JP2008135287A - All-solid battery member and manufacturing method of the member, and all-solid battery - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an all-solid battery with excellent battery characteristics capable of reducing interface resistance between an electrode material layer and a solid electrolyte layer by enlarging a contact and jointing area of the electrode material layer and the solid electrolyte layer in the all-solid battery. <P>SOLUTION: The all-solid battery member has a thin film layer with a thickness of 10 nm-1 μm and a solid electrolyte layer with a thickness of 1-500 μm laminated in this order on an electrode material layer, and the thin film layer is composed of same material as the solid electrolyte layer and same material as the electrode material layer or an admixture of these. Furthermore, the all-solid battery has a solid electrolyte layer with a thickness of 1-500 μm interposed between a positive electrode layer and a negative electrode layer and further, has respectively a thin film layer with a thickness of 10 nm-1 μm between the positive electrode layer and the negative electrode layer and the solid electrolyte layer, and the two thin film layers are respectively composed of same material as the solid electrolyte layer and same material as the electrode material layer or an admixture of these. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to an all-solid battery member, a method for producing the member, and an all-solid battery.

In recent years, the demand for secondary batteries such as high-performance lithium batteries used in personal digital assistants, portable electronic devices, small household power storage devices, motorcycles powered by motors, electric vehicles, hybrid electric vehicles, etc. has increased. Yes. As described above, as the applications for use expand, further improvements in safety and performance of secondary batteries are required.
In order to ensure the safety of the lithium battery, it is effective to use an inorganic solid electrolyte instead of the organic solvent electrolyte. Inorganic solid electrolytes are generally nonflammable or flame retardant in nature and are safer materials than commonly used organic solvent electrolytes. Therefore, development of an all-solid lithium battery with high safety using the electrolyte is desired.

  By the way, in an all-solid-state battery, in order to achieve interfacial bonding between the electrode material layer (positive electrode layer and negative electrode layer) and the electrolyte layer, the battery itself is pressurized or the particle diameter of the material forming the electrode material layer and the electrolyte layer is adjusted. It was necessary to control the combination and secure the contact surface. Here, the smaller the particle size of the material forming the electrolyte layer, the larger the contact area. However, it is difficult to pulverize the solid electrolyte to, for example, the submicron order, and the electrolyte and electrode material having a particle size of the micron order are joined. However, good interface bonding could not be obtained.

  For example, Patent Document 1 discloses a lithium ion conductive solid electrolyte using lithium sulfide and phosphorous pentasulfide as raw materials, a negative electrode material produced by mixing the solid electrolyte and carbon graphite, and lithium cobalt oxide as a positive electrode active material. An all-solid secondary battery manufactured by combining positive electrode materials is disclosed (see Patent Document 1 and Example 3). This all-solid-state secondary battery shows an excellent operating potential of 3.5 V. However, since the lithium ion conductive solid electrolyte is not in the submicron order, the negative electrode layer is formed by mixing with carbon graphite as a negative electrode active material. Even if it is formed, it is not always sufficient to secure the joint surface with the solid electrolyte layer, and further improvement has been desired particularly in terms of discharge current density and the like.

  Patent Document 2 discloses a method for forming an inorganic solid electrolyte thin film substantially composed of Li, P, and S. A lithium ablation method, a vacuum evaporation method, a sputtering method, an ion plating method, and a lithium metal A thin film layer of about 0.5 μm made of the inorganic solid electrolyte is formed on the thin film. However, although Patent Document 2 discloses a secondary battery using the laminate obtained by the method together with an organic electrolyte, there is no description of an all-solid battery using this, and therefore the above-mentioned in all-solid batteries is described. There is no disclosure or suggestion about such issues.

International Publication 2005/119706 JP 2005-32731 A

  In view of the above problems, the present invention increases the contact / bonding area between the electrode material layer and the solid electrolyte layer in the all-solid battery, lowers the interface resistance between the electrode material layer and the solid electrolyte layer, and provides good battery characteristics. I want to get it.

  As a result of intensive research, the inventors have deposited nano-level sputtered grains and nano-level fine grains generated by ion beam or resistance heating on the surface of the electrode material layer to form a specific thin film layer. Thus, it has been found that the contact / joint area between the electrode material layer and the solid electrolyte layer can be increased. The present invention has been completed based on such findings.

