with 90% of the bottom of the container open with a normal frame-type blade, an evaluation sample of Comparative Example 1, which is an electrode composite powder, and a solid-state battery were obtained in the same manner as in Example 1. When Comparative Example 1 was performed 10 times, adhesion of the kneaded material to the bottom of the container during kneading occurred four times.

[0067] Comparative Example 2 Except for replacing the frame-type blade in which 90% of the bottom side of the container was opened with a normal frame-type blade, an evaluation sample of Comparative Example 2, which was an electrode composite powder, was obtained in the same manner as in Example 2. When Comparative Example 2 was performed 10 times, adhesion of the kneaded material to the bottom of the container occurred twice during kneading.

[0068] <Evaluation> The samples of Examples 1 and 2 and Comparative Examples 1 and 2 were subjected to the following evaluations, and the results were compared.

[0069] (Number of times stuck) In Comparative Examples 1 and 2, adhesion of the kneaded material to the bottom of the container during kneading occurred four times and two times, respectively. However, in Examples 1 and 2, adhesion of the kneaded material to the bottom of the container during kneading did not occur. Therefore, the method of the present disclosure reduces adhesion of the kneaded material to the bottom of the container during kneading.

[0070] (Device power consumption) The average power consumption and maximum power consumption of the device in the above "(6) Kneading" were compared between Example 1 and Comparative Example 1, and between Example 2 and Comparative Example 2.

[0071] FIG. 1 shows the power consumption of the kneading device in Example 1 and Comparative Example 1. Table 1 shows the power consumption of the kneading device in Example 2 and Comparative Example 2. Examples 1 and 2, which used a frame blade with 90% of the container bottom side open, both showed lower average power consumption and maximum power consumption than Comparative Examples 1 and 2, which used a normal frame blade. Therefore, the method of the present disclosure, which uses a frame blade with 90% of the container bottom side open, can reduce the power consumption of the device during kneading, i.e., the mechanical load on the device during kneading.

[0072] [Table 1]

[0073] (Particle diameter of electrode composite powder) The particle size measurement device used was an "XPT-C particle size analyzer for dispersions (manufactured by Sanyo Trading Co., Ltd.)." A sample dispersion prepared by the following method was sent to the measurement device, and an image of the sample dispersion was taken during the sending. The images were binarized to detect particles and measure the particle size. 1,000 images were taken for each measurement. Measurements were performed three times, and the average value of all measurement results was taken as the average particle size. The average particle sizes of the electrode composite powders were measured for Examples 1 and 2 and Comparative Examples 1 and 2.

[0074] 0.025 g of electrode composite powder and approximately 25 g of tetralin were treated with an ultrasonic homogenizer for 3 minutes to prepare a sample dispersion with a concentration of approximately 0.01% by mass. Just before the liquid was delivered, it was treated with the ultrasonic homogenizer for 1 minute and then measured. Sample dispersions for Examples 1 and 2 and Comparative Examples 1 and 2 were prepared in the same manner.

[0075] Table 2 shows the average particle diameters of the electrode composite powders of Example 1 and Comparative Example 1, and Example 2 and Comparative Example 2. The electrode composite powders of Example 1 and Example 2 have lower D 95 Also, D 50 D against 95 Percentage D 95 / D50 is lower in Examples 1 and 2 than in Comparative Examples 1 and 2. 95 / D 50 A low value indicates that the number of agglomerates in the kneaded material is reduced and the electrode composite powder has high homogeneity. Therefore, the method of the present disclosure, which uses a frame blade in which 90% of the bottom side of the container is opened, can reduce the number of agglomerates in the kneaded material, i.e., can produce an electrode composite powder with high homogeneity.

[0076] [Table 2]

[0077] (Battery performance) The discharge resistance and charge resistance of the solid state batteries fabricated in Example 1 and Comparative Example 1 were measured by the following method.

[0078] The SOC (State of Charge) of the all-solid-state battery was adjusted to 60%. The all-solid-state battery was discharged for 2 seconds at an hourly rate of 72C. The initial discharge resistance (DC resistance) was calculated from the voltage drop and current during discharge. The discharge resistance was calculated at 0.1 seconds, 1 second, and 2 seconds after the start of discharge.

[0079] The solid-state battery was then charged for 5 seconds at a time rate of 32 C. The initial charging resistance (DC resistance) was calculated from the voltage rise and current during charging. The charging resistance was measured at 0.1 seconds, 1 second, and 5 seconds after the start of charging.

[0080] Table 3 shows the battery performance of the batteries of Example 1 and Comparative Example 1. The battery of Example 1 exhibited lower discharge resistance and charge resistance than the battery of Comparative Example 1. Therefore, the method of the present disclosure, which uses a frame-type blade with 90% of the bottom side of the container open, can produce an electrode composite powder with high uniformity.

[0081] [Table 3]

Claims

1. kneading active material particles and a sulfide solid electrolyte to at least partially deform the sulfide solid electrolyte and to coat at least a portion of the surfaces of the active material particles with the sulfide solid electrolyte to form an electrode composite powder, The kneading is performed using a frame blade having at least a portion of the bottom side of the kneading container open. Manufacturing method of electrode composite powder.

2. The electrode composite powder has a value of 1.30≦D ９０ / D ５０ And D ９５ / D ５０ 10. The method of claim 1, wherein the granules have a particle size of ≦1.

75.

3. The method according to claim 1 , wherein the active material particles are pre-coated active material particles, at least a portion of the surface of which is pre-coated with a coating solid electrolyte.

4. The method of claim 3 , wherein the coating solid electrolyte is a fluorine-containing solid electrolyte.

5. The solid electrolyte for coating is Li ６－（４－ｘ）ｂ (Ti １－ｘ Al ｘ ) ｂ F ６ 5. The method of claim 4, wherein (0<x<1, 0<b≦1.5).

6. A method for manufacturing a battery, comprising the steps of: Producing an electrode composite powder by the method according to any one of claims 1 to 5, and forming an active material layer containing the electrode composite powder;

7. An electrode composite powder containing active material particles and a sulfide solid electrolyte, At least a portion of the surface of the active material particles is coated with the sulfide solid electrolyte, and 1.30≦D ９０ / D ５０ And D ９５ / D ５０ having a particle size of ≦1.75; Electrode composite powder.

Images