All-solid-state batteries

Abstract

The present invention aims to provide a new all-solid-state battery. [Solution] This all-solid-state battery 1b comprises a positive electrode 17, a solid electrolyte portion 15, and a negative electrode 14 in this order. The positive electrode 17 includes a positive electrode active material 27 and a first solid electrolyte 26, and the solid electrolyte portion 15 consists of a second solid electrolyte 25. The positive electrode active material 27 and the first solid electrolyte 26 are oxides, and the second solid electrolyte 26 is a sulfide. The all-solid-state battery 1b has an oxide coating film 16 at the interface between the positive electrode 17 and the solid electrolyte portion 15.

Description

[Technical Field]

[0001] This invention relates to an all-solid-state battery. [Background technology]

[0002] Patent Document 1 discloses (A) composite particles comprising positive electrode active material particles and a coating film, wherein the coating film 24 covers at least a portion of the surface of the positive electrode active material particles 23, and the coating film comprises composite particles comprising fluorine, phosphorus, glass network forming elements, etc.; (B) a positive electrode 13 comprising the composite particles and a sulfide solid electrolyte; and (C) an all-solid-state battery 1a comprising the positive electrode, etc. (see Figure 2). [Prior art documents] [Patent Documents]

[0003] [Patent Document 1] Publication number: JP 2024-11259 [Overview of the project] [Problems that the invention aims to solve]

[0004] The present invention aims to manufacture a new all-solid-state battery. [Means for solving the problem]

[0005] Conventionally, in the manufacturing of all-solid-state batteries as described in Patent Document 1, a coating film 24 is coated onto the positive electrode active material 23 (powder) (see Patent Document 1, Figure 2), which results in poor uniformity and may cause localized interfacial reactions between the positive electrode active material and the sulfide solid electrolyte, potentially degrading the cycle characteristics of the all-solid-state battery. Conventionally, in the manufacturing of all-solid-state batteries, the entire positive electrode active material is coated, and the coating film is present to a similar extent as the positive electrode active material, potentially reducing the energy density.

[0006] In order to solve the problems left by such conventional technologies, the inventors of the present invention have conducted intensive studies. As a result, in a all-solid-state battery including a positive electrode containing a positive electrode active material and a first solid electrolyte, a solid electrolyte part composed of a second solid electrolyte, and a negative electrode in this order, at the interface between the positive electrode and the solid electrolyte part, preferably, a coating film made of an oxide solid electrolyte is provided on the solid electrolyte part side of the positive electrode, and it has been found that a all-solid-state battery with good cycle characteristics can be manufactured.

[0007] The present invention includes the all-solid-state battery shown below.

[0008] Item 1. A all-solid-state battery, The all-solid-state battery includes a positive electrode, a solid electrolyte part, and a negative electrode in this order, The positive electrode includes a positive electrode active material and a first solid electrolyte, The solid electrolyte part is composed of a second solid electrolyte, The positive electrode active material and the first solid electrolyte are oxides, The second solid electrolyte is a sulfide, The all-solid-state battery has an oxide coating film at the interface between the positive electrode and the solid electrolyte part.

[0009] Item 2. The oxide coating film coats the positive electrode active material and the first solid electrolyte that form the positive electrode at the interface between the positive electrode and the solid electrolyte part. The all-solid-state battery according to Item 1.

[0010] Item 3. The oxide coating film is provided on the surface of the positive electrode on the solid electrolyte part side at the interface between the positive electrode and the solid electrolyte part. The all-solid-state battery according to Item 1.

[0011] Item 4. The positive electrode active material includes lithium element (Li), nickel element (Ni), manganese element (Mn), cobalt element (Co), and oxygen element (O), The first solid electrolyte contains lithium element (Li), aluminum element (Al), titanium element (Ti), phosphorus element (P), and oxygen element (O). The all-solid-state battery according to item 1, wherein the second solid electrolyte contains lithium element (Li), phosphorus element (P), sulfur element (S), and chlorine element (Cl).