That is, the present invention
[1] An all-solid battery member in which a thin film layer having a thickness of 10 nm to 1 μm and a solid electrolyte layer having a thickness of 1 to 500 μm are laminated in this order on an electrode material layer, the thin film layer being a solid electrolyte layer An all-solid-state battery member comprising the same material, the same material as the electrode layer, or a mixture thereof,
[2] The above-mentioned [1], wherein the thin film layer is obtained by a vapor deposition method or a chemical vapor deposition method (CVD method), and the solid electrolyte layer is obtained by coating, spraying, coating, or powder compression by fine particle collision. A member for an all-solid-state battery,
[3] A thin film layer having a thickness of 10 nm to 1 μm is formed on the electrode material layer by vapor deposition or chemical vapor deposition (CVD), and coating, spraying, coating, or powdering by fine particle collision is formed thereon. A method for producing an all-solid battery member in which a solid electrolyte layer having a thickness of 1 to 500 μm is formed by compression of a body, wherein the thin film layer is the same material as the solid electrolyte layer, the same material as the electrode material layer, or these A method for producing a member for an all-solid-state battery, comprising a mixture,
[4] A solid electrolyte layer having a thickness of 1 to 500 μm is formed, and a thin film layer having a thickness of 10 nm to 1 μm is formed on the surface of the solid electrolyte layer by a vapor deposition method or a chemical vapor deposition method (CVD method). Further, a method for producing an all-solid battery member in which an electrode material layer is provided thereon, wherein the thin film layer is made of the same material as the solid electrolyte layer, the same material as the electrode material layer, or a mixture thereof. A method for producing an all-solid battery member,
[5] The method for producing an all-solid battery member according to the above [4], wherein the solid electrolyte layer is obtained by coating or compressing powder.
[6] An all solid state battery in which a thin film layer having a thickness of at least 10 nm to 2 μm is interposed between the positive electrode layer and the negative electrode layer, wherein the thin film layer is made of a solid electrolyte material,
[7] An all-solid battery obtained by laminating a thin film layer having a thickness of 10 nm to 1 μm on each of the positive electrode layer and the negative electrode layer and bonding the thin film layers, and at least one of the two thin film layers is made of a solid electrolyte material. An all-solid-state battery,
[8] The all-solid-state battery according to the above [6] or [7], wherein the thin film layer is obtained by vapor deposition or chemical vapor deposition (CVD).
[9] An all-solid battery in which a solid electrolyte layer having a thickness of 1 to 500 μm is interposed between a positive electrode layer and a negative electrode layer, and each of the positive electrode layer, the negative electrode layer, and the solid electrolyte layer is further thickened. An all-solid battery comprising a thin film layer having a thickness of 10 nm to 1 μm, wherein the two thin film layers are each made of the same material as the solid electrolyte layer, the same material as the electrode layer, or a mixture thereof,
[10] A method for producing an all-solid-state battery in which a thin film layer having a thickness of 10 nm to 2 μm is formed on an electrode material layer by vapor deposition or chemical vapor deposition (CVD method), and an electrode material layer is provided thereon. ,
[11] A first thin film layer having a thickness of 10 nm to 1 μm is formed on the electrode material layer by vapor deposition or chemical vapor deposition (CVD), and vapor deposition or chemical vapor is formed thereon. An all-solid-state battery manufacturing method in which a second thin film layer having a thickness of 10 nm to 1 μm is formed by a vapor deposition method (CVD method), and an electrode material layer is further provided thereon;
[12] A first thin film layer having a thickness of 10 nm to 1 μm is formed on the electrode material layer by vapor deposition or chemical vapor deposition (CVD), and coating, spraying by fine particle collision, A solid electrolyte layer having a thickness of 1 to 500 μm is formed by coating or powder compression to produce a member for an all solid state battery, and a vapor deposition method or a chemical vapor deposition method (CVD method) is formed on the other electrode material layer. ) To form a second thin film layer having a thickness of 10 nm to 1 μm to produce an electrode, and join the all-solid battery member and the electrode so that the solid electrolyte layer and the second thin film layer are in contact with each other. A method of manufacturing a battery, wherein the first thin film layer and the second thin film layer are each made of the same material as the solid electrolyte layer, the same material as the electrode material layer, or a mixture thereof. Solid battery manufacturing method,
[13] A method for producing an all-solid battery, comprising preparing two members for an all-solid battery according to [1] or [2], and joining the members for an all-solid battery so that the respective solid electrolyte layers are in contact with each other. ,
[14] A first thin film layer having a thickness of 10 nm to 1 μm is formed on the electrode material layer by vapor deposition or chemical vapor deposition (CVD), and coating, spraying by fine particle collision, A solid electrolyte layer having a thickness of 1 to 500 μm is formed by coating or powder compression, and a second thin film layer having a thickness of 10 nm to 1 μm is formed thereon by a vapor phase growth method or a chemical vapor deposition method (CVD method). An all-solid battery manufacturing method in which an electrode material layer is further formed thereon, wherein the first thin film layer and the second thin film layer are the same material and the same electrode material layer as the solid electrolyte layer, respectively. An all-solid-state battery manufacturing method comprising a material or a mixture thereof,
[15] A solid electrolyte layer having a thickness of 1 to 500 μm is formed, and a thin film layer having a thickness of 10 nm to 1 μm is formed on the front and back surfaces of the solid electrolyte layer by vapor deposition or chemical vapor deposition (CVD), respectively. An all-solid battery manufacturing method in which an electrode material layer is further formed thereon, wherein the two thin film layers are made of the same material as the solid electrolyte layer, the same material as the electrode material layer, or a mixture thereof. A method for producing an all-solid battery, and [16] an assembled battery obtained by combining the all-solid battery according to any one of [6] to [9],
Is to provide.

  According to the present invention, the contact / bonding area between the electrode material layer and the solid electrolyte layer in the all-solid battery can be increased, the interfacial resistance between the electrode material layer and the solid electrolyte layer can be reduced, and all the batteries having good battery characteristics can be obtained. A solid state battery can be provided. Moreover, according to this invention, a thin all-solid-state battery can be provided.

The all-solid-state battery member of the present invention is formed by laminating a thin film layer having a thickness of 10 nm to 1 μm and a solid electrolyte layer having a thickness of 1 to 500 μm in this order on an electrode material layer.
Here, the electrode material layer means a positive electrode layer and a negative electrode layer in an all solid state battery.

[Positive electrode material]
The positive electrode material constituting the positive electrode layer is not particularly limited as long as it is used as a positive electrode active material in the battery field. For example, in a sulfide system, titanium sulfide (TiS ₂ ), molybdenum sulfide (MoS ₂ ). Iron sulfide (FeS, FeS ₂ ), copper sulfide (CuS), nickel sulfide (Ni ₃ S ₂ ) and the like can be used. Of these, TiS ₂ can be suitably used in the present invention.
In the oxide system, bismuth oxide (Bi ₂ O ₃ ), bismuth leadate (Bi ₂ Pb ₂ O ₅ ), copper oxide (CuO), vanadium oxide (V ₆ O ₁₃ ), lithium cobaltate (LiCoO ₂ ) Lithium nickelate (LiNiO ₂ ), lithium manganate (LiMnO ₂ ) and the like can be used. These may be used alone or in combination of two or more. Of these, lithium cobaltate is particularly preferred in the present invention.
In addition to the above, niobium selenide (NbSe ₃ ) can also be used.
Moreover, what is called a positive electrode mixture formed by mixing said compound and the solid electrolyte used by the electrolyte layer mentioned later as a positive electrode material can also be used. Hereinafter, in the present invention, the positive electrode material includes this positive electrode mixture.

  Moreover, in the positive electrode material, a substance having electrical conductivity for allowing electrons to move smoothly in the positive electrode active material may be appropriately added as a conductive assistant. The electrically conductive substance is not particularly limited, but a conductive carbon material such as acetylene black, carbon black, and carbon nanotube or a conductive polymer such as polyaniline, polyacetylene, and polypyrrole is used alone. Or 2 or more types can be mixed and used.

[Negative electrode material]
Next, the negative electrode material is not particularly limited as long as it is used as a negative electrode active material in the battery field. For example, a carbon material, specifically, artificial graphite, graphite carbon fiber, resin-fired carbon, heat Decomposed vapor-grown carbon, coke, mesocarbon microbeads (MCMB), furfuryl alcohol resin calcined carbon, polyacene, pitch-based carbon fiber, vapor-grown carbon fiber, natural graphite and non-graphitizable carbon. These may be used alone or in combination of two or more. Of the above materials, artificial graphite is particularly preferable.
A metal such as metallic lithium, metallic indium, metallic aluminum, metallic silicon, or an alloy obtained by combining these metals with another element or compound can also be used as the negative electrode material.
Furthermore, a so-called negative electrode mixture formed by mixing the carbon material, metal, or the like and a solid electrolyte used in an electrolyte layer described later can also be used. Hereinafter, in the present invention, the negative electrode material includes this negative electrode mixture.

[Formation of electrode material layer]
In a solid electrode material (electrode material) that is a member of an all-solid battery, in order to improve ion conductivity in addition to electron conductivity, the particles of the electrode material are in close contact with each other, and the junction points and surfaces between the particles are determined. It is important to ensure that there are many ion conduction paths. Therefore, as described above, for example, a method in which an ion conductive active material such as an electrolyte is mixed to form an electrode material is used.
In addition, the smaller the space generated in the gaps between the polar particles (the ratio of the volume of the polar particles to the volume of the polar particles: the porosity), the denser the polar layer and the higher the ionic conductivity. preferable.

The electrode material layer in the present invention can be produced by forming the electrode material (positive electrode material or negative electrode material) in a film shape on at least a part of the current collector. Examples of the film forming method include a blast method, an aerosol deposition method, a cold spray method, a sputtering method, a vapor deposition method, and a thermal spraying method. Alternatively, the electrode material layer can be formed by a method in which the electrode material is dissolved and applied to a current collector, or a method in which the electrode material is compressed and laminated on the current collector.
By forming a film by such a method, the porosity of the electrode material layer can be further reduced, and the ionic conductivity can be improved.
Among the above methods, the blast method and the aerosol deposition method are preferable because they are simple apparatuses and can be formed at room temperature, that is, in a temperature range that does not change the crystal state of the electrolyte.
In the present invention, the current collector is a plate or foil made of copper, magnesium, stainless steel, titanium, iron, cobalt, nickel, zinc, aluminum, germanium, indium, lithium, or an alloy thereof. Etc. can be used.

[Formation of thin film layer]
The member for an all-solid-state battery of the present invention is characterized in that a thin film layer having a thickness of 10 nm to 1 μm is laminated on the electrode material layer. The thin film layer functions to increase the contact / bonding area between the electrode material layer and the solid electrolyte layer in the all-solid battery and to reduce the interface resistance between the electrode material layer and the solid electrolyte layer.
As the material constituting the thin film layer, the same material as the material constituting the solid electrolyte layer described later, the same material as the material constituting the electrode layer, or a mixture thereof is used. By using these materials, the interface resistance between the electrode material layer and the solid electrolyte layer can be reduced. Here, the material constituting the electrode material layer means the material constituting the electrode material layer in contact with the thin film layer, and means that the material in the thin film layer in contact with the positive electrode layer is the same as the material of the positive electrode layer, In the thin film layer which touches a negative electrode layer, it means that it is the same as the material of a negative electrode layer.
The thickness of the thin film layer is in the range of 10 nm to 1 μm. When the thickness is less than 10 nm, the thin film may not be uniformly formed on the electrode material layer, which is not preferable. On the other hand, if the thickness of the thin film layer exceeds 1 μm, it is not preferable in terms of productivity of the member for an all solid state battery. From the above viewpoint, the thickness of the thin film layer is more preferably in the range of 50 nm to 1 μm, and particularly preferably in the range of 50 nm to 500 nm.

  The thin film layer is usually formed by laminating materials constituting the thin film layer in the form of fine particles, and the average particle diameter of the fine particles is preferably in the range of 10 to 500 nm. By having an average particle diameter in this range, the interface resistance between the electrode material layer and the solid electrolyte layer can be effectively reduced. From the above viewpoint, the average particle size of the material constituting the thin film layer is more preferably in the range of 10 to 50 nm.

Next, there are various methods for forming the thin film layer, but a vapor deposition method or a chemical vapor deposition method (CVD method) is preferable. More specifically, a sputtering method, a vacuum deposition method, a laser ablation method, an ion plating method, and the like can be given. Note that the degree of vacuum in the vapor phase growth method is preferably 1.33 × 10 ⁻⁴ Pa (1 × 10 ⁻⁶ Torr) or less.

[Formation of solid electrolyte layer]
The all-solid-state battery member of the present invention is formed by laminating the thin film layer and a solid electrolyte layer having a thickness of 1 to 500 μm in this order on an electrode material layer.
If the thickness of the solid electrolyte layer is less than 1 μm, a short circuit may occur in the electrolyte layer, and if it exceeds 500 μm, ion conductivity may be lowered. From the above viewpoint, the thickness of the solid electrolyte layer is more preferably in the range of 10 to 100 μm.

There are various methods for forming the solid electrolyte layer, and methods such as coating by fine particle collision, thermal spraying, coating, and powder compression are preferable.
Coating by fine particle collision is a method of forming a film made of microcrystals by spraying submicron diameter raw material powder at high speed under a low vacuum, and includes an aerosol deposition method (AD method), a gas deposition method ( GD method), cold spray method, sand blast method (SB method) and the like.
Among these, it is particularly preferable to use the AD method. The AD method is suitable for forming a solid electrolyte layer made of a lithium ion conductive solid material by mixing a solid material in the form of fine particles or ultrafine particles with a gas to form an aerosol and injecting it into a thin film layer through a nozzle. According to this method, the electrolyte layer can be formed without exposing the lithium ion conductive solid material to a high temperature.
In addition, for example, Japanese Patent Application Laid-Open No. 2004-213938 and Japanese Patent Application Laid-Open No. 2005-78985 can be referred to for apparatuses and film forming conditions used in the AD method.
Next, thermal spraying is a method in which a solid electrolyte is heated and melted and sprayed with a gas or the like, and coating is a solution in which a solid electrolyte is mixed with a solvent or a binder (such as a binder or a polymer compound). After coating, the solvent is removed to form a film. In addition, the compression of the powder means that the solid electrolyte itself, the solid electrolyte and the binder (binder, polymer compound, etc.) and the support (strengthening the strength of the solid electrolyte layer or preventing short circuit of the solid electrolyte itself) A method of forming a film by press-pressing a mixture of materials and compounds.
In addition, it is preferable that the average particle diameter of the solid electrolyte which comprises a solid electrolyte layer is the range of 1-10 micrometers in the point which can form a thinner solid electrolyte layer.

The solid battery member of the present invention can be produced by laminating a thin film layer and a solid electrolyte layer on the electrode material layer as described above.
In addition, a solid electrolyte layer having a thickness of 1 to 500 μm is previously formed, and a thin film having a thickness of 10 nm to 1 μm is formed on the surface of the solid electrolyte layer by a vapor deposition method or a chemical vapor deposition method (CVD method). The solid battery member of the present invention can also be produced by forming a layer and further providing an electrode material layer thereon.
Here, the method for forming the solid electrolyte layer is not particularly limited, and it can also be obtained by compressing the powder, coating the solid electrolyte on the substrate by fine particle collision, or spraying and applying the solid electrolyte. Can do. Of these, a method by compression of powder or a method by coating, which is simple, is particularly preferable.
In addition, as a method of providing an electrode material layer, for example, a method of laminating an electrode material layer on a solid electrolyte layer, pressurizing and pressure bonding, a method of applying pressure between two rolls (roll to roll), and the like. is there

[Solid electrolyte]
Next, the solid electrolyte used in the present invention will be described in detail below.
Although it does not specifically limit as a solid electrolyte used by this invention, A lithium ion conductive solid electrolyte is preferable from a viewpoint that it is a high output battery. The substance which comprises a lithium ion conductive solid electrolyte is not specifically limited, The material which consists of an organic compound, an inorganic compound, or both organic and inorganic compounds can be used, A well-known thing can be used in the lithium ion battery field | area. However, the solid electrolyte used for the thin film layer formed on the electrode material layer is required to be able to use a technique called vapor deposition or chemical vapor deposition (CVD).

  As such a solid electrolyte, a sulfide-based inorganic solid electrolyte is preferably used. A sulfide-based inorganic solid electrolyte is known to have higher ionic conductivity than other inorganic compounds, and an inorganic solid electrolyte described in JP-A-4-202024 can be used. Specifically, an inorganic solid electrolyte obtained by appropriately adding Li3PO4, a halogen, or a halogen compound to an inorganic solid electrolyte composed of a combination of Li2S and SiS2, GeS2, P2S5, and B2S3 can be used. However, as described in Japanese Patent Application Laid-Open No. 2005-32731, it is necessary to consider compatibility with the material of the pole material, and it is necessary to select a compatible inorganic solid electrolyte.