[0012] Item 5. The positive electrode active material is LiNi Mn 0.2 Co 0.3 O2, The first solid electrolyte is Li 1.3 Al 0.3 Ti 1.7 (PO4)3, The all-solid-state battery according to item 1, wherein the second solid electrolyte is Li6PS5Cl.

[0013] Item 6. The all-solid-state battery according to item 1, wherein the oxide coating film has a thickness of 7.5 nm to 45 nm.

[0014] Item 7. The all-solid-state battery according to item 1, wherein the oxide coating film is formed of a component containing lithium element (Li), aluminum element (Al), titanium element (Ti), phosphorus element (P), and oxygen element (O).

[0015] Item 8. The all-solid-state battery according to claim 1, wherein the oxide coating film is formed of Li 1.3 Al 0.3 Ti / 1.7 (PO4)3.

[0016] In the all-solid-state battery of the present invention, a coating film made of an oxide solid electrolyte is provided at the interface between the positive electrode and the solid electrolyte portion, and the cycle characteristics are good.

Effects of the Invention

[0017] The present invention can newly provide an all-solid-state battery. [Brief explanation of the drawing]

[0018] [Figure 1] Figure 1 is a diagram illustrating a cross-sectional view of an all-solid-state battery 1b having an oxide coating film 16 of the present invention, in comparison with a conventional all-solid-state battery 1a. [Figure 2] Figure 2 illustrates, in comparison with the conventional all-solid-state battery 1a, that the all-solid-state battery 1b of the present invention has an oxide coating film 16 at the interface between the positive electrode 17 and the solid electrolyte portion 15. [Figure 3] Figure 3 illustrates a vacuum processing apparatus 4 used when manufacturing the all-solid-state battery 1b of the present invention. [Figure 4] Figure 4 illustrates a vessel 44 used when manufacturing the all-solid-state battery 1b of the present invention. [Figure 5] Figure 5 illustrates the cycle characteristics of an all-solid-state battery 1b having the oxide coating film 16 of the present invention, in comparison with an example of a conventional all-solid-state battery 1a without the oxide coating film 16. [Modes for carrying out the invention]

[0019] The present invention will be described in detail below.

[0020] The embodiments illustrating the present invention are intended to provide a better understanding of the invention's intent and, unless otherwise specified, do not limit the scope of the invention.

[0021] In this specification, "contains" and "include" are concepts that encompass all of the following: "comprise," "consist essentially of," and "consist of."

[0022] In this specification, when a numerical range is indicated as "A to B", the numerical range means "greater than or equal to A and less than or equal to B".

[0023] [1] Method for manufacturing solid-state batteries The all-solid-state battery of the present invention is manufactured by the following manufacturing method.

[0024] Figure 1 is a diagram illustrating a comparison between a cross-sectional view of a conventional all-solid-state battery 1a and a cross-sectional view of the all-solid-state battery 1b of the present invention. The conventional all-solid-state battery 1a has a negative electrode 11, a solid electrolyte portion 12, and a positive electrode 13, as shown on the left of Figure 1. The all-solid-state battery 1b of the present invention has a negative electrode 14, a solid electrolyte portion 15, an oxide coating film 16, and a positive electrode 17, as shown on the right of Figure 1.

[0025] Figure 2 illustrates, in comparison with the conventional all-solid-state battery 1a, that the all-solid-state battery 1b of the present invention has an oxide coating film 16 at the interface between the positive electrode 17 and the solid electrolyte portion 15. Note that the negative electrodes 11 and 14 are omitted from Figure 2.

[0026] As shown on the left of Figure 2, the solid electrolyte portion 12 of the conventional all-solid-state battery 1a is formed by a second solid electrolyte 21. The positive electrode 13 of the conventional all-solid-state battery 1a is formed by a first solid electrolyte 22, a positive electrode active material 23, and a coating film 24 that coats the positive electrode active material 23. The second solid electrolyte 21 is a sulfide, and the first solid electrolyte 22 and positive electrode active material 23 are oxides.