  Lithium sulfide and diphosphorus pentasulfide, or lithium sulfide and simple phosphorus and simple sulfur, as well as lithium sulfide, diphosphorus pentasulfide, simple phosphorus and the like in terms of compatibility with the electrode material or high lithium ion conductivity It is preferable to use a lithium ion conductive inorganic solid electrolyte generated from / or elemental sulfur. Hereinafter, a preferable solid electrolyte will be described.

The lithium ion conductive inorganic solid electrolyte can be produced from lithium sulfide and diphosphorus pentasulfide (P ₂ S ₅ ) and / or simple phosphorus and simple sulfur. Specifically, as described in detail later, these raw materials can be melt-reacted and then rapidly cooled. In addition, sulfide glass obtained by treating these raw materials by a mechanical milling method (hereinafter, sometimes referred to as MM method), or a heat-treated product thereof.

As lithium sulfide, those commercially available without limitation can be used, but those having high purity are preferable as described below.
That is, lithium sulfide has a total content of at least a lithium salt of sulfur oxide of 0.15% by mass or less, preferably 0.1% by mass or less, and a content of lithium N-methylaminobutyrate of 0.15%. It is not more than mass%, preferably not more than 0.1 mass%. When the total content of the lithium salt of sulfur oxide is 0.15% by mass or less, the solid electrolyte obtained by the melt quenching method or the mechanical milling method described later is a glassy electrolyte (fully amorphous). That is, when the total content of the lithium salt of sulfur oxide exceeds 0.15% by mass, the obtained electrolyte is a crystallized product from the beginning, and the ionic conductivity of this crystallized product is low. Furthermore, even if the crystallized product is subjected to the following heat treatment, the crystallized product is not changed, and a lithium ion conductive inorganic solid electrolyte having a high ion conductivity cannot be obtained.

Further, when the content of lithium N-methylaminobutyrate is 0.15% by mass or less, the deteriorated product of lithium N-methylaminobutyrate does not deteriorate the cycle performance of the lithium battery.
Thus, in order to obtain a high ion conductive electrolyte, it is necessary to use lithium sulfide with reduced impurities.

  The method for producing lithium sulfide used in the production of the high ion conductive electrolyte is not particularly limited as long as it can reduce at least the above-mentioned impurities. For example, the method described in JP-A-7-330312 can be employed. . Although there is no restriction | limiting in particular as a purification method of lithium sulfide, As a preferable purification method, the method as described in international publication WO2005 / 40039 etc. is mentioned, for example.

Any phosphorous pentasulfide (P ₂ S ₅ ) can be used without particular limitation as long as it is industrially produced and sold. In place of P ₂ S ₅ , elemental phosphorus (P) and elemental sulfur (S) in a corresponding molar ratio can also be used. Simple phosphorus (P) and simple sulfur (S) can be used without particular limitation as long as they are industrially produced and sold.

  In the present invention, as the solid electrolyte, both a glassy solid electrolyte and a solid electrolyte containing a crystal component can be used. The type should be selected according to the required characteristics. Both may be used.

The mixing molar ratio of the lithium sulfide to diphosphorus pentasulfide or simple phosphorus and simple sulfur is usually 50:50 to 80:20, preferably 60:40 to 75:25. Particularly preferably, it is about Li ₂ S: P ₂ S ₅ = 68: 32 to 74:26 (molar ratio).

Examples of the method for producing a sulfide glass that is a glassy electrolyte include a melt quenching method and a mechanical milling method.
In the case of the melt quenching method, a predetermined amount of P ₂ S ₅ and Li ₂ S are mixed in a mortar, and the pellets are placed in a carbon-coated quartz tube and sealed in a vacuum. After reacting at a predetermined reaction temperature, the glass is put into ice and quenched to obtain a sulfide glass.
The reaction temperature at this time is preferably 400 ° C to 1000 ° C, more preferably 800 ° C to 900 ° C. Moreover, reaction time becomes like this. Preferably it is 0.1 to 12 hours, More preferably, it is 1 to 12 hours. The quenching temperature of the reaction product is usually 10 ° C. or lower, preferably 0 ° C. or lower, and the cooling rate is about 1 to 10,000 K / sec, preferably 1 to 1000 K / sec.

In the case of the MM method, sulfide glass is obtained by mixing a predetermined amount of P ₂ S ₅ and Li ₂ S in a mortar and reacting for a predetermined time.
The mechanical milling method using the above raw materials can be reacted at room temperature. According to the MM method, since a glassy electrolyte can be produced at room temperature, there is an advantage that a raw material is not thermally decomposed and a glassy electrolyte having a charged composition can be obtained. Further, the MM method has an advantage that the glassy electrolyte can be made into fine powder simultaneously with the production of the glassy electrolyte.

Although various types of pulverization methods can be used for the MM method, it is particularly preferable to use a planetary ball mill. The planetary ball mill can efficiently generate very high impact energy by rotating the platform while the pot rotates.
Although the rotation speed and rotation time of the MM method are not particularly limited, the faster the rotation speed, the faster the glassy electrolyte production rate, and the longer the rotation time, the higher the conversion rate of the raw material into the glassy electrolyte.

The electrolyte thus obtained is a glassy electrolyte and usually has an ionic conductivity of about 1.0 × 10 ^{−5 to} 8.0 × 10 ⁻⁴ (S / cm).
As conditions for the MM method, for example, when a planetary ball mill is used, the rotational speed is set to several tens to several hundreds of revolutions / minute, and the treatment may be performed for 0.5 hours to 100 hours.
Although specific examples of the sulfide glass by the melt quenching method and the MM method have been described above, manufacturing conditions such as temperature conditions and processing time can be appropriately adjusted according to the equipment used.

Thereafter, the obtained sulfide glass is heat-treated at a predetermined temperature to produce a solid electrolyte containing a crystal component. The heat treatment temperature for producing such a solid electrolyte is preferably 190 ° C to 340 ° C, more preferably 195 ° C to 335 ° C, and particularly preferably 200 ° C to 330 ° C. When the temperature is lower than 190 ° C., it may be difficult to obtain a crystal with high ion conductivity. When the temperature is higher than 340 ° C., a crystal with low ion conductivity may be generated.
In the case of a temperature of 190 ° C. or higher and 220 ° C. or lower, the heat treatment time is preferably 3 to 240 hours, particularly preferably 4 to 230 hours. Moreover, in the case of the temperature higher than 220 degreeC and 340 degrees C or less, 0.1 to 240 hours are preferable, 0.2 to 235 hours are especially preferable, Furthermore, 0.3 to 230 hours are preferable. If the heat treatment time is shorter than 0.1 hour, it may be difficult to obtain a crystal with high ion conductivity, and if it is longer than 240 hours, a crystal with low ion conductivity may be formed.
The lithium ion conductive inorganic solid electrolyte containing the crystal component thus obtained usually has an ionic conductivity of about 7.0 × 10 ^{−4 to} 5.0 × 10 ⁻³ (S / cm). It is.