[0027] As shown on the right in Figure 2, the solid electrolyte portion 15 of the all-solid-state battery 1b of the present invention is formed by a second solid electrolyte 25. The positive electrode 17 of the all-solid-state battery 1b of the present invention is formed by a first solid electrolyte 26 and a positive electrode active material 27. The all-solid-state battery 1b of the present invention has an oxide coating film 16 at the interface between the solid electrolyte portion 15 and the positive electrode 17. The second solid electrolyte 25 is a sulfide, and the first solid electrolyte 26 and the positive electrode active material 27 are oxides.

[0028] The manufacturing method for all-solid-state battery 1b is as follows: (1) A step of molding a positive electrode 17 with a mixture containing a positive electrode active material 27 and a first solid electrolyte 26, (2) A step of molding the solid electrolyte portion 15 with the second solid electrolyte 25, (3) A step of providing an oxide coating film 16 at the interface between the molded positive electrode 17 and the solid electrolyte portion 15, (4) The process includes stacking the positive electrode 17, the solid electrolyte portion 15, and the negative electrode 14 in this order and pressing them together.

[0029] The following explains the above steps (1) to (4) in order. (1) A step of molding a positive electrode 17 with a mixture containing a positive electrode active material 27 and a first solid electrolyte 26. The method for manufacturing an all-solid-state battery 1b includes the step of (1) compacting a mixture containing a positive electrode active material 27 and a first solid electrolyte 26 into powder to form a positive electrode 17.

[0030] Step (1) is preferably carried out in a first environment with a dew point of -60°C or lower in order to suppress deterioration of properties due to moisture adsorption, etc.

[0031] The positive electrode active material 27 is an oxide, for example, an oxide containing lithium (Li), nickel (Ni), manganese (Mn), cobalt (Co), and oxygen (O).

[0032] The positive electrode active material particles are preferably LiCoO2, LiNiO2, LiMnO2, LiMn2O4, Li(NiCoMn)O2, Li(NiCoAl)O2, LiFePO4, etc. Li(NiCoMn)O2 is, for example, LiNi 1 / 3 Co 1 / 3 Mn 1 / 3 O2, LiLiLi 0.5 Co 0.2 Mn 0.3 O2, LiLiLi 0.8 Co 0.1 Mn 0.1 This includes O2, etc. The positive electrode active material 27 is more preferably LiNi 0.5 Mn 0.2 Co 0.3 It is O2.

[0033] The first solid electrolyte 26 uses an oxide because it is relatively stable and exhibits little diffusion of material into the positive electrode active material 27, which is an oxide. Preferably, the first solid electrolyte 26 uses an oxide containing lithium (Li), aluminum (Al), titanium (Ti), phosphorus (P), and oxygen (O). More preferably, the first solid electrolyte 26 contains Li 1.3 Al 0.3 Ti 1.7 Use (PO4)3).

[0034] The positive electrode 17 may further contain a conductive material. The conductive material can form electron conduction paths within the positive electrode 17. Preferably, the conductive material is acetylene black, carbon black, vapor-grown carbon fiber (VGCF), carbon nanotubes (CNT), graphene flakes, etc.

[0035] The positive electrode 17 may further contain a binder. Preferably, the binder is polyvinylidene fluoride (PVdF), vinylidene fluoride-hexafluoropropylene copolymer (PVDF-HFP), styrene-butadiene rubber (SBR), polytetrafluoroethylene (PTFE), etc.

[0036] (2) A step of molding the solid electrolyte portion 15 with the second solid electrolyte 25. The manufacturing method for the all-solid-state battery 1b includes (2) a step of molding a solid electrolyte portion 15 with a second solid electrolyte 25. The step of molding the solid electrolyte portion 15 preferably involves sintering or compacting only the second solid electrolyte 25 or a mixture containing the second solid electrolyte 25.

[0037] Step (2) is preferably carried out in a first environment with a dew point of -60°C or lower in order to suppress deterioration of properties due to moisture adsorption, etc.

[0038] The second solid electrolyte 25 is a sulfide. Preferably, the second solid electrolyte 25 is a sulfide containing lithium (Li), phosphorus (P), sulfur (S), and chlorine (Cl), and more preferably Li6PS5Cl.

[0039] (3) Steps to provide an oxide coating film 16 at the interface between the molded positive electrode 17 and the solid electrolyte portion 15. The manufacturing method for the all-solid-state battery 1b includes (3) the step of providing an oxide coating film 16 at the interface between the molded positive electrode 17 and the solid electrolyte portion 15.

[0040] Figure 3 illustrates a vacuum processing apparatus 4 used when manufacturing the all-solid-state battery 1b of the present invention. Figure 4 illustrates a vessel 44 used when manufacturing the all-solid-state battery 1b of the present invention.

[0041] As shown in Figure 3, the vacuum processing apparatus 4 includes a load lock chamber 4a and a plasma processing chamber 4b.

[0042] In the vacuum processing apparatus 4, a gate valve is provided to separate the load lock chamber 4a and the plasma processing chamber 4b. With the gate valve open, the sample transport mechanism 47 can transport the sample holder 44c (see Figure 4), on which the object to be processed is placed, between the load lock chamber 4a and the plasma processing chamber 4b shown in Figure 3.

[0043] An inert gas (Ar gas, nitrogen, etc.) is introduced from the gas piping (gas inlet) 41 to purge the inside of the load lock chamber 4a, thereby minimizing the inflow of outside air into the load lock chamber 4a through the opening of the door.

[0044] The operator introduces the vessel 44 into the load lock chamber 4a through the opening of the door and places it on the fixing part of the vessel 44. The vessel 44 maintains a vacuum even after the atmosphere is removed. Vacuum piping 42 is connected to the load lock chamber 4a, making it possible to evacuate the load lock chamber 4a.

[0045] Plasma processing chamber 4b is equipped with a processing chamber 46 and performs film deposition and plasma processing while maintaining a vacuum environment for the sample. Plasma processing chamber 4b is equipped with an antenna 48 for generating inductively coupled plasma within the plasma processing chamber. Vacuum piping 43 is connected to processing chamber 46, making it possible to evacuate processing chamber 46.

[0046] The vessel 44 applied to the vacuum processing apparatus 4 is a portable vacuum transport container capable of housing an object to be processed while maintaining a vacuum. As shown in Figure 4, the vessel 44 consists of a vessel plate 44a and a vessel cover 44b, and houses the object to be processed together with a sample holder 44c on which the object to be processed is placed in the internal space partitioned by the vessel plate 44a and the vessel cover 44b.

[0047] The vessel 44 enables the transport of the object to be processed while it is held in a vacuum between the vacuum processing apparatus 4 and other devices. For this purpose, the load lock chamber 4a is configured to receive the vessel 44 at the vessel fixing section, detach the vessel cover 44b of the vessel 44 from the vessel plate 44a, and remove or store the object to be processed together with the sample holder 44c.

[0048] The upper surface of the ceiling portion of the vessel cover 44b is provided with two screw fastening portions 44d for the opening and closing drive units. The screw fastening portions 44d of the vessel cover 44b engage with the screw portions of the load lock chamber 4a. The upper surface of the vessel plate 44a is provided with a dovetail groove 44e for an O-ring that encircles the outer edge of the vessel plate 44a.

[0049] Step (3) is preferably carried out in a second environment of about 100 Pa or less, in terms of ease of plasma ignition and maintenance. In particular, when generating inductively coupled plasma, as in plasma processing chamber 4b (processing chamber 46) in Figure 3, the above pressure range is preferred.