  This lithium ion conductive inorganic solid electrolyte has 2θ = 17.8 ± 0.3 deg, 18.2 ± 0.3 deg, 19.8 ± 0.3 deg, X-ray diffraction (CuKα: λ = 1.5418４), It is preferable to have diffraction peaks at 21.8 ± 0.3 deg, 23.8 ± 0.3 deg, 25.9 ± 0.3 deg, 29.5 ± 0.3 deg, 30.0 ± 0.3 deg. A solid electrolyte having such a crystal structure has extremely high lithium ion conductivity.

The lithium ion conductive solid material used in the present invention is also a solid electrolyte containing lithium (Li) element, phosphorus (P) element and sulfur (S) element, and the following (1) and (2) Those satisfying the condition are preferred.
(1) The solid ³¹ P-NMR spectrum of the solid electrolyte has peaks due to crystals at 90.9 ± 0.4 ppm and 86.5 ± 0.4 ppm.
(2) The ratio (xc) of crystals that produce the peak (1) in the solid electrolyte is 60 mol% to 100 mol%.
The two peaks of condition (1) are observed when a high ion conductive crystal component is present in the solid electrolyte. Specifically, a peak due to P ₂ S ₇ ^4- and PS ₄ ^3- in the crystal.

Condition (2) defines the ratio xc of the crystal in the solid electrolyte. When a high ion conductive crystal component is present in a predetermined amount or more, specifically 60 mol% or more in the solid electrolyte, lithium ions move mainly through the high ion conductive crystal. Therefore, the non-crystalline portion in the solid electrolyte (glass portion) and a crystal lattice that does not exhibit high ionic conductivity (e.g., P ₂ S ₆ ^4-) than when moving, thereby improving lithium ion conductivity. The ratio xc is preferably 65 mol% to 100 mol%. The crystal ratio xc can be controlled by adjusting the heat treatment time and temperature of the sulfide glass as a raw material.

The solid ³¹ P-NMR spectrum can be measured, for example, using a JNM-CMXP302 NMR apparatus manufactured by JEOL Ltd., with an observation nucleus of ³¹ P, an observation frequency of 121.339 MHz, a measurement temperature of room temperature, and a measurement method. Performed as MAS method.
The method for measuring the ratio xc is to calculate a resonance line observed at 70 to 120 ppm into a Gaussian curve using a nonlinear least square method and calculate from the area ratio of each curve for the solid ³¹ P-NMR spectrum. For details, refer to Japanese Patent Application No. 2005-356889.

In this solid electrolyte, the spin-lattice relaxation time T _1Li at room temperature (25 ° C.) measured by solid-state ⁷ Li-NMR method is preferably 400 ms or less. Relaxation time T _1Li becomes a molecular mobility of indicators in the solid electrolyte in comprising a glass state or a crystalline state and a glass state, molecular mobility is high and T _1Li short. Accordingly, since lithium ions are easily diffused during discharge, the ion conductivity is increased. In the present invention, as described above, since a high ion conductive crystal component is contained in a predetermined amount or more, T _1Li can be 400 ms or less. T _1Li is preferably 350 ms or less.

The spin-lattice relaxation time T _1Li of ⁷ Li can be obtained, for example, as follows.
When a JNM-CMXP302 NMR apparatus manufactured by JEOL Ltd. is used and measured under the following conditions, a ⁷ Li-NMR spectrum having a peak in the range of 0-1 ppm is obtained.
· NMR measurement conditions observing nucleus: ⁷ Li
Observation frequency: 116.489 MHz
Measurement temperature: Room temperature (25 ° C)
Measurement method: Saturation recovery method (Pulse sequence: see FIG. 7 of Japanese Patent Application No. 2005-356889)
90 ° pulse width: 4μs
Magic angle rotation speed: 6000Hz
Wait time until the next pulse application after FID measurement: 5s
Accumulation count: 64 times The chemical shift is determined using LiBr (chemical shift-2.04 ppm) as an external reference.

T 1 _Li is obtained by optimizing the change in the intensity of this peak obtained when measurement is performed by changing τ in FIG. 7 of Japanese Patent Application No. 2005-356889 using the nonlinear least square method. decide.

M (τ) = M (∞) (1-e ⁻ τ ^{/ T1Li} )

  M (τ): Peak intensity at τ

This solid electrolyte has a decomposition voltage of at least 10V or more. Further, while maintaining the property that the lithium ion transport number is 1, it exhibits extremely high lithium ion conductivity of 10 ⁻³ S / cm level at room temperature. Therefore, it is extremely suitable as a material for a solid electrolyte of a lithium battery. Moreover, it is a solid electrolyte excellent in heat resistance.

[All-solid battery]
Next, the all solid state battery of the present invention will be described with reference to FIG.
In the all solid state battery 1 of the present invention, a solid electrolyte layer (second solid electrolyte layer) 2 having a thickness of 1 to 500 μm is interposed between a positive electrode layer 4 and a negative electrode layer 5 respectively provided on a current collector 6. The thin film layers 3 and 3 ′ having a thickness of 10 nm to 1 μm are further provided between the positive electrode layer 4 and the solid electrolyte layer 2 and between the negative electrode layer 5 and the solid electrolyte layer 2, respectively.
As the material constituting the thin film layers 3 and 3 ′, the same material as the material constituting the solid electrolyte layer, the same material as the material constituting the electrode layer, or a mixture thereof is used. The two thin film layers 3 and 3 ′ may be formed of the same material or different materials. For example, the thin film layer 3 on the positive electrode layer 4 side is formed of a solid electrolyte, and the negative electrode The thin film layer 3 ′ on the layer 5 side may be made of the same material as that of the negative electrode layer 5. On the other hand, the thin film layer 3 ′ on the negative electrode layer 5 side may be formed of a solid electrolyte, and the thin film layer 3 on the positive electrode layer 4 side may be made of the same material as that of the positive electrode layer 4. Further, the thin film layer 3 on the positive electrode layer 4 side is made of the same material as the material constituting the positive electrode layer 4, and the thin film layer 3 ′ on the negative electrode layer 5 side is made of the same material as the material constituting the negative electrode layer 5. You may comprise.

When at least one of the thin film layers 3 and 3 ′ is the same as the material constituting the solid electrolyte layer, the solid battery of the present invention may have a configuration in which the solid electrolyte layer 2 is not interposed. That is, the all solid state battery of the present invention in this aspect is an all solid state battery in which a thin film layer having a thickness of 10 nm to 1 μm is laminated on each of a positive electrode layer and a negative electrode layer, and the thin film layers are joined. At least one of the layers is made of a solid electrolyte material. By adopting such a configuration, it is possible to obtain a thin all-solid battery that has sufficient performance as a solid battery and has no problems such as a short circuit.
When one of the thin film layers is made of a solid electrolyte material, the other thin film layer may be a solid electrolyte material, or the same material as the electrode material layer or the material constituting the electrode material layer and the solid electrolyte material It may consist of a mixture of
When the thin film layer is made of a solid electrolyte material, the thin film layer may be composed of one layer, and more specifically, a thin film layer having a thickness of at least 10 nm to 2 μm between the positive electrode layer and the negative electrode layer. An all-solid-state battery including the intervening material is also included in the present invention.