[0050] The oxide coating film 16 may be provided at the interface between the positive electrode 17 and the solid electrolyte portion 15, either on the surface of the positive electrode 17 facing the solid electrolyte portion 15, or on the surface of the solid electrolyte portion 15 facing the positive electrode 17. Preferably, the oxide coating film 16 coats the positive electrode active material 27 forming the positive electrode 17 and the first solid electrolyte 26 at the interface between the positive electrode 17 and the solid electrolyte portion 15. Preferably, the oxide coating film 16 is provided at the interface between the positive electrode 17 and the solid electrolyte portion 15, on the surface of the positive electrode 17 facing the solid electrolyte portion 15.

[0051] In this manner, the all-solid-state battery 1b of the present invention can further suppress the diffusion of sulfur contained in the second solid electrolyte 25 into the positive electrode active material 27, even when the amount of film deposited on the positive electrode 17 surface, which has irregularities on the order of μm, is on the order of nm.

[0052] The oxide coating film 16 can be manufactured, for example, by sputtering or plasma CVD. In this case, it becomes possible to continuously manufacture the oxide coating film 16 in the plasma processing chamber 4b (processing chamber 46) where the plasma processing is performed, thereby forming a high-quality oxide coating film 16 / plasma processing interface, and reducing mass production costs by shortening the cycle time.

[0053] The oxide coating film 16 preferably has a thickness of 7.5 nm to 45 nm.

[0054] The oxide coating film 16 is preferably formed from components containing lithium (Li), aluminum (Al), titanium (Ti), phosphorus (P), and oxygen (O), and more preferably Li 1.3 Al 0.3 Ti 1.7 It is formed from (PO4)3.

[0055] The all-solid-state battery 1b of the present invention exhibits good cycle characteristics by having an oxide coating film 16 at the interface between the positive electrode 17 and the solid electrolyte portion 15.

[0056] (4) A process of stacking the positive electrode 17, the solid electrolyte portion 15, and the negative electrode 14 in this order and pressing them together. The manufacturing method for the all-solid-state battery 1b includes (4) stacking the positive electrode 17, the solid electrolyte portion 15, and the negative electrode (Li / In, etc.) 14 in this order and pressing them together.

[0057] (5) A process of transporting the sample between the first environment and the second environment. A method for manufacturing an all-solid-state battery 1b preferably includes (5) a step of transporting a sample between a first environment and a second environment.

[0058] Step (5) preferably includes storing the sample in a vacuum-sealed vessel 44.

[0059] (6) A process of applying plasma treatment to the surface of the solid electrolyte portion 15 side of the positive electrode 17 after molding. The method for manufacturing the all-solid-state battery 1b may further include (6) a step of applying plasma treatment to the surface of the positive electrode on the solid electrolyte side after molding.

[0060] The surface of the molded positive electrode 17 on the solid electrolyte portion 15 side is the interface between the molded positive electrode 17 and the solid electrolyte portion 15.

[0061] Plasma treatment can preferably be performed on the workpiece in a vacuum. In the plasma treatment chamber 4b (treatment chamber 46), the workpiece can be treated in a vacuum, and plasma treatment, sputtering, plasma CVD (Chemical Vapor Deposition) treatment, plasma etching treatment, plasma ashing treatment, etc. Plasma treatment is more preferably plasma ashing treatment. Plasma ashing treatment is a treatment in which oxygen plasma is used to react (combine) with organic matter (carbon), vaporize and decompose (ash) as CO2 (remove by gasification of carbon dioxide).

[0062] Plasma treatments such as ashing that do not involve film formation exhibit effects other than suppression of sulfur atom diffusion, such as dehydration and removal of organic matter. Even without sulfur, plasma treatments such as ashing that do not involve film formation result in the formation of a good bond between the positive electrode 17 and the solid electrolyte layer 15 through dehydration and removal of organic matter, and also suppress excess interfacial reactions with moisture, resulting in good cycle characteristics.

[0063] Alternatively, different plasma treatments may be combined.

[0064] [2] All-solid-state battery The all-solid-state battery 1b of the present invention has the following features. The all-solid-state battery 1b of the present invention has a coating film 16 made of an oxide solid electrolyte at the interface between the positive electrode 17 and the solid electrolyte portion 15, and has good cycle characteristics.

[0065] The all-solid-state battery 1b comprises a positive electrode 17, a solid electrolyte 15, and a negative electrode 14 in this order. The positive electrode 17 includes a positive electrode active material 27 and a first solid electrolyte 26. The solid electrolyte section 15 consists of a second solid electrolyte 25.

[0066] The positive electrode active material 27 and the first solid electrolyte 26 of the all-solid-state battery 1b are oxides.

[0067] The second solid electrolyte 25 of the all-solid-state battery 1b is a sulfide.

[0068] The all-solid-state battery 1b has an oxide coating film 16 at the interface between the positive electrode 17 and the solid electrolyte portion 15.

[0069] The all-solid-state battery 1b of the present invention can reduce internal resistance by comprising a solid electrolyte section 15 consisting of a sulfide solid electrolyte (second solid electrolyte 25) with high ionic conductivity.

[0070] In the all-solid-state battery 1b of the present invention, a coating film 16 made of an oxide solid electrolyte is further provided at the interface between the positive electrode 17 and the solid electrolyte portion 15, preferably on the solid electrolyte portion 15 side of the positive electrode 17. This virtually eliminates the interface region where the oxide positive electrode active material 27 and the sulfide second solid electrolyte 25 are in direct contact, thereby suppressing the diffusion of sulfur contained in the second solid electrolyte 25 into the positive electrode active material 27.

[0071] The all-solid-state battery 1b of the present invention suppresses the degradation of the positive electrode active material 27 and improves cycle characteristics. Furthermore, since the all-solid-state battery 1b of the present invention has a coating film 16 only at the interface between the positive electrode 17 and the solid electrolyte portion 15, it has a higher energy density and can suppress an increase in internal resistance compared to coating the entire positive electrode active material 27 (powder). [Examples]

[0072] The all-solid-state battery 1b of the present invention will be explained below with reference to examples.

[0073] However, the present invention is not limited to the examples provided.

[0074] In the examples, "%" for gas refers to "volume flow rate %" unless otherwise specified.

[0075] [1] Manufacturing of all-solid-state batteries A coin-shaped all-solid-state battery 1b with a diameter of approximately φ10 mm was fabricated, and charge / discharge evaluations were performed.

[0076] First, the positive electrode active material 27 (LiNi 0.5 Co 0.2 Mn 0.3 O2) and solid electrolyte (Li 1.3 Al 0.3 Ti 1.7 (PO4)3: The first solid electrolyte 26) was mixed with a binder (polyvinylidene fluoride) and a conductive additive (acetylene black), and the mixture was compacted to produce a positive electrode 17.

[0077] Next, a sputtering treatment is performed on the surface of the positive electrode 17 under the conditions of an atmosphere containing oxygen (5%) and argon (95%), a pressure of 0.8 Pa, a high-frequency power of 150 W, and room temperature, to form an oxide coating film 16 (Li 1.3 Al 0.3 Ti 1.7 (PO4)3) was deposited as a film with a thickness of 7.5 nm to 45 nm.

[0078] Finally, a compacted solid electrolyte 15 (Li6PS5Cl: second solid electrolyte 25) was laminated onto the plasma-treated side of the positive electrode 17, and the negative electrode 14 (Li / In) was laminated on top of it.

[0079] [2] Evaluation of all-solid-state batteries Figure 5 illustrates the cycle characteristics of an all-solid-state battery 1b having the oxide coating film 16 of the present invention, in comparison with an example without the oxide coating film 16.