  About the formation method of the thin film layer in the said aspect, it is the same as that of the above, and it is preferable to use a vapor phase growth method or a chemical vapor deposition method (CVD method). In addition, the thickness of the thin film layer in this aspect is in the range of 10 nm to 2 μm. When the thickness is less than 10 nm, the thin film may not be uniformly formed on the electrode material layer, and there is a possibility of short circuit, which is not preferable. On the other hand, when the thickness of the thin film layer exceeds 2 μm, it is not preferable in terms of productivity of the all-solid-state battery.

[All-solid battery manufacturing method]
Hereinafter, a method for producing an all solid state battery of the present invention will be described with reference to FIG. As the method for producing the all solid state battery of the present invention, it is efficient to use the member for all solid state battery of the present invention. Specifically, the procedure is as follows.
First, a first thin film layer 3 having a thickness of 10 nm to 1 μm and a solid electrolyte layer 2 having a thickness of 1 to 500 μm are laminated in this order on an electrode material layer (positive electrode layer) 4 formed on a current collector 6. An all-solid battery member of the present invention is manufactured in advance. On the other hand, a second thin film layer having a thickness of 10 nm to 1 μm is formed on the other electrode material layer (negative electrode layer) 5 formed on the current collector 6 by vapor deposition or chemical vapor deposition (CVD). 3 ′ is formed to manufacture an electrode, and the all solid state battery of the present invention is manufactured by joining the all solid state battery member and the electrode so that the solid electrolyte layer 2 and the second thin film layer 3 ′ are in contact with each other. Can be manufactured. At this time, the material constituting the first thin film layer 3 and the second thin film layer 3 ′ is the same as the material constituting the solid electrolyte layer as described above, and the same material as the electrode material layer. Or a mixture thereof. The first thin film layer 3 and the second thin film layer 3 ′ may be formed of the same solid electrolyte, or one of the first thin film layer 3 and the second thin film layer 3 ′. May be formed of the same material as the electrode layer that is formed of a solid electrolyte and the other one contacts. Further, both the first thin film layer 3 and the second thin film layer 3 ′ may be formed of the same material as the electrode material layer in contact therewith.
Moreover, the all-solid-state battery of this invention can be manufactured by preparing two members for the all-solid-state battery of this invention, and joining so that the solid electrolyte layer of each member may contact (refer FIG. 3). .

  In the case where at least one of the above-described thin film layers 3 and 3 ′ is the same as the material constituting the solid electrolyte layer and does not have the solid electrolyte layer 2, an all-solid battery is manufactured by the following method. Can do. That is, the first thin film layer 3 having a thickness of 10 nm to 1 μm is formed on the electrode material layer (positive electrode layer) 4 formed on the current collector 6 by vapor deposition or chemical vapor deposition (CVD). Is formed. On the other hand, a second thin film layer having a thickness of 10 nm to 1 μm is formed on the other electrode material layer (negative electrode layer) 5 formed on the current collector 6 by vapor deposition or chemical vapor deposition (CVD). An electrode is manufactured by forming 3 ', and these are joined so that each thin film layer 3 and 3' may contact, and the all-solid-state battery of this invention can be manufactured.

  As a method of joining solid electrolyte layers or a solid electrolyte layer and a thin film layer, there are a method of laminating and pressurizing and pressure bonding, a method of pressurizing between two rolls (roll to roll), and the like. Moreover, you may join to the joining surface through the active material which has ion conductivity, and the adhesive material which does not inhibit ion conductivity. Furthermore, in the joining, heat fusion may be performed as long as the crystal structure of the solid electrolyte does not change.

Another manufacturing method will be described with reference to FIG. First, the first thin film layer 3 having a thickness of 10 nm to 1 μm is formed on the electrode material layer (positive electrode layer) 4 formed on the current collector 6 by vapor deposition or chemical vapor deposition (CVD). Formed thereon, the solid electrolyte layer 2 having a thickness of 1 to 500 μm is formed by coating, spraying, coating or powder compression by colliding with fine particles, and the member for an all-solid battery of the present invention is manufactured, A second thin film layer 3 ′ having a thickness of 10 nm to 1 μm is formed on the solid electrolyte layer 2 by vapor deposition or chemical vapor deposition (CVD), and an electrode material layer (negative electrode layer) is further formed thereon. ) 5 may be used. The method of providing the electrode material layer (negative electrode layer) 5 on the second thin film layer 3 ′ is not particularly limited, and is a method of laminating and pressurizing and pressing, or a method of pressing through two rolls ( roll to roll), a method of bonding via an adhesive substance that does not inhibit ionic conductivity, and the like.
In the case where at least one of the thin film layers 3 and 3 ′ is the same as the material constituting the solid electrolyte layer and does not have the solid electrolyte layer 2, first, it is formed on the current collector 6. A first thin film layer 3 having a thickness of 10 nm to 1 μm is formed on the electrode material layer (positive electrode layer) 4 by a vapor deposition method or a chemical vapor deposition method (CVD method), and a vapor deposition method is formed thereon. Alternatively, a method of forming a second thin film layer 3 ′ having a thickness of 10 nm to 1 μm by a chemical vapor deposition method (CVD method) and further providing an electrode material layer (negative electrode layer) 5 thereon can be employed.

  Furthermore, as another manufacturing method, a solid electrolyte layer 2 having a thickness of 1 to 500 μm is formed, and a thickness of 10 nm to 10 nm is formed on the front and back surfaces of the solid electrolyte layer by vapor deposition or chemical vapor deposition (CVD). A method of forming 1 μm thin film layers 3 and 3 ′ and further providing electrode material layers 4 (positive electrode layer) and 5 (negative electrode layer) on the respective thin film layers 3 and 3 ′ may be employed. In addition, as a method for providing the electrode material layers 4 and 5, the same method as described above can be used.

Next, the assembled battery of the present invention is obtained by connecting a plurality of high performance all solid state batteries as described above to obtain a high output. Since the all-solid-state battery of the present invention can be thinned, it can be stacked to obtain a high output, and can be highly integrated.
The method for producing the assembled battery is not particularly limited as long as the all solid state battery of the present invention is connected in series, but the connection part has one positive electrode active material constituting the positive electrode and one negative electrode active material constituting the negative electrode. By using bipolar electrodes held on both sides of the current collector, the electric resistance inside the battery can be further reduced.

Hereinafter, the present invention will be described more specifically with reference to examples.
Production Example (1) Production of Lithium Sulfide (Li ₂ S) Lithium sulfide was produced according to the method of the first aspect (two-step method) of JP-A-7-330312. Specifically, N-methyl-2-pyrrolidone (NMP) 3326.4 g (33.6 mol) and lithium hydroxide 287.4 g (12 mol) were charged into a 10 liter autoclave equipped with a stirring blade, and 300 rpm, 130 The temperature was raised to ° C. After the temperature rise, hydrogen sulfide was blown into the liquid at a supply rate of 3 liters / minute for 2 hours. Subsequently, this reaction solution was heated in a nitrogen stream (200 cc / min) to dehydrosulfide a part of the reacted hydrogen sulfide. As the temperature increased, water produced as a by-product due to the reaction between hydrogen sulfide and lithium hydroxide started to evaporate, but this water was condensed by the condenser and extracted out of the system. While water was distilled out of the system, the temperature of the reaction solution rose, but when the temperature reached 180 ° C., the temperature increase was stopped and the temperature was kept constant. After the dehydrosulfurization reaction was completed (about 80 minutes), the reaction was completed to obtain lithium sulfide.

(2) Purification of lithium sulfide After decanting NMP in the 500 mL slurry reaction solution (NMP-lithium sulfide slurry) obtained in (1) above, 100 mL of dehydrated NMP was added and stirred at 105 ° C. for about 1 hour. did. NMP was decanted at that temperature. Further, 100 mL of NMP was added, stirred at 105 ° C. for about 1 hour, NMP was decanted at that temperature, and the same operation was repeated a total of 4 times. After completion of the decantation, lithium sulfide was dried at 230 ° C. (temperature higher than the boiling point of NMP) under a nitrogen stream for 3 hours under normal pressure. The impurity content in the obtained lithium sulfide was measured.

Incidentally, lithium sulfite (Li ₂ SO _3), the content of each sulfur oxide lithium sulfate (Li ₂ SO ₄₎ and lithium thiosulfate _{(Li 2 S 2 O 3)} , and N- methylamino acid lithium (LMAB) Was quantified by ion chromatography. As a result, the total content of sulfur oxides was 0.13% by mass, and LMAB was 0.07% by mass.
The Li ₂ S thus purified was used in the following examples and comparative examples.

Example 1
(1) Production of solid electrolyte 0.6508 g (0.01417 mol) of high purity lithium sulfide (Li ₂ S, purity: 99.9%) produced in the above production example and diphosphorus pentasulfide (manufactured by Aldrich) 1.3492 g (0.00607 mol) was mixed well, and these powders were put into an alumina pot and completely sealed. The pot was attached to a planetary ball mill and mechanical milling was performed. At this time, milling was performed at a low speed (85 rpm) for the first few minutes in order to sufficiently mix the starting materials. Thereafter, the rotational speed was gradually increased and mechanical milling was performed at 370 rpm for 20 hours. As a result of evaluating the obtained powder by X-ray measurement, it was confirmed that it was vitrified (sulfide glass).
The obtained sulfide glass was heat-treated at 330 ° C. for 1 hour to form a glass ceramic, thereby producing a solid electrolyte.
When the ionic conductivity of this solid electrolyte was measured by the alternating current impedance method (measurement frequency: 100 Hz to 15 MHz), it showed 4.5 × 10 ⁻³ S / cm at room temperature. The spectrum obtained by solid ³¹ P-NMR measurement had peaks due to crystals at 90.9 ppm and 86.5 ppm, and the ratio of the crystals was 78 mol%.

(2) Formation of positive electrode layer The solid electrolyte synthesized in the above (1) and lithium cobalt oxide are mixed at a mass ratio of 5: 8 (solid electrolyte: lithium cobaltate), and the thickness is measured using a press molding machine. A positive electrode layer having a thickness of 0.5 mm and a diameter of 10 mm was formed on a stainless steel current collector having a thickness of 1.0 mm and a diameter of 10 mm.

(3) Formation of negative electrode layer The solid electrolyte synthesized in (1) above and carbon graphite are mixed at a ratio of 1: 1 (mass ratio), and are made of stainless steel having a thickness of 1.0 mm and a diameter of 10 mm using a press molding machine. A negative electrode layer having a thickness of 0.5 mm and a diameter of 10 mm was formed on the current collector.

(4) Formation of thin film layer On the positive electrode layer obtained in (2) above, the solid electrolyte produced in (1) above was vapor-deposited using an ion plating apparatus to form a thin film layer on the positive electrode layer. . The vapor deposition was performed so that the average film thickness of the thin film layer was 200 nm. As the ion plating apparatus, “IPB-450-VHS” manufactured by ULVAC, Inc. was used.
Next, on the negative electrode layer obtained in the above (3), the solid electrolyte produced in the above (1) was vapor-deposited using an ion plating apparatus in the same manner as described above, thereby forming a thin film layer on the negative electrode layer. The vapor deposition was performed so that the average film thickness of the thin film layer was 200 nm. The apparatus used is the same as described above.

(5) Production of single-layer all-solid battery The solid electrolyte powder produced in (1) above is sandwiched between the positive electrode layer having the thin film layer obtained in (4) above and the thin film layer side of the negative electrode layer, and pressed. Using a molding machine, a pressure of 980 MPa was applied to form a solid electrolyte layer, and a single-layer all-solid battery was produced. When the cross-sectional photograph by SEM was observed, the total average film thickness of the solid electrolyte layer and the two thin film layers was 0.1 mm (100 μm).
This single-layer all-solid-state battery was covered with an exterior body using the apparatus shown in FIG. That is, the single-layer all-solid battery 1 was loaded into a resin sealing mold 10, and a polybutadiene resin (“Epol” manufactured by Idemitsu Kosan Co., Ltd.) as a molten resin P was injected into the cavity 7. After cooling and curing the butadiene resin, the mold was removed, and the laminated battery sealed with the outer package 11 was taken out (see FIG. 5). A stainless steel electrode terminal 9 was joined to the uppermost current collector 6 and the lowermost current collector 6 by welding before coating with resin.
The initial charge / discharge efficiency of the single-layer all-solid battery was 83%, and the operating potential was 3.6V. Moreover, it was 18.3 mA / cm < ² > when the discharge current density was measured.

Comparative Example 1
Using the positive electrode layer and the negative electrode layer obtained in (2) and (3) above, without forming a thin film layer, the solid electrolyte powder produced in (1) above is sandwiched between the positive electrode layer and the negative electrode layer, and pressed. Using a molding machine, a pressure of 980 MPa was applied to form a solid electrolyte layer, and a single-layer all-solid battery was produced. When the cross-sectional photograph by SEM was observed, the average film thickness of the solid electrolyte layer was 0.1 mm (100 micrometers).
The single-layer all-solid-state battery was covered with an exterior body in the same manner as in Example 1 and evaluated in the same manner as in Example 1. The single-layer all-solid battery had an initial charge / discharge efficiency of 81% and an operating potential of 3.4V. The discharge current density was measured and found to be 8.7 mA / cm ² .

Example 2
An assembled battery in which five single-layer all-solid-state batteries manufactured in Example 1 (before coating the outer package) were stacked in series was covered with the outer package in the same manner as in Example 1 and evaluated in the same manner as in Example 1.
The obtained assembled battery had an initial charge / discharge efficiency of 80% and an operating potential of 17.2V. Moreover, it was 16.5 mA / cm < ² > when the discharge current density was measured.