[0080] The charge and discharge capacity was evaluated under the conditions of a voltage range of 1.9V to 3.7V and a charge / discharge rate of 0.1CA.

[0081] The all-solid-state battery 1b of the present invention has an oxide coating film 16 at the interface between the positive electrode 17 and the solid electrolyte portion 15, and exhibited better cycle characteristics compared to an example without the oxide coating film 16.

[0082] Based on the evaluation of the charge and discharge capacity, it is considered that the amount of sulfur contained in the second solid electrolyte 25 diffusing into the positive electrode active material 27 was suppressed, even with a film deposition amount on the order of nanometers on the positive electrode surface which has irregularities on the order of micrometers.

[0083] However, these factors and mechanisms are speculative and do not limit the technical scope of this disclosure. [Industrial applicability]

[0084] The all-solid-state battery of the present invention can improve cycle characteristics. Furthermore, the all-solid-state battery of the present invention can increase energy density and suppress the increase in internal resistance. [Explanation of Symbols]

[0085] 1a (Conventional) All-Solid-State Battery 11 Negative electrode 12 Solid electrolyte section 13 Positive electrode 1b (The present invention) All-solid-state battery 14 Negative electrode 15 Solid electrolyte section 16 Coating film 17 Positive electrode 21. Second Solid Electrolyte 22. First Solid Electrolyte 23 Cathode active material 24 Coating film 25. Second Solid Electrolyte 26. First solid electrolyte 27 Cathode active material 4a Load Lock Room 4b Plasma Processing Room 41 Gas piping 42 Vacuum piping 43 Vacuum piping 44 Vessel 44a Vessel Plate 44b Vessel cover 44c Sample Holder 44d Screw fastening part (of the opening / closing drive unit) 44e Dovetail groove for O-ring 46 Processing Room 47 Sample transport mechanism 48 Antennas

Claims

1. All-solid-state battery, The all-solid-state battery comprises a positive electrode, a solid electrolyte, and a negative electrode in this order. The positive electrode comprises a positive electrode active material and a first solid electrolyte. The solid electrolyte portion consists of a second solid electrolyte. The positive electrode active material and the first solid electrolyte are oxides. The second solid electrolyte is a sulfide, The all-solid-state battery is an all-solid-state battery having an oxide coating film at the interface between the positive electrode and the solid electrolyte portion.

2. The all-solid-state battery according to claim 1, wherein the oxide coating film coats the positive electrode active material forming the positive electrode and the first solid electrolyte at the interface between the positive electrode and the solid electrolyte portion.

3. The all-solid-state battery according to claim 1, wherein the oxide coating film is provided on the surface of the positive electrode on the solid electrolyte side at the interface between the positive electrode and the solid electrolyte.

4. The positive electrode active material comprises lithium (Li), nickel (Ni), manganese (Mn), cobalt (Co), and oxygen (O). The first solid electrolyte comprises lithium (Li), aluminum (Al), titanium (Ti), phosphorus (P), and oxygen (O). The all-solid-state battery according to claim 1, wherein the second solid electrolyte comprises lithium (Li), phosphorus (P), sulfur (S), and chlorine (Cl).

5. The positive electrode active material is LiNi 0.5 Mn 0.2 Co 0.3 O 2 And, The first solid electrolyte is Li 1.3 Al 0.3 Ti 1.7 (PO 4 ) 3 and The previous second solid electrolyte is Li 6 PS 5 Cl is The all-solid-state battery according to claim 1.

6. The oxide coating film has a thickness of 7.5 nm to 45 nm. The all-solid-state battery according to claim 1.

7. The oxide coating film is formed from components containing lithium (Li), aluminum (Al), titanium (Ti), phosphorus (P), and oxygen (O). The all-solid-state battery according to claim 1.

8. The oxide coating film is Li 1.3 Al 0.3 Ti 1.7 (PO 4 ) 3 It is formed by The all-solid-state battery according to claim 1.

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