  According to the present invention, the contact / bonding area between the electrode material layer and the solid electrolyte layer in the all-solid-state battery can be increased, the interface resistance between the electrode material layer and the solid electrolyte layer can be reduced, and the battery characteristics are particularly good. An all-solid battery having a high discharge current density can be provided. Therefore, it can be suitably used for a wide range of applications such as driving a vehicle such as a hybrid vehicle or a motorcycle, a power storage device, an emergency power source, a mobile phone, a personal computer, and the like.

It is a schematic diagram which shows the structure of the all-solid-state battery of this invention. It is a schematic diagram which shows an example of the manufacturing method of the all-solid-state battery of this invention. It is a schematic diagram which shows an example of the manufacturing method of the all-solid-state battery of this invention. It is a schematic diagram which shows the apparatus which coat | covers a solid battery element with an exterior body. It is a schematic diagram which shows the all-solid-state battery coat | covered with the exterior body.

Explanation of symbols

1: All-solid-state battery 2: Solid electrolyte layer 3, 3 ': Thin film layer 4: Electrode material layer (positive electrode layer)
5: Polar material layer (negative electrode layer)
6: Current collector 7: Cavity 8: Pressurizing jig 9: Electrode terminal 10: Mold for resin sealing 11: Exterior body P: Molten resin

Claims (16)

  An all-solid battery member in which a thin film layer having a thickness of 10 nm to 1 μm and a solid electrolyte layer having a thickness of 1 to 500 μm are laminated in this order on an electrode material layer, the thin film layer being the same as the solid electrolyte layer An all-solid-state battery member comprising the material, the same material as the electrode material layer, or a mixture thereof.   2. The total film according to claim 1, wherein the thin film layer is obtained by a vapor deposition method or a chemical vapor deposition method (CVD method), and the solid electrolyte layer is obtained by coating, spraying, coating, or powder compression by fine particle collision. Solid battery member.   A thin film layer having a thickness of 10 nm to 1 μm is formed on the electrode material layer by vapor deposition or chemical vapor deposition (CVD), and coating, spraying, coating or powder compression by fine particle collision is formed thereon. Is a method for producing an all-solid battery member that forms a solid electrolyte layer having a thickness of 1 to 500 μm, wherein the thin film layer is made of the same material as the solid electrolyte layer, the same material as the electrode layer, or a mixture thereof. A method for producing an all solid state battery member.   A solid electrolyte layer having a thickness of 1 to 500 μm is formed, and a thin film layer having a thickness of 10 nm to 1 μm is formed on the surface of the solid electrolyte layer by a vapor deposition method or a chemical vapor deposition method (CVD method). A method for producing an all-solid battery member in which an electrode material layer is provided, wherein the thin film layer is made of the same material as the solid electrolyte layer, the same material as the electrode material layer, or a mixture thereof. A method for producing a battery member.   The manufacturing method of the member for all-solid-state batteries of Claim 4 with which the said solid electrolyte layer is obtained by application | coating or compression of powder.   An all-solid battery comprising a thin film layer having a thickness of at least 10 nm to 2 μm interposed between a positive electrode layer and a negative electrode layer, wherein the thin film layer is made of a solid electrolyte material.   It is an all solid state battery in which a thin film layer having a thickness of 10 nm to 1 μm is laminated on each of a positive electrode layer and a negative electrode layer and bonded together, and at least one of the two thin film layers is made of a solid electrolyte material. All-solid battery featuring.   The all-solid-state battery according to claim 6 or 7, wherein the thin film layer is obtained by a vapor deposition method or a chemical vapor deposition method (CVD method).   An all-solid battery in which a solid electrolyte layer having a thickness of 1 to 500 μm is interposed between a positive electrode layer and a negative electrode layer, and further a thickness of 10 nm to each of the positive electrode layer, the negative electrode layer, and the solid electrolyte layer. An all-solid battery comprising a thin film layer of 1 μm, wherein the two thin film layers are each made of the same material as the solid electrolyte layer, the same material as the electrode material layer, or a mixture thereof.   A method for producing an all-solid-state battery, in which a thin film layer having a thickness of 10 nm to 2 μm is formed on a polar material layer by vapor deposition or chemical vapor deposition (CVD), and the polar material layer is provided thereon.   A first thin film layer having a thickness of 10 nm to 1 μm is formed on the electrode material layer by vapor deposition or chemical vapor deposition (CVD), and then vapor deposition or chemical vapor deposition ( A method for producing an all-solid battery in which a second thin film layer having a thickness of 10 nm to 1 μm is formed by a CVD method, and an electrode material layer is further provided thereon.   A first thin film layer having a thickness of 10 nm to 1 μm is formed on the electrode material layer by vapor deposition or chemical vapor deposition (CVD), and coating, spraying, coating or powdering by fine particle collision is formed thereon. A solid electrolyte layer having a thickness of 1 to 500 μm is formed by compressing the body to produce a member for an all-solid battery, and is thickened by vapor deposition or chemical vapor deposition (CVD) on another electrode material layer. Manufacturing an electrode by forming a second thin film layer having a thickness of 10 nm to 1 μm, and manufacturing the all solid state battery in which the all solid state battery member and the electrode are joined so that the solid electrolyte layer and the second thin film layer are in contact with each other A method for an all solid state battery, wherein the first thin film layer and the second thin film layer are each made of the same material as the solid electrolyte layer, the same material as the electrode layer, or a mixture thereof. Production method.   A method for producing an all-solid battery, comprising preparing all the members for an all-solid-state battery according to claim 1 or 2 and joining the members for an all-solid-state battery so that the respective solid electrolyte layers are in contact with each other.   A first thin film layer having a thickness of 10 nm to 1 μm is formed on the electrode material layer by vapor deposition or chemical vapor deposition (CVD), and coating, spraying, coating or powdering by fine particle collision is formed thereon. A solid electrolyte layer having a thickness of 1 to 500 μm is formed by compressing the body, and a second thin film layer having a thickness of 10 nm to 1 μm is formed thereon by a vapor deposition method or a chemical vapor deposition method (CVD method), Furthermore, there is provided a method for producing an all-solid battery in which an electrode material layer is provided thereon, wherein the first thin film layer and the second thin film layer are respectively the same material as the solid electrolyte layer, the same material as the electrode material layer, or these A method for producing an all-solid battery comprising a mixture of   A solid electrolyte layer having a thickness of 1 to 500 μm is formed, and a thin film layer having a thickness of 10 nm to 1 μm is formed on the front and back surfaces of the solid electrolyte layer by a vapor deposition method or a chemical vapor deposition method (CVD method), Furthermore, the manufacturing method of an all-solid-state battery in which an electrode material layer is provided thereon, wherein the two thin film layers are each made of the same material as the solid electrolyte layer, the same material as the electrode material layer, or a mixture thereof. A method for producing an all-solid battery.   The assembled battery formed by combining the all-solid-state battery in any one of Claims 6-9.

